Zinc sorption to three gram-negative bacteria: combined titration, modeling, and EXAFS study.

PubMed

Guiné, V; Spadini, L; Sarret, G; Muris, M; Delolme, C; Gaudet, J P; Martins, J M F

2006-03-15

The acid-base and Zn sorption properties of three bacteria, Cupriavidus metallidurans CH34, Pseudomonas putida ATCC12633, and Escherichia coli K12DH5alpha, were investigated through an original combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and equilibrium titration studies. Acid-base titration curves of the three strains were fitted with a model accounting for three conceptual reactive sites: an acidic (carboxyl and/or phosphodiester), a neutral (phosphomonoester), and a basic (amine and/or hydroxyl) group. Calculated proton and Zn equilibrium constants and site densities compare with literature data. The nature of Zn binding sites was studied by EXAFS spectroscopy. Phosphoester, carboxyl, and unexpectedly sulfhydryl ligands were identified. Their proportions depended on Zn loading and bacterial strain and were consistent with the titration results. These findings were compared to the structure and site density of the major cell wall components. It appeared that the cumulated theoretical site density of these structures (<2 Zn nm(-2)) was much lower than the total site density of the investigated strains (16-56 Zn nm(-2)). These results suggest a dominant role of extracellular polymeric substances in Zn retention processes, although Zn binding to inner cell components cannot be excluded.

X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

NASA Astrophysics Data System (ADS)

Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

1986-01-01

K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

Local structure analysis of materials for increased energy efficiency

NASA Astrophysics Data System (ADS)

Medling, Scott

In this dissertation, a wide range of materials which exhibit interesting properties with potential for energy efficiency applications are investigated. The bulk of the research was conducted using the Extended X-ray Absorption Fine Structure (EXAFS) technique. EXAFS is a powerful tool for elucidating the local structure of novel materials, and it's advantages are presented in Chapter 2. In Chapter 3, I present details on two new techniques which are used in studies later in this dissertation, but are also promising for other, unrelated studies and, therefore, warrant being discussed generally. I explain the presence of and present a method for subtracting the X-ray Raman background in the fluorescence window when collecting fluorescence EXAFS data of a dilute dopant Z in a Z+1 host. I introduce X-ray magnetic circular dichroism (XMCD) and discuss the process to reduce XMCD data, including the self-absorption corrections for low energy K-edges. In Chapter 4, I present a series of investigations on ZnS:Cu electroluminescent phosphors. Optical microscopy indicates that the emission centers do not degrade uniformly or monotonically, but rather, most of the emission centers blink on and off during degradation. The effect of this on various proposed degradation mechanisms is discussed. EXAFS data of ZnS:Cu phosphors ground to enable thinner, lower-voltage devices indicate that grinding preferentially causes damage to the CuS nanoprecipitates, quenching electroluminescence (EL) and concluding that smaller particles must be built up from nanoparticles instead. EXAFS data of nanoparticles show that adding a ZnS shell outside a ZnS:Cu core provides significant additional encapsulation of the Cu, increasing photoluminescence and indicating that this may increase EL if devices can be fabricated. Data from extremely dilute (0.02% Cu) ZnS:Cu nanoparticles is presented in order to specifically study the non-precipitate and suggests that the Cu dopant substitutes for Zn and is adjacent to a S vacancy. In Chapter 5, I present a study into thermoelectric clathrates to determine how differences in size of one of the cage atoms affects the local structure and, therefore, the thermoelectric properties. I then discuss the effect of additional cage disorder on the scattering of phonons and the scattering of electrons, and thus the thermoelectric figure of merit. In Chapter 6, I present an XMCD study of La1 --xSrxCoO 3, finding results that are consistent with Sr-induced formation of ferromagnetic clusters within the non-magnetic, insulating matrix. We also show that not only are the O states spin-polarized, but a significant fraction of holes from Sr-doping go onto the O sites. Further, experimental results are compared to density functional calculations and discussed.

Influence of depositional environment in fossil teeth: a micro-XRF and XAFS study

NASA Astrophysics Data System (ADS)

Zougrou, I. M.; Katsikini, M.; Pinakidou, F.; Papadopoulou, L.; Tsoukala, E.; Paloura, E. C.

2014-04-01

The formation of metal-rich phases during the fossilization of vertebrate fossil teeth, recovered from various deposition environments in northern Greece, is studied by means of synchrotron radiation X-ray fluorescence (SR-XRF) as well as Fe and Mn K edge X-ray absorption fine structure (XAFS) spectroscopy. XRF line-scans from the samples' cross-sections revealed different contamination paths for Mn and Fe. The two-dimensional XRF maps illustrate the spatial distribution of P, Ca, Mn and Fe as well as the precipitation of Fe-rich phases in cementum, dentin and dentinal tubules. Goethite, lepidocrocite and ferrihydrite were detected in the samples' cross-section by means of Fe K edge EXAFS spectroscopy. Moreover the Fe and Mn K edge EXAFS revealed the presence of vivianite and birnessite (MnO2) on the external surface of two samples.

XAS study of TiO2-based nanomaterials

NASA Astrophysics Data System (ADS)

Schneider, K.; Zajac, D.; Sikora, M.; Kapusta, Cz.; Michalow-Mauke, K.; Graule, Th.; Rekas, M.

2015-07-01

X-Ray Absorption Spectroscopy studies of the W (0-1 at% W) and Mo-doped TiO2 (0-1 at% Mo) nanoparticle specimens at the K edges of titanium and molybdenum as well as at the L2 L3 edges of tungsten are presented. The materials were prepared with Flame Spray Synthesis process by oxidation of metal-organic precursors. The Ti:K edge spectra in the XANES range show pre-edge and post-edge features characteristic for anatase. A decrease of the amplitude of the EXAFS function with doping is observed and attributed to a softening of the crystal lattice. The Mo EXAFS functions show a considerable decrease of the second-neighbour-shell peak with increasing Mo content, which is attributed to an increased number of cation vacancies. For tungsten a less pronounced effect is observed. The Mo and W XANES spectra do not show noticeable changes with doping level, which indicates their unchanged oxidation states.

Zinc speciation in the suspended particulate matter of an urban river (Orge, France): influence of seasonality and urbanization gradient.

PubMed

Le Pape, Pierre; Quantin, Cécile; Morin, Guillaume; Jouvin, Delphine; Kieffer, Isabelle; Proux, Olivier; Ghanbaja, Jaafar; Ayrault, Sophie

2014-10-21

Among trace metal pollutants, zinc is the major one in the rivers from the Paris urban area, such as the Orge River, where Zn concentration in the suspended particulate matter (SPM) can reach 2000 mg/kg in the most urbanized areas. In order to better understand Zn cycling in such urban rivers, we have determined Zn speciation in SPM as a function of both the seasonal water flow variations and the urbanization gradient along the Orge River. Using TEM/SEM-EDX and linear combination fitting (LCF) of EXAFS data at the Zn K-edge, we show that Zn mainly occurs as tetrahedrally coordinated Zn(2+) sorbed to ferrihydrite (37-46%), calcite (0-37%), amorphous SiO2 (0-21%), and organic-P (0-30%) and as octahedrally coordinated Zn(2+) in the octahedral layer of phyllosilicates (18-25%). Moreover, the Zn speciation pattern depends on the river flow rate. At low water flow, Zn speciation changes along the urbanization gradient: geogenic forms of Zn inherited from soil erosion decrease relative to Zn bound to organic-phosphates and amorphous SiO2. At high water flow, Zn speciation is dominated by soil-borne forms of Zn regardless the degree of urbanization, indicating that erosion of Zn-bearing minerals dominates the Zn contribution to SPM under such conditions.

Nano-scale mechanisms of metal rhizostabilization in mine tailings

NASA Astrophysics Data System (ADS)

Chorover, J.; Rushforth, R. R.; Hayes, S.; Root, R.; Maier, R.

2010-12-01

Desert mine tailings pose significant health risks to proximal communities and ecosystems because metal-laden particles in the un-vegetated landscapes are readily transported via wind and water erosion. Therefore, establishment of a bioactive, vegetated cover and associated root mass can contribute significantly to site remediation. As a result of delivery to the subsurface of labile forms of reduced carbon, the incipient rhizosphere presents a bioactive zone where geochemical disequilibria are strongly influenced by root-microbe-metal-mineral interactions. Infusion of biota and carbon affect local mineral transformations and the associated speciation of toxic metal(loid)s. We investigated biogeochemical transformations in Pb and Zn containing mine tailings from Klondyke State Superfund site (AZ) as affected by phytostabilization. The research approach was to combine instrumented column experiments with molecular spectroscopy of the solid phase. Pb LIII-edge and Zn K-edge EXAFS spectroscopy, synchrotron-based XRF and XRD, and Raman microspectroscopy were employed to assess local coordination and mineralogy of Pb and Zn. Prior to plant introduction, contaminant Pb in the weathered surficial tailings was dominantly present in the minerals plumbojarosite (PbFe6(SO4)4(OH)12) and PbSO4, whereas Zn was dominantly present as hemimorphite (Zn4Si2O7(OH)2.H2O), Zn phyllosilicate, and ZnSO4(s). Column experiments showed that planted columns diminished pore water and effluent concentrations of both Pb and Zn, whereas transport of some other metals (e.g., Cu) was enhanced by complexation with dissolved organic matter. Spectroscopic studies of fine root tissues and root-microbe-metal associations revealed the formation of apparently biogenic Mn oxide plaques that were highly enriched in Zn and Pb.

Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi-Histidine Complexes of CuII, CuI and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

PubMed Central

Pushie, M. Jake; Nienaber, Kurt H.; McDonald, Alex; Millhauser, Glenn L.; George, Graham N.

2014-01-01

The metal coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of copper interaction with PrP just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, and yet the structural details of the various metal coordination modes have not been fully elucidated in some cases. Herein we employ X-ray absorption near edge spectroscopy as well as extended X-ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for CuII, CuI and ZnII with an N-terminal fragment of PrP. The PrP fragment constitutes four tandem repeats representative of the mammalian octarepeat domain, designated OR4, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations provide additional structural and thermodynamic data, and candidate structures are used to inform EXAFS data analysis. The optimized geometries from DFT calculations are used to identify potential coordination complexes for multi-histidine coordination of CuII, CuI and ZnII in an aqueous medium, modeled using 4-methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve fitting, using full multiple scattering on candidate structures from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of CuII, CuI and ZnII with the OR4 peptide at pH 7.4 at atomic resolution, which are best represented as a square planar [CuII(His)4]2+, digonal [CuI(His)2]+ and tetrahedral [ZnII(His)3(OH2)]2+, respectively. PMID:25042361

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

A new insight into the immobilization mechanism of Zn on biochar: the role of anions dissolved from ash

PubMed Central

Qian, Tingting; Wang, Yujun; Fan, Tingting; Fang, Guodong; Zhou, Dongmei

2016-01-01

Biochar is considered to be a promising material for heavy metal immobilization in soil. However, the immobilization mechanisms of Zn2+ on biochars derived from many common waste biomasses are not completely understood. Herein, biochars (denoted as PN350, PN550, WS350, and WS550) derived from pine needle (PN) and wheat straw (WS) were prepared at two pyrolysis temperatures (350 °C and 550 °C). The immobilization behaviors and mechanisms of Zn2+ on these biochars were systematically investigated. The results show that compared with biochars produced at low temperature, biochars produced at high temperature contained higher amounts of ash and exhibited much higher sorption capacities of Zn2+. By using Zn K-edge EXAFS spectroscopy, we find that the formation of various Zn precipitates/minerals, which was caused by the release of OH−, CO32−, and Si species from biochar, was the immobilization mechanism of Zn2+ on PN and WS biochars. Hydrozincite and Zn(OH)2 were the main species formed on PN350, PN550, and WS350; while on WS550, besides hydrozincite, a large fraction of hemimorphite was formed. The occurrence of hydrozincite and hemimorphite on biochar during Zn2+ immobilization is firstly reported in our study, which provides a new insight into the immobilization mechanism of Zn2+ on biochar. PMID:27641899

A new insight into the immobilization mechanism of Zn on biochar: the role of anions dissolved from ash

NASA Astrophysics Data System (ADS)

Qian, Tingting; Wang, Yujun; Fan, Tingting; Fang, Guodong; Zhou, Dongmei

2016-09-01

Biochar is considered to be a promising material for heavy metal immobilization in soil. However, the immobilization mechanisms of Zn2+ on biochars derived from many common waste biomasses are not completely understood. Herein, biochars (denoted as PN350, PN550, WS350, and WS550) derived from pine needle (PN) and wheat straw (WS) were prepared at two pyrolysis temperatures (350 °C and 550 °C). The immobilization behaviors and mechanisms of Zn2+ on these biochars were systematically investigated. The results show that compared with biochars produced at low temperature, biochars produced at high temperature contained higher amounts of ash and exhibited much higher sorption capacities of Zn2+. By using Zn K-edge EXAFS spectroscopy, we find that the formation of various Zn precipitates/minerals, which was caused by the release of OH-, CO32-, and Si species from biochar, was the immobilization mechanism of Zn2+ on PN and WS biochars. Hydrozincite and Zn(OH)2 were the main species formed on PN350, PN550, and WS350; while on WS550, besides hydrozincite, a large fraction of hemimorphite was formed. The occurrence of hydrozincite and hemimorphite on biochar during Zn2+ immobilization is firstly reported in our study, which provides a new insight into the immobilization mechanism of Zn2+ on biochar.

A new insight into the immobilization mechanism of Zn on biochar: the role of anions dissolved from ash.

PubMed

Qian, Tingting; Wang, Yujun; Fan, Tingting; Fang, Guodong; Zhou, Dongmei

2016-09-19

Biochar is considered to be a promising material for heavy metal immobilization in soil. However, the immobilization mechanisms of Zn(2+) on biochars derived from many common waste biomasses are not completely understood. Herein, biochars (denoted as PN350, PN550, WS350, and WS550) derived from pine needle (PN) and wheat straw (WS) were prepared at two pyrolysis temperatures (350 °C and 550 °C). The immobilization behaviors and mechanisms of Zn(2+) on these biochars were systematically investigated. The results show that compared with biochars produced at low temperature, biochars produced at high temperature contained higher amounts of ash and exhibited much higher sorption capacities of Zn(2+). By using Zn K-edge EXAFS spectroscopy, we find that the formation of various Zn precipitates/minerals, which was caused by the release of OH(-), CO3(2-), and Si species from biochar, was the immobilization mechanism of Zn(2+) on PN and WS biochars. Hydrozincite and Zn(OH)2 were the main species formed on PN350, PN550, and WS350; while on WS550, besides hydrozincite, a large fraction of hemimorphite was formed. The occurrence of hydrozincite and hemimorphite on biochar during Zn(2+) immobilization is firstly reported in our study, which provides a new insight into the immobilization mechanism of Zn(2+) on biochar.

EXAFS and XANES investigation of the ETS-10 microporous titanosilicate.

PubMed

Prestipino, C; Solari, P L; Lamberti, C

2005-07-14

In this work, we report state-of-the-art analysis of both Ti K-edge high-resolution XANES and EXAFS data collected on the ETS-10 molecular sieve at the GILDA BM8 beamline of the ESRF facility. The interatomic distances and the angles obtained in our EXAFS study are in fair agreement with the single-crystal XRD data of Wang and Jacobson (Chem. Commun. 1999, 973) and with the recent ab initio periodic study of Damin et al. (J. Phys. Chem. B 2004, 108, 1328) Differently from previous EXAFS work (J. Phys. Chem. 1996, 100, 449), our study supports a model of ETS-10 where the Ti atoms are bonded with two equivalent axial oxygen atoms. This model is also able to reproduce the edge and the post-edge region of the XANES spectrum. Conversely, the weak but well-defined pre-edge peak at 4971.3 eV can be explained only by assuming that a fraction of Ti atoms are in a local geometry similar to that of the pentacoordinated Ti sites in the ETS-4 structure. These Ti atoms in ETS-10 should be the terminal of the -Ti-O-Ti-O-Ti- chains, of which the actual number is strongly increased by the high crystal defectivity (Ti vacancies).

Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

NASA Astrophysics Data System (ADS)

Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

2005-11-01

Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

Bayes-Turchin Analysis of Overlapping L-Edges EXAFS Data of Iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossner, H. H.; Schmitz, D.; Imperia, P.

2007-02-02

Spin polarized and spin averaged extended x-ray absorption fine structure ((M)EXAFS) data were measured at temperatures of 180 K and 296 K in the soft x-ray energy regime of the overlapping L-edges of an iron film grown on V(110). The absorption coefficients were analyzed with the Bayes-Turchin procedure. The analysis yields the correction function to the atomic-like background-absorption coefficient calculated by FEFF8 and reveals components of atomic EXAFS oscillations. The EXAFS Debye-Waller (DW) parameters were determined. Their split into a thermal and a structural contribution was not possible without theoretical input since the two temperatures in this experiment were notmore » sufficiently far apart from each other and the k range of the data was too small. The a priori values of the thermal contribution to the DW parameters were therefore derived from a force-field model with two spring constants. They were adjusted to DW parameters calculated from Born-von Karman force constants which had been obtained from inelastic neutron scattering. Those two spring constants also nicely reproduce the unprojected vibrational density of states deduced from phonon dispersion curves. The MEXAFS oscillations can be described by the rigid-band model and the L2- and L3-EXAFS components. A negative exchange-related energy is obtained by fitting the MEXAFS signal in the extended energy region. This is in contrast to the predictions of the Hedin-Lundquist functional and the Dirac-Hara functional used in the FEFF8 code.« less

Fate of zinc in an electroplating sludge during electrokinetic treatments.

PubMed

Liu, Shou-Heng; Wang, H Paul

2008-08-01

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.

On the coordination of Zn2+ ion in Tf2N- based ionic liquids: structural and dynamic properties depending on the nature of the organic cation.

PubMed

Sessa, Francesco; Migliorati, Valentina; Serva, Alessandra; Lapi, Andrea; Aquilanti, Giuliana; Mancini, Giordano; D'Angelo, Paola

2018-01-24

A synergic approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy has been used to investigate diluted solutions of zinc bis(trifluoromethanesulfonyl)imide (Zn(Tf 2 N) 2 ) in Tf 2 N - based ionic liquids (ILs) having different organic cations, namely the 1-butyl-3-methylimidazolium ([C 4 (mim)] + ), 1,8-bis(3-methylimidazolium-1-yl)octane ([C 8 (mim) 2 ] 2+ ), N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium ([Choline] + ) and butyltrimethylammonium ([BTMA] + ) ions. All of the ILs tend to dissolve the Zn(Tf 2 N) 2 species giving rise to a different structural arrangement around the Zn 2+ as compared to that of the salt crystallographic structure. A quantitative analysis of the Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra of the solutions has been carried out based on the microscopic description of the systems derived from the MD simulations. A very good agreement between theoretical and experimental EXAFS signals has been obtained, allowing us to assess the reliability of the MD structural results for all the investigated solutions. The Zn 2+ ion has been shown to be coordinated by six oxygen atoms of the Tf 2 N - anions arranged in an octahedral geometry in all the Tf 2 N - based ILs, regardless of the organic cation of the IL solvent. However, the nature of the organic cation has a small influence on the overall spatial arrangement of the Tf 2 N - anions in the Zn 2+ first solvation shell: two different Zn-Tf 2 N complexes are found in solution, a 5-fold one, with one bidentate and four monodentate Tf 2 N - anions, and a 6-fold one with only monodentate ligands, with the ratio between the two species being slightly dependent on the IL cation. The IL ion three-dimensional arrangements in the different IL solutions were also investigated by carrying out a thorough analysis of the MD simulations, highlighting similarities and differences between imidazolium and ammonium based IL systems.

X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

NASA Astrophysics Data System (ADS)

Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

2017-05-01

Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Grace O.

1993-06-01

X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it,more » from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.« less

Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction.

PubMed

Minkina, Tatiana; Nevidomskaya, Dina; Bauer, Tatiana; Shuvaeva, Victoria; Soldatov, Alexander; Mandzhieva, Saglara; Zubavichus, Yan; Trigub, Alexander

2018-09-01

For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations. Copyright © 2018 Elsevier B.V. All rights reserved.

A X-Ray Absorption Study of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Bunker, Grant Byrd

This work is an experimental and theoretical study of the x-ray absorption near-edge structure of selected 3d transition metal compounds. The goal is to understand the physical mechanisms of XANES, using the competing multiple scattering (MS) and single scattering formalisms of Durham et al, and of Muller and Schaich, respectively. Careful experimental measurements of the K edge absorption of Mn oxides and KMnO(,4) at 300(DEGREES)K, 140(DEGREES)K and 80(DEGREES)K were made. These materials were chosen because they exhibit a variety of structures and oxidation states. Computer simulations of the XANES using the formalisms above were also performed. The experimental results show that atoms beyond the first coordination shell significantly affect the XANES near and above the edge; in particular the temperature dependent XANES and the "white line" in MnO establish this. We conclude that XANES, like EXAFS, is primarily sensitive to geometrical structure, except within about 1 Rydberg of the Fermi level. Two types of MS are distinguished: type 1 (forward scattering) is important in both XANES and EXAFS regions; type 2 (large angle scattering) is important only at and below the edge. MS of the photoelectron among the first shell Oxygen atoms in KMnO(,4) is observed experimentally, and found to become negligible above (DBLTURN) 1 Rydberg past the edge. The sharp features in XANES are primarily due to scattering from distant atoms, rather than localized states, except below the edge. This is supported by the observation that (alpha)-Mn(,2)O(,3) and Mn(,3)O(,4) spectra are nearly identical; their structures are the same, but the average oxidation states are different. We find the bond length strongly affects the edge position and the intensity of the 3d absorption in tetrahedrally coordinated transition metals. Other new results are the first shell EXAFS amplitude in MnO shows an anomalous energy dependence, which apparently cannot be explained by current theory. A new deconvolution algorithm is proposed to minimize truncation effects in Fourier filtering.

Cation distribution in NiZn-ferrite films via extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.; Kirkland, J. P.

1996-04-01

We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films. A least-squares fitting of experimental EXAFS data with theoretical, multiple-scattering, EXAFS data allowed the quantitative determination of site distributions for all transition metal cations.

X-ray absorption spectroscopic studies of mononuclear non-heme iron enzymes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westre, Tami E.

Fe-K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the electronic and geometric structure of the iron active site in non-heme iron enzymes. A new theoretical extended X-ray absorption fine structure (EXAFS) analysis approach, called GNXAS, has been tested on data for iron model complexes to evaluate the utility and reliability of this new technique, especially with respect to the effects of multiple-scattering. In addition, a detailed analysis of the 1s→3d pre-edge feature has been developed as a tool for investigating the oxidation state, spin state, and geometry of iron sites. Edge and EXAFS analyses have then been appliedmore » to the study of non-heme iron enzyme active sites.« less

Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite.

PubMed

Zougrou, I M; Katsikini, M; Brzhezinskaya, M; Pinakidou, F; Papadopoulou, L; Tsoukala, E; Paloura, E C

2016-08-01

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

Ca L2,3-edge XANES and Sr K-edge EXAFS study of hydroxyapatite and fossil bone apatite

NASA Astrophysics Data System (ADS)

Zougrou, I. M.; Katsikini, M.; Brzhezinskaya, M.; Pinakidou, F.; Papadopoulou, L.; Tsoukala, E.; Paloura, E. C.

2016-08-01

Upon burial, the organic and inorganic components of hard tissues such as bone, teeth, and tusks are subjected to various alterations as a result of interactions with the chemical milieu of soil, groundwater, and presence of microorganisms. In this study, simulation of the Ca L 2,3-edge X-ray absorption near edge structure (XANES) spectrum of hydroxyapatite, using the CTM4XAS code, reveals that the different symmetry of the two nonequivalent Ca(1) and Ca(2) sites in the unit cell gives rise to specific spectral features. Moreover, Ca L 2,3-edge XANES spectroscopy is applied in order to assess variations in fossil bone apatite crystallinity due to heavy bacterial alteration and catastrophic mineral dissolution, compared to well-preserved fossil apatite, fresh bone, and geologic apatite reference samples. Fossilization-induced chemical alterations are investigated by means of Ca L 2,3-edge XANES and scanning electron microscopy (SEM) and are related to histological evaluation using optical microscopy images. Finally, the variations in the bonding environment of Sr and its preference for substitution in the Ca(1) or Ca(2) sites upon increasing the Sr/Ca ratio is assessed by Sr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy.

The effect of doping on global lattice properties of magnetite Fe{sub 3-x}Me{sub x}O{sub 4} (Me=Zn, Ti and Al)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kakol, Z.; Owoc, D.; Przewoznik, J.

2012-08-15

X-ray powder diffraction was measured in Fe{sub 3-x}Me{sub x}O{sub 4} (Me=Zn, Ti, Al; x<0.065), in T range 70-300 K to see the effect of different doping on global lattice properties. The experimental results have shown that some lattice properties (e.g., the cell volume) are dopand specific. This can be attributed to the difference in preferential sites occupation by dopants. As confirmed by EXAFS, Zn enters tetrahedral, while Ti octahedral lattice sites, differently affecting crucial octahedral iron positions in the spinel lattice. However, despite this fact, it was found that T dependence of both monoclinic angle and lattice parameters is universalmore » for studied samples above and below the Verwey transition temperature T{sub V}. So, not the iron atoms in octahedral positions individually, but interactions between them are responsible for the Verwey transition character change with doping. - Graphical abstract: A low temperature magnetite cell volume vs. dopants content. Apparently, Zn, Ti and Al atoms have different effect on the global lattice properties at individual temperatures. However, the Verwey transition reacts to dopants in a similar manner, despite the different way the octahedral iron positions are affected. Highlights: Black-Right-Pointing-Pointer We measure powder diffraction and EXAFS on Fe{sub 3-x}Me{sub x}O{sub 4}, Me=Zn, Ti, Al (x<0.065), in T range 70-300 K. Black-Right-Pointing-Pointer XRD: atom-type independent changes of lattice parameters with T. Black-Right-Pointing-Pointer EXAFS: Zn replaces Fe on tetrahedral positions, Ti on octahedral positions. Black-Right-Pointing-Pointer Thus, some secondary interactions between ordering orbitals, not the primary one driving the Verwey transition, control the transition order.« less

XANES and EXAFS study of Au-substituted YBa2Cu3O(7-delta)

NASA Technical Reports Server (NTRS)

Ruckman, Mark W.; Hepp, Aloysius F.

1990-01-01

The near-edge structure (XANES) of the Au L3 and Cu K edges of YBa2Au(0.3)Cu(2.7)O(7-delta) was studied. X ray diffraction suggests that Au goes on the Cu(1) site and XANES shows that this has little effect on the oxidation state of the remaining copper. The gold L3 edge develops a white line feature whose position lies between that of trivalent gold oxide (Au2O3) and monovalent potassium gold cyanide (KAu(CN)2) and whose intensity relative to the edge step is smaller than in the two reference compounds. The L3 EXAFS for Au in the superconductor resembles that of Au2O3. However, differences in the envelope of the Fourier filtered component for the first shell suggest that the local structure of the Au in the superconductor is not equivalent to Au2O3.

Bayes-Turchin analysis of x-ray absorption data above the Fe L{sub 2,3}-edges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossner, H. H.; Schmitz, D.; Imperia, P.

2006-10-01

Extended x-ray absorption fine structure (EXAFS) data and magnetic EXAFS (MEXAFS) data were measured at two temperatures (180 and 296 K) in the energy region of the overlapping L-edges of bcc Fe grown on a V(110) crystal surface. In combination with a Bayes-Turchin data analysis procedure these measurements enable the exploration of local crystallographic and magnetic structures. The analysis determined the atomic-like background together with the EXAFS parameters which consisted of ten shell radii, the Debye-Waller parameters, separated into structural and vibrational components, and the third cumulant of the first scattering path. The vibrational components for 97 different scattering pathsmore » were determined by a two parameter force-field model using a priori values adjusted to Born-von Karman parameters of inelastic neutron scattering data. The investigations of the system Fe/V(110) demonstrate that the simultaneous fitting of atomic background parameters and EXAFS parameters can be performed reliably. Using the L{sub 2}- and L{sub 3}-components extracted from the EXAFS analysis and the rigid-band model, the MEXAFS oscillations can only be described when the sign of the exchange energy is changed compared to the predictions of the Hedin Lundquist exchange and correlation functional.« less

Effect of metal complex formation on the potential of organic aerosols as cloud condensation nuclei

NASA Astrophysics Data System (ADS)

Furukawa, T.; Takahashi, Y.

2010-12-01

Secondary organic aerosols (SOA) play a key role on the solar radiation balance in troposphere, since SOA can act as cloud condensation nuclei (CCN) due to its high hygroscopic nature. Oxalic acid is one of the most dominant components of SOA, which has cooling effects of the earth by acting as CCN. However, it is uncertain whether the oxalic acid can exist as free oxalic acid or metal-oxalate complexes in aerosols, even if there is a largedifference in their solubilities into water. Consequently, XAFS measurement was conducted to demonstrate the presence of metal-oxalate complexes. Size fractionated aerosol samples were collected in Tsukuba (located at northeast about 60 km from Tokyo) using a low-volume Andersen-type air sampler. The sampler had eight stages and a back-up filter. The sampling was conducted during winter and summer in 2002. Calcium oxalate was observed in finer particles in each period from Ca K-edge XANES, and its fractions among total Ca were approximately 20%. Similarly,, Zn oxalate was also detected in finer particles from Zn K-edge XANES and EXAFS. The [Zn-oxalate] / [Zn]total ratio in each period clearly increased with the decrease in the particle diameter. This result revealed that Zn-oxalate was formed in the aqueous phase at particle surfaces or in cloud processing. In other words, Zn-oxalate was abundant at the particle surface, resulting from the increase in the [surface]/[bulk] ratio with decreasing particle size. Based on (i) total concentrations of oxalate, Ca, and Zn determined by ion-chromatography and ICP-AES analyses and (ii) Ca- and Zn- oxalate fractions obtained by XAFS, we determined the fraction of metal-oxalate complexes among total oxalate in aerosols. In winter, Ca- and Zn- oxalate fractions reached about 60% of total oxalate in the ranges of 1.1-2.1 μm and 0.65-1.1 μm, while the value was about 60-80% in the same particle size range in summer. On the other hand, Ca- and Zn- oxalates are highly insoluble, showing that the complexes cannot act as CCN. Therefore, the ability of oxalic acid as CCN is needed to be reconsidered, because most of oxalic acid in aerosols exists as metal-oxalate complexes as shown by XAFS spectroscopy in this study.

Long- and Short-Range Structure of Ferrimagnetic Iron-Chromium Maghemites.

PubMed

García-Guaderrama, Marco; Montero-Cabrera, María E; Morán, Emilio; Alario-Franco, Miguel A; Fuentes-Cobas, Luis E; Macías-Ríos, Edgar; Esparza-Ponce, Hilda E; Fuentes-Montero, María E

2015-12-07

Maghemite-like materials containing Fe(3+) and Cr(3+) in comparable amounts have been prepared by solution-combustion synthesis. The conditions of synthesis and the magnetic properties are described. These materials are ferrimagnetic and are much more stable than pure iron maghemite since their maghemite-hematite transformation takes place at about ∼ 700 °C instead of ∼ 300 °C, as usually reported. These materials were studied by synchrotron radiation X-ray diffraction (XRD) and by X-ray absorption fine structure (XAFS) of the K-absorption edge of two elements. High-resolution XRD patterns were processed by means of the Rietveld method. Thus, maghemites were studied by XAFS in both Fe and Cr K-edges to clarify the short-range structure of the investigated systems. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure transitions were performed. The extended X-ray absorption fine structure (EXAFS) spectra were fitted considering the facts that the central atom of Fe is able to occupy octahedral and tetrahedral sites, each with a weight adjustment, while Cr occupies only octahedral sites. Interatomic distances were determined for x = 1, by fitting simultaneously both Fe and Cr K-edges average EXAFS spectra. The results showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO3).

Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

NASA Astrophysics Data System (ADS)

Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

1995-05-01

Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

Geometry of sorbed arsenate on ferrihydrite and crystalline FeOOH: Re-evaluation of EXAFS results and topological factors in predicting sorbate geometry, and evidence for monodentate complexes

USGS Publications Warehouse

Waychunas , Glenn A.; Davis, James A.; Fuller, Christopher C.

1995-01-01

Manceau's (1995) reinterpretation of some of our EXAFS results (Waychunas et al., 1993) has been analyzed using both old and newly collected data in an attempt to clarify the nature of proposed monodentate and edge-sharing bidentate arsenate complexes on the ferrihydrite surface. It is shown that EXAFS analysis utilizing data with sufficient k-range does indicate the presence of relatively short AsFe bonds, suggestive of an edge-sharing complex as indicated by Manceau (1995). However, a variety of data analysis factors and crystal chemical considerations create doubt in this assignment. Most significantly, X-ray scattering data collected on a sample of ferrihydrite with a large density of sorbed arsenate, which should show a substantial fraction of the edge-sharing complex, does not show any such correlation within fitting uncertainty. We also suggest that it is unnecessary to invoke the presence of edge-sharing bidentate arsenate to explain the surface growth poisoning of ferrihydrite with increasing sorbed arsenate, as Manceau (1995) claims.Further, we show that a model based on the topology of close packed oxygen ions offers a clear explanation why monodentate arsenate should appear on some surfaces and not on others, and why differing AsFe distances might be observed on a single surface with a single type of complex. This model also explains why bidentate sorbed arsenate can occupy positions with consistent “tilt” angles. Without such consistency, the sorbed arsenate would be highly positionally disordered, and difficult to detect accurately via EXAFS methods.

Cation distribution in NiZn-ferrite films determined using x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.

1996-04-01

We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films, Ni0.15ZnyFe2.85-yO4 (y=0.16, 0.23, 0.40, 0.60). The Ni, Zn, and Fe EXAFS were collected from each sample and analyzed to Fourier transforms. Samples of Ni-ferrite, Zn-ferrite, and magnetite were similarly studied as empirical standards. These standards, together with EXAFS data generated from the theoretical EXAFS FEFF codes, allowed the correlation of features in the Fourier transforms with specific lattice sites in the spinel unit cell. We find that the Ni ions reside mostly on the octahedral (B) sites whereas the Zn ions are predominantly on the tetrahedral (A) sites. The Fe ions reside on both A and B sites in a ratio determined by the ratio of Zn/Fe. The addition of Zn displaces a larger fraction of Fe cations onto the B sites serving to increase the net magnetization. The fraction of A site Ni ions is measured to increase peaking at ≊25% for y=0.6. At higher Zn concentrations (y≥0.5) the lattice experiences local distortions around the Zn sites causing a decrease in the superexchange resulting in a decrease in the net magnetization.

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

PubMed

Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

2013-08-07

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

X-ray absorption spectral studies of copper (II) mixed ligand complexes

NASA Astrophysics Data System (ADS)

Soni, B.; Dar, Davood Ah; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2014-09-01

X-ray absorption spectra at the K-edge of copper have been studied in two copper mixed ligand complexes, one having tetramethyethylenediamine (tmen) and the other having tetraethyethylenediamine (teen) as one of the ligands. The spectra have been recorded at BL-8 dispersive extended X-ray absorption fine structure (EXAFS) beamline at the 2.5 GeV INDUS- 2 synchrotron, RRCAT, Indore, India. The data obtained has been processed using the data analysis program Athena. The energy of the K-absorption edge, chemical shift, edge-width and shift of the principal absorption maximum in the complexes have been determined and discussed. The values of these parameters have been found to be approximately the same in both the complexes indicating that the two complexes possess similar chemical environment around the copper metal atom. The chemical shift has been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length because of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase- uncorrected bond length. Bond length has also been determined by Levy's, Lytle's and Lytle, Sayers and Stern's (LSS) methods. The results obtained from LSS and the Fourier transformation methods are comparable with each other, since both are phase uncorrected bond lengths.

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

NASA Astrophysics Data System (ADS)

Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, Hsuan-Yu; Hsieh, Shang-Hsien; Limaye, Mukta V.; Chuang, Chen-Hao; Hsueh, Hung-Chung; Wang, Hsaiotsu; Chiou, Jau-Wern; Tsai, Hung-Ming; Pao, Chih-Wen; Chen, Chia-Hao; Lin, Hong-Ji; Lee, Jyh-Fu; Wu, Chun-Te; Wu, Jih-Jen; Pong, Way-Faung; Ohigashi, Takuji; Kosugi, Nobuhiro; Wang, Jian; Zhou, Jigang; Regier, Tom; Sham, Tsun-Kong

2014-07-01

Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO. Electronic supplementary information (ESI) available: Scanning photoelectron microscopy (SPEM) results of ZnO NCs and NWs. Computational details and calculated total and partial density of states (PDOS) of bulk wurtzite ZnO with oxygen anion vacancies (VO). See DOI: 10.1039/c4nr01961j

X-ray source development for EXAFS measurements on the National Ignition Facility.

PubMed

Coppari, F; Thorn, D B; Kemp, G E; Craxton, R S; Garcia, E M; Ping, Y; Eggert, J H; Schneider, M B

2017-08-01

Extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first time on the NIF laser, and the requirements for optimization have been established.

Studying the local structures of novel materials using the Extended X-ray Absorption Fine Structure technique

NASA Astrophysics Data System (ADS)

Jiang, Yu

2009-12-01

In this dissertation, investigations on the local lattice structures for a variety of novel materials using Extended X-ray Absorption Fine Structure (EXAFS) technique are presented. Different experiment schemes were applied to obtain EXAFS data with high quality, and some interesting results were obtained by careful analysis. The power of the EXAFS technique was once again proved. In Chapter 1, I first briefly introduce the EXAFS theory and experiments, then give readers who are not familiar with this technique a short introduction on data reduction and analysis, and finally discuss some problems that are easily ignored in the interpretation of the experiment results. In Chapter 2, a temperature-dependent EXAFS investigation of La 1-xCaxMnO 3 is presented for the concentration range that spans the ferromagnetic-insulator (FMI) to ferromagnetic-metal (FMM) transition region, x = 0.16, 0.18, 0.20, and 0.22; the titrated hole concentrations are slightly higher y = 0.2, 0.22, 0.24, and 0.25 respectively. In Chapter 3, I report EXAFS studies of n- and p-type Ba8Ga 16Ge30 samples (type I clathrate) at the Ga, Ge, and Ba K-edges, to probe the local structure, particularly around the Ba atoms located inside 20- and 24-atom cages (Ba1 and Ba2 sites respectively) formed of Ga/Ge atoms. In agreement with diffraction analysis we find Ba2 is off-center, with a component in the bc plane (0.15 A) comparable to that found in diffraction; however, under the assumption of a stiff cage we also require a significant a component. This suggests a coupling or attraction between the Ba2 atoms and the hexagonal rings at the top or bottom of the cage that encloses the Ba2 site. In Chapter 4, I report detailed degradation and rejuvenation studies for AC electro-luminescence (EL) devices made using the phosphor ZnS:Cu,CI. We find that the AC EL emission spectra vary considerably with AC driving frequency but all spectra can be fit to a sum of four Gaussians. The combined experiments place strong constraints on the mechanisms for degradation and rejuvenation and suggest that EL degradation is most likely caused by either Cu or Cl diffusion under high E-fields, while thermal diffusion at slightly elevated temperatures without E-fields present, re-randomizes the (isolated) dopant distributions. In Chapter 5, I present a temperature-dependent EXAFS/XANES investigation of La1-xSrxCoO 3 (LSCO) over a wide doping concentration range (0 ≤ x ≤ 0.35). These experiments do not support the existence of a significant fraction of Co sites with an intermediate spin (IS) state, for which there is a JT active eg electron on the Co atoms. We cannot, however, exclude the possibility of a tiny fraction of sites having a JT distortion or some other (non-JT active) means of producing an IS state. The bulk samples are well ordered out to at least the third neighbors (Co-Co) while the nano-particles show increased disorder and a reduction in coordination for Co-Co. XANES data are also presented and, for both bulk and nano-particle samples, there is essentially no edge shift with increasing Sr concentration and no significant change in the first pre-edge peak with Sr concentration or changing temperature (4-300K). This indicates that when holes are introduced via Sr doping, Co remains close to Co3+; we argue that the holes go primarily into the O 2p bands. Bond-valence sums also indicate no change in Co valence.

2D XANES-XEOL mapping: observation of enhanced band gap emission from ZnO nanowire arrays

NASA Astrophysics Data System (ADS)

Wang, Zhiqiang; Guo, Xiaoxuan; Sham, Tsun-Kong

2014-05-01

Using 2D XANES-XEOL spectroscopy, it is found that the band gap emission of ZnO nanowire arrays is substantially enhanced i.e. that the intensity ratio between the band gap and defect emissions increases by more than an order of magnitude when the excitation energy is scanned across the O K-edge. Possible mechanisms are discussed.Using 2D XANES-XEOL spectroscopy, it is found that the band gap emission of ZnO nanowire arrays is substantially enhanced i.e. that the intensity ratio between the band gap and defect emissions increases by more than an order of magnitude when the excitation energy is scanned across the O K-edge. Possible mechanisms are discussed. Electronic supplementary information (ESI) available: XEOL spectra with different excitation energies. X-ray attenuation length vs. photon energy. Details of surface defects in ZnO NWs. The second O K-edge and Zn L-edge 2D XANES-XEOL maps. Comparison of the first and second TEY at O K-edge and Zn L-edge scans, respectively. Raman spectra of the ZnO NWs with different IBGE/IDE ratios. See DOI: 10.1039/c4nr01049c

Development of high resolution x-ray spectrometers for the investigation of bioinorganic chemistry in metalloproteins

NASA Astrophysics Data System (ADS)

Drury, Owen Byron

We have built an X-ray spectrometer for synchrotron-based high-resolution soft X-ray spectroscopy. The spectrometer uses four 9-pixel arrays of superconducting tunnel junctions (STJs) as sensors. They infer the energy of an absorbed X-ray from a temporary increase in tunneling current. The STJs are operated in a two-stage adiabatic demagnetization refrigerator (ADR) that uses liquid nitrogen and helium for precooling to 77 K and 4.2 K, and gallium gadolinium garnet and iron ammonium sulfate to attain a base temperature below 0.1 K. The sensors are held at the end of a 40-cm-long cold finger within ˜1 cm of a sample located inside the vacuum chamber of a synchrotron beam line end station. The spectrometer has an energy resolution between 10 eV and 20 eV FWHM below 1 keV, can be operated at rates up to ˜106 counts/s. STJ spectrometers are suited for chemical analysis of dilute samples by fluorescence-detected X-ray absorption spectroscopy (XAS) in cases where conventional germanium detectors do not have enough energy resolution. We have used this STJ spectrometer at the Advanced Light Source synchrotron for spectroscopy on the lower energy X-ray absorption edges of the elements Mo, S, Fe and N. These elements play an important role in biological nitrogen fixation at the metalloprotein nitrogenase, and we have examined if STJ spectrometers can be used to provide new insights into some of the open questions regarding the reaction mechanism of this protein. We have taken X-ray absorption near-edge spectra (XANES) and extended fine structure spectra (EXAFS) of an Fe 6N(CO)15-compound containing a single N atom inside a cluster of six Fe atoms, as postulated to exist inside the Fe-S cluster of the FeMo-cofactor (FeMo-co) in nitrogenase. The STJ detector has enabled the first-ever extended range EXAFS scans on nitrogen through the oxygen K-edge, enabling a comparison with N EXAFS on FeMo-co. We have taken iron L23-edge spectra of the Fe-S cluster in FeMo-co, which can be used to measure its oxidation state despite the very small chemical shifts. We also have taken spectra on the molybdenum M-edges and on the sulfur L-edges of inorganic model compounds.

X-ray source development for EXAFS measurements on the National Ignition Facility

DOE PAGES

Coppari, F.; Thorn, D. B.; Kemp, G. E.; ...

2017-08-28

We present that extended X-ray absorption Fine Structure (EXAFS) measurements require a bright, spectrally smooth, and broad-band x-ray source. In a laser facility, such an x-ray source can be generated by a laser-driven capsule implosion. In order to optimize the x-ray emission, different capsule types and laser irradiations have been tested at the National Ignition Facility (NIF). A crystal spectrometer is used to disperse the x-rays and high efficiency image plate detectors are used to measure the absorption spectra in transmission geometry. Finally, EXAFS measurements at the K-edge of iron at ambient conditions have been obtained for the first timemore » on the NIF laser, and the requirements for optimization have been established.« less

High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung

The addition of Lewis or Brönsted acids (LA = Zn(OTf) 2, B(C 6F 5) 3, HBAr F, TFA) to the high-valent manganese–oxo complex Mn V(O)(TBP 8Cz) results in the stabilization of a valence tautomer Mn IV(O-LA)(TBP 8Cz •+). The Zn II and B(C 6F 5) 3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn–N avemore » = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal oxo ligand. This Mn–O bond length is elongated compared to the Mn V(O) starting material (Mn–O = 1.55 Å). The reactivity of Mn IV(O-LA)(TBP 8Cz •+) toward C–H substrates was examined, and it was found that H • abstraction from C–H bonds occurs in a 1:1 stoichiometry, giving a Mn IV complex and the dehydrogenated organic product. The rates of C–H cleavage are accelerated for the Mn IV(O-LA)(TBP 8Cz •+) valence tautomer as compared to the MnV(O) valence tautomer when LA = Zn II, B(C 6F 5) 3, and HBArF, whereas for LA = TFA, the C–H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of k H/ k D = 25–27 was observed for LA = B(C 6F 5) 3 and HBAr F, indicating that H-atom transfer (HAT) is the rate-limiting step in the C–H cleavage reaction and implicating a potential tunneling mechanism for HAT. Furthermore, the reactivity of Mn IV(O-LA)(TBP 8Cz •+) toward C–H bonds depends on the strength of the Lewis acid. The HAT reactivity is compared with the analogous corrole complex Mn IV(O–H)(tpfc •+) recently reported.« less

High-valent manganese–oxo valence tautomers and the influence of Lewis/Brönsted acids on C–H bond cleavage

DOE PAGES

Baglia, Regina A.; Krest, Courtney M.; Yang, Tzuhsiung; ...

2016-09-30

The addition of Lewis or Brönsted acids (LA = Zn(OTf) 2, B(C 6F 5) 3, HBAr F, TFA) to the high-valent manganese–oxo complex Mn V(O)(TBP 8Cz) results in the stabilization of a valence tautomer Mn IV(O-LA)(TBP 8Cz •+). The Zn II and B(C 6F 5) 3 complexes were characterized by manganese K-edge X-ray absorption spectroscopy (XAS). The position of the edge energies and the intensities of the pre-edge (1s to 3d) peaks confirm that the Mn ion is in the +4 oxidation state. Fitting of the extended X-ray absorption fine structure (EXAFS) region reveals 4 N/O ligands at Mn–N avemore » = 1.89 Å and a fifth N/O ligand at 1.61 Å, corresponding to the terminal oxo ligand. This Mn–O bond length is elongated compared to the Mn V(O) starting material (Mn–O = 1.55 Å). The reactivity of Mn IV(O-LA)(TBP 8Cz •+) toward C–H substrates was examined, and it was found that H • abstraction from C–H bonds occurs in a 1:1 stoichiometry, giving a Mn IV complex and the dehydrogenated organic product. The rates of C–H cleavage are accelerated for the Mn IV(O-LA)(TBP 8Cz •+) valence tautomer as compared to the MnV(O) valence tautomer when LA = Zn II, B(C 6F 5) 3, and HBArF, whereas for LA = TFA, the C–H cleavage rate is slightly slower than when compared to MnV(O). A large, nonclassical kinetic isotope effect of k H/ k D = 25–27 was observed for LA = B(C 6F 5) 3 and HBAr F, indicating that H-atom transfer (HAT) is the rate-limiting step in the C–H cleavage reaction and implicating a potential tunneling mechanism for HAT. Furthermore, the reactivity of Mn IV(O-LA)(TBP 8Cz •+) toward C–H bonds depends on the strength of the Lewis acid. The HAT reactivity is compared with the analogous corrole complex Mn IV(O–H)(tpfc •+) recently reported.« less

Arsenic Scavenging by Al-Substituted Ferrihydrites in a Circumneutral pH River Impacted by the Acid Mine Drainage of Carnoulès, Gard, France

NASA Astrophysics Data System (ADS)

ADRA, A.; Morin, G.; ona-Nguema, G.; Maillot, F.; Casiot, C.; Bruneel, O.

2013-12-01

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure and reactivity of aluminum-rich Fh from river-bed sediments collected in a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. EXAFS analysis indicates that Al(III) substitutes for Fe(III) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 20-37×7 mol%Al range, in agreement with bulk chemical compositions. Synthetic aluminous Fh analogues prepared in the present study are found to be less Al-substituted (14-18×4 mol%Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidences for the scavenging of arsenic by natural Al- Fh, with possible implications for other pollutants in natural or engineered systems.

Local order structure and surface acidity properties of a Nb 2O 5/SiO 2 mixed oxide prepared by the sol-gel processing method

NASA Astrophysics Data System (ADS)

Francisco, Maria Suzana P.; Landers, Richard; Gushikem, Yoshitaka

2004-07-01

The sol-gel processing method was used as an alternative route to obtain Nb 2O 5 phase homogenously dispersed in the SiO 2 matrix, improving the thermal stability of the Brønsted acid sites, Nb-OH and Nb-OH-Si groups. The local niobium structure and the influence of the amount of niobia on the surface of the Nb 2O 5/SiO 2 system were studied by XAS and XPS, respectively. For the samples calcined at 423 and 873 K, the 3 d5/2 BE values are at ca. 208.2 eV, indicating an ionic character for Nb(V) species in the SiO 2 matrix, probably associated to Si-O-Nb linkages. The features of Nb K-edge XANES spectra of samples show the absence of NbO species. The Nb K-edge EXAFS oscillations exhibit a shoulder at ca. 5.6 Å -1, which probably arises from Nb-O-Si. This fact corroborates the EXAFS simulation data of the second coordination shell, whose best fitting is achieved with three distances, two Nb-Nb lengths and one Nb-Si.

Revealing the Bonding Environment of Zn in ALD Zn(O,S) Buffer Layers through X-ray Absorption Spectroscopy

PubMed Central

2017-01-01

Zn(O,S) buffer layer electronic configuration is determined by its composition and thickness, tunable through atomic layer deposition. The Zn K and L-edges in the X-ray absorption near edge structure verify ionicity and covalency changes with S content. A high intensity shoulder in the Zn K-edge indicates strong Zn 4s hybridized states and a preferred c-axis orientation. 2–3 nm thick films with low S content show a subdued shoulder showing less contribution from Zn 4s hybridization. A lower energy shift with film thickness suggests a decreasing bandgap. Further, ZnSO4 forms at substrate interfaces, which may be detrimental for device performance. PMID:29083141

Structural investigations in helium implanted cubic zirconia using grazing incidence XRD and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Kuri, G.; Degueldre, C.; Bertsch, J.; Döbeli, M.

2010-06-01

The crystal structure and local atom arrangements surrounding Zr atoms were determined for a helium implanted cubic stabilized zirconia (CSZ) using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively, measured at glancing angles. The implanted specimen was prepared at a helium fluence of 2 × 10 16 cm -2 using He + beams at two energies (2.54 and 2.74 MeV) passing through a 8.0 μm Al absorber foil. XRD results identified the formation of a new rhombohedral phase in the helium embedded layer, attributed to internal stress as a result of expansion of the CSZ-lattice. Zr K-edge EXAFS data suggested loss of crystallinity in the implanted lattice and disorder of the Zr atoms environment. EXAFS Fourier transforms analysis showed that the average first-shell radius of the Zr sbnd O pair in the implanted sample was slightly larger than that of the CSZ standard. Common general disorder features were explained by rhombohedral type short-range ordered clusters. The average structural parameters estimated from the EXAFS data of unimplanted and implanted CSZ are compared and discussed. Potential of EXAFS as a local probe of atomic-scale structural modifications induced by helium implantation in CSZ is demonstrated.

X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems

PubMed Central

Sarangi, Ritimukta

2012-01-01

Metal K-edge X-ray absorption spectroscopy (XAS) has been extensively applied to bioinorganic chemistry to obtain geometric structure information on metalloprotein and biomimetic model complex active sites by analyzing the higher energy extended X-ray absorption fine structure (EXAFS) region of the spectrum. In recent years, focus has been on developing methodologies to interpret the lower energy K-pre-edge and rising-edge regions (XANES) and using it for electronic structure determination in complex bioinorganic systems. In this review, the evolution and progress of 3d-transition metal K-pre-edge and rising-edge methodology development is presented with particular focus on applications to bioinorganic systems. Applications to biomimetic transition metal–O2 intermediates (M = Fe, Co, Ni and Cu) are reviewed, which demonstrate the power of the method as an electronic structure determination technique and its impact in understanding the role of supporting ligands in tuning the electronic configuration of transition metal–O2 systems. PMID:23525635

An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

PubMed

Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

2013-01-30

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

Bond compressibility and bond Grüneisen parameters of CdTe

NASA Astrophysics Data System (ADS)

Fornasini, P.; Grisenti, R.; Irifune, T.; Shinmei, T.; Mathon, O.; Pascarelli, S.; Rosa, A. D.

2018-06-01

Extended x-ray absorption fine structure (EXAFS) at the Cd K edge and diffraction patterns have been measured on CdTe as a function of pressure from 100 kPa (1 bar) to 5 GPa using a cell with nano-polycrystalline diamond anvils and an x-ray focussing scanning spectrometer. Three phases—zincblende (ZB), mixed cinnabar-ZB and rocksalt (RS)—are well distinguished in different pressure intervals. The bond compressibility measured by EXAFS in the ZB phase is slightly smaller than the one measured by diffraction and decreases significantly faster when the pressure increases; the difference is attributed to the effect of relative vibrations perpendicular to the Cd–Te bond. The parallel mean square relative displacement (MSRD) decreases, the perpendicular MSRD increases when the pressure increases, leading to an increasing anisotropy of relative atomic vibrations. A constant-temperature bond Grüneisen parameter (GP) has been evaluated for the ZB phase and compared with the constant-pressure bond GP measured in a previous experiment; an attempt is made to connect the bond GPs measured by EXAFS and the more familiar thermodynamic GP and mode GPs; the comparisons suggest the inadequacy of the quasi-harmonic approximation to deal with the local vibrational properties sampled by EXAFS.

Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E.

2015-07-23

The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-rangemore » structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})« less

Characterization of local atomic structure in Co/Zn based ZIFs by XAFS

NASA Astrophysics Data System (ADS)

Podkovyrina, Yulia; Butova, Vera; Bulanova, Elena; Budnyk, Andriy; Kremennaya, Maria; Soldatov, Alexander; Lamberti, Carlo

2018-03-01

The local atomic structure in bimetallic Co/Zn zeolitic imidazolate frameworks (ZIFs) was studied using X-ray Absorption Fine Structure (XAFS) spectroscopy and theoretical calculations. The experimental Co K-edge and Zn K-edge XANES (X-ray Absorption Near Edge Structure) spectra of Zn1-xCoxC8H10N4 samples (x = 0.05, 0.25, 0.75) synthesized by microwave synthesis were compared with the data for the ZIF-67 (x=1) and ZIF-8 (x=0). Theoretical XANES spectra for the bimetallic ZIFs were calculated. It was shown that in bimetallic ZIFs the Co and Zn atoms have the similar local environment.

Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

PubMed

Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

2016-02-03

Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

PubMed Central

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using micro-focused Extended X-ray Absorption Fine Structure (EXAFS) and X-ray fluorescence (μSXRF) mapping , bulk EXAFS, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and micro-focused EXAFS spectra of Zn in the biogenic Mn oxides coating are indicative of Zn forming triple corner sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to decreasing in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in solid to solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating desorption is not controlled by dissolution of secondary Zn phases. In sum, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process in Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present. PMID:24460038

Weathering and precipitation after meteorite impact of Ni, Cr, Fe, Ca and Mn in K-T boundary clays from Stevns Klint

NASA Astrophysics Data System (ADS)

Miyano, Yumiko; Yoshiasa, Akira; Tobase, Tsubasa; Isobe, Hiroshi; Hongu, Hidetomo; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

2016-05-01

Ni, Cr, Fe, Ca and Mn K-edge XANES and EXAFS spectra were measured on K-T boundary clays from Stevns Klint in Denmark. According to XANES spectra and EXAFS analyses, the local structures of Ni, Cr and Fe in K-T boundary clays is similar to Ni(OH)2, Cr2O3 and FeOOH, respectively. It is assumed that the Ni, Cr and Fe elements in impact related glasses is changing into stable hydrate and oxide by the weathering and diagenesis at the surface of the Earth. Ca in K-T boundary clays maintains the diopside-like structure. Local structure of Ca in K-T clays seems to keep information on the condition at meteorite impact. Mn has a local structure like MnCO3 with divalent state. It is assumed that the origin on low abundant of Mn in the Fe-group element in K-T clays was the consumption by life activity and the diffusion to other parts.

Speciation and solubility of heavy metals in contaminated soil using X-ray microfluorescence, EXAFS spectroscopy, chemical extraction, and thermodynamic modeling

NASA Astrophysics Data System (ADS)

Kirpichtchikova, Tatiana A.; Manceau, Alain; Spadini, Lorenzo; Panfili, Fré; dé; ric; Marcus, Matthew A.; Jacquet, Thierry

2006-05-01

Synchrotron-based X-ray radiation microfluorescence (μ-SXRF) and micro-focused and powder extended X-ray absorption fine structure (EXAFS) spectroscopy measurements, combined with desorption experiments and thermodynamic calculations, were used to evaluate the solubility of metal contaminants (Zn, Cu, Pb) and determine the nature and fractional amount of Zn species in a near-neutral pH (6.5-7.0) truck-farming soil contaminated by sewage irrigation for one hundred years. Zn is the most abundant metal contaminant in the soil (1103 mg/kg), followed by Pb (535 mg/kg) and Cu (290 mg/kg). The extractability of Zn, Pb, and Cu with citrate, S, S-ethylenediaminedisuccinic acid (EDDS), and ethylenediaminetetraacetic acid (EDTA) was measured as a function of time (24 h, 72 h, 144 h), and also as a function of the number of applications of the chelant (5 applications each with 24 h of contact time). Fifty-three percent of the Zn was extracted after 144 h with citrate, 51% with EDDS and 46% with EDTA, compared to 69, 87, and 61% for Cu, and 24, 40, and 34% for Pb. Renewing the extracting solution removed more of the metals. Seventy-nine, 65, and 57% of the Zn was removed after five cycles with citrate, EDDS and EDTA, respectively, compared to 88, 100, and 72% for Cu, and 91, 65, and 47% for Pb. Application to the untreated soil of μ-SXRF, laterally resolved μ-EXAFS combined with principal component analysis, and bulk averaging powder EXAFS with linear least-squares combination fit of the data, identified five Zn species: Zn-sorbed ferrihydrite, Zn phosphate, Zn-containing trioctahedral phyllosilicate (modeled by the Zn kerolite, Si 4(Mg 1.65Zn 1.35)O 10(OH) 2 · nH 2O), willemite (Zn 2SiO 4), and gahnite (ZnAl 2O 4), in proportions of ˜30, 28, 24, 11, and less than 10%, respectively (precision: 10% of total Zn). In contrast to Cu and Pb, the same fractional amount of Zn was extracted after 24 h contact time with the three chelants (40-43% of the initial content), suggesting that one of the three predominant Zn species was highly soluble under the extraction conditions. Comparison of EXAFS data before and after chemical treatment revealed that the Zn phosphate component was entirely and selectively dissolved in the first 24 h of contact time. Preferential dissolution of the Zn phosphate component is supported by thermodynamic calculations. Despite the long-term contamination of this soil, about 79% of Zn, 91% of Pb, and 100% of Cu can be solubilized in the laboratory on a time scale of a few days by chemical complexants. According to metal speciation results and thermodynamic calculations, the lower extraction level measured for Zn is due to the Zn phyllosilicate component, which is less soluble than Zn phosphate and Zn ferrihydrite.

Arsenic scavenging by aluminum-substituted ferrihydrites in a circumneutral pH river impacted by acid mine drainage.

PubMed

Adra, Areej; Morin, Guillaume; Ona-Nguema, Georges; Menguy, Nicolas; Maillot, Fabien; Casiot, Corinne; Bruneel, Odile; Lebrun, Sophie; Juillot, Farid; Brest, Jessica

2013-11-19

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure of aluminum-rich Fh, and their role in arsenic scavenging in river-bed sediments from a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. TEM-EDXS elemental mapping and SEM-EDXS analyses combined with EXAFS analysis indicates that Al(3+) substitutes for Fe(3+) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 25-30 ± 10 mol %Al range. Synthetic aluminous Fh prepared in the present study are found to be less Al-substituted (14-20 ± 5 mol %Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidence for the scavenging of arsenic by natural Al-Fh, which emphasize the possible implication of such material for scavenging pollutants in natural or engineered systems.

The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L3 edge XAS.

PubMed

Tew, Min Wei; Nachtegaal, Maarten; Janousch, Markus; Huthwelker, Thomas; van Bokhoven, Jeroen A

2012-04-28

The catalytically active phase of silica-supported palladium catalysts in the selective and non-selective hydrogenation of 1-pentyne was determined using in situ X-ray absorption spectroscopy at the Pd K and L(3) edges. Upon exposure to alkyne, a palladium carbide-like phase rapidly forms, which prevents hydrogen to diffuse into the bulk of the nano-sized particles. Both selective and non-selective hydrogenation occur over carbided particles. The palladium carbide-like phase is stable under reaction conditions and only partially decomposes under high hydrogen partial pressure. Non-selective hydrogenation to pentane is not indicative of hydride formation. The palladium carbide phase was detected in the EXAFS analysis and the K edge XANES showed representative features. This journal is © the Owner Societies 2012

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

NASA Astrophysics Data System (ADS)

McKeown, David A.; Gan, Hao; Pegg, Ian L.; Stolte, W. C.; Demchenko, I. N.

2011-01-01

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl 2, where Cl - is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl 2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na distances; Cl sbnd Ca contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include Cl sbnd Cl, Cl sbnd O, and Cl sbnd Na correlations, where Cl sbnd O and Cl sbnd Na distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl - is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that Cl sbnd Cl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl - was associated with Ca 2+ and Na + in network modifier sites.

Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

NASA Astrophysics Data System (ADS)

Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

2009-04-01

The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically reflected in particle morphology and SAED patterns. The P K-edge XANES spectra revealed that phosphate was bound to both Fe as well as Ca (if present). The Ca K-edge XANES spectra showed that the mode of Ca uptake by the Fe(III)-precipitates shifted from mainly adsorption at high Fe/P to coprecipitation at low Fe/P ratio. Despite oversaturation, neither calcite nor hydroxyapatite formed to a significant extent. The results from this study indicated that, depending on water composition, Fe(II) oxidation in natural waters leads to different types of short-range-ordered Fe(III)-phases. Since these phases are expected to differ in their effect on contaminant and nutrient dynamics, their specific physical and chemical properties warrant further research. Methodologically, this work demonstrated the usefulness of investigating the local structure of short-range-ordered precipitates along compositional gradients and by combining the element-selective information from different X-ray absorption edges.

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques.

PubMed

Yang, Jianjun; Liu, Jin; Dynes, James J; Peak, Derek; Regier, Tom; Wang, Jian; Zhu, Shenhai; Shi, Jiyan; Tse, John S

2014-02-01

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu2S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.

Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

PubMed Central

Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

2016-01-01

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils. PMID:27212680

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jianjun; Wang, Jian; Pan, Weinan

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

Retention mechanisms of citric acid in ternary kaolinite-Fe(III)-citrate acid systems using Fe K-edge EXAFS and L 3,2-edge XANES spectroscopy

DOE PAGES

Yang, Jianjun; Wang, Jian; Pan, Weinan; ...

2016-05-23

Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L- 3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorptionmore » and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤ 0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. In conclusion, these findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.« less

The effect of phytostabilization on Zn speciation in a dredged contaminated sediment using scanning electron microscopy, X-ray fluorescence, EXAFS spectroscopy, and principal components analysis

NASA Astrophysics Data System (ADS)

Panfili, Frédéric; Manceau, Alain; Sarret, Géraldine; Spadini, Lorenzo; Kirpichtchikova, Tatiana; Bert, Valérie; Laboudigue, Agnès; Marcus, Matthew A.; Ahamdach, Noureddine; Libert, Marie-Françoise

2005-05-01

The maintenance of waterways generates large amounts of dredged sediments, which are deposited on adjacent land surfaces. These sediments are often rich in metal contaminants and present a risk to the local environment. Understanding how the metals are immobilized at the molecular level is critical for formulating effective metal containment strategies such as phytoremediation. In the present work, the mineralogical transformations of Zn-containing phases induced by two graminaceous plants (A grostis tenuis and Festuca rubra) in a contaminated sediment ([Zn] = 4700 mg kg -1, [P 2O 5] = 7000 mg kg -1, pH = 7.8), untreated or amended with hydroxylapatite (AP) or Thomas basic slag (TS), were investigated after two yr of pot experiment by scanning electron microscopy coupled with energy-dispersive spectrometry (SEM-EDS), synchrotron-based X-ray microfluorescence (μ-SXRF), and powder and laterally resolved extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. The number and nature of Zn species were evaluated by principal component (PCA) and least-squares fitting (LSF) analysis of the entire set of μ-EXAFS spectra, which included up to 32 individual spectra from regions of interest varying in chemical composition. Seven Zn species were identified at the micrometer scale: sphalerite, gahnite, franklinite, Zn-containing ferrihydrite and phosphate, (Zn-Al)-hydrotalcite, and Zn-substituted kerolite-like trioctahedral phyllosilicate. Bulk fractions of each species were quantified by LSF of the powder EXAFS spectra to linear combinations of the identified Zn species spectra. In the untreated and unvegetated sediment, Zn was distributed as ˜50% (mole ratio of total Zn) sphalerite, ˜40% Zn-ferrihydrite, and ˜10 to 20% (Zn-Al)-hydrotalcite plus Zn-phyllosilicate. In unvegetated but amended sediments (AP and TS), ZnS and Zn-ferrihydrite each decreased by 10 to 20% and were replaced by Zn-phosphate (˜30˜40%). In the presence of plants, ZnS was almost completely dissolved, and the released Zn bound to phosphate (˜40-60%) and to Zn phyllosilicate plus (Zn,Al)-hydrotalcite (˜20-40%). Neither the plant species nor the coaddition of mineral amendment affected the Zn speciation in the vegetated sediment. The sediment pore waters were supersaturated with respect to Zn-containing trioctahedral phyllosilicate, near saturation with respect to Zn-phosphate, and strongly undersaturated with respect to (Zn,Al)-hydrotalcite. Therefore, the formation of (Zn,Al)-hydrotalcite in slightly alkaline conditions ought to result from heterogeneous precipitation on mineral surface.

Combined Mössbauer spectroscopic, multi-edge X-ray absorption spectroscopic, and density functional theoretical study of the radical SAM enzyme spore photoproduct lyase.

PubMed

Silver, Sunshine C; Gardenghi, David J; Naik, Sunil G; Shepard, Eric M; Huynh, Boi Hanh; Szilagyi, Robert K; Broderick, Joan B

2014-03-01

Spore photoproduct lyase (SPL), a member of the radical S-adenosyl-L-methionine (SAM) superfamily, catalyzes the direct reversal of the spore photoproduct, a thymine dimer specific to bacterial spores, to two thymines. SPL requires SAM and a redox-active [4Fe-4S] cluster for catalysis. Mössbauer analysis of anaerobically purified SPL indicates the presence of a mixture of cluster states with the majority (40 %) as [2Fe-2S](2+) clusters and a smaller amount (15 %) as [4Fe-4S](2+) clusters. On reduction, the cluster content changes to primarily (60 %) [4Fe-4S](+). The speciation information from Mössbauer data allowed us to deconvolute iron and sulfur K-edge X-ray absorption spectra to uncover electronic (X-ray absorption near-edge structure, XANES) and geometric (extended X-ray absorption fine structure, EXAFS) structural features of the Fe-S clusters, and their interactions with SAM. The iron K-edge EXAFS data provide evidence for elongation of a [2Fe-2S] rhomb of the [4Fe-4S] cluster on binding SAM on the basis of an Fe···Fe scatterer at 3.0 Å. The XANES spectra of reduced SPL in the absence and presence of SAM overlay one another, indicating that SAM is not undergoing reductive cleavage. The X-ray absorption spectroscopy data for SPL samples and data for model complexes from the literature allowed the deconvolution of contributions from [2Fe-2S] and [4Fe-4S] clusters to the sulfur K-edge XANES spectra. The analysis of pre-edge features revealed electronic changes in the Fe-S clusters as a function of the presence of SAM. The spectroscopic findings were further corroborated by density functional theory calculations that provided insights into structural and electronic perturbations that can be correlated by considering the role of SAM as a catalyst or substrate.

Functionalized polyethylene fibers for the selective capture of palladium ions from aqueous solution

NASA Astrophysics Data System (ADS)

Pang, Li-juan; Li, Rong; Hu, Jiang-tao; Zhang, Lin-juan; Zhang, Ming-xing; Yang, Chen-guang; Wu, Guo-zhong

2018-03-01

An innovative ultrahigh molecular weight polyethylene (UHMWPE) fibrous adsorbent was successfully synthesized via radiation grafting and applied to the selective capture of palladium ions from dilute aqueous solutions. The influence of the pH, initial Pd(II) concentration, and temperature on the adsorption performance was examined in a batch adsorption experiment. Pd K-edge extended X-ray absorption fine structure (EXAFS) spectra indicated that Pd(II) was immobilized on the adsorbent surface via a ligand exchange reaction that formed a stable UHMWPE-PMDA-Pd complex. Although the concentrations of coexisting ions (Cu(II), Zn(II), Cr(VI), Fe(III), and Ni(II)) in the solution were much higher than that of Pd(II), the adsorption capacity for Pd(II) of the as-prepared absorbent was significantly greater than that for other metal ions. Kinetic studies showed good correlation with the pseudo-second-order model. The maximum capacity for Pd(II) adsorption was approximately 221.8 mg·g-1 at 298 K. The adsorption behavior conformed to the Langmuir isotherm model. Thermodynamic studies revealed that the adsorption of Pd(II) was a feasible, spontaneous, and endothermic process.

Electronic structure, magnetic and structural properties of Ni doped ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Shalendra, E-mail: shailuphy@gmail.com; Vats, Prashant; Gautam, S.

Highlights: • XRD, and HR-TEM results show the single phase nature of Ni doped ZnO nanoparticles. • dc magnetization results indicate the RT-FM in Ni doped ZnO nanoparticles. • Ni L{sub 3,2} edge NEXAFS spectra infer that Ni ions are in +2 valence state. • O K edge NEXAFS spectra show that O vacancy increases with Ni doping in ZnO. - Abstract: We report structural, magnetic and electronic structural properties of Ni doped ZnO nanoparticles prepared by auto-combustion method. The prepared nanoparticles were characterized by using X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), near edge X-ray absorption finemore » structure (NEXAFS) spectroscopy, and dc magnetization measurements. The XRD and HR-TEM results indicate that Ni doped ZnO nanoparticles have single phase nature with wurtzite lattice and exclude the presence of secondary phase. NEXAFS measurements performed at Ni L{sub 3,2}-edges indicates that Ni ions are in +2 valence state and exclude the presence of Ni metal clusters. O K-edge NEXAFS spectra indicate an increase in oxygen vacancies with Ni-doping, while Zn L{sub 3,2}-edge show the absence of Zn-vacancies. The magnetization measurements performed at room temperature shows that pure and Ni doped ZnO exhibits ferromagnetic behavior.« less

Effect of Fe-substitution on the structure and magnetism of single crystals Mn2-xFexBO4

NASA Astrophysics Data System (ADS)

Platunov, M. S.; Kazak, N. V.; Knyazev, Yu. V.; Bezmaternykh, L. N.; Moshkina, E. M.; Trigub, A. L.; Veligzhanin, A. A.; Zubavichus, Y. V.; Solovyov, L. A.; Velikanov, D. A.; Ovchinnikov, S. G.

2017-10-01

Single crystalline Mn2-xFexBO4 with x = 0.3, 0.5, 0.7 grown by the flux method have been studied by means of X-ray diffraction and X-ray absorption spectroscopy at both Mn and Fe K edges. The compounds were found to crystallize in an orthorhombic warwickite structure (sp. gr. Pnam). The lattice parameters change linearly with x thus obeying the Vegard's law. The Fe3+ substitution for Mn3+ has been deduced from the X-ray absorption near-edge structure (XANES) spectra. Two energy positions of the absorption edges have been observed in Mn K-edge XANES spectra indicating the presence of manganese in two different oxidation states. Extended X-ray absorption fine structure (EXAFS) analysis has shown the reduction of local structural distortions upon Fe substitution. The magnetization data have revealed a spin-glass transition at TSG = 11, 14 and 18 K for x = 0.3, 0.5 and 0.7, respectively.

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

NASA Astrophysics Data System (ADS)

van Aken, P. A.; Sharp, T. G.; Seifert, F.

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced.

Formation of crystalline Zn-Al layered double hydroxide precipitates on γ-alumina: the role of mineral dissolution.

PubMed

Li, Wei; Livi, Kenneth J T; Xu, Wenqian; Siebecker, Matthew G; Wang, Yujun; Phillips, Brian L; Sparks, Donald L

2012-11-06

To better understand the sequestration of toxic metals such as nickel (Ni), zinc (Zn), and cobalt (Co) as layered double hydroxide (LDH) phases in soils, we systematically examined the presence of Al and the role of mineral dissolution during Zn sorption/precipitation on γ-Al(2)O(3) (γ-alumina) at pH 7.5 using extended X-ray absorption fine structure spectroscopy (EXAFS), high-resolution transmission electron microscopy (HR-TEM), synchrotron-radiation powder X-ray diffraction (SR-XRD), and (27)Al solid-state NMR. The EXAFS analysis indicates the formation of Zn-Al LDH precipitates at Zn concentration ≥0.4 mM, and both HR-TEM and SR-XRD reveal that these precipitates are crystalline. These precipitates yield a small shoulder at δ(Al-27) = +12.5 ppm in the (27)Al solid-state NMR spectra, consistent with the mixed octahedral Al/Zn chemical environment in typical Zn-Al LDHs. The NMR analysis provides direct evidence for the existence of Al in the precipitates and the migration from the dissolution of γ-alumina substrate. To further address this issue, we compared the Zn sorption mechanism on a series of Al (hydr)oxides with similar chemical composition but differing dissolubility using EXAFS and TEM. These results suggest that, under the same experimental conditions, Zn-Al LDH precipitates formed on γ-alumina and corundum but not on less soluble minerals such as bayerite, boehmite, and gibbsite, which point outs that substrate mineral surface dissolution plays an important role in the formation of Zn-Al LDH precipitates.

Soil properties controlling Zn speciation and fractionation in contaminated soils

NASA Astrophysics Data System (ADS)

Jacquat, Olivier; Voegelin, Andreas; Kretzschmar, Ruben

2009-09-01

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1-7.7) and total Zn content (251-30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.

EXAFS Study on LiFePO4 Powders Produced From Two Sol-Gel Routes

NASA Astrophysics Data System (ADS)

Negara, V. S. I.; Latif, C.; Wongtepa, W.; Pratapa, S.

2018-04-01

The local structure of LiFePO4 powders has been investigated using Fe K-edge Extended X-Ray Absorption Fine Structure (EXAFS) Spectroscopy data. The synthesis of LFP powders was carried out using two different sol-gel methods. The raw materials for Fe source were ironstone and commercial precursor of FeCl2·4H2O. Synthesis using natural materials produced two phases, namely LiFePO4 olivine and Li3Fe2(PO4)3 nasicon, whereas that using a commercial product produced a single phase of LiFePO4 olivine. The EXAFS data for both samples were collected at Synchrotron Light Research Institute (SLRI), Thailand. Fitting of the model on the experimental curve provided parameters that can be interpreted as the distance between Fe as the absorber and the nearest atoms on the LFP materials. The EXAFS data analysis has shown that synthesis of LFPs using different Fe sources gives slightly different nearest-neighbor distances, namely Fe-O of 0.21% -0.23%, Fe-P of 0.14% - 0.16%, Fe-Fe of 0.12% for both samples, respectively.

Coupling CP-MD simulations and X-ray absorption spectroscopy: exploring the structure of oxaliplatin in aqueous solution.

PubMed

Beret, Elizabeth C; Provost, Karine; Müller, Diane; Marcos, Enrique Sánchez

2009-09-10

A combined experimental-theoretical approach applying X-ray absorption spectroscopy and ab initio molecular dynamics (CP-MD) simulations is used to get insight into the structural determination of oxaliplatin, a third-generation anticancer drug of the cisplatin family, in aqueous solution. Experimental Pt L(III)-edge EXAFS and XANES spectra of oxaliplatin in water are compared with theoretical XAS spectra. The latter are obtained as statistically averaged spectra computed for a set of selected snapshots extracted from the MD trajectory of ethyldiamineoxalatoplatinum(II) (EDO-Pt) in liquid water. This compound is a simplified structure of oxaliplatin, where the outer part of the cyclohexane ring contained in the cyclohexanediamine ligand of oxaliplatin has been removed. We show that EDO-Pt is an appropriate model to simulate the spectroscopical properties of oxaliplatin given that the cyclohexane ring does not generate particular features in neither the EXAFS nor the XANES spectra. The computation of average EXAFS spectra using structures from the MD simulation in which atoms are selected according to different cutoff radii around the Pt center allows the assignment of spectral features to particular structural motifs, both in k and R-spaces. The outer oxygen atoms of the oxalate ligand (R(Pt-O(II)) = 3.97 +/- 0.03 A) are responsible for a well-defined hump at around 6.5 A(-1) in the k(2)-weighted EXAFS spectrum. The conventional EXAFS analysis data procedure is reexamined by its application to the simulated average EXAFS spectra. The structural parameters resulting from the fit may then be compared with those obtained from the simulation, providing an estimation of the methodological error associated with the global fitting procedure. A thorough discussion on the synergy between the experimental and theoretical XAS approaches is presented, and evidence for the detection of a slight hydration structure around the Pt complex is shown, leading to the suggestion of a new challenge to experimental XAS measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Shuning; Roy, Amitava; Lichtenberg, Henning

The micro-segmented flow technique was applied for continuous synthesis of ZnO micro- and nanoparticles with short residence times of 9.4 s and 21.4 s, respectively. The obtained particles were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Small angle X-ray scattering (SAXS) and photoluminescence spectroscopy were used to determine the size and optical properties of ZnO nanoparticles. In addition, extended X-ray absorption fine structure (EXAFS) spectroscopy was employed to investigate local structural properties. The EXAFS measurements reveal a larger degree of structural disorder in the nanoparticles than the microparticles. These structural changes should be taken into considerationmore » while evaluating the size-dependent visible emission of ZnO nanoparticles.« less

Local structural effects in Sr 3NiRhO 6 across magnetic transitions

DOE PAGES

Singh, Navneet; Khalid, S.; Bindu, R.

2016-04-06

Here, we investigate the temperature dependence of the structural parameters of quasi-one-dimensional Sr 3NiRhO 6 across the region of magnetic phase transitions using Ni K-edge and Sr K-edge x-ray absorption spectroscopy (XAS). The features in the x-ray absorption near-edge region are identified using multiple scattering calculations. The temperature-dependent extended x-ray absorption fine structure (EXAFS) studies show that the setting of the intra-chain super exchange interaction starts at ~200 K, which is well above the first transition temperature (45 K) revealed by magnetic susceptibility studies. The onset of the inter-chain super–super exchange interaction appears to be at ~125 K. Interestingly, themore » role played by direct exchange interaction between the Ni 3d and Rh 4d states in stabilising the magnetic interaction is less significant. The present results shed light on the generic features exhibited by isostructural compounds and may help in identifying the magnetic exchange pathways useful for understanding the unusual properties exhibited by such compounds.« less

Uptake of Nickel by Synthetic Mackinawite | Science Inventory ...

EPA Pesticide Factsheets

The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as XNi = 0.56 (Fe1-xNixS; 0  x  1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13 ± 0.03 (1σ) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (α-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)9S8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c = 5.07 ± 0.01 Å at XNi = 0.02 to c = 5.10 ± 0.01 Å at XNi = 0.38. Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with XNi = 0.42 indicated a coordination number of 4.04 ± 0.30 and an average Ni-S bond distance of 2.28 Å, in good a

Origin of Blue-Green Emission in α-Zn2P2O7 and Local Structure of Ln3+ Ion in α-Zn2P2O7:Ln3+ (Ln = Sm, Eu): Time-Resolved Photoluminescence, EXAFS, and DFT Measurements.

PubMed

Gupta, Santosh Kumar; Ghosh, Partha Sarathi; Yadav, Ashok Kumar; Jha, Shambhu Nath; Bhattacharyya, Dibyendu; Kadam, Ramakant Mahadeo

2017-01-03

Considering the fact that pyrophosphate-based hosts are in high demand for making highly efficient luminescence materials, we doped two visible lanthanide ions, viz. Sm 3+ and Eu 3+ , in Zn 2 P 2 O 7 . Interestingly, it was oberved that pure Zn 2 P 2 O 7 displayed blue-green dual emission on irradiation with ultraviolet light. Emission and lifetime spectroscopy shows the presence of defects in pyrophosphate samples which are responsible for such emission. DFT calculations clearly pinpointed that the electronic transitions between defect states located at just below the conduction band minimum (arises due to V O 1+ and V O 2+ defects) and valence band maximum, as well as impurity states situated in the band gap, can lead to dual emission in the blue-green region, as is also indicated by emission and lifetime spectra. X-ray absorption near edge spectroscopy (XANES) shows the stabilization of europium as well as samarium ion in the +3 oxidation state in α-Zn 2 P 2 O 7 . The fact that α-Zn 2 P 2 O 7 has two different coordination numbers for zinc ions, i.e. five- and six-coordinate, the study of dopant ion distribution in this particular matrix will be an important step in realizing a highly efficient europium- and samarium-based red-emitting phosphor. Time resolved photoluminescence (TRPL) shows that both of these ions are heterogeneously distributed between five- and six-coordinated Zn 2+ sites and it is the six-coordinated Zn 2+ site which is the most favorable for lanthanide ion doping. Extended X-ray absorption fine structure (EXAFS) measurements also suggested that a six-coordinated zinc ion is the preferred site occupied by trivalent lanthanide ions, which is in complete agreement with TRPL results. It was observed that there is almost complete transfer of photon energy from Zn 2 P 2 O 7 to Eu 3+ , whereas this transfer is inefficient and almost incomplete in case of Sm 3+ , which is indeed important information for the realization of pyrophosphate-based tunable phosphors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siqueira, M. C.; Maia, R. N. A.; Araujo, R. M. T.

In this article, we investigated structural and thermal properties of an amorphous alloy of the Ga–Se system. The amorphous GaSe{sub 9} alloy was produced by mechanical alloying and it was studied using EXAFS spectroscopy and cumulant expansion method. We also made reverse Monte Carlo simulations using the total structure factor S(K) obtained from x-ray diffraction and the EXAFS χ(k) oscillations on Se and Ga K edges as input data. Several parameters, such as average coordination numbers and interatomic distances, structural and thermal disorders, asymmetry of the partial distribution functions g{sub ij}(r), and Einstein and Debye temperatures, were determined. The g{submore » ij}{sup E}(r) functions were reconstructed from the cumulants C{sub 1}, C{sub 2}, and C{sub 3} obtained from the Einstein model, and they were compared to the g{sub ij}{sup RMC}(r) functions obtained from the simulations. The simulations also furnished the partial bond angle distribution functions Θ{sub ijℓ}(cosθ), which describe the angular distribution of bonds between first neighbors, and give information about the kind of structural units present in the alloy.« less

A quantum perturbative pair distribution for determining interatomic potentials from extended x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Piazza, F.

2002-11-01

In this paper we develop a technique for determining interatomic potentials in materials in the quantum regime from single-shell extended x-ray absorption spectroscopy (EXAFS) spectra. We introduce a pair distribution function, based on ordinary quantum time-independent perturbation theory. In the proposed scheme, the model potential parameters enter the distribution through a fourth-order Taylor expansion of the potential, and are directly refined in the fit of the model signal to the experimental spectrum. We discuss in general the validity of our theoretical framework, namely the quantum regime and perturbative treatment, and work out a simple tool for monitoring the sensitivity of our theory in determining lattice anharmonicities based on the statistical F-test. As an example, we apply our formalism to an EXAFS spectrum at the Ag K edge of AgI at T = 77 K. We determine the Ag-I potential parameters and find good agreement with previous studies.

Identification of F impurities in F-doped ZnO by synchrotron X-ray absorption near edge structures

NASA Astrophysics Data System (ADS)

Na-Phattalung, Sutassana; Limpijumnong, Sukit; Min, Chul-Hee; Cho, Deok-Yong; Lee, Seung-Ran; Char, Kookrin; Yu, Jaejun

2018-04-01

Synchrotron X-ray absorption near edge structure (XANES) measurements of F K-edge in conjunction with first-principles calculations are used to identify the local structure of the fluorine (F) atom in F-doped ZnO. The ZnO film was grown by pulsed laser deposition with an Nd:YAG laser, and an oxyfluoridation method was used to introduce F ions into the ZnO films. The measured XANES spectrum of the sample was compared against the first-principles XANES calculations based on various models for local atomic structures surrounding F atoms. The observed spectral features are attributed to ZnF2 and FO defects in wurtzite bulk ZnO.

Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

DOE PAGES

Hu, Yanyun; Chen, Ning; Clancy, J. P.; ...

2017-12-29

We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

Local structure investigation of Ga and Yb dopants in Co4Sb12 skutterudites

NASA Astrophysics Data System (ADS)

Hu, Yanyun; Chen, Ning; Clancy, J. P.; Salvador, James R.; Kim, Chang-Yong; Shi, Xiaoya; Li, Qiang; Kim, Young-June

2017-12-01

We report comprehensive x-ray absorption spectroscopy studies at both the Ga K edge and Yb L2 edge to elucidate the local structure of Ga and Yb dopants in YbxGayCo4Sb12 . Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24 g site replacing Sb, and the other is the 2 a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2 a on-center site. At low concentrations of Yb, Ga24 g and Ga2 a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Funct. Mater. 23, 3194 (2013), 10.1002/adfm.201202571]. The Ga24 g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24 g site for the highest Yb concentration studied (x =0.4 ). In addition to the local structural evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K -edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga2 a to Ga24 g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co4Sb12 skutterudites is due to the increased Ga24 g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.

Local structure investigation of Ga and Yb dopants in Co 4 Sb 12 skutterudites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Yanyun; Chen, Ning; Clancy, J. P.

We report our x-ray absorption spectroscopy studies at both Ga K-edge and Yb L 2-edge to elucidate the local structure of Ga and Yb dopants in Yb xGa yCo 4Sb 12. Our extended x-ray absorption fine structure (EXAFS) data confirm that Ga atoms occupy two crystallographic sites: one is the 24g site replacing Sb, and the other is the 2a site in the off-center void position. We find that the occupancy ratio of these two sites varies significantly as a function of the filling fraction of additional Yb, which exclusively occupies the 2a on-center site. At low concentrations of Yb,more » Ga 24g and Ga 2a dopants coexist and they form a charge-compensated compound defect proposed by Qiu et al. [Adv. Mater. 23, 3194 (2013)]. The Ga 24g occupancy increases gradually with increasing Yb concentration, and almost all Ga occupies the 24g site for the highest Yb concentration (x = 0.4). In addition to the local crystal structure evidence provided by our EXAFS data, we also present x-ray absorption near-edge structure (XANES) spectra, which show a small Ga K-edge energy shift as a function of Yb concentration consistent with the change from predominantly Ga 2a to Ga 24g states. Our result suggests that the increased solubility of Yb in Yb-Ga co-doped Co 4Sb 12 skutterudites is due to the increased Ga 24g electron acceptor, and thus provides an important strategy to optimize the carrier concentration in partially filled skutterudites.« less

Magnetic properties of Gd T2Zn20 (T =Fe , Co) investigated by x-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Mardegan, J. R. L.; Francoual, S.; Fabbris, G.; Veiga, L. S. I.; Strempfer, J.; Haskel, D.; Ribeiro, R. A.; Avila, M. A.; Giles, C.

2016-01-01

We investigate the magnetic and electronic properties of the Gd T2Zn20 (T =Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo2Zn20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector τ ⃗=(1/2 ,1/2 ,1/2 ) below the Néel temperature (TN˜ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ6. For the ferromagnetic GdFe2Zn20 compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5 % and 9.7 % is observed below the Curie temperature (TC˜85 K ) at the Gd L2 and L3 edges, respectively. In addition, a small magnetic signal of about 0.06 % of the jump is recorded at the Zn K edge, suggesting that the Zn 4 p states are spin polarized by the Gd 5 d extended orbitals.

Magnetic properties of GdT 2Zn 20 (T = Fe, Co) investigated by x-ray diffraction and spectroscopy

DOE PAGES

J. R. L. Mardegan; Fabbris, G.; Francoual, S.; ...

2016-01-26

In this study, we investigate the magnetic and electronic properties of the GdT 2Zn 20 (T=Fe and Co) compounds using x-ray resonant magnetic scattering (XRMS), x-ray absorption near-edge structure (XANES), and x-ray magnetic circular dichroism (XMCD). The XRMS measurements reveal that GdCo 2Zn 20 has a commensurate antiferromagnetic spin structure with a magnetic propagation vector →/ τ = (12,12,12) below the Néel temperature (T N ~ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation Γ 6. For the ferromagnetic GdFe 2Zn 20 compound, an extensive investigation was performed at low temperaturemore » and under magnetic field using XANES and XMCD. A strong XMCD signal of about 12.5% and 9.7% is observed below the Curie temperature (T C ~ 85K) at the Gd L 2 and L 3 edges, respectively. In addition, a small magnetic signal of about 0.06% of the jump is recorded at the Zn K edge, suggesting that the Zn 4p states are spin polarized by the Gd 5d extended orbitals.« less

Sorption of Metal Ions on Clay Minerals.

PubMed

Schlegel; Manceau; Chateigner; Charlet

1999-07-01

The local structural environment of Co sorbed on hectorite (a magnesian smectite) has been investigated by polarized EXAFS (P-EXAFS) spectroscopy on a self-supporting film of Co-sorbed hectorite. This sorption sample was prepared by contacting Co and hectorite at pH 6.5 and at high ionic strength (0.3 M NaNO3) to favor pH-dependent sorption reaction over cation exchange. A self-supporting film was elaborated after 120 h of reacting time, when apparent quasi-equilibrium conditions were attained. The half-width at half maximum of the orientation distribution of c* axis of individual clay platelets off the film normal was determined by quantitative texture analysis, and found to be equal to 18.9 degrees. Co K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 0 degrees, 35 degrees, 50 degrees, and 60 degrees; the 90 degrees spectrum was obtained by extrapolation. Spectral analysis led to the identification of the two nearest cationic subshells containing 1.6 +/- 0.4 Mg at 3.03 Å and 2.2 +/- 0.5 Si at 3.27 Å. These distances are respectively characteristic of edge-sharing linkages between Mg and Co octahedra and of corner-sharing linkages between Co octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Co-Mg and Co-Si contributions indicates that Co-Mg pairs are oriented parallel to the film plane, whereas Co-Si pairs are not. These results are interpreted by the formation of Co inner-sphere mononuclear surface complexes located at the edges of hectorite platelets, in the continuity of the (Mg, Li) octahedral sheet. Copyright 1999 Academic Press.

High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xin

1996-12-01

X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

Studies of EXAFSSpectra using Copper (II) Schiff Base complexes and Determination of Bond lengths Using Synchrotron Radiation

NASA Astrophysics Data System (ADS)

Mishra, A.; Vibhute, V.; Ninama, S.; Parsai, N.; Jha, S. N.; Sharma, P.

2016-10-01

X-ray absorption fine structure (XAFS) at the K-edge of copper has been studied in some copper (II) complexes with substituted anilines like (2Cl, 4Br, 2NO2, 4NO2 and pure aniline) with o-PDA (orthophenylenediamine) as ligand. The X-ray absorption measurements have been performed at the recently developed BL-8 dispersive EXAFS beam line at 2.5 GeV Indus-2 Synchrotron Source at RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena.The graphical method gives the useful information about bond length and also the environment of the absorbing atom. The theoretical bond lengths of the complexes were calculated by using interactive fitting of EXAFS using fast Fourier inverse transformation (IFEFFIT) method. This method is also called as Fourier transform method. The Lytle, Sayers and Stern method and Levy's method have been used for determination of bond lengths experimentally of the studied complexes. The results of both methods have been compared with theoretical IFEFFIT method.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

Evidence for Different Reaction Pathways for Liquid and Granular Micronutrients in a Calcareous Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hettiarachchi, Ganga M.; McLaughlin, Mike J.; Scheckel, Kirk G.

2008-06-16

The benefits of Mn and Zn fluid fertilizers over conventional granular products in calcareous sandy loam soils have been agronomically demonstrated. We hypothesized that the differences in the effectiveness between granular and fluid Mn and Zn fertilizers is due to different Mn and Zn reaction processes in and around fertilizer granules and fluid fertilizer bands. We used a combination of several synchrotron-based x-ray techniques, namely, spatially resolved micro-x-ray fluorescence (?-XRF), micro-x-ray absorption near edge structure spectroscopy (?-XANES), and bulk-XANES and -extended x-ray absorption fine structure (EXAFS) spectroscopy, along with several laboratory-based x-ray techniques to speciate different fertilizer-derived Mn and Znmore » species in highly calcareous soils to understand the chemistry underlying the observed differential behavior of fluid and granular micronutrient forms. Micro-XRF mapping of soil-fertilizer reactions zones indicated that the mobility of Mn and Zn from liquid fertilizer was greater than that observed for equivalent granular sources of these micronutrients in soil. After application of these micronutrient fertilizers to soil, Mn and Zn from liquid fertilizers were found to remain in comparatively more soluble solid forms, such as hydrated Mn phosphate-like, Mn calcite-like, adsorbed Zn-like, and Zn silicate-like phases, whereas Mn and Zn from equivalent granular sources tended to transform into comparatively less soluble solid forms such as Mn oxide-like, Mn carbonate-like, and Zn phosphate-like phases.« less

Electrochemical and in situ spectroscopic studies of materials of relevance to energy storage and electrocatalysis

NASA Astrophysics Data System (ADS)

Mo, Yibo

In situ X-ray absorption (XAS), surface enhanced Raman spectroscopy (SERS) and rotating ring disk electrode techniques have been employed for the characterization of materials of relevance to electrochemical energy storage and electrocatalysis. In particular, analysis of in situ Ir LIII-edge extended X-ray absorption fine structure (EXAFS) of IrO2 films electrodeposited on Au substrates yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97 and 1.93 A, for Ir3+, Ir4+ and Ir5+ sites, respectively. Although features consistent with the presence of crystalline IrO2 in the highly hydrated films were found from in situ SERS, the lack of intense shells in the FT of the EXAFS function beyond the nearest oxygen neighbors indicates that the films by and large do not display long range order. In similar studies, the Fourier transform of the k3-weighted Ru K-edge EXAFS of electrodeposited RuO2 films recorded in situ were characterized by two shells attributed to Ru-O and Ru-Ru interactions at 1.94(1) and 3.12(2) A, in agreement with results obtained ex situ for Ru4+ in hydrous RuO2, whereas films in the reduced state yielded a single Ru-O interaction shell at 2.02(1) A. Extensions of these in situ XAS to the study of electrocatalysts for the nitrite reduction made it possible to identify and characterize the electronic and structural properties of a nitrosyl iron porphyrin adduct adsorbed on an electrode surface via the analysis of Fe K-edge XAS data. The effects of Se and S ad-atoms on the electrocatalytic activity of Pt electrodes have been examined using RRDE techniques. In acid, within a rather narrow range of coverages, both S- and Se-modified Pt surfaces promote the 2-electron reduction of dioxygen to hydrogen peroxide at ca. 100% faradaic efficiency over a wide potential region. Also developed were methods for immobilizing unsupported dispersed high area Pt particles a glassy carbon (GC) disk of a rotating Pt(ring)/GC(disk) electrode assembly allowing electrochemical measurements to be performed under forced convection with only minimal losses of Pt from the surface.

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

2002-05-01

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Characterization by 27Al NMR, X-ray absorption spectroscopy, and density functional theory techniques of the species responsible for benzene hydrogenation in Y zeolite-supported carburized molybdenum catalysts.

PubMed

Rocha, Angela S; da Silva, Victor Teixeira; Eon, Jean G; de Menezes, Sônia M C; Faro, Arnaldo C; Rocha, Alexandre B

2006-08-17

Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

USGS Publications Warehouse

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (μSXRF) mapping, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.

Revisiting the hydration structure of aqueous Na +

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galib, M.; Baer, M. D.; Skinner, L. B.

In this paper, a combination of theory, X-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) are used to probe the hydration structure of aqueous Na +. The high spatial resolution of the XRD measurements corresponds to Qmax = 24 Å –1 while the first-reported Na K-edge EXAFS measurements have a spatial resolution corresponding to 2k = Qmax = 16 Å –1. Both provide an accurate measure of the shape and position of the first peak in the Na–O pair distribution function, g NaO(r). The measured Na–O distances of 2.384 ± 0.003 Å (XRD) and 2.37 ± 0.024 Åmore » (EXAFS) are in excellent agreement. These measurements show a much shorter Na–O distance than generally reported in the experimental literature (Na–O avg ~ 2.44 Å) although the current measurements are in agreement with recent neutron diffraction measurements. The measured Na–O coordination number from XRD is 5.5 ± 0.3. The measured structure is compared with both classical and first-principles density functional theory (DFT) simulations. Both of the DFT-based methods, revPBE and BLYP, predict a Na–O distance that is too long by about 0.05 Å with respect to the experimental data (EXAFS and XRD). The inclusion of dispersion interactions (–D3 and –D2) significantly worsens the agreement with experiment by further increasing the Na–O distance by 0.07 Å. In contrast, the use of a classical Na–O Lennard-Jones potential with SPC/E water accurately predicts the Na–O distance as 2.39 Å although the Na–O peak is over-structured with respect to experiment.« less

Revisiting the hydration structure of aqueous Na +

DOE PAGES

Galib, M.; Baer, M. D.; Skinner, L. B.; ...

2017-02-27

In this paper, a combination of theory, X-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) are used to probe the hydration structure of aqueous Na +. The high spatial resolution of the XRD measurements corresponds to Qmax = 24 Å –1 while the first-reported Na K-edge EXAFS measurements have a spatial resolution corresponding to 2k = Qmax = 16 Å –1. Both provide an accurate measure of the shape and position of the first peak in the Na–O pair distribution function, g NaO(r). The measured Na–O distances of 2.384 ± 0.003 Å (XRD) and 2.37 ± 0.024 Åmore » (EXAFS) are in excellent agreement. These measurements show a much shorter Na–O distance than generally reported in the experimental literature (Na–O avg ~ 2.44 Å) although the current measurements are in agreement with recent neutron diffraction measurements. The measured Na–O coordination number from XRD is 5.5 ± 0.3. The measured structure is compared with both classical and first-principles density functional theory (DFT) simulations. Both of the DFT-based methods, revPBE and BLYP, predict a Na–O distance that is too long by about 0.05 Å with respect to the experimental data (EXAFS and XRD). The inclusion of dispersion interactions (–D3 and –D2) significantly worsens the agreement with experiment by further increasing the Na–O distance by 0.07 Å. In contrast, the use of a classical Na–O Lennard-Jones potential with SPC/E water accurately predicts the Na–O distance as 2.39 Å although the Na–O peak is over-structured with respect to experiment.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Atomic and electronic structure of Pd40Ni40P20 bulk metallic glass from ab initio simulations

NASA Astrophysics Data System (ADS)

Kumar, Vijay; Fujita, T.; Konno, K.; Matsuura, M.; Chen, M. W.; Inoue, A.; Kawazoe, Y.

2011-10-01

The atomic structure of Pd40Ni40P20 bulk metallic glass has been simulated using an ab initio molecular dynamics method with projector-augmented wave pseudopotentials for electron-ion interaction and generalized gradient approximation for exchange-correlation energy. The calculated extended x-ray absorption fine structure (EXAFS) spectra of Pd-K and Ni-K edges, the mass density, and the electronic structure agree remarkably well with the available experimental data and the EXAFS spectra measured at the SPring-8 synchrotron radiation facility. Our results show that the atomic structure can be described in terms of P-centered polyhedra. There are no two P atoms that are nearest neighbors at this composition, and this could be a reason for the observed optimal P concentration of about 20 at.%. The neighboring polyhedra share metal (M) atoms and form a polar covalently bonded random network of P-M-P favoring certain angles. The remaining M atoms act as metallic glue with a tendency of nanoscale clustering of Pd-Pd and Ni-Ni atoms.

Self-irradiation damage to the local structure of plutonium and plutonium intermetallics

NASA Astrophysics Data System (ADS)

Booth, C. H.; Jiang, Yu; Medling, S. A.; Wang, D. L.; Costello, A. L.; Schwartz, D. S.; Mitchell, J. N.; Tobash, P. H.; Bauer, E. D.; McCall, S. K.; Wall, M. A.; Allen, P. G.

2013-03-01

The effect of self-irradiation damage on the local structure of δ-Pu, PuAl2, PuGa3, and other Pu intermetallics has been determined for samples stored at room temperature using the extended x-ray absorption fine-structure (EXAFS) technique. These measurements indicate that the intermetallic samples damage at a similar rate as indicated in previous studies of PuCoGa5. In contrast, δ-Pu data indicate a much slower damage accumulation rate. To explore the effect of storage temperature and possible room temperature annealing effects, we also collected EXAFS data on a δ-Pu sample that was held at less than 32 K for a two month period. This sample damaged much more quickly. In addition, the measurable damage was annealed out at above only 135 K. Data from samples of δ-Pu with different Ga concentrations and results on all samples collected from different absorption edges are also reported. These results are discussed in terms of the vibrational properties of the materials and the role of Ga in δ-Pu as a network former.

Comparison of the Manganese Cluster in Oxygen-Evolving Photosystem II with Distorted Cubane Manganese Compounds through X-ray Absorption Spectroscopy

PubMed Central

Cinco, Roehl M.; Rompel, Annette; Visser, Hendrik; Aromí, Guillem; Christou, George; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

X-ray absorption spectroscopy has been employed to assess the degree of similarity between the oxygen-evolving complex (OEC) in photosystem II (PS II) and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride, or bromide). These [Mn4(μ3-O)3(μ3-X)] cubanes possess C3v symmetry except for the X = benzoate species, which is slightly more distorted with only Cs symmetry. In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The Mn K-edge X-ray absorption near edge structure (XANES) from the oxygen-ligated complexes begin to resemble general features of the PS II (S1 state) spectrum, although the second derivatives are distinct from those in PS II. The extended X-ray absorption fine structure (EXAFS) of these Mn compounds also displays superficial resemblance to that of PS II, but major differences emerge on closer examination of the phases and amplitudes. The most obvious distinction is the smaller magnitude of the Fourier transform (FT) of the PS II EXAFS compared to the FTs from the distorted cubanes. Curve fitting of the Mn EXAFS spectra verifies the known core structures of the Mn cubanes, and shows that the number of the crucial 2.7 and 3.3 Å Mn–Mn distances differs from that observed in the OEC. The EXAFS method detects small changes in the core structures as X is varied in this series, and serves to exclude the distorted cubane of C3v symmetry as a topological model for the Mn catalytic cluster of the OEC. Instead, the method shows that even more distortion of the cubane framework, altering the ratio of the Mn–Mn distances, is required to resemble the Mn cluster in PS II. PMID:11671305

Transport Measurements and Synchrotron-Based X-Ray Absorption Spectroscopy of Iron Silicon Germanide Grown by Molecular Beam Epitaxy

NASA Astrophysics Data System (ADS)

Elmarhoumi, Nader; Cottier, Ryan; Merchan, Greg; Roy, Amitava; Lohn, Chris; Geisler, Heike; Ventrice, Carl, Jr.; Golding, Terry

2009-03-01

Some of the iron-based metal silicide and germanide phases have been predicted to be direct band gap semiconductors. Therefore, they show promise for use as optoelectronic materials. We have used synchrotron-based x-ray absorption spectroscopy to study the structure of iron silicon germanide films grown by molecular beam epitaxy. A series of Fe(Si1-xGex)2 thin films (2000 -- 8000å) with a nominal Ge concentration of up to x = 0.04 have been grown. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) measurements have been performed on the films. The nearest neighbor co-ordination corresponding to the β-FeSi2 phase of iron silicide provides the best fit with the EXAFS data. Temperature dependent (20 < T < 350 K) magneto transport measurements were done on the Fe(Si1-xGex)2 thin films via Van Der Paw (VDP) Hall configuration using a 0.5-1T magnetic field and a current of 10-200 μA through indium ohmic contacts, the Hall coefficient was calculated. Results suggest semiconducting behavior of the films which is consistent with the EXAFS results.

Mn K-Edge X-ray Absorption Studies of Oxo- and Hydroxo-manganese(IV) Complexes: Experimental and Theoretical Insights into Pre-Edge Properties

PubMed Central

2015-01-01

Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [MnII(Cl)2(Me2EBC)], [MnIV(OH)2(Me2EBC)]2+, and [MnIV(O)(OH)(Me2EBC)]+, which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [MnIV(O)(OH)(Me2EBC)]+ revealed Mn–O scatterers at 1.71 and 1.84 Å and Mn–N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [MnII(Cl)2(Me2EBC)] and [MnIV(OH)2(Me2EBC)]2+ are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn–O(H) distances and pre-edge peak areas of MnIV=O and MnIV–OH complexes, but this trend was strongly modulated by the MnIV coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn–O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal MnIV=O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn=O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn=O σ* molecular orbital (MO) but also show intense transitions to 3dx2–y2 and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal MnIV=O adducts. These results underscore the importance of reporting experimental pre-edge areas rather than peak heights. Finally, the TD-DFT method was applied to understand the pre-edge properties of a recently reported S = 1 MnV=O adduct; these findings are discussed within the context of previous examinations of oxomanganese(V) complexes. PMID:24901026

Mn K-edge X-ray absorption studies of oxo- and hydroxo-manganese(IV) complexes: experimental and theoretical insights into pre-edge properties.

PubMed

Leto, Domenick F; Jackson, Timothy A

2014-06-16

Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)═O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)═O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn═O σ* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn═O σ* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)═O adducts. These results underscore the importance of reporting experimental pre-edge areas rather than peak heights. Finally, the TD-DFT method was applied to understand the pre-edge properties of a recently reported S = 1 Mn(V)═O adduct; these findings are discussed within the context of previous examinations of oxomanganese(V) complexes.

Ti K-edge EXAFS and XANES study on tektites from different strewnfields

NASA Astrophysics Data System (ADS)

Wang, L.; Furuta, T.; Okube, M.; Yoshiasa, A.

2011-12-01

The concentration and local structure of each element may have various kinds of information about the asteroid impact and mass extinction. Farges and Brown have discussed about the Ti local structure by XANES, and concluded that Ti in tektite occupies 4-coordinated site. EXAFS can be analyzed to give precise information about the distance from Ti to near neighbors. The XAFS measurement of Ti local structure was preformed at the beamline 9C of the Photon Factory in KEK, Tsukuba, Japan. The specimens of tektites are from different strewnfields, they are: indochinite, bediasite, hainanite, philippinite, australite and moldavite. Sample for comparison are Libya desert glass and suevite. The k3χ(k) function was transformed into the radial structure function (RSF) for Ti K-edge of six tektites. The RSF for the Ti atom in indochinite and bediasite are similar; hainanite, australite and philippinite are similar; and moldavite is discriminated from others. It indicates that they have the same local atomic environmental around the Ti atoms and extended structure respectively. Coordination numbers and radial structure function are determined by EXAFS analyses (Table 1). We classified the tektites in three types: in indochinite and bediasite, Ti occupies 4-coordinated tetrahedral site and Ti-O distances are 1.84-1.81 Å; in hainanite, australite and philippinite, Ti occupies 5-coordinated trigonal bi-pyramidal or tetragonal pyramidal site and Ti-O distances are 1.92-1.87 Å; in moldavite, Ti occupies the 6-coordinated octahedral site and Ti-O distance is 2.00-1.96 Å. Formation of tektites is related to the impact process. It is generally recognized that tektites were formed under higher temperature and high pressure. But through this study, local structures of Ti are differing in three strewnfields and even different locations of the same strewnfield. What caused the various local structures will be another topic of tektite studies. Local structure of Ti may be changed in the impact event and the following stage. Tektites splashed to the space and travel in several kinds of processes and routes, which lead to different temperature and pressure history. Local structure of Ti should be related with the temperature, pressure, quenching rate, sizes of impact meteorite and size of falling melts. [1] Koeberl. Ann.Rev.Earth Planet.Sci. 14, 323-350 (1986) [2] François Farges & Gordon E. Brown Jr Geochim. Cosmo. Acta.61, 1863-1870 (1997). [3]Paris, E., Dingwell, D., Seifert, F., Mottana, A. & Romano, C. (1994). Phys. Chem. Miner. 21, 520-525.
Table 1 Structure parameters determined by EXAFS

Structural, magnetic and electronic structure properties of Co doped ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Shalendra, E-mail: shailuphy@gmail.com; School of Materials Science and Engineering, Changwon National University, Changwon, Gyeongnam 641-773; Song, T.K., E-mail: tksong@changwon.ac.kr

Highlights: • XRD and HR-TEM results show the single phase nature of Co doped ZnO nanoparticles. • XMCD and dc magnetization results indicate the RT-FM in Co doped ZnO nanoparticles. • Co L{sub 3,2} NEXAFS spectra infer that Co ions are in 2+ valence state. • O K edge NEXAFS spectra show that O vacancy increases with Co doping in ZnO. - Abstract: We reported structural, magnetic and electronic structure studies of Co doped ZnO nanoparticles. Doping of Co ions in ZnO host matrix has been studied and confirmed using various methods; such as X-ray diffraction (XRD), field emission scanningmore » electron microscopy (FE-SEM), energy dispersed X-ray (EDX), high resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FT-IR), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, magnetic hysteresis loop measurements and X-ray magnetic circular dichroism (XMCD). From the XRD and HR-TEM results, it is observed that Co doped ZnO nanoparticles have single phase nature with wurtzite structure and exclude the possibility of secondary phase formation. FE-SEM and TEM micrographs show that pure and Co doped nanoparticles are nearly spherical in shape. O K edge NEXAFS spectra indicate that O vacancies increase with Co doping. The Co L{sub 3,2} edge NEXAFS spectra revealed that Co ions are in 2+ valence state. DC magnetization hysteresis loops and XMCD results clearly showed the intrinsic origin of temperature ferromagnetism in Co doped ZnO nanoparticles.« less

Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

2014-05-01

Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

A high pressure La K-edge X-ray absorption fine structure spectroscopy investigation of La1/3NbO3

NASA Astrophysics Data System (ADS)

Marini, C.; Joseph, B.; Noked, O.; Shuker, R.; Kennedy, B. J.; Mathon, O.; Pascarelli, S.; Sterer, E.

2018-01-01

La K-edge X-ray absorption spectroscopy has been used to elucidate the changes in the local electronic and lattice structure that occur in the A-site deficient double perovskite La?NbO? up to 6 GPa. The pressure evolution of the oxygen dodecahedrum around the A-site has been examined. XANES (X-ray absorption near edge structure) data show modifications ascribed to the increase of bands overlapping as a consequence of the bond distance contraction, which has been directly probed by EXAFS (extended x-ray absorption fine structure) spectra. The La-O Debye Waller factors (DWFs) tend to increase whereas the La-Nb bond DWFs show only a tendency to decrease indicating the robustness of the crystal lattice structure, even in presence of the oxygen disordering. This permits the system to reverse back to its original conditions in this pressure range as evident from the measurements upon pressure release. The present results have been interpreted in the light of charge transfer related to the two-step reduction mechanism acting at the Nb site (with niobium ions passing from Nb? to Nb?) which also results in the elongation of the Nb-O bond distances in the octahedra, in agreement with the Nb K-edge results reported earlier.

Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KL II&III, KL I) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas

2015-07-02

We probe, at high energy resolution, the double electron excitation (KL II&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KL II&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂Omore » the KL II&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KL II&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KL II&III and KL I onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle under Contract # AC05-76RL01830.« less

High-performance thermoelectricity in edge-over-edge zinc-porphyrin molecular wires.

PubMed

Noori, Mohammed; Sadeghi, Hatef; Lambert, Colin J

2017-04-20

If high efficiency organic thermoelectric materials could be identified, then these would open the way to a range of energy harvesting technologies and Peltier coolers using flexible and transparent thin-film materials. We have compared the thermoelectric properties of three zinc porphyrin (ZnP) dimers and a ZnP monomer and found that the "edge-over-edge" dimer formed from stacked ZnP rings possesses a high electrical conductance, negligible phonon thermal conductance and a high Seebeck coefficient of the order of 300 μV K -1 . These combine to yield a predicted room-temperature figure of merit of ZT ≈ 4, which is the highest room-temperature ZT ever reported for a single organic molecule. This high value of ZT is a consequence of the low phonon thermal conductance arising from the stacked nature of the porphyrin rings, which hinders phonon transport through the edge-over-edge molecule and enhances the Seebeck coefficient.

Sequestration of Sr(II) By Calcium Oxalate - a Batch Uptake Study And EXAFS Analysis of Model Compounds And Reaction Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singer, D.M.; Johnson, S.B.; Catalano, J.G.

Calcium oxalate monohydrate (CaC{sub 2}O{sub 4}{center_dot}H{sub 2}O -- abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II){sub aq} following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4--10, with initial Sr solution concentrations, [Sr]{sub aq}, ranging from 1 x 10{sup -4} to 1 x 10{sup -3} M and ionic strengths ranging of 0.001--0.1more » M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr{sub aq} for two days, the solution Ca concentration, [Ca]{sup aq}, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr{sub aq} removed from solution was nearly equal to the total [Ca]{sup aq} after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC{sub 2}O{sub 4} of mixed hydration state (i.e. SrO{sub x}{center_dot}nH{sub 2}O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO3 phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.« less

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles.

Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

PubMed

Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

2017-04-01

In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L 3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents. Copyright © 2016 Elsevier Inc. All rights reserved.

Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

2015-03-01

The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

Cd(II) Sorption on Montmorillonite-Humic acid-Bacteria Composites

PubMed Central

Du, Huihui; Chen, Wenli; Cai, Peng; Rong, Xingmin; Dai, Ke; Peacock, Caroline L.; Huang, Qiaoyun

2016-01-01

Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria. PMID:26792640

Planar Lattice Instability in LA2CUO4.1 across the Superconducting Transition

NASA Astrophysics Data System (ADS)

Acosta-Alejandro, Manuel; Mustre-de Leon, Jose; Conradson, Steven

2001-03-01

The local atomic structure of La2CuO4.1 around Cu K-edge is analyzed for 10

Near-edge X-ray absorption spectra for metallic Cu and Mn

NASA Astrophysics Data System (ADS)

Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

1981-11-01

The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

Pinned orbital moments in uncompensated antiferromagnetic Co doped ZnO

NASA Astrophysics Data System (ADS)

Buchner, Martin; Henne, Bastian; Ney, Verena; Lumetzberger, Julia; Wilhelm, Fabrice; Rogalev, Andrei; Hen, Amir; Ney, Andreas

2018-05-01

Low temperature Co K-edge x-ray magnetic circular dichroism spectra at different field cooling conditions were recorded to study the imprinted magnetization in antiferromagnetic (AFM) Co doped ZnO (Co:ZnO) films which manifests itself in a vertical exchange bias effect. Co:ZnO films with 50% and 60% doping concentrations were investigated to provide a high degree of pinned magnetic moments. The measurements reveal a change at the main absorption energy of the spectra, while the signal obtained at the pre-edge stays unaffected by the cooling conditions. Therefore, the pinned uncompensated AFM moments, resulting in an imprinted magnetization, are predominantly of orbital character and are independent of ferromagnetic layers.

Ge K-Edge Extended X-Ray Absorption Fine Structure Study of the Local Structure of Amorphous GeTe and the Crystallization

NASA Astrophysics Data System (ADS)

Maeda, Yoshihito; Wakagi, Masatoshi

1991-01-01

The local structure and crystallization of amorphous GeTe (a-GeTe) were examined by means of Ge K-edge EXAFS. In a-GeTe, both Ge-Ge and Ge-Te bonds were observed to exist in nearest neighbors of Ge. The average coordination number around Ge is 3.7, which is close to the tetrahedral structure. A random covalent network (RCN) model seems to be suitable for the local Structure. After a-GeTe crystallizes at 129°C, the Ge-Ge bond disappears and the Ge-Te bond length increases considerably. As temperature rises, in a-GeTe the Debye-Waller factor of the Ge-Te bond increases greatly, while that of the Ge-Ge bond increases only slightly. At the crystallization, it is found that the fluctuation of the Ge-Te bond length plays a major role in the change of the local structure and bonding state around Ge.

Rational Design Synthesis and Evaluation of First Generation Inhibitors of the Giardia Lamblia Fructose-1 6-biphosphate Aldolase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Z Li; Z Liu; D Cho

2011-12-31

Inhibitors of the Giardia lamblia fructose 1,6-bisphosphate aldolase (GlFBPA), which transforms fructose 1,6-bisphosphate (FBP) to dihydroxyacetone phosphate and glyceraldehyde 3-phosphate, were designed based on 3-hydroxy-2-pyridone and 1,2-dihydroxypyridine scaffolds that position two negatively charged tetrahedral groups for interaction with substrate phosphate binding residues, a hydrogen bond donor to the catalytic Asp83, and a Zn{sup 2+} binding group. The inhibition activities for the GlFBPA catalyzed reaction of FBP of the prepared alkyl phosphonate/phosphate substituted 3-hydroxy-2-pyridinones and a dihydroxypyridine were determined. The 3-hydroxy-2-pyridone inhibitor 8 was found to bind to GlFBPA with an affinity (K{sub i} = 14 {micro}M) that is comparable tomore » that of FBP (K{sub m} = 2 {micro}M) or its inert analog TBP (K{sub i} = 1 {micro}M). The X-ray structure of the GlFBPA-inhibitor 8 complex (2.3 {angstrom}) shows that 8 binds to the active site in the manner predicted by in silico docking with the exception of coordination with Zn{sup 2+}. The observed distances and orientation of the pyridone ring O=C-C-OH relative to Zn{sup 2+} are not consistent with a strong interaction. To determine if Zn{sup 2+} coordination occurs in the GlFBPA-inhibitor 8 complex in solution, EXAFS spectra were measured. A four coordinate geometry comprised of the three enzyme histidine ligands and an oxygen atom from the pyridone ring O=C-C-OH was indicated. Analysis of the Zn{sup 2+} coordination geometries in recently reported structures of class II FBPAs suggests that strong Zn{sup 2+} coordination is reserved for the enediolate-like transition state, accounting for minimal contribution of Zn{sup 2+} coordination to binding of 8 to GlFBPA.« less

Rational design, synthesis and evaluation of first generation inhibitors of the Giardia lamblia fructose-1,6-biphosphate aldolase.

PubMed

Li, Zhimin; Liu, Zhengang; Cho, Dae Won; Zou, Jiwen; Gong, Maozhen; Breece, Robert M; Galkin, Andrey; Li, Ling; Zhao, Hong; Maestas, Gabriel D; Tierney, David L; Herzberg, Osnat; Dunaway-Mariano, Debra; Mariano, Patrick S

2011-04-01

Inhibitors of the Giardia lamblia fructose 1,6-bisphosphate aldolase (GlFBPA), which transforms fructose 1,6-bisphosphate (FBP) to dihydroxyacetone phosphate and glyceraldehyde 3-phosphate, were designed based on 3-hydroxy-2-pyridone and 1,2-dihydroxypyridine scaffolds that position two negatively charged tetrahedral groups for interaction with substrate phosphate binding residues, a hydrogen bond donor to the catalytic Asp83, and a Zn(2+) binding group. The inhibition activities for the GlFBPA catalyzed reaction of FBP of the prepared alkyl phosphonate/phosphate substituted 3-hydroxy-2-pyridinones and a dihydroxypyridine were determined. The 3-hydroxy-2-pyridone inhibitor 8 was found to bind to GlFBPA with an affinity (K(i)=14μM) that is comparable to that of FBP (K(m)=2μM) or its inert analog TBP (K(i)=1μM). The X-ray structure of the GlFBPA-inhibitor 8 complex (2.3Å) shows that 8 binds to the active site in the manner predicted by in silico docking with the exception of coordination with Zn(2+). The observed distances and orientation of the pyridone ring O=C-C-OH relative to Zn(2+) are not consistent with a strong interaction. To determine if Zn(2+)coordination occurs in the GlFBPA-inhibitor 8 complex in solution, EXAFS spectra were measured. A four coordinate geometry comprised of the three enzyme histidine ligands and an oxygen atom from the pyridone ring O=C-C-OH was indicated. Analysis of the Zn(2+) coordination geometries in recently reported structures of class II FBPAs suggests that strong Zn(2+) coordination is reserved for the enediolate-like transition state, accounting for minimal contribution of Zn(2+) coordination to binding of 8 to GlFBPA. Copyright © 2010 Elsevier Inc. All rights reserved.

Synchrotron speciation data for zero-valent iron nanoparticles

EPA Pesticide Factsheets

This data set encompasses a complete analysis of synchrotron speciation data for 5 iron nanoparticle samples (P1, P2, P3, S1, S2, and metallic iron) to include linear combination fitting results (Table 6 and Figure 9) and ab-initio extended x-ray absorption fine structure spectroscopy fitting (Figure 10 and Table 7).Table 6: Linear combination fitting of the XAS data for the 5 commercial nZVI/ZVI products tested. Species proportions are presented as percentages. Goodness of fit is indicated by the chi^2 value.Figure 9: Normalised Fe K-edge k3-weighted EXAFS of the 5 commercial nZVI/ZVIproducts tested. Dotted lines show the best 4-component linear combination fit ofreference spectra.Figure 10: Fourier transformed radial distribution functions (RDFs) of the five samplesand an iron metal foil. The black lines in Fig. 10 represent the sample data and the reddotted curves represent the non-linear fitting results of the EXAFS data.Table 7: Coordination parameters of Fe in the samples.This dataset is associated with the following publication:Chekli, L., B. Bayatsarmadi, R. Sekine, B. Sarkar, A. Maoz Shen, K. Scheckel , W. Skinner, R. Naidu, H. Shon, E. Lombi, and E. Donner. Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review. Richard P. Baldwin ANALYTICA CHIMICA ACTA. Elsevier Science Ltd, New York, NY, USA, 903: 13-35, (2016).

Synchrotron-based XAS on structure investigation of La0.99-xSrx(Na, K, Ba)0.01MnO3 nanoparticles: Evidence of magnetic properties

NASA Astrophysics Data System (ADS)

Daengsakul, Sujittra; Saengplot, Saowalak; Kidkhunthod, Pinit; Pimsawat, Adulphan; Maensiri, Santi

2018-04-01

This work presents the structural study of La0.99-xSrx(Na, K, Ba)0.01MnO3 or LSAM nanoparticles synthesized using thermal-hydro decomposition method where A denotes Na, K, Sr and Ba, respectively. The effect of ionic radii size of A dopants or rA from the substitution of A for La and Sr on the MnO6 octrahedral structure, where the average size of the cations occupying in A-site or 〈rA〉 is fixed at ∼ 1.24 Å, is focused. The LSAM nanoparticles are carefully studied using X-ray diffraction (XRD) including Rietveld refinement and X-ray Absorption Spectroscopy (XAS) including X-ray Absorption Near edge Structure (XANES) and X-ray Absorption Fine Structure (EXAFS). The Rietveld refinement shows all nano-powder samples have rhombohedral structure. By XANES technique we found that the effect of A substitutions at A-site causes a slight change of mean oxidation state of Mn between 3.54 and 3.60. Furthermore, the structural distortion of MnO6 octrahedral in samples is analysed and obtained from EXAFS. The observed trend of ferromagnetism for all LSAM samples can be clearly explained by evidences of A-site doping, structural distortion around Mn atoms and mixing Mn3+/Mn4+ valence states.

Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption nearmore » edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of Fe(III)-(hydr)oxides plays a very important role in reducing As mobility.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaspar, Tiffany C.; Sushko, Peter V.; Bowden, Mark E.

Epitaxial thin films of Cr2-xTixO3 were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) for 0.04 ≤ x ≤ 0.26. Ti speciation is verified by both x-ray photoelectron spectroscopy (XPS) and Ti K-edge x-ray absorption near-edge spectroscopy (XANES) to be Ti4+. Substitution of Ti for Cr in the corundum lattice is confirmed by modeling of the Ti K-edge extended x-ray absorption fine structure (EXAFS). Room temperature electrical transport measurements confirm the highly insulating nature of Ti-doped Cr2O3, despite the presence of aliovalent Ti4+. The resistivity of highly pure, undoped Cr2O3 was measured to be three orders of magnitude higher than formore » Ti-doped Cr2O3. Although the formation of Cr vacancies in Ti-doped Cr2O3 is found by density functional theory (DFT) calculations to be the energetically preferable defect compensation mechanism to maintain charge neutrality, an analysis of the XPS and EXAFS data reveal the presence of both Cr vacancies and oxygen interstitials at intermediate and high Ti concentrations, with a weak trend towards Cr vacancies as the Ti concentration increases. At low Ti concentrations, a strong dependence of the XPS Ti 2p core level peak width on concentration is observed. This dependence is attributed to the presence of widely spaced Ti dopants, which renders compensation of two or three Ti by a single oxygen interstitial or Cr vacancy, respectively, less probable. Instead, defect clusters of unknown type occur, although they may involve Cr vacancies. The defect compensation model developed here provides insight into previous, conflicting reports of n-type versus p-type conductivity in Ti-doped Cr2O3 at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum-structure oxides.« less

X-ray absorption spectroscopy and neutron diffraction study of the perovskite-type rare-earth cobaltites

NASA Astrophysics Data System (ADS)

Sikolenko, V.; Efimova, E.; Franz, A.; Ritter, C.; Troyanchuk, I. O.; Karpinsky, D.; Zubavichus, Y.; Veligzhanin, A.; Tiutiunnikov, S. I.; Sazonov, A.; Efimov, V.

2018-05-01

Correlations between local and long-range structure distortions in the perovskite-type RE1-xSrxCoO3-δ (RE = La, Pr, Nd; x = 0.0 and 0.5) compounds have been studied at room temperature by extended X-ray absorption fine structure (EXAFS) at the Co K-edge and high-resolution neutron powder diffraction (NPD). The use of two complementary experimental techniques allowed us to explore the influence of the type of rare-earth element and strontium substitution on unusual behavior of static and dynamic features of both the Co-O bond lengths.

Insights into the effect of iron and cobalt doping on the structure of nanosized ZnO.

PubMed

Giuli, Gabriele; Trapananti, Angela; Mueller, Franziska; Bresser, Dominic; d'Acapito, Francesco; Passerini, Stefano

2015-10-05

Here we report an in-depth structural characterization of transition metal-doped zinc oxide nanoparticles that have recently been used as anode materials for Li-ion batteries. Structural refinement of powder X-ray diffraction (XRD) data allowed the determination of small though reproducible changes in the unit cell dimensions of four ZnO samples (wurtzite structure) prepared with different dopants or different synthesis conditions. Moreover, large variations of the full width at half-maximum of the XRD reflections indicate that the crystallinity of the samples decreases in the order ZnO, Zn0.9Co0.1O, Zn0.9Fe0.1O/C, and Zn0.9Fe0.1O (the crystallite sizes as determined by Williamson-Hall plots are 42, 29, 15, and 13 nm, respectively). X-ray absorption spectroscopy data indicate that Co is divalent, whereas Fe is purely trivalent in Zn0.9Fe0.1O and 95% trivalent (Fe(3+)/(Fe(3+) + Fe(2+)) ratio = 0.95) in Zn0.9Fe0.1O/C. The aliovalent substitution of Fe(3+) for Zn(2+) implies the formation of local defects around Fe(3+) such as cationic vacancies or interstitial oxygen for charge balance. The EXAFS (extended X-ray absorption fine structure) data, besides providing local Fe-O and Co-O bond distances, are consistent with a large amount of charge-compensating defects. The Co-doped sample displays similar EXAFS features to those of pure ZnO, suggesting the absence of a large concentration of defects as found in the Fe-doped samples. These results are of substantial importance for understanding and elucidating the modified electrochemical lithiation mechanism by introducing transition metal dopants into the ZnO structure for the application as lithium-ion anode material.

XAFS studies of nickel and sulfur speciation in residual oil fly-ash particulate matters (ROFA PM).

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P; Linak, William P; Miller, C Andrew

2007-02-15

XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, depending upon the combustion conditions, lesser amounts of thiophenic sulfur, metal sulfide, and elemental sulfur may also be observed. Least-squares fitting of Ni K-edge XANES reveals that most of the nickel in PM is present as bioavailable NiSO4.nH2O. The insoluble Ni mainly exists as a minor species, as nickel ferrite in PM2.5 (PM < 2.5 microm) and nickel sulfide, Ni(x)SY(y) in PM2.5+ (PM > 2.5 microm). The Ni K-edge XANES results are in agreement with the EXAFS data. Such detailed speciation of Ni and S in PM is needed for determining their mobility, bioavailability, and reactivity, and hence, their role in PM toxicity. This information is also important for understanding the mechanism of PM formation, developing effective remediation measures, and providing criteria for identification of potential emission sources. Transition metals complexing with sulfur is ubiquitous in nature. Therefore, this information on metal sulfur complex can be critical to a large body of environmental literature.

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

DOE PAGES

Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

2016-05-30

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al 2O 3 and α-Fe 2O 3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-hmore » exposure time, Pb(II) binds preferentially to the alpha-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) surfaces at low Pb concentration ([Pb] = 10 –7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10 –6 to 10 –4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10 –7 to 10 –4 M). In comparison, the α-Al 2O 3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al 2O 3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al 2O 3 (1-102) and α-Fe 2O 3 (0001) at [Me(II)] of 10 –7 M; at 10 –5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10 –5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb L-III-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10 –5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Lastly, our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.« less

Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

NASA Astrophysics Data System (ADS)

Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Gordon E.

2016-09-01

Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) surfaces at low Pb concentration ([Pb] = 10-7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10-6 to 10-4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10-7 to 10-4 M). In comparison, the α-Al2O3 (0 0 0 1) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0 0 0 1) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) at [Me(II)] of 10-7 M; at 10-5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10-5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb LIII-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be complexed by carboxyl groups in S. oneidensis biofilms after 3-h exposure at pH 6.0 and [Me(II)] = 10-5 M. In contrast with Burkholderia cepacia, which was used in our previous studies of monolayer biofilm-coated metal-oxide surfaces (Templeton et al., 2001), S. oneidensis MR-1 forms relatively thick biofilm coatings (6-20 μm) that are rich in reactive functional groups and are expected to dominate metal-ion adsorption. Our results show that even thick and highly reactive biofilms like S. oneidensis do not cause much change in the intrinsic chemical reactivities of the underlying metal-oxide surfaces with respect to aqueous Pb(II) and Zn(II) and don't block reactive sites on the metal-oxide surfaces; instead they reduce the rate of Pb(II) and Zn(II) sorption onto these surfaces.

Structural instability and electronic localization in the 2:1 salts: The case of the Fabre and the (DMtTTF){2}CIO{4}salts

NASA Astrophysics Data System (ADS)

Ravy, S.; Foury-Leylekian, P.; Le Bolloc'h, D.; Pouget, J.-P.; Fabre, J. M.; Prado, R. J.; Lagarde, P.

2004-04-01

The charge ordering observed in the (TMTTF){2}X family has been studied by X-ray absorption spectroscopy. XANES measurements at the Sulfur K-edge show no evidence of charge disproportionation larger than 0.5 e, and EXAFS at the Phosphorus K-edge indicate no displacements of the PF{6} anion larger than 0.05 Å. The difficulty to observe a structural signature of this charge ordering is due to the triclinic symmetry of these salts. By contrast, in the monoclinic charge transfer salt (DMtTTF){2}ClO{4}, a screw axis symmetry constrains the molecular stacks to be uniform. In this real 1/4-filled system, charge localization is observed at about 150 K. We show that around this temperature an incommensurate modulation of reduced wave vector (0.58,0,-0.275) is stabilized. The transition is strongly hysteretic, but no long range order is established. We suggest that this modulation, which has the 4k{F} periodicity in the chain direction, stabilizes a local antiferroelectric state similar to the one previously observed in (TMTTF){2}SCN. Key words. Charge ordering, Structural phase transition.

Fischer–Tropsch Synthesis: XANES Spectra of Potassium in Promoted Precipitated Iron Catalysts as a Function of Time On-stream

DOE PAGES

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela; ...

2017-06-06

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Atomistic simulation and XAS investigation of Mn induced defects in Bi{sub 12}TiO{sub 20}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rezende, Marcos V dos S.; Santos, Denise J.; Jackson, Robert A.

2016-06-15

This work reports an investigation of the valence and site occupancy of Mn dopants in Bi{sub 12}TiO{sub 20} (BTO: Mn) host using X-ray Absorption (XAS) and atomistic simulation techniques based on energy minimisation. X-ray Absorption Near Edge Structure (XANES) at the Mn K-edges gave typical results for Mn ions with mixed valences of 3+ and 4+. Extended X-ray Absorption Fine Structure (EXAFS) results indicated that Mn ions are probably substituted at Ti sites. Atomistic simulation was performed assuming the incorporation of Mn{sup 2+}, Mn{sup 3+} and Mn{sup 4+} ions at either Bi{sup 3+} or Ti{sup 4+} sites, and the resultsmore » were compared to XANES and EXAFS measurements. Electrical conductivity for pure and doped samples was used to evaluate the consistency of the proposed model. - Graphical abstract: The structure of Bi{sub 12}TiO{sub 20} (BTO). Display Omitted - Highlights: • Pure and Mn-doped Bi{sub 12}TiO{sub 20} samples were studied by experimental techniques combined with atomistic simulation. • Good agreement between experimental and simulation results was obtained. • XANES results suggest a mixture of 3+ and 4+ valences for Mn, occupying the Ti4+ site in both cases. • Charge compensation by holes is most energetically favoured, explaining the enhancement observed in AC dark conductivity.« less

The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

NASA Astrophysics Data System (ADS)

Majzlan, Juraj; Lalinská, Bronislava; Chovan, Martin; Jurkovič, L.'ubomír; Milovská, Stanislava; Göttlicher, Jörg

2007-09-01

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ˜380,000 m 3 of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS 2; arsenopyrite, FeAsS; berthierite, FeSb 2S 4) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As 5+). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As 2O 5 and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As 5+. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.

Assignment of the zinc ligands in RsrA, a redox-sensing ZAS protein from Streptomyces coelicolor.

PubMed

Zdanowski, Konrad; Doughty, Phillip; Jakimowicz, Piotr; O'Hara, Liisa; Buttner, Mark J; Paget, Mark S B; Kleanthous, Colin

2006-07-11

ZAS proteins are widespread bacterial zinc-containing anti-sigma factors that regulate the activity of sigma factors in response to diverse cues. One of the best characterized ZAS proteins is RsrA from Streptomyces coelicolor, which responds to disulfide stress. Zn-RsrA binds and represses the transcriptional activity of sigmaR in the reducing environment of the cytoplasm but undergoes reversible, intramolecular disulfide bond formation during oxidative stress. This expels the single metal ion and causes dramatic structural changes in RsrA that result in its dissociation from sigmaR, leaving the sigma factor free to activate the transcription of antioxidant genes. We showed recently that Zn2+ serves a critical role in modulating the redox activity of RsrA thiols but uncertainty remains as to how the metal ion is coordinated in RsrA and related ZAS proteins. Using a combination of random and site-specific mutagenesis with zinc K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, we have assigned unambiguously the metal ligands in RsrA, thereby distinguishing between the different ligation models that have been proposed. The data show that the zinc site in RsrA is comprised of Cys11, His37, Cys41, and Cys44. Three of these residues are part of a conserved ZAS-specific sequence motif (H37xxxC41xxC44), with the fourth ligand, Cys11, found in a subset of ZAS proteins. Cys11 and Cys44 form the trigger disulfide in RsrA, explaining why the metal ion is expelled during oxidation. We discuss these data in the context of redox sensing by RsrA and the sensory mechanisms of other ZAS proteins.

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

The solubility of sphalerite (ZnS) in sulfidic solutions at 25°C and 1 atm pressure

NASA Astrophysics Data System (ADS)

Daskalakis, Kostas D.; Helz, George R.

1993-10-01

The solubility of both synthetic and natural sphalerite have been measured at 25°, pH 2.2 to 9.1, and ΣS(-II) 0.1 to 0.0004 M. Inversion of wurtzite to sphalerite during equilibration precluded measuring wurtzite solubilities. To hinder colloid formation, we used well-crystallized ZnS preleached with EDTA. Run durations were several months. Clean-room analytical procedures were used. Measured solubilities are much lower than those of GüBELI and STE-MARIE (1967), whose solutions probably contained colloids. Colloidal ZnS sols are shown not to equilibrate with sphalerite even over several months. The new data are consistent with, and complementary to those of HAYASHI et al. (1990). The solubility of Zn 2+ in equilibrium with sphalerite is given by a Zn2+a 2HS-/a H2 S = 10 18.47 +- 0.01. Aqueous Zn-polysulfides appear to be unimportant under the conditions studied. In terms of anhydrous, mononuclear complexes, Zn solubility can be described by a series of complexes whose formation is represented by: ZnS( sp) + (2 y- z-2) HS- + ( z- y+1) H2SaqZnSyHz-(2 y- z-2) , Kyz. Three complexes are essential to model the results adequately: Zn( HS) -24, logK44 = -3.83 ± 0.17; ZnS( HS) -, logK21 = -4.64 ± 0.08; and ZnS( HS) -22, logK32 = -5.33 ± 0.07. Additional complexes improve the fit marginally. Others have suggested that ZnS(HS) -22 should be represented by its hydrated formula, Zn(OH)(HS) -23. The observed stability of this complex is much greater than predicted for a mixed ligand complex derived from Zn(HS) -24 and Zn(OH) -24. Based on recent calculations, less than 3/4 of the discrepancy can be accounted for by molecular orbital stabilization. A tetranuclear formula suggested by known Zn-thiolate structures and supported by EXAFS evidence of multinuclearity is a possible alternative. The solubility of Zn in anoxic marine waters is determined largely by ZnS(HS) -, which dominates in mildly alkaline solutions at low σS(-II). According to the new data, anoxic zones in Framvaren Fjord and the Black Sea are undersaturated with respect to sphalerite, except immediately below the oxic/anoxic interface. This suggests that scavenging, rather than precipitation, controls Zn.

X-ray absorption fine structure and X-ray excited optical luminescence studies of II-VI semiconducting nanostructures

NASA Astrophysics Data System (ADS)

Murphy, Michael Wayne

2010-06-01

Various II-VI semiconducting nanomaterials such as ZnO-ZnS nanoribbons (NRs), CdSxSe1-x nanostructures, ZnS:Mn NRs, ZnS:Mn,Eu nanoprsims (NPs), ZnO:Mn nanopowders, and ZnO:Co nanopowders were synthesized for study. These materials were characterized by techniques such as scanning electron microscopy, transmission electron microscopy, element dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The electronic and optical properties of these nanomaterials were studied by X-ray absorption fine structure (XAFS) spectroscopy and X-ray excited optical luminescence (XEOL) techniques, using tuneable soft X-rays from a synchrotron light source. The complementary nature ofthe XAFS and XEOL techniques give site, element and chemical specific measurements which allow a better understanding of the interplay and role of each element in the system. Chemical vapour deposition (CVD) of ZnS powder in a limited oxygen environment resulted in side-by-side biaxial ZnO-ZnS NR heterostructures. The resulting NRs contained distinct wurtzite ZnS and wurtzite ZnO components with widths of 10--100 nm and 20 --500 nm, respectively and a uniform interface region of 5-15 nm. XAFS and XEOL measurements revealed the luminescence of ZnO-ZnS NRs is from the ZnO component. The luminescence of CdSxSe1-x nanostructures is shown to be dependent on the S to Se ratio, with the band-gap emission being tunable between that of pure CdS and CdSe. Excitation of the CdSxSe 1-x nanostructures by X-ray in XEOL has revealed new de-excitation channels which show a defect emission band not seen by laser excitation. CVD of Mn2+ doped ZnS results in nanostructures with luminescence dominated by the yellow Mn2+ emission due to energy transfer from the ZnS host to the Mn dopant sites. The addition of EuCl3 to the reactants in the CVD process results in a change in morphology from NR to NP. Zn1-xMnxO and Zn1-xCOxO nanopowders were prepared by sol-gel methods at dopant concentrations of 0, 1,3, and 10% and annealed at 400, 600 and 800°C in air. XAFS spectra show that low dopant concentrations and low processing temperatures limit the amount of secondary phase formation. The nanopowders did not show roomtemperature ferromagnetism and increased secondary phase formation increases the paramagnetic character of the hysteresis curves at 5°K. Keywords: X-ray absorption fine structures (XAFS), X-ray absorption near-edge structures (XANES), extended X-ray absorption fine structure (EXAFS), X-ray absorption spectroscopy(XAS), X-ray excited optical luminescence (XEOL), time-resolved, II-VI semiconductors, nanostructure, nanomaterial, nanoribbon, nanowire, nanopartic1e, heterostructure, ZnO, ZnS, ZnO-ZnS, CdS, CdSe, CdSSe, ZnO:Mn, ZnO:Co, ZnS:Mn, dilute magnetic semiconductor (DMS), dilute magnetic oxide (DMO), spintronics, magnetism, paramagnetism, ferromagnetism.

Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

2012-01-01

We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

Hydrogen-induced structural changes at the nickel site of the regulatory [NiFe] hydrogenase from Ralstonia eutropha detected by X-ray absorption spectroscopy.

PubMed

Haumann, Michael; Porthun, Antje; Buhrke, Thorsten; Liebisch, Peter; Meyer-Klaucke, Wolfram; Friedrich, Bärbel; Dau, Holger

2003-09-23

For the first time, the nickel site of the hydrogen sensor of Ralstonia eutropha, the regulatory [NiFe] hydrogenase (RH), was investigated by X-ray absorption spectroscopy (XAS) at the nickel K-edge. The oxidation state and the atomic structure of the Ni site were investigated in the RH in the absence (air-oxidized, RH(ox)) and presence of hydrogen (RH(+H2)). Incubation with hydrogen is found to cause remarkable changes in the spectroscopic properties. The Ni-C EPR signal, indicative of Ni(III), is detectable only in the RH(+H2) state. XANES and EXAFS spectra indicate a coordination of the Ni in the RH(ox) and RH(+H2) that pronouncedly differs from the one in standard [NiFe] hydrogenases. Also, the changes induced by exposure to H(2) are unique. A drastic modification in the XANES spectra and an upshift of the K-edge energy from 8339.8 (RH(ox)) to 8341.1 eV (RH(+H2)) is observed. The EXAFS spectra indicate a change in the Ni coordination in the RH upon exposure to H(2). One likely interpretation of the data is the detachment of one sulfur ligand in RH(+H2) and the binding of additional (O,N) or H ligands. The following Ni oxidation states and coordinations are proposed: five-coordinated Ni(II)(O,N)(2)S(3) for RH(ox) and six-coordinated Ni((III))(O,N)(3)X(1)S(2) [X being either an (O,N) or H ligand] for RH(+H2). Implications of the structural features of the Ni site of the RH in relation to its function, hydrogen sensing, are discussed.

Effect of Co and O defects on ferromagnetism in Co-doped ZnO: An X-ray absorption spectroscopic investigation

NASA Astrophysics Data System (ADS)

Singhal, Rishi K.; Jakhar, Narendra; Samariya, A.; Dolia, S. N.; Kumar, Sudhish

2018-02-01

Understanding of origin of ferromagnetism in dilute magnetic oxides (DMO's) has become one of the most challenging research problems in condensed matter physics. Here we are reporting a detailed study of magnetic properties and electronic structure of two 5% Co-doped ZnO samples (the as-prepared sample Zn0.95Co0.05O and the hydrogenated sample Zn0.95Co0.05O:H). The as-prepared sample is found to be paramagnetic while through hydrogenation, we observed inducement of remarkable ferromagnetism in it. The H-mediated magnetic transition is accompanied by electronic structure modifications with no structural deviations. To get in-depth information into electronic structure correlations of the observed ferromagnetism, we have investigated their electronic properties in detail. For this purpose, we have employed the site-selective and element-sensitive X-ray-absorption spectroscopy (XAS) in the vicinity of the Cobalt L2,3 edge, the oxygen K edge, and the Zinc L3 edge using synchrotron radiation. The Co L2,3 edge spectra clearly show that Co dopants reside at the Zn sites for both these samples and that they are tetrahedrally coordinated with the ligand O atoms. Very minor changes are observed in the Zn L3 edge spectra. However, the O 1s edge spectra display dominant additional components in the ferromagnetic hydrogenated sample Zn0.95Co0.05O:H, not observed in the as-prepared non-magnetic sample Zn0.95Co0.05O. We conclude that the observed spectral features can be attributed to the presence of O vacancies and the hybridization of Co 3d states with O 2p vacancy states. These two factors together are likely to play important role in inducement of ferromagnetic ordering in this Co-doped ZnO system. However, which of these two weighs more in this mechanism, cannot be pinpointed and more studies are required in this regard.

Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce2(C8H8)3 and Ce(C8H8)2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W.

2009-02-02

New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolatedmore » f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a"triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules.« less

Stoichiometry of mercury-thiol complexes on bacterial cell envelopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, Bhoopesh; Shoenfelt, Elizabeth; Yu, Qiang

We have examined the speciation of Hg(II) complexed with intact cell suspensions (1013 cells L- 1) of Bacillus subtilis, a common gram-positive soil bacterium, Shewanella oneidensis MR-1, a facultative gram-negative aquatic organism, and Geobacter sulfurreducens, a gram-negative anaerobic bacterium capable of Hg-methylation at Hg(II) loadings spanning four orders of magnitude (120 nM to 350 μM) at pH 5.5 (± 0.2). The coordination environments of Hg on bacterial cells were analyzed using synchrotron based X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy at the Hg LIII edge. The abundance of thiols on intact cells wasmore » determined by a fluorescence-spectroscopy based method using a soluble bromobimane, monobromo(trimethylammonio)bimane (qBBr) to block thiol sites, and potentiometric titrations of biomass with and without qBBr treatment. The chemical forms of S on intact bacterial cells were determined using S k-edge XANES spectroscopy.« less

Investigating the evolution of local structure around Er and Yb in ZnO:Er and ZnO:Er, Yb on annealing using X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Anjana, R.; Jayaraj, M. K.; Yadav, A. K.; Jha, S. N.; Bhattacharyya, D.

2018-04-01

The local structure around Er and Yb centre in ZnO favouring upconversion luminescence was studied using EXAFS (Extended X-ray absorption fine structure spectroscopy). Due to the ionic radii difference between Zn and Er, Yb ions, the dopants cannot replace Zn in the ZnO lattice properly. Er2O3 and Yb2O3 impurity phases are formed at the grain boundaries of ZnO. It is found that the local structure around the Er centre in ZnO is modified on annealing in air. The symmetry around both erbium and ytterbium reduces with increase in annealing temperature. Symmetry reduction will favour the intra-4f transition and the energy transitions causing upconversion luminescence. By fitting the EXAFS data with theoretically simulated data, it is found that the Er centre forms a local structure similar to C4ν symmetry which is a distorted octahedron. On annealing the sample to 1200 °C, all the erbium centres are transformed to C4ν symmetry causing enhanced upconversion emission. Yb centre has also been modified on annealing. The decrease in co-ordination number with annealing temperature will decrease the symmetry and increase the near infrared absorption cross section. The decrease in symmetry around both the erbium and ytterbium centre and formation of C4ν symmetry around Er centre is the reason behind the activation of upconversion luminescence with high temperature annealing in both Er doped and Er, Yb co-doped ZnO samples. The study will be useful for the synthesis of high efficiency upconversion materials.

Probing the CZTS/CdS heterojunction utilizing photoelectrochemistry and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Turnbull, Matthew J.; Vaccarello, Daniel; Wong, Jonathan; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

2018-04-01

The importance of renewable resources is becoming more and more influential on research due to the depletion of fossil fuels. Cost-effective ways of harvesting solar energy should also be at the forefront of these investigations. Cu2ZnSnS4 (CZTS) solar cells are well within the frame of these goals, and a thorough understanding of how they are made and processed synthetically is crucial. The CZTS/CdS heterojunction was examined using photoelectrochemistry and synchrotron radiation (SR) spectroscopy. These tools provided physical insights into this interface that was formed by the electrophoretic deposition of CZTS nanocrystals and chemical bath deposition (CBD) of CdS for the respective films. It was discovered that CBD induced a change in the local and long range environment of the Zn in the CZTS lattice, which was detrimental to the photoresponse. X-ray absorption near-edge structures and extended X-ray absorption fine structures (EXAFSs) of the junction showed that this change was at an atomic level and was associated with the coordination of oxygen to zinc. This was confirmed through FEFF fitting of the EXAFS and through IR spectroscopy. It was found that this change in both photoresponse and the Zn coordination can be reversed with the use of low temperature annealing. Investigating CZTS through SR techniques provides detailed structural information of minor changes from the zinc perspective.

Hydrothermal Synthesis and Characterization of Ni-Al Montmorillonite-Like Phyllosilicates

PubMed Central

Reinholdt, Marc X.; Brendlé, Jocelyne; Tuilier, Marie-Hélène; Kaliaguine, Serge; Ambroise, Emmanuelle

2013-01-01

This work describes the first hydrothermal synthesis in fluoride medium of Ni-Al montmorillonite-like phyllosilicates, in which the only metallic elements in the octahedral sheet are Ni and Al. X-ray diffraction , chemical analysis, thermogravimetric and differential thermal analysis, scanning electron microscopy and transmission electron microscopy confirm that the synthesized samples are montmorillonite-like phyllosilicates having the expected chemical composition. The specific surface areas of the samples are relatively large (>100 m2 g−1) compared to naturally occurring montmorillonites. 29Si and 27Al nuclear magnetic resonance (NMR) indicate substitutions of Al for Si in the tetrahedral sheet. 19F NMR and Ni K-edge extended X-ray absorption fine structure (EXAFS) local probes highlight a clustering of the metal elements and of the vacancies in the octahedral sheet of the samples. These Ni-Al phyllosilicates exhibit a higher local order than in previously synthesized Zn-Al phyllosilicates. Unlike natural montmorillonites, where the distribution of transition metal cations ensures a charge equilibrium allowing a stability of the framework, synthetic montmorillonites entail clustering and instability of the lattice when the content of divalent element in the octahedral sheet exceeds ca. 20%. Synthesis of Ni-Al montmorillonite-like phyllosilicates, was successfully achieved for the first time. These new synthetic materials may find potential applications as catalysts or as materials with magnetic, optical or staining properties. PMID:28348321

Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

NASA Astrophysics Data System (ADS)

Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

2015-07-01

Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of heavy Zn from the soil to cell wall remains and release of light Zn to the soil. Overall, this study provides a complete overview of Zn cycling in an urban wetland soil-plant system, and describes several changes in Zn speciation with Zn isotopic fractionation processes in a complex system.

Local structural and chemical ordering of nanosized Pt3±δCo probed by multiple-scattering x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Greco, Giorgia; Witkowska, Agnieszka; Principi, Emiliano; Minicucci, Marco; di Cicco, Andrea

2011-04-01

This work reports a detailed investigation of the local structure and chemical disorder of a Pt3±δCo thin film and Pt3±δCo nanoparticles. We have used a combination of techniques including x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and high-resolution transmission electron microscopy (TEM). High-quality XAS spectra at the Co K edge and Pt L3 edge have been analyzed using double-edge multiple-scattering data analysis. Structural extended x-ray absorption fine structure (EXAFS) refinements have been performed accounting for the reduction of the coordination numbers and degeneracy of three-atom configurations, resulting from the measured size distribution and stoichiometry. The important effect of chemical ordering on pair and three-atom configurations has been studied using computer simulations based on a simple model accounting for substitutional disorder, defined by an order parameter s. It has been found that individual EXAFS signals related to the minority species (Co) are extremely sensitive to substitutional disorder so their intensities, especially those of the collinear three-atom configurations, can be used as a measure of the ordering level. The thin film has been found to be chemically disordered (s⩽0.4), in agreement with previous estimates. The Pt3±δCo nanoalloy has been found to be partially ordered (s=0.6±0.1) while the local structure around Co atoms is characterized by a higher level of structural disorder as compared to the bulk-like thin film. The robust approach for nanomaterial characterization used in this work combining different techniques can, in principle, be applied for structural refinements of any binary nanocrystalline functional system.

Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

DTIC Science & Technology

2013-01-01

health risk. In addition Pb corrosion products may be sinks for other metals such as chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn). These...Vanadium K-Edge X-ray Absorption Near-Edge Structure Interpretation: Application to the Speciation of Vanadium in Oxide Phases from Steel Slag ’, Journal

The characterization of Cr secondary oxide phases in ZnO films studied by X-ray spectroscopy and photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Chiou, J. W.; Chang, S. Y.; Huang, W. H.; Chen, Y. T.; Hsu, C. W.; Hu, Y. M.; Chen, J. M.; Chen, C.-H.; Kumar, K.; Guo, J.-H.

2011-03-01

X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES), and X-ray photoemission spectroscopy (XPS) were used to characterize the Cr secondary oxide phases in ZnO films that had been prepared using a co-sputtering method. Analysis of the Cr L3,2-edge XANES spectra reveals that the intensity of white-line features decreases subtly as the sputtering power increases, indicating that the occupation of Cr 3 d orbitals increases with Cr concentration in (Zn, Cr)O films. The O K-edge spectra show that the intensity of XANES features of (Zn, Cr)O films is lower than those of ZnO film, suggesting enhanced occupation of O 2 p-derived states through O 2 p-Cr 3 d hybridization. The XES and XPS spectra indicate that the line shapes in the valence band of (Zn, Cr)O films are quite different from those of ZnO and that the Cr 2O 3 phase dominates the spinel structure of (Zn, Cr)O films increasingly as the Cr sputtering power is increased. Over all results suggest that the non-ferromagnetic behavior of (Zn, Cr)O films can be attributed to the dominant presence of Cr 2O 3, whereas the bulk comprise phase segregations of Cr 2O 3 and/or ZnCr 2O 4, which results them the most stable TM-doped ZnO material against etching.

XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

NASA Astrophysics Data System (ADS)

Evans, K. A.; O'Neill, H. St. C.; Mavrogenes, J. A.; Keller, N. S.; Jang, L.-Y.; Lee, J.-F.

2009-11-01

S K-edge XANES and Mn-, W- and Ni-XANES and EXAFS spectra of silicate glasses synthesised at 1400 °C and 1 bar with compositions in the CaO-MgO-Al 2O 3-SiO 2-S plus MnO, NiO, or WO 3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S 2-, and a peak of variable height with an edge at 2480.2-2480.8 eV, which is consistent with the presence of S 6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1 and 2476.2 eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S-XANES spectra cannot be reproduced by a combination of the spectra of the component element monosulphides. Mn-, W- and Ni-XANES and EXAFS for synthetic glasses without sulphide exsolution did not show any sensitivity to the presence of sulphur, which is unsurprising as S:O ratios were sufficiently low that metals would be mostly co-ordinated by O. Mn EXAFS spectra were consistent with divalent Mn in 5 co-ordinated Mn-O melt species. W spectra were consistent with tetrahedrally co-ordinated hexavalent W, most likely in scheelite-like melt species, and Ni spectra were consistent with [4] co-ordinated divalent Ni. These results indicate lower co-ordinations for both W and Ni than those inferred by some previous workers. Cation co-ordination may reflect the proportion of non-bridging oxygens, which is lower in the Ca-rich and Al-poor samples investigated here than for previous studies.

Alteration of sediments by hyperalkaline K-rich cement leachate: implications for strontium adsorption and incorporation.

PubMed

Wallace, Sarah H; Shaw, Samuel; Morris, Katherine; Small, Joe S; Burke, Ian T

2013-04-16

Results are presented from 1 year batch experiments where K-rich hyperalkaline pH 13.5 young cement water (YCW) was reacted with sediments to investigate the effect of high pH, mineral alteration, and secondary mineral precipitation on (90)Sr sorption. After reaction with YCW, Sr sorption was found to be greater than 75% in all samples up to 365 days and 98% in a sample reacted for 365 days at 70 °C. Scanning electron microscopy analysis of sediment samples reacted at room temperature showed surface alteration and precipitation of a secondary phase, likely a K-rich aluminosilicate gel. The presence of Sr-Si(Al) bond distances in Sr K-edge extended X-ray absorption fine structure (EXAFS) analysis suggested that the Sr was present as an inner-sphere adsorption complex. However, sequential extractions found the majority of this Sr was still exchangeable with Mg(2+) at pH 7. For the sample reacted for 1 year at 70 °C, EXAFS analysis revealed clear evidence for ∼6 Sr-Si(Al) backscatters at 3.45 Å, consistent with Sr incorporation into the neoformed K-chabazite phase that was detected by X-ray diffraction and electron microscopy. Once incorporated into chabazite, (90)Sr was not exchangeable with Mg(2+), and chemical leaching with pH 1.5 HNO3 was required to remobilize 60% of the (90)Sr. These results indicate that, in high pH cementitious leachate, there is significantly enhanced Sr retention in sediments due to changes in the adsorption mechanism and incorporation into secondary silicate minerals. This suggests that Sr retention may be enhanced in this high pH zone and that the incorporation process may lead to irreversible exchange of the contaminant over extended time periods.

Mineral transformation controls speciation and pore-fluid transmission of contaminants in waste-weathered Hanford sediments

NASA Astrophysics Data System (ADS)

Perdrial, Nicolas; Thompson, Aaron; O'Day, Peggy A.; Steefel, Carl I.; Chorover, Jon

2014-09-01

Portions of the Hanford Site (WA, USA) vadose zone were subjected to weathering by caustic solutions during documented releases of high level radioactive waste (containing Sr, Cs and I) from leaking underground storage tanks. Previous studies have shown that waste-sediment interactions can promote variable incorporation of contaminants into neo-formed mineral products (including feldspathoids and zeolites), but processes regulating the subsequent contaminant release from these phases into infiltrating background pore waters remain poorly known. In this paper, reactive transport experiments were conducted with Hanford sediments previously weathered for one year in simulated hyper-alkaline waste solutions containing high or low 88Sr, 127I, and 133Cs concentrations, with or without CO2(aq). These waste-weathered sediments were leached in flow-through column experiments with simulated background pore water (characteristic of meteoric recharge) to measure contaminant release from solids formed during waste-sediment interaction. Contaminant sorption-desorption kinetics and mineral transformation reactions were both monitored using continuous-flow and wet-dry cycling regimes for ca. 300 pore volumes. Less than 20% of contaminant 133Cs and 88Sr mass and less than 40% 127I mass were released over the course of the experiment. To elucidate molecular processes limiting contaminant release, reacted sediments were studied with micro- (TEM and XRD) and molecular- (Sr K-edge EXAFS) scale methods. Contaminant dynamics in column experiments were principally controlled by rapid dissolution of labile solids and competitive exchange reactions. In initially feldspathoidic systems, time-dependent changes in the local zeolitic bonding environment observed with X-ray diffraction and EXAFS are responsible for limiting contaminant release. Linear combination fits and shell-by-shell analysis of Sr K-edge EXAFS data revealed modification in Sr-Si/Al distances within the zeolite cage. Wet-dry cycling did not affect significantly molecular-scale transformations relative to continuous-flow controls. Results indicate that contaminants bound to the solid phase in distinct micro- and molecular-scale coordinative environments can generate similar macro-scale release behaviors, highlighting the need for multi-scale interrogations to constrain mechanisms of reactive transport. Data also indicate that weathering-induced change in ion exchange selectivity coefficients should be incorporated in simulations of contaminant release from caustic high-level radioactive waste impacted sediments.

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy

DOE PAGES

Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2016-06-06

Copper ferrite, CuFe 2 O 4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe 2 O 4. A phase pure tetragonal CuFe 2 O 4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. We used ex situ X-ray absorption spectroscopy (XAS) measurements to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structuremore » (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(II) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(III) cations to octahedral positions previously occupied by copper(II). Then, upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(III) was achieved. Our results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.« less

Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

PubMed

Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

2016-06-22

Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

Coexistence of strongly and weakly confined energy levels in (Cd,Zn)Se quantum dots: Tailoring the near-band-edge and defect-levels for white light emission

NASA Astrophysics Data System (ADS)

Das, Tapan Kumar; Ilaiyaraja, P.; Sudakar, C.

2017-05-01

We demonstrate white light emission (WLE) from (Cd,Zn)Se system, which is a composite of Zn alloyed CdSe quantum dot and ZnSe-amorphous (ZnSe-a) phase. Detailed structural and photoluminescence emission studies on pure CdSe and (Cd,Zn)Se show cubic zinc blende structure in the size range of 2.5 to 5 nm. (Cd,Zn)Se quantum dots (QDs) also have a significant fraction of ZnSe-a phase. The near-band-edge green-emission in crystalline CdSe and (Cd,Zn)Se is tunable between 500 to 600 nm. The (Cd,Zn)Se system also exhibits a broad, deep defect level (DL) red-emission in the range 600 to 750 nm and a sharp ZnSe near-band-edge blue-emission (ZS-NBE) between 445 to 465 nm. While DL and CdSe near-band-edge (CS-NBE) emissions significantly shift with the size of QD due to strong confinement effect, the ZS-NBE show minimal change in peak position indicating a weak confinement effect. The intensities of ZS-NBE and DL emissions also exhibit a strong dependence on the QD size. A gamut of emission colors is obtained by combining the CS-NBE with the ZS-NBE emission and broad DL emission in (Cd,Zn)Se system. Interestingly, we find the convergence of Commission Internationale de l'Eclairage (CIE) coordinates towards the white light with increasing Zn concentration in CdSe. We demonstrate by combining these three emissions in a proper weight ratio WLE can be achieved. Cd1-yZnySe (y = 0. 5; QD size ˜4.9 nm) alloy with a maximum quantum yield of 57% exhibits CIE coordinates of (0.39, 0.4), color rendering index (CRI) of 82, correlated color temperature (CCT) of 3922 K, and Duv of 0.0078 which is very promising for white light applications.

Structural evidence for the sorption of Ni(II) atoms on the edges of montmorillonite clay minerals: a polarized X-ray absorption fine structure study

NASA Astrophysics Data System (ADS)

Dähn, Rainer; Scheidegger, André M.; Manceau, Alain; Schlegel, Michel L.; Baeyens, Bart; Bradbury, Michael H.; Chateigner, Daniel

The nature of surface complexes formed on Ni uptake onto montmorillonite (a dioctahedral smectite) has been investigated over an extended time period by polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Self-supporting films of Ni-sorbed montmorillonite were prepared by contacting Ni and montmorillonite at pH 7.2, high ionic strength (0.3 M NaClO 4), and low Ni concentration ([Ni] initial = 19.9 μM) for 14- and 360-d reaction time. The resulting Ni concentration on the clay varied from 4 to 7 μmol/g. Quantitative texture analysis indicates that the montmorillonite particles were well orientated with respect to the plane of the film. The full width at half maximum of the orientation distribution of the c* axes of individual clay platelets about the normal to the film plane was 44.3° (14-d reaction time) and 47.1° (360-d reaction time). These values were used to correct the coordination numbers determined by P-EXAFS for texture effects. Ni K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 10, 35, 55, and 80°. Spectral analysis led to the identification of three nearest cationic subshells containing 2.0 ± 0.5 Al at 3.0 Å and 2.0 ± 0.5 Si at 3.12 Å and 4.0 ± 0.5 Si at 3.26 Å. These distances are characteristic of edge-sharing linkages between Al and Ni octahedra and of corner-sharing linkages between Ni octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Ni-Al and Ni-Si contributions indicates that Ni-Al pairs are oriented parallel to the film plane, whereas Ni-Si pairs are not. The study reveals the formation of Ni inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and thus that heavy metals binding to edge sites is a possible sorption mechanism for dioctahedral smectites. Data analysis further suggests that either the number of neighboring Al atoms slightly increases from 1.6 to 2 or that the structural order of the observed surface complexes increases from 0.01 Å 2 to 0.005 Å 2 with increasing reaction time. On the basis of the low Ni-Al coordination numbers, it appears that over an extended reaction time period of 1 yr the diffusion of Ni atoms in the octahedral layer is not the major uptake mechanism of Ni onto montmorillonite.

XAS study of chromium in Li 2MSiO 4 (M=Mg, Zn)

NASA Astrophysics Data System (ADS)

Jousseaume, C.; Ribot, F.; Kahn-Harari, A.; Vivien, D.; Villain, F.

2003-01-01

X-ray absorption spectroscopy (XAS) investigations at the Cr K-edge on Cr:Li 2MSiO 4 (M=Mg, Zn) have been performed to understand the exceptionally long fluorescence lifetime of Cr IV. Previous work has shown the simultaneous presence of three oxidation states Cr IV, Cr V and Cr VI. X-ray absorption near edge structure measurements confirm that Cr in Li 2MSiO 4 (M=Mg, Zn) single crystals is in tetrahedral coordination. They also reveal that Cr VI is the dominant species in Li 2MgSiO 4, and that Li 2ZnSiO 4 contains more Cr V than Li 2MgSiO 4. The extended X-ray absorption fine structure spectra of Cr:Li 2MgSiO 4 single crystals recorded at the Cr K-edge, are fitted with two types of Cr environments: the first one corresponds to oxygen atoms at a mean distance of 1.68 Å and the second to oxygen atoms at a mean distance of 2.07 Å. This second environment is attributed to Cr III in the minor parasitic phase LiCr IIIO 2. The first environment corresponds to Cr that substitutes silicon in the Li 2MgSiO 4 lattice in the silicon site if the cations sizes are considered.

Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

NASA Astrophysics Data System (ADS)

Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

2016-06-01

Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon

In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

Phytostabilization of Mining Soils By the Plant Anthyllis Vulneraria: A Micro-XRF and XAS Study

NASA Astrophysics Data System (ADS)

Isaure, M. P.

2014-12-01

Mine tailings are typical highly metal contaminated areas with very scarce vegetation. They are affected by intensive rain and wind erosion processes, thus representing a source of environmental and health hazard. Due to their large area and high level of contamination, conventional remediation techniques are not appropriate, and phytostabilization has emerged as an alternative technique during the last decade. The legume plant Anthyllis vulneraria has been identified as a pionner plant to revegetalize mining sites from South of France where an experimental site has been set up for 10 years. Our objective was to clarify the role of Anthyllis vulneraria in the distribution and speciation of Cd and Zn in the soil. For that, we used a combination of micro X-ray fluorescence (μXRF) and micro X-ray Absorption Near Edge Structure spectroscopy (μXANES) combined to Extended X-ray Absorption Fine Structure spectroscopy (EXAFS). Results showed that the vegetation process had homogeneized the metal distribution in the soil compared to unvegetalized soil, and had decreased the Zn and Cd amount in the surface soil. Undisturbed cross-sections of soils showed that the top of the rhizosphere was highly enriched with organic matter after 10 years of vegetalization. Cd and Zn forms, mainly identified as CdCO3 and ZnCO3 in the unvegetalized soil, did not change significantly in the bulk rhizosphere but investigations at the micrometer scale allowed the identification of Cd and Zn organic phases in the upper part, probably related to the shoots decomposition, and thus to the organic matter recycling. At the close vicinity of the roots, some minor organic metallic forms were found whilst CdCO3 and ZnCO3 minerals were still present, thus highlighting the low direct impact of the roots in the soil. Finally, this study indicated that the direct impact of the plant on Cd and Zn speciation in the soil was weak, while an indirect effect resulting from shoots decomposition could be observed.

In situ XAFS and micro-XAFS studies on LiNi 0.8Co 0.15Al 0.05O 2 cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Nonaka, T.; Okuda, C.; Seno, Y.; Nakano, H.; Koumoto, K.; Ukyo, Y.

We have applied in situ X-ray absorption fine structure (XAFS) and in situ micro-XAFS techniques to study LiNi 0.8Co 0.15Al 0.05O 2 cathode materials in Li-ion coin cells that show various levels of capacity fading: fresh cell, cycle tested cell and aging tested cell. The change in the oxidation state and local structure of Ni and Co during charge has been investigated. Ni and Co K-edge X-ray absorption near edge structure (XANES) show that the Ni oxidation state is converted from Ni 3+ to Ni 4+ upon charging, whereas the Co oxidation state hardly changes. Ni K-edge extended X-ray absorption fine structure (EXAFS) reveals that the Jahn-Teller distorted NiO 6 octahedron turns into the symmetric octahedron upon charging, which is consistent with the change in the Ni oxidation state. Ni K-edge micro-XANES show that the oxidation of Ni proceeds homogeneously in a grain of LiNi 0.8Co 0.15Al 0.05O 2 within the special resolution of ∼2 μm, and proceeds independently of the grain size. All the behaviors of Ni and Co observed in these experiments for the fresh cell remain unchanged after the capacity fade is induced by cycle tests or aging tests, which demonstrates the considerable stability of the LiNi 0.8Co 0.15Al 0.05O 2 cathode material.

Enhanced luminescence in Eu-doped ZnO nanocrystalline films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Keigo, E-mail: ksuzuki@murata.com; Murayama, Koji; Tanaka, Nobuhiko

We found an enhancement of Eu{sup 3+} emissions in Eu-doped ZnO nanocrystalline films fabricated by microemulsion method. The Eu{sup 3+} emission intensities were increased by reducing annealing temperatures from 633 K to 533 K. One possible explanation for this phenomenon is that the size reduction enhances the energy transfer from ZnO nanoparticles to Eu{sup 3+} ions. Also, the shift of the charge-transfer band into the low-energy side of the absorption edge is found to be crucial, which seems to expedite the energy transfer from O atoms to Eu{sup 3+} ions. These findings will be useful for the material design of Eu-doped ZnOmore » phosphors.« less

Effect of molecular intercalation on the local structure of superconducting Nax(NH3)yMoSe2 system

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Wakita, T.; Marini, C.; Terashima, K.; Miao, X.; Olszewski, W.; Ramanan, N.; Heinis, D.; Kubozono, Y.; Yokoya, T.; Saini, N. L.

2017-12-01

We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature (ΘE) of Mo-Mo distance hardly changes (∼264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of ΘE from ∼364 K to ∼350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

Low resistivity of graphene nanoribbons with zigzag-dominated edge fabricated by hydrogen plasma etching combined with Zn/HCl pretreatment

NASA Astrophysics Data System (ADS)

Liu, Fengkui; Li, Qi; Wang, Rubing; Xu, Jianbao; Hu, Junxiong; Li, Weiwei; Guo, Yufen; Qian, Yuting; Deng, Wei; Ullah, Zaka; Zeng, Zhongming; Sun, Mengtao; Liu, Liwei

2017-11-01

Graphene nanoribbons (GNRs) have attracted intensive research interest owing to their potential applications in high performance graphene-based electronics. However, the deterioration of electrical performance caused by edge disorder is still an important obstacle to the applications. Here, we report the fabrication of low resistivity GNRs with a zigzag-dominated edge through hydrogen plasma etching combined with the Zn/HCl pretreatment method. This method is based on the anisotropic etching properties of hydrogen plasma in the vicinity of defects created by sputtering zinc (Zn) onto planar graphene. The polarized Raman spectra measurement of GNRs exhibits highly polarization dependence, which reveals the appearance of the zigzag-dominated edge. The as-prepared GNRs exhibit high carrier mobility (˜1332.4 cm2 v-1 s-1) and low resistivity (˜0.7 kΩ) at room temperature. Particularly, the GNRs can carry large current density (5.02 × 108 A cm-2) at high voltage (20.0 V) in the air atmosphere. Our study develops a controllable method to fabricate zigzag edge dominated GNRs for promising applications in transistors, sensors, nanoelectronics, and interconnects.

X-ray absorption spectroscopy and X-ray photoelectron spectroscopy studies of CaSO 4:Dy thermoluminescent phosphors

NASA Astrophysics Data System (ADS)

Bakshi, A. K.; Jha, S. N.; Olivi, L.; Phase, D. M.; Kher, R. K.; Bhattacharyya, D.

2007-11-01

Extended X-ray absorption fine structure (EXAFS) measurements have been carried out on CaSO4:Dy phosphor samples at the Dy L3 edge with synchrotron radiation. Measurements were carried out on a set of samples which were subjected to post-preparation annealing at different temperatures and for different cycles. The EXAFS data have been analysed to find the Dy-S and Dy-O bond lengths in the neighbourhood of the Dy atoms in a CaSO4 matrix. The observations from EXAFS measurements were verified with XANES and XPS techniques. On the basis of these measurements, efforts were made to explain the loss of thermoluminescence sensitivity of CaSO4:Dy phosphors after repeated cycles of annealing at 400 °C in air for 1 h.

Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate.

PubMed

Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J

2017-06-19

The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am L III -edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

Electrosynthesis of ZnO nanorods and nanotowers: Morphology and X-ray Absorption Near Edge Spectroscopy studies

NASA Astrophysics Data System (ADS)

Sigircik, Gokmen; Erken, Ozge; Tuken, Tunc; Gumus, Cebrail; Ozkendir, Osman M.; Ufuktepe, Yuksel

2015-06-01

Deposition mechanism of nano-structured ZnO films has been investigated in the absence and presence of chloride ions from aqueous solution. The resulting opto-electronic properties were interpreted extensively, using X-ray diffraction (XRD), X-ray Absorption Near Edge Spectroscopy (XANES), field emission scanning electron microscopy (FE-SEM), UV-Visible spectroscopy and four probe techniques. The ZnO deposition is mass transport controlled process and the interaction of chloride ions with the surface has great influence on diffusion kinetics, considering the substantial species (Zn2+ and OH-) involved in the construction of ZnO film. This effect does not change major lattice parameters, as shown with detailed analysis of XRD data. However, the texture coefficient (Tc) (0 0 2) value is higher in presence of chloride ions containing synthesis solution which gave vertically aligned, well defined and uniformly dispersed nanorods structure. The calculated Eg values are in the range 3.28-3.41 eV and 3.22-3.31 eV for ZnO nanorods and nanotowers synthesized at different deposition periods, respectively. Furthermore, the charge mobility values regarding the deposition periods were measured to be in the ranges from 130.4 to 449.2 cm2 V-1 s-1 and 126.2 to 204.7 cm2 V-1 s-1 for nanorods and nanotowers, respectively. From XANES results, it was shown that the Zn K-edge spectrum is dominated by the transition of Zn 1s core electrons into the unoccupied Zn 4p states of the conduction band. Comparing the rod and tower nano-structured ZnO thin films, the excitation behavior of valence band electrons is different. Moreover, the density states of Zn 4p are higher for ZnO nanorods.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, M. M.; Cheah, S.; Kuhn, J. N.

The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorptionmore » near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.« less

Papers from U.S. Department of Energy Science Undergraduate Laboratory Internship Program (SULI) 2010

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2011-06-22

The solvation sphere of halides in water has been investigated using a combination of extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis techniques. The results have indicated that I{sup -} and Br{sup -} both have an asymmetric, 8 water molecule primary solvation spheres. These spheres are identical, with the Br{sup -} sphere about .3 {angstrom} smaller than the I{sup -} sphere. This study utilized near-edge analysis to supplement EXAFS analysis which suffers from signal dampening/broadening due to thermal noise. This paper has reported on the solvation first sphere of I{sup -} and Br{sup -} inmore » water. Using EXAFS and XANES analysis, strong models which describe the geometric configuration of water molecules coordinated to a central anion have been developed. The combination of these techniques has provided us with a more substantiated argument than relying solely on one or the other. An important finding of this study is that the size of the anion plays a smaller role than previously assumed in determining the number of coordinating water molecules. Further experimental and theoretical investigation is required to understand why the size of the anion plays a minor role in determining the number of water molecules bound.« less

EXAFS, ab Initio Molecular Dynamics, and NICIS Spectroscopy Studies on an Organic Dye Model at the Dye-Sensitized Solar Cell Photoelectrode Interface.

PubMed

Liu, Peng; Johansson, Viktor; Trilaksana, Herri; Rosdahl, Jan; Andersson, Gunther G; Kloo, Lars

2017-06-14

The organization of dye molecules in the dye layer adsorbed on the semiconductor substrate in dye-sensitized solar cells has been studied using a combination of theoretical methods and experimental techniques. The model system is based on the simple D-π-A dye L0, which has been chemically modified by substituting the acceptor group CN with Br (L0Br) to offer better X-ray contrast. Experimental EXAFS data based on the Br K-edge backscattering show no obvious difference between dye-sensitized titania powder and titania film samples, thus allowing model systems to be based on powder slurries. Ab initio molecular dynamic (aiMD) calculations have been performed to extract less biased information from the experimental EXASF data. Using the aiMD calculation as input, the EXAFS structural models can be generated a priori that match the experimental data. Our study shows that the L0Br dye adsorbs in the trans-L0Br configuration and that adsorption involves both a proximity to other L0Br dye molecules and the titanium atoms in the TiO 2 substrate. These results indicate direct coordination of the dye molecules to the TiO 2 surface in contrast to previous results on metal-organic dyes. The molecular coverage of L0Br on mesoporous TiO 2 was also estimated using NICIS spectroscopy. The NICISS results emphasized that the L0Br dye on nanoporous titania mainly forms monolayers with a small contribution of multilayer coverage.

Synthesis and characterization of nickel and zinc ferrite nanocatalysts for decomposition of CO2 greenhouse effect gas.

PubMed

Lin, Kuen-Song; Adhikari, Abhijit Krishna; Wang, Chi-Yu; Hsu, Pei-Ju; Chan, Ho-Yang

2013-04-01

The decomposition of CO2 over oxygen deficient nickel ferrite nanoparticles (NFNs) and zinc ferrite nanoparticles (ZFNs) at 573 K was studied. The oxidation states with fine structure of Fe/Ni or Fe/Zn species were also measured in NFNs and ZFNs catalysts, respectively. Oxygen deficiency of catalysts was obtained by reduction in hydrogen. Decomposition of CO2 into carbon and oxygen has been carried out within few minutes when it comes into contact with oxygen deficient catalysts through incorporation of oxygen into ferrite nanoparticles. Oxygen and carbon rather than CO were produced in the decomposition process. The complete decomposition of CO2 was possible because of higher degree of oxygen deficiency andsurface-to-volume ratio of the catalysts. The pre-edge XANES spectra of Fe species in both catalysts exhibit an absorbance feature at 7114 eV for the 1s to 3d transition which is forbidden by the selection rule in case of perfect octahedral symmetry. The EXAFS data showed that the NFNs had two central Fe atoms coordinated by primarily Fe-O and Fe-Fe with bond distances of 1.871 and 3.051 angstroms, respectively. In case of ZFNs these values are 1.889 and 3.062 A, respectively. Methane gas was produced during the reactivation of NFNs by flowing hydrogen gas. Decomposition of CO2, moreover, recovery of valuable methane using heat energy of offgas produced from power generation plant or steel industry is an appealing alternative for energy recovery.

Spectroscopic ellipsometry studies on ZnCdO thin films with different Cd concentrations grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Chen, Shuai; Li, Qingxuan; Ferguson, Ian; Lin, Tao; Wan, Lingyu; Feng, Zhe Chuan; Zhu, Liping; Ye, Zhizhen

2017-11-01

A set of Zn1-xCdxO thin films with different Cd concentrations was deposited on quartz substrates by Pulsed Laser Deposition (PLD). The properties of these films were investigated by variable angle and temperature dependent spectroscopic ellipsometry (SE). The experimental Zn1-xCdxO thin films showed a red shift in the absorption edge with increasing Cd contents at room temperature. For ZnCdO films with the similar Cd concentration, it has been found that the film thickness has important effects on the optical constants (n, k). The variations of optical constants (n, k) and the band gap, E0, with temperature (T) in 25 °C-600 °C for a typical Zn0.95Cd0.05O sample were obtained. The E0 vs T relationship is described by a T- quadratic equation.

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

USGS Publications Warehouse

Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

1996-01-01

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Thermally activated decomposition of (Ga,Mn)As thin layer at medium temperature post growth annealing

NASA Astrophysics Data System (ADS)

Melikhov, Y.; Konstantynov, P.; Domagala, J.; Sadowski, J.; Chernyshova, M.; Wojciechowski, T.; Syryanyy, Y.; Demchenko, I. N.

2016-05-01

The redistribution of Mn atoms in Ga1-xMnxAs layer during medium-temperature annealing, 250-450 oC, by Mn K-edge X-ray absorption fine structure (XAFS) recorded at ALBA facility, was studied. For this purpose Ga1-xMnxAs thin layer with x=0.01 was grown on AlAs buffer layer deposited on GaAs(100) substrate by molecular beam epitaxy (MBE) followed by annealing. The examined layer was detached from the substrate using a “lift-off” procedure in order to eliminate elastic scattering in XAFS spectra. Fourier transform analysis of experimentally obtained EXAFS spectra allowed to propose a model which describes a redistribution/diffusion of Mn atoms in the host matrix. Theoretical XANES spectra, simulated using multiple scattering formalism (FEFF code) with the support of density functional theory (WIEN2k code), qualitatively describe the features observed in the experimental fine structure.

Large local disorder in superconducting K(0.8)Fe(1.6)Se2 studied by extended x-ray absorption fine structure.

PubMed

Iadecola, A; Joseph, B; Simonelli, L; Puri, A; Mizuguchi, Y; Takeya, H; Takano, Y; Saini, N L

2012-03-21

We have measured the local structure of superconducting K(0.8)Fe(1.6)Se(2) chalcogenide (T(c) = 31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for the Fe-Se bondlength (k ~ 5.8 eV Å(-2)) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to be flexible (k ~ 2.1 eV Å(-2)) in comparison to the binary FeSe (k ~ 3.5 eV Å(-2)), an indication of partly relaxed Fe-Fe networks in K(0.8)Fe(1.6)Se(2). The results suggest a glassy nature for the title system, with the superconductivity being similar to that in the granular materials. © 2012 IOP Publishing Ltd

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

2017-02-01

Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

Roman coloured and opaque glass: a chemical and spectroscopic study

NASA Astrophysics Data System (ADS)

Arletti, R.; Dalconi, M. C.; Quartieri, S.; Triscari, M.; Vezzalini, G.

2006-05-01

This work reports the results of an archaeometrical investigation of opaque Roman glass and is mainly focussed on the role of configuration and oxidation state of copper on the colour and opacity of red and green opaque finds (mosaic tesserae, game counters, and glass artefacts) from Sicily and Pompeii excavations. The glass fragments were characterised by EMPA, SEM-EDS, TEM, and XRPD analyses and the copper local environment was investigated using X-ray absorption spectroscopy. The analyses of high-resolution Cu-K edge XANES and EXAFS spectra suggest that, in red samples, copper is present as monovalent cations coordinated to the oxygen atoms of the glass framework, accompanied by metallic clusters. In green samples all the copper cations are incorporated in the glass matrix.

The active site structure of tetanus neurotoxin resolved by multiple scattering analysis in X-Ray absorption spectroscopy.

PubMed Central

Meneghini, C; Morante, S

1998-01-01

A detailed study of the x-ray absorption spectrum of tetanus neurotoxin in the K-edge EXAFS region of the zinc absorber is presented that allows the complete identification of the amino acid residues coordinated to the zinc active site. A very satisfactory interpretation of the experimental data can be given if multiple scattering contributions are included in the analysis. Comparing the absorption spectrum of tetanus neurotoxin to that of two other structurally similar zinc-endopeptidases, thermolysin and astacin, in which the zinc coordination mode is known from crystallographic data, we conclude that in tetanus neurotoxin, besides a water molecule, zinc is coordinated to two histidines and a tyrosine. PMID:9746536

X-Ray Absorption Near Edge Structure And Extended X-Ray Absorption Fine Structure Analysis of Standards And Biological Samples Containing Mixed Oxidation States of Chromium(III) And Chromium(VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parsons, J.G.; Dokken, K.; Peralta-Videa, J.R.

For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI):Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately {+-}10%more » of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 {angstrom} for the Cr(VI) and Cr(III) in the sample, respectively.« less

Low Temperature Photoluminescence of PVT Grown ZnSe and ZnSeTe

NASA Technical Reports Server (NTRS)

Wang, Ling Jun; Su, Ching-Hua; Lehoczky, S. L.

1999-01-01

ZnSe and ZnSeTe single crystals were grown by physical vapor transport (PVT) technique horizontally and vertically. The grown ZnSe and ZnSeTe single crystals were characterized by low temperature photoluminescence at 5 to 10 K using the 3.4 eV emission of an argon laser. The intensity of the sharp near band edge defect lines at 2.799, 2.783 eV and the intrinsic free exciton line at 2.802 eV were mapped on various crystal surfaces with different orientations to the gravitational field. The results show the effects of gravity vector orientation on the defect segregation. Comparison of the photoluminescence spectra of the ZeSe crystal before and after annealing in the Zn vapor shows that the 2.783 eV line of ZnSe crystal is related to the zinc vacancy. The photoluminescence spectra of the ternary ZnSeTe crystal were characterized by a single broad band from 2.2 to 2.4 eV, with a Full Width at Half Maximum (FWHM) of about 100 meV. The temperature dependence of the peak position and intensity were determined from 7 to 150 K.

Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Just, J.; Lützenkirchen-Hecht, D.; Müller, O.

The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

Depth distribution of secondary phases in kesterite Cu 2ZnSnS 4 by angle-resolved X-ray absorption spectroscopy

DOE PAGES

Just, J.; Lützenkirchen-Hecht, D.; Müller, O.; ...

2017-12-12

The depth distribution of secondary phases in the solar cell absorber material Cu 2ZnSnS 4 (CZTS) is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES) analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

Charge transfer transitions in the photoluminescence spectra of Zn1-xMexO (Me = Mn, Ni, Co) oxide compounds

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Gruzdev, N. B.; Pustovarov, V. A.; Churmanov, V. N.

2013-01-01

Crystals of Zn1-xCoxO and Zn1-xNixO are studied by photoluminescence at temperatures of 8 and 90 K. By resolving the spectra into sums of gaussian distributions and using the known positions of donor and acceptor levels of 3d-impurities relative to the edges of the allowed bands, the observed peaks in the photoluminescence spectra are interpreted in terms of radiative recombination through donor and acceptor levels of nickel and cobalt ions. These results are compared with previously observed features of the photoluminescence spectra of Zn1-xMnxO crystals.

Effect of different thickness crystalline SiC buffer layers on the ordering of MgB{sub 2} films probed by extended x-ray absorption fine structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Putri, W. B. K.; Tran, D. H.; Kang, B., E-mail: bwkang@chungbuk.ac.kr

2014-03-07

Extended X-ray absorption fine structure (EXAFS) spectroscopy is a powerful method to investigate the local structure of thin films. Here, we have studied EXAFS of MgB{sub 2} films grown on SiC buffer layers. Crystalline SiC buffer layers with different thickness of 70, 100, and 130 nm were deposited on the Al{sub 2}O{sub 3} (0001) substrates by using a pulsed laser deposition method, and then MgB{sub 2} films were grown on the SiC buffer layer by using a hybrid physical-chemical vapor deposition technique. Transition temperature of MgB{sub 2} film decreased with increasing thickness of SiC buffer layer. However, the T{sub c} droppingmore » went no farther than 100 nm-thick-SiC. This uncommon behavior of transition temperature is likely to be created from electron-phonon interaction in MgB{sub 2} films, which is believed to be related to the ordering of MgB{sub 2} atomic bonds, especially in the ordering of Mg–Mg bonds. Analysis from Mg K-edge EXAFS measurements showed interesting ordering behavior of MgB{sub 2} films. It is noticeable that the ordering of Mg–B bonds is found to decrease monotonically with the increase in SiC thickness of the MgB{sub 2} films, while the opposite happens with the ordering in Mg–Mg bonds. Based on these results, crystalline SiC buffer layers in MgB{sub 2} films seemingly have evident effects on the alteration of the local structure of the MgB{sub 2} film.« less

Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

2016-01-01

The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis. PMID:28044099

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4CaO 5 cluster in the oxygen-evolving complex of photosystem II

DOE PAGES

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

2016-05-09

The Mn 4CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in themore » S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

Structural Analysis of the Mn(IV)/Fe(III) Cofactor of Chlamydia Trachomatis Ribonucleotide Reductase By Extended X-Ray Absorption Fine Structure Spectroscopy And Density Functional Theory Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Younker, J.M.; Krest, C.M.; Jiang, W.

2009-05-28

The class Ic ribonucleotide reductase from Chlamydia trachomatis (C{bar A}) uses a stable Mn(lV)/ Fe(lll) cofactor to initiate nucleotide reduction by a free-radical mechanism. Extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculations are used to postulate a structure for this cofactor. Fe and Mn K-edge EXAFS data yield an intermetallic distance of -2.92 {angstrom}. The Mn data also suggest the presence of a short 1.74 {angstrom} Mn-O bond. These metrics are compared to the results of DFT calculations on 12 cofactor models derived from the crystal structure of the inactive Fe2(lll/ III) form of themore » protein. Models are differentiated by the protonation states of their bridging and terminal OH{sub x} ligands as well as the location of the Mn(lV) ion (site 1 or 2). The models that agree best with experimental observation feature a{mu}-1, 3-carboxylate bridge (E120), terminal solvent (H{sub 2}O/OH) to site 1, one {mu}-O bridge, and one {mu}-OH bridge. The site-placement of the metal ions cannot be discerned from the available data.« less

Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals.

PubMed

Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui; Zhao, Jincai; Zhang, Lizhi

2016-02-16

In this study, the adsorption process of Cr(VI) on the hematite facets was systematically investigated with synchrotron-based Cr K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, density-functional theory calculation, and surface complexation models. Structural model fitting of EXAFS spectroscopy suggested that the interatomic distances of Cr-Fe were, respectively, 3.61 Å for the chromate coordinated hematite nanoplates with exposed {001} facets, 3.60 and 3.30 Å for the chromate coordinated hematite nanorods with exposed {001} and {110} facets, which were characteristic of inner-sphere complexation. In situ ATR-FTIR spectroscopy analysis confirmed the presence of two inner-sphere surface complexes with C3ν and C2ν symmetry, while the C3ν and C2ν species were assigned to monodentate and bidentate inner-sphere surface complexes with average Cr-Fe interatomic distances of 3.60 and 3.30 Å, respectively. On the basis of these experimental and theoretical results, we concluded that HCrO4(-) as dominated Cr(VI) species was adsorbed on {001} and {110} facets in inner-sphere monodentate mononuclear and bidentate binuclear configurations, respectively. Moreover, the Cr(VI) adsorption performance of hematite facets was strongly dependent on the chromate complexes formed on the hematite facets.

Bromine speciation in hydrous haplogranitic melts up to 7 GPa

NASA Astrophysics Data System (ADS)

Cochain, B.; de Grouchy, C.; Crepisson, C.; Kantor, I.; Irifune, T.; Sanloup, C.

2013-12-01

Halogens are minor volatiles in the Earth's mantle and crust, but they have significant and specific influences on magmatic and degassing processes. They also provide insights about subsurface magma movement and eruption likelihood in subduction-related volcanism. Their speciation in silicate melts affects volatile exsolution, rheology, and the thermodynamic properties of the melts but still remains relatively unknown. A few studies have explored halogen speciation at room conditions, i.e. in glasses but no firm conclusion has yet been reached. Furthermore, halogen speciation remains unexplored at high pressures and temperatures. In this work we investigate the speciation of Br in subduction-related melt (hydrous haplogranite melt) up to 1200°C and 7 GPa using X-ray absorption spectroscopy (XANES and EXAFS) at the Br K-edge. High P-T conditions were generated by the Paris-Edinburgh press. The use of nanocrystalline diamond capsules enabled us to avoid glitches in the EXAFS spectra. The results provide valuable information on Br speciation and its evolution with pressure. It gives insights into solubility mechanisms for halogens in magmas at depth and on their degassing from the melt. In addition, we were able to identify quench effects on the atomic environment of Br by comparison of high P-T in-situ spectra and ex-situ spectra recorded on quenched samples.

Synthesis of nanocrystalline NiO/ZnO heterostructured composite powders by sol-gel auto combustion method and their characterizations

NASA Astrophysics Data System (ADS)

Tangcharoen, Thanit; Klysubun, Wantana; Kongmark, Chanapa

2018-03-01

Nanocrystalline NiO/ZnO heterostructured composite powders were prepared by the sol-gel auto combustion method, based on nickel and zinc nitrate precursors and using diethanolamine (DEA) as novel fuel. The composition of different NiO and ZnO ratios, ranging from 100/0, 95/5, 90/10, 80/20, 60/40, 50/50, 40/60, 20/80, 10/90, 5/95 to 0/100, were studied. The structural, chemical bonding, morphological, optical, and fluorescence properties including the local atomic structure of each calcined sample were systematically investigated by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence (PL) spectroscopy, and synchrotron X-ray absorption spectroscopy (XAS), respectively. For the ZnO concentration below 20%, both XRD and Raman spectroscopy results revealed only the NiO phase. This conformed to the observation of Zn K-edge and Ni K-edge X-ray absorption near edge structure (XANES). The Zn ions found in the samples of low ZnO concentration exhibited six-fold coordination with oxygen atoms rather than the four-fold coordination found in the wurtzite (WZ) structure of ZnO. In contrast, the Ni ions which are found in the samples of low NiO concentration (≤10%) are coordinated both tetrahedrally and octahedrally by four or six oxygen atoms, respectively, rather than the six-fold coordination which is usually observed for Ni ions in the rock salt (RS) form of NiO. All analytical results obtained from experimental XANES spectra were verified by the theoretical calculation of absorption spectra using the FEFF9.7 code. The UV-DRS results showed that there was an increase in the reflectance efficiency for both infrared and visible light conditions as the content of ZnO increases; meanwhile, the values for the energy gap (Eg) of all composite samples were higher than that of pure NiO and ZnO. In addition, the PL spectra revealed major blue emission bands observed at 490 nm when the excitation wavelength was 300 nm. As the ZnO phase developed, a variety of violet emission bands occurred within the range of 400 nm-450 nm, which was obviously related to the change in Eg. The intrinsic defects occurred in the NiO/ZnO composite powders were probably responsible for this phenomenon.

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

NASA Astrophysics Data System (ADS)

Arzumanyan, Grigory M.; Kuznetsov, Evgeny A.; Zhilin, Aleksandr A.; Dymshits, Olga S.; Shemchuk, Daria V.; Alekseeva, Irina P.; Mudryi, Alexandr V.; Zhivulko, Vadim D.; Borodavchenko, Olga M.

2016-12-01

Glasses of the K2Osbnd ZnOsbnd Al2O3sbnd SiO2 system co-doped with Eu2O3 and Yb2O3 were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass-ceramics were obtained by secondary heat-treatments at 680-860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu3+ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu3+ ions dominated by the 5D0-7F2 (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu3+-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400-850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar.

PubMed

Alam, Md Samrat; Gorman-Lewis, Drew; Chen, Ning; Flynn, Shannon L; Ok, Yong Sik; Konhauser, Kurt O; Alessi, Daniel S

2018-05-21

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni(II) and Zn(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H + ) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal-biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni(II) and Zn(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni(II) and Zn(II) adsorption occurred primarily through proton-active carboxyl (-COOH) and hydroxyl (-OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni(II) and Zn(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water.

Local structure of gallate proton conductors

NASA Astrophysics Data System (ADS)

Giannici, F.; Messana, D.; Longo, A.; Sciortino, L.; Martorana, A.

2009-11-01

Lanthanum barium gallate proton conductors are based on disconnected GaO4 groups. The insertion of hydroxyls in the LaBaGaO4 network proceeds through self-doping with Ba2+, consequent O2- vacancy formation to fulfill charge neutrality. With a structural investigation on self-doped LaBaGaO4 oxides using synchrotron XRD and EXAFS on the Ga K-edge, we find that: (a) the GaO4 tetrahedra retain their size throughout the whole series; (b) the GaO4 tetrahedra rotate as rigid bodies on hydration, leading to the formation of a network of shorter O-O configurations that are stabilized by hydrogen bonds; (c) contraction of the lattice occurs along the a unit cell axis, as a consequence of an overall structural rearrangement of the hydrated solid.

A multi-technique approach to assess chemical speciation of phosphate in soils

NASA Astrophysics Data System (ADS)

Belchior Abdala, Dalton; Rodrigues, Marcos; Herrera, Wilfrand; Pavinato, Paulo Sergio

2017-04-01

Soil scientists see chemical characterization of phosphorus (e.g., chemical speciation) as a winning strategy to increase phosphorus use efficiency in agriculture, to understand the fate of applied P fertilizer in soils and to devise strategies to minimize P losses to the environment. Phosphorus (P) is majorly presented in soils as phosphate, bound to mineral components of soils such as Al-, Ca- and Fe-(hydr)oxides or associated with organic molecules, being thus generally referred to as organic phosphates. In addition, because of the turnover of P between plants and microbes, it delivers P back to soils as a mixture of species with high spatial and chemical heterogeneity, adding complexity to the determination of the P species contained in environmental samples. Therefore, due to the variety of forms that phosphate can present in soils, its precise chemical characterization can only be achieved using a set of analytical techniques. Although established methodologies (e. g., soil test P, sequential chemical fractionation, P isotherms) have been useful to subsidize information for the establishment of policies and guidelines for soil management and P fertilizers use, they have failed to provide detailed information on P chemistry and reactivity in soils in a more satisfactory manner, which are critical to predict P bioavailability to plants and loss potential to the environment. More recently, the association of wet chemistry analysis with spectroscopy and microscopy techniques has arguably represented the most successful means to chemically speciate phosphate in soils. This is because using qualitative (chemical speciation), quantitative (chemical fractionation) and spatial (microscopy) data allows for triangulation of information, thereby reducing bias and increasing validity of the results. The analysis framework that we propose in this study includes the use of (i) sequential chemical fractionation of soil P to determine the partitioning of P within the different P pools considered in the fractionation protocol, (ii) two synchrotron-based X-ray absorption spectroscopic techniques, XANES and EXAFS, for chemical characterization of the P forms and mineralogy of Fe-(hydr)oxides present in a sample, and (iii) Scanning Electron Microscopy and Energy-Dispersive spectroscopy, SEM/EDS, to provide complimentary information to corroborate and aid in the interpretation of our P XANES data. It was shown that the combination of techniques can assist us not only in the determination of the P chemical species present in a given material, but also to better understand the complex and dynamic processes to which P is subjected in soils. The association of spectroscopy (XANES and EXAFS) and microscopy (SEM/EDS) with wet chemistry data in this study was key to shift our understanding of the relationship between P and other soil mineral components from a macroscopic into a microscopic one. This represents a strong driving force to integrate the results of multi-analytical techniques into a more complete understanding of the systems under study. In addition, we provide a library of reference spectra for P K-edge XANES containing P sorbed to single and binary mixtures of mineral analogues intended to assist in the identification of P sorbed species commonly found in soils and sediments. Key-words: P K-edge XANES, Fe K-edge EXAFS, sequential chemical fractionation, soil phosphorus

Hybrid Functional Study of Sodium and Potassium Incorporation in Cu2ZnSnS4

NASA Astrophysics Data System (ADS)

Tse, Kin Fai; Wong, Manhoi; Zhang, Yiou; Zhang, Jingzhao; Zhu, Junyi

The thermodynamics of Na and K incorporation and its effects in Cu2ZnSnS4 (CZTS) is studied using density functional theory with hybrid functional. The allowed chemical potential of Na/K in CZTS is established. Formation energy calculations shows that Na can be significantly incorporated as both substitutional defects and interstitial defects, and incorporation of K related defects are generally less favorable. Transition energy calculations is performed showing that both Na and K exhibit benign defect properties and act as a p-type dopant. The qualitative disagreement between GGA with rigid band edge shifting and HSE calculations, formation of defect complexes, and implications in experiment will also be discussed. The understandings on the defect properties of Na and K provides an essential knowledge to further understand the surfactant effects of Na and K observed in experiments. This work is supported by General Research Fund Ref. No: 14319416.

Self-Supported Copper Oxide Electrocatalyst for Water Oxidation at Low Overpotential and Confirmation of Its Robustness by Cu K-edge X-ray Absorption Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiang; Cui, Shengsheng; Sun, Zijun

Developing efficient water oxidation catalysts made of earth-abundant elements is a demanding challenge that should be met to fulfill the promise of water splitting for clean energy. Herein we report an annealing approach to synthesize binder-free, self-supported heterogeneous copper oxide (CuO) on conductive electrodes for oxygen evolution reaction (OER), producing electrodes with excellent electrocatalytic properties such as high efficiency, low overpotential, and good stability. The catalysts were grown in situ on fluorine-doped tin oxide (FTO) by electrodeposition from a simple Cu(II) salt solution, followed by annealing at a high temperature. Under optimal conditions, the CuO-based OER catalyst shows an onsetmore » potential of <0.58 V (vs Ag/AgCl) in 1.0 M KOH at pH 13.6. From the Tafel plot, the required overpotentials for current densities of 0.1 and 1.0 mA/cm2 are only 360 and 430 mV, respectively. The structure and the presence of a CuO motif in the catalyst have been identified by high-energy X-ray diffraction (HE-XRD), Cu K-edge X-ray absorption (XAS) spectra including X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS). To the best of our knowledge, this represents the best catalytic activity for CuO-based OER catalysts to date.« less

Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis

NASA Astrophysics Data System (ADS)

Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

2012-02-01

Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

Spectroscopic ellipsometry characterization of ZnO:Sn thin films with various Sn composition deposited by remote-plasma reactive sputtering

NASA Astrophysics Data System (ADS)

Janicek, Petr; Niang, Kham M.; Mistrik, Jan; Palka, Karel; Flewitt, Andrew J.

2017-11-01

ZnO:Sn thin films were deposited onto thermally oxidized silicon substrates using a remote plasma reactive sputtering. Their optical constants (refractive index n and extinction coefficient k) were determined from ellipsometric data recorded over a wide spectral range (0.05-6 eV). Parametrization of ZnO:Sn complex dielectric permittivity consists of a parameterized semiconductor oscillator function describing the short wavelength absorption edge, a Drude oscillator describing free carrier absorption in near-infrared part of spectra and a Lorentz oscillator describing the long wavelength absorption edge and intra-band absorption in the ultra-violet part of the spectra. Using a Mott-Davis model, the increase in local disorder with increasing Sn doping is quantified from the short wavelength absorption edge onset. Using the Wemple-DiDomenico single oscillator model for the transparent part of the optical constants spectra, an increase in the centroid distance of the valence and conduction bands with increasing Sn doping is shown and only slight increase in intensity of the inter-band optical transition due to Sn doping occurs. The Drude model applied in the near-infrared part of the spectra revealed the free carrier concentration and mobility of ZnO:Sn. Results show that the range of transparency of prepared ZnO:Sn layers is not dramatically affected by Sn doping whereas electrical conductivity could be controlled by Sn doping. Refractive index in the transparent part is comparable with amorphous Indium Gallium Zinc Oxide allowing utilization of prepared ZnO:Sn layers as an indium-free alternative.

Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

PubMed

Hao, Yao-Ming; Lou, Shi-Yun; Zhou, Shao-Min; Yuan, Rui-Jian; Zhu, Gong-Yu; Li, Ning

2012-02-02

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

DOE PAGES

Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.; ...

2016-10-17

Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level ofmore » Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.« less

Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1991-08-01

The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

XRD and XAS structural study of CuAlO2 under high pressure.

PubMed

Pellicer-Porres, J; Segura, A; Ferrer-Roca, Ch; Polian, A; Munsch, P; Kim, D

2013-03-20

We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO(2) under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO(6) octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.

XRD and XAS structural study of CuAlO2 under high pressure

NASA Astrophysics Data System (ADS)

Pellicer-Porres, J.; Segura, A.; Ferrer-Roca, Ch; Polian, A.; Munsch, P.; Kim, D.

2013-03-01

We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO2 under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO6 octahedra. The anisotropic compression is related to the chemical trends observed in the lattice parameters when Al is substituted by other trivalent cations. Both experiments evidence the existence of an irreversible phase transition that clearly manifests at 35 ± 2 GPa. The structure of the high-pressure polymorph could not be determined, but it implies a change of the Cu environment, which remains anisotropic. Precursor effects are observed from the lowest pressures, which are possibly related to crystal breaking at a submicroscopic scale with partial reorientation of the crystallites.

Evolution of Defect Structures and Deep Subgap States during Annealing of Amorphous In-Ga-Zn Oxide for Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Jia, Junjun; Suko, Ayaka; Shigesato, Yuzo; Okajima, Toshihiro; Inoue, Keiko; Hosomi, Hiroyuki

2018-01-01

We investigate the evolution behavior of defect structures and the subgap states in In-Ga-Zn oxide (IGZO) films with increasing postannealing temperature by means of extended x-ray absorption fine-structure (EXAFS) measurements, positron annihilation lifetime spectroscopy (PALS), and cathodoluminescence (CL) spectroscopy, aiming to understand the relationship between defect structures and subgap states. EXAFS measurements reveal the varied oxygen coordination numbers around cations during postannealing and confirm two types of point defects, namely, excess oxygen around Ga atoms and oxygen deficiency around In and/or Zn atoms. PALS suggests the existence of cation-vacancy (VM )-related clusters with neutral or negative charge in both amorphous and polycrystalline IGZO films. CL spectra show a main emission band at approximately 1.85 eV for IGZO films, and a distinct shoulder located at about 2.15 eV for IGZO films postannealed above 600 °C . These two emission bands are assigned to a recombination between the electrons in the conduction band and/or in the shallow donor levels near the conduction band and the acceptors trapped above the valence-band maximum. The shallow donors are attributed to the oxygen deficiency, and the acceptors are thought to possibly arise from the excess oxygen or the VM-related clusters. These results open up an alternative route for understanding the device instability of amorphous IGZO-based thin-film transistors, especially the presence of the neutral or negatively charged VM-related clusters in amorphous IGZO films.

Effects of Pressure on Optically Active Deep Levels in Phosphorus Doped ZnSe

NASA Astrophysics Data System (ADS)

Weinstein, B. A.; Iota, V.

1998-03-01

We report high pressure photoluminescence (PL) and PL-excitation (PLE) studies at 8K of the 'midgap' emission in P-doped ZnSe using a diamond-cell with He medium. The dominant emission at low pressure is due to donor-acceptor-pair (DAP) transitions between shallow donors and deep trigonally relaxed P_Se acceptors.(J. Davies, et al., J. Luminescence 18/19, 322 (1979)) Its PL and PLE peaks shift by 8.2meV/kbar and 5.9meV/kbar, respectively -- Stokes shift decreasing with pressure. At 35kbar a new PL band, shifting to lower energy (-5.4meV/kbar), emerges from above the absorption edge, and concurrently the original DAP PL quenches. This shows that a resonant level, a deep donor or possibly a P_Se antibonding state,(R. Watts, et al., Phys. Rev. B3), 404 (1971) crosses the conduction edge into the gap. A third PL band is seen only with internse UV excitation. It occurs initially as a high energy shoulder of the original DAP peak, but shifts more rapidly upward (9.4meV/kbar) until it crosses the edge and quenches at 40kbar. We discuss candidates for this band, including donor-P_Se complexes, and we compare our results to similar work on the Zn vacancy in ZnSe. (figures)

A Comparative XAFS Study of Gold-thiolate Nanoparticles and Nanoclusters

NASA Astrophysics Data System (ADS)

Chevrier, D. M.; Chatt, A.; Sham, T. K.; Zhang, P.

2013-04-01

Tiopronin-capped gold nanoparticles and gold nanoclusters of sizes 3.0 and 1.5 nm, respectively, were investigated with XAFS at the gold L3-edge. The specific EXAFS fitting procedure is discussed for obtaining reliable fit parameters for each system. The difficulties and challenges faced when analysing EXAFS data for gold nanoparticles and nanoclusters are also mentioned. Fitting results for gold nanoparticles reveal a small amount of surface Au-thiolate interactions with a large Au-Au metal core. For gold nanoclusters, only a one-shell fit was obtainable. Instead of Au-Au metal core, long-range interactions are expected for gold nanoclusters. Tiopronin-capped gold nanoclusters are proposed to be polymeric in nature, which helps explain the observed red luminescence.

The Amyloid-β Peptide of Alzheimer’s Disease Binds CuI in a Linear Bis-His Coordination Environment: Insight into a Possible Neuroprotective Mechanism for the Amyloid-β Peptide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shearer, J.; Szalai, V

Oxidative stress has been suggested to contribute to neuronal apoptosis associated with Alzheimer's disease (AD). Copper may participate in oxidative stress through redox-cycling between its +2 and +1 oxidation states to generate reactive oxygen species (ROS). In vitro, copper binds to the amyloid-? peptide of AD, and in vivo, copper is associated with amyloid plaques characteristic of AD. As a result, the A?CuI complex may be a critical reactant involved in ROS associated with AD etiology. To characterize the A?CuI complex, we have pursued X-ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopy of A?CuII and A?CuI (produced by ascorbatemore » reduction of A?CuII). The A?CuII complex Cu K-edge XAS spectrum is indicative of a square-planar CuII center with mixed N/O ligation. Multiple scattering analysis of the extended X-ray absorption fine structure (EXAFS) data for A?CuII indicates that two of the ligands are imidazole groups of histidine ligands, indicating a (NIm)2(N/O)2 CuII ligation sphere for A?CuII. After reduction of the A?CuII complex with ascorbate, the edge region decreases in energy by 4 eV. The X-ray absorption near-edge spectrum region of A?CuI displays an intense pre-edge feature at 8984.1(2) eV. EXAFS data fitting yielded a two-coordinate geometry, with two imidazole ligands coordinated to CuI at 1.877(2) A in a linear geometry. Ascorbate reduction of A?CuII under inert atmosphere and subsequent air oxidation of A?CuI to regenerate A?CuII was monitored by low-temperature EPR spectroscopy. Slow reappearance of the A?CuII EPR signal indicates that O2 oxidation of the A?CuI complex is kinetically sluggish and A? damage is occurring following reoxidation of A?CuI by O2. Together, these results lead us to hypothesize that CuI is ligated by His13 and His14 in a linear coordination environment in ??, that A? may be playing a neuroprotective role, and that metal-mediated oxidative damage of A? occurs over multiple redox cycles.« less

Characterization of yellow and colorless decorative glasses from the Temple of the Emerald Buddha, Bangkok, Thailand

NASA Astrophysics Data System (ADS)

Klysubun, Wantana; Ravel, Bruce; Klysubun, Prapong; Sombunchoo, Panidtha; Deenan, Weeraya

2013-06-01

Yellow and colorless ancient glasses, which were once used to decorate the Temple of the Emerald Buddha, Bangkok, Thailand, around 150 years ago, are studied to unravel the long-lost glass-making recipes and manufacturing techniques. Analyses of chemical compositions, using synchrotron x-ray fluorescence (SRXRF), indicate that the Thai ancient glasses are soda lime silica glasses (60 % SiO2; 10 % Na2O; 10 % CaO) bearing lead oxide between 2-16 %. Iron (1.5-9.4 % Fe2O3) and manganese (1.7 % MnO) are present in larger abundance than the other 3 d transition metals detected (0.04-0.2 %). K-edge x-ray absorption near edge spectroscopy (XANES) and extended x-ray absorption fine structure spectroscopy (EXAFS) provide conclusive evidence on the oxidation states of Fe being 3+ and Mn being 2+ and on short-length tetrahedral structures around the cations. This suggests that iron is used as a yellow colorant with manganese as a decolorant. L 3-edge XANES results reveal the oxidation states of lead as 2+. The results from this work provide information crucial for replicating these decorative glasses for the future restoration of the Temple of the Emerald Buddha.

Mn K-Edge XANES and Kβ XES Studies of Two Mn–Oxo Binuclear Complexes: Investigation of Three Different Oxidation States Relevant to the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Visser, Hendrik; Anxolabéhère-Mallart, Elodie; Bergmann, Uwe; Glatzel, Pieter; Robblee, John H.; Cramer, Stephen P.; Girerd, Jean-Jacques; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono-μ-oxo compounds in equivalent oxidation states. The energy shifts observed due to oxidation are also similar for the two different compounds. The study of the different behavior of the XANES pre-edge and main-edge features in conjunction with Kβ XES provides significant information about the oxidation state and character of the ligand environment of manganese atoms. PMID:11459481

Characterization of Infrared Properties of Layered Semiconductors.

DTIC Science & Technology

1987-02-20

candidate -10- V. PUBLICATIONS INCLUDED WITH REPORT 1) R. Braunstein, R. K . Kim, D. Matthews, and M. Braunstein: "Derivative Absorption Spectroscopy of...34Wavelength Modulation Spectra of a-Ag0.7Zn0 .3 Near the Optical Absorption Edge," Phys. Stat. Sol.(b) 131, 659 (1983). 5) R. K . Kim and R. Braunstein...34Infrared Wavelength Modulation Spectroscopy of Some Optical Material," Appl. Optics 23(8), 1166 (1984). 6) C.E. Jones, K . James, J. Merz, R. Braunstein, M

Alternative difference analysis scheme combining R -space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhan, Fei; Tao, Ye; Zhao, Haifeng

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions.R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure changemore » in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3spin crossover complex and yielded reliable distance change and excitation population.« less

Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

PubMed

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

2004-02-01

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.

Effect of humic acid on nickel(II) sorption to Ca-montmorillonite by batch and EXAFS techniques study.

PubMed

Hu, Jun; Tan, Xiaoli; Ren, Xuemei; Wang, Xiangke

2012-09-21

The influence of humic acid (HA) on Ni(II) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(II) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(II) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(II) consists of ∼6 O atoms at the interatomic distances of ∼2.04 Å in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(II) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(II), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(II) in the natural environment.

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Complex vibrations in arsenide skutterudites and oxyskutterudites

NASA Astrophysics Data System (ADS)

Bridges, F.; Car, B.; Sutton, L.; Hoffman-Stapleton, M.; Keiber, T.; Baumbach, R. E.; Maple, M. B.; Henkie, Z.; Wawryk, R.

2015-01-01

The local structure of two skutterudite families—Ce M4As12 (M =Fe , Ru, Os) and L n Cu3Ru4O12 (L n =La , Pr, and Nd)—have been studied using the extended x-ray absorption fine structure (EXAFS) technique with a focus on the lattice vibrations about the rare-earth "rattler atoms" and the extent to which these vibrations can be considered local modes, with the rattler vibrating inside a nearly rigid cage. X-ray absorption data at all the metal edges were collected over a temperature range of 4 to 300 K and analyzed using standard procedures. The pair distances from EXAFS results agree quite well with the average structure obtained from diffraction. The cage structure is formed by the M and As atoms in Ce M4As12 and by Cu, O, and Ru atoms in L n Cu3Ru4O12 . Although some of the bonds within the cage are quite stiff (correlated Debye temperatures, θcD, are ˜500 K for Ce M4As12 and above 800 K for L n Cu3Ru4O12 ), we show that the structure is not completely rigid. For the rattler atom the nearest-neighbor pairs have a relatively low Einstein temperature, θE:˜100 - 120 K for Ce-As and ˜130 K for L n -O . Surprisingly, the behaviors of the second-neighbor pairs are quite different: for Ce M4As12 the second-neighbor pairs (Ce -M ) have a weaker bond while for L n Cu3Ru4O12 the L n -Ru second-neighbor pair has a stiffer effective spring constant than the first-neighbor pair. In addition, we show that the As4 or CuO4 rings are relatively rigid units and that their vibrations are anisotropic within these cubic structures, with stiff restoring forces perpendicular to the rings and much weaker restoring forces in directions parallel to the rings. Consequently vibrations of the rings may also act as "rattlers" and help suppress thermal conductivity. In general neither the rigid-cage approximation nor the simple reduced-mass approximation are sufficient for describing rattler behavior.

Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals.

PubMed

Kerisit, Sebastien; Bylaska, Eric J; Massey, Michael S; McBriarty, Martin E; Ilton, Eugene S

2016-11-21

Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation states (VI, V, and IV) and charge compensation schemes were varied. Simulated trajectories were used to calculate the U L III -edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO 2 ), and constrained the S 0 2 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to addition of one electron into the solid (-1 H + , +1 e - ). The ability of AIMD to model higher energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with applications over a broad swath of chemistry and materials science.

Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien; Bylaska, Eric J.; Massey, Michael S.

2016-11-21

Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking, yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation state (VI, V, and IV) and chargemore » compensation scheme (CCS) were varied. Simulated trajectories were used to calculate the U LIII-edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO2), and constrained the S02 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to injection of one electron into the solid (–1 H+, + 1 e-). The ability of AIMD to model higher-energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with applications over a broad swath of chemistry and materials science.« less

Investigation of the nanoscale two-component ZnS-ZnO heterostructures by means of HR-TEM and X-ray based analysis

NASA Astrophysics Data System (ADS)

Pankin, I. A.; Polozhentsev, O. E.; Soldatov, M. A.; Bugaev, A. L.; Tsaturyan, A.; Lomachenko, K. A.; Guda, A. A.; Budnyk, A. P.; Lamberti, C.; Soldatov, A. V.

2018-06-01

This article is devoted to the spectroscopic characterization of ZnS-ZnO nanoscale heterostructures synthesized by the microwave-assisted solvothermal method. The synthesized samples were investigated by means of X-ray powder diffraction (XRPD), high energy resolution fluorescence detected X-ray absorption near-edge-structure (HERFD-XANES) spectroscopy, valence-to-core X-ray emission spectroscopy (VtC-XES) and high resolution transmission electron microscopy (HR-TEM) as well as energy dispersive X-ray spectroscopy (EDX). The average crystallite size estimated by the broadening of XRPD peaks increases from 2.7 nm to 3.7 nm in the temperature range from 100 °C to 150 °C. HR-TEM images show that nanoparticles are arranged in aggregates with the 60-200 nm size. Theoretical estimation shows that the systems synthesized at higher temperatures more prone to the agglomeration. The full profile Reitveld analysis of XRPD data reveals the formation of hexagonal zinc sulfide structure, whereas electron diffraction data reveal also the formation of cubic zinc sulfide and claim the polymorphous character of the system. High energy resolution Zn K-edge XANES data unambiguously demonstrate the presence of a certain amount of the zinc oxide which is likely to have an amorphous structure and could not be detected by XRPD. Qualitative analysis of XANES data allows deriving ZnS/ZnO ratio as a function of synthesis temperature. EDX analysis depicts homogeneous distribution of ZnS and amorphous ZnO phases across the conglomerates. A complementary element-selective valence to core X-ray emission spectroscopy evidences formation of two-component system and confirms estimations of ZnS/ZnO fractions obtained by linear combination fit of XANES data.

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure.

PubMed

Guo, Xuejun; Wu, Zhijun; He, Mengchang; Meng, Xiaoguang; Jin, Xin; Qiu, Nan; Zhang, Jing

2014-07-15

Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl3, was oxidized into Sb(V) probably due to the involvement of O2 in the long duration of sample preservation. Only one Sb-Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0-1.9 attributed to bidentate mononuclear edge-sharing ((2)E) between Sb and HFO. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization and analysis of thermoelectric transport using SPB model in nanostructured aluminum doped zinc tellurium

NASA Astrophysics Data System (ADS)

Bhaskar, Ankam; Pai, Yi-Hsuan; Liu, Chia-Jyi

2017-11-01

Low-temperature electronic and thermal transport measurements are carried out on nanostructured Zn1-x Al x Te (0  ⩽  x  ⩽  0.15) fabricated using hydrothermal synthesis followed by evacuated-and-encapsulated sintering. A single parabolic band with acoustic phonon scattering is used to analyze thermoelectric transport data. It is found that reduced Fermi energy gets closer to the valence band edge and density of states effective mass, effective density of states, and Hall factor decrease with increasing x in doped samples. The chemical carrier concentration, carrier density independent mobility, β, and theoretical zT values increase with increasing x in doped samples. The nanostructured Zn1-x Al x Te exhibits significant reduction of thermal conductivity at 300 K (1.82-3.71 W m-1 K-1) as compared to bulk ZnTe (18 W m-1 K-1). The point-defect scattering and phonon-grain scattering play an important role in reducing the lattice thermal conductivity. In addition, partial substitution of Al3+ for Zn2+ significantly improves both the power factor and zT values.

Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

USGS Publications Warehouse

Waychunas, G.A.; Rea, B.A.; Fuller, C.C.; Davis, J.A.

1993-01-01

EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, ?? (goethite), ?? (akaganeite), and ?? (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface (3.28 ??0.01 A ??) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces (3.25 ?? 0.02 A ??). Mono-dentate arsenate linkages (3.60 ?? 0.03 A ??) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ?? 0.01 A ??. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe ratio is increased. Coherent crystallite size is probably no more than 10 A?? in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe) indicates ferrihydrite units consisting mainly of Fe oxyhydroxyl octahedra arranged in short dioctahedral chains with minimal interchain linking by octahedra corners. This is consistent with an enlarged surface area and a larger proportion of sites for bidentate arsenate bonding in CPT samples as compared to the ADS samples, which saturate with arsenate at lower As Fe ratios. The latter samples have larger crystallite sizes and a definite proportion of ferric octahedra sharing corners. The ratio of corner-sharing to edge-sharing Fe oxyhydroxyl octahedra in the ADS samples, and CPT samples with small As loadings, is very similar to what would be present in very small particles of goethite or akaganeite. The difference in the polymeric structure of ADS and CPT samples at higher As Fe ratios is due to strong arsenate bidentate adsorption that poisons the surface of particles of ferrihydrite precipitated in the presence of substantial arsenate, limiting their normal crystallization, and preventing further Fe-O-Fe polymerization. If the arsenate is applied after precipitation much less adsorption occurs since polymerization has already progressed. In both ADS and CPT samples, Fe-O-Fe polymerization increases with age, though at different rates for each type of sample. ?? 1993.

Sorption of Metal Ions on Clay Minerals.

PubMed

Schlegel; Charlet; Manceau

1999-12-15

The mechanism of Co uptake from aqueous solution onto hectorite (a magnesian smectite) and its impact on the stability of this clay mineral were investigated as a function of Co concentration (TotCo = 20 to 200 µM, 0.3 M NaNO(3)) and ionic strength (0.3 and 0.01 M NaNO(3), TotCo = 100 µM) by combining kinetics measurements and Co K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The morphology of the sorbent phase was characterized by atomic force microscopy (AFM) and consists of lath-type particles bounded by large basal planes and layer edges. At low ionic strength (0.01 M NaNO(3)), important Co uptake occurred within the first 5 min of reaction, consistent with Co adsorption on exchange sites of hectorite basal planes. Thereafter, the sorption rate dramatically decreased. In contrast, at high ionic strength (0.3 M NaNO(3)), Co uptake rate was much slower within the first 5 min and afterward higher than at 0.01 M NaNO(3), consistent with Co adsorption on specific surface sites located on the edges of hectorite. Time-dependent isotherms for Co uptake at high ionic strength indicated the existence of several sorption mechanisms having distinct equilibration times. The dissolution of hectorite was monitored before and after Co addition. A congruent dissolution regime was observed prior to Co addition. Just after Co addition, an excess release of Mg relatively to congruent dissolution rates occurred at both high and low ionic strengths. At high ionic strength, this excess release nearly equaled the amount of sorbed Co. The dissolution rate of hectorite then decreased at longer Co sorption times. EXAFS spectra of hectorite reacted with Co at high and low ionic strengths and for reaction times longer than 6 h, exhibited similar features, suggesting that the local structural environments of Co atoms are similar. Spectral simulations revealed the occurrence of approximately 2 Mg and approximately 2 Si neighboring cations at interatomic distances characteristic of edge-sharing linkages between Co and Mg octahedra and corner-sharing linkages between Co octahedra and Si tetrahedra, respectively. This local structure is characteristic of inner sphere mononuclear surface complexes at layer edges of hectorite platelets. The occurrence of these complexes even at low ionic strength apparently conflicts with kinetics results, as exchangeable divalent cations are known to form outer sphere surface complexes. To clarify this issue, the amount of Co adsorbed on exchange sites was calculated from the solute Co concentration, assuming that cation exchange was always at equilibrium. These calculations showed that sorbed Co was transferred within 48 h from exchange sites to edge sorption sites. Copyright 1999 Academic Press.

High-and low-affinity binding sites for Cd on the bacterial cell walls of Bacillus subtilis and Shewanella oneidensis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, B.; Boyanov, M.; Bunker, B. A.

2010-08-01

Bulk Cd adsorption isotherm experiments, thermodynamic equilibrium modeling, and Cd K edge EXAFS were used to constrain the mechanisms of proton and Cd adsorption to bacterial cells of the commonly occurring Gram-positive and Gram-negative bacteria, Bacillus subtilis and Shewanella oneidensis, respectively. Potentiometric titrations were used to characterize the functional group reactivity of the S. oneidensis cells, and we model the titration data using the same type of non-electrostatic surface complexation approach as was applied to titrations of B. subtilis suspensions by Fein et al. (2005). Similar to the results for B. subtilis, the S. oneidensis cells exhibit buffering behavior frommore » approximately pH 3-9 that requires the presence of four distinct sites, with pK{sub a} values of 3.3 {+-} 0.2, 4.8 {+-} 0.2, 6.7 {+-} 0.4, and 9.4 {+-} 0.5, and site concentrations of 8.9({+-}2.6) x 10{sup -5}, 1.3({+-}0.2) x 10{sup -4}, 5.9({+-}3.3) x 10{sup -5}, and 1.1({+-}0.6) x 10{sup -4} moles/g bacteria (wet mass), respectively. The bulk Cd isotherm adsorption data for both species, conducted at pH 5.9 as a function of Cd concentration at a fixed biomass concentration, were best modeled by reactions with a Cd:site stoichiometry of 1:1. EXAFS data were collected for both bacterial species as a function of Cd concentration at pH 5.9 and 10 g/L bacteria. The EXAFS results show that the same types of binding sites are responsible for Cd sorption to both bacterial species at all Cd loadings tested (1-200 ppm). Carboxyl sites are responsible for the binding at intermediate Cd loadings. Phosphoryl ligands are more important than carboxyl ligands for Cd binding at high Cd loadings. For the lowest Cd loadings studied here, a sulfhydryl site was found to dominate the bound Cd budgets for both species, in addition to the carboxyl and phosphoryl sites that dominate the higher loadings. The EXAFS results suggest that both Gram-positive and Gram-negative bacterial cell walls have a low concentration of very high-affinity sulfhydryl sites which become masked by the more abundant carboxyl and phosphoryl sites at higher metal:bacteria ratios. This study demonstrates that metal loading plays a vital role in determining the important metal-binding reactions that occur on bacterial cell walls, and that high affinity, low-density sites can be revealed by spectroscopy of biomass samples. Such sites may control the fate and transport of metals in realistic geologic settings, where metal concentrations are low.« less

A Study of Ziegler–Natta Propylene Polymerization Catalysts by Spectroscopic Methods

PubMed Central

Tkachenko, Olga P.; Kucherov, Alexey V.; Kustov, Leonid M.; Virkkunen, Ville; Leinonen, Timo; Denifl, Peter

2017-01-01

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom. PMID:28772850

Lead is not off center in PbTe: the importance of r-space phase information in extended x-ray absorption fine structure spectroscopy.

PubMed

Keiber, T; Bridges, F; Sales, B C

2013-08-30

PbTe is a well-known thermoelectric material. Recent x-ray total scattering studies suggest that Pb moves off center along 100 in PbTe, by ∼0.2  Å at 300 K, producing a split Pb-Te pair distribution. We present an extended x-ray absorption fine structure spectroscopy (EXAFS) study of PbTe (and Tl doped PbTe) to determine if Pb or Te is off center. EXAFS provides sensitive r- or k-space phase information which can differentiate between a split peak for the Pb-Te distribution (indicative of off-center Pb) and a thermally broadened peak. We find no evidence for a split peak for Pb-Te or Te-Pb. At 300 K, the vibration amplitude for Pb-Te (or Te-Pb) is large; this thermally induced disorder is indicative of weak bonds, and the large disorder is consistent with the low thermal conductivity at 300 K. We also find evidence of an anharmonic potential for the nearest Pb-Te bonds, consistent with the overall anharmonicity found for the phonon modes. This effect is modeled by a "skew" factor (C3) which significantly improves the fit of the Pb-Te and Te-Pb peaks for the high temperature EXAFS data; C3 becomes significant above approximately 150-200 K. The consequences of these results will be discussed.

Influence of processing conditions on the optical properties of chemically deposited zinc sulphide (ZnS) thin film

NASA Astrophysics Data System (ADS)

Igweoko, A. E.; Augustine, C.; Idenyi, N. E.; Okorie, B. A.; Anyaegbunam, F. N. C.

2018-03-01

In this paper, we present the influence of post deposition annealing and varying concentration on the optical properties of ZnS thin films fabricated by chemical bath deposition (CBD) at 65 °C from chemical baths comprising NH3/SC(NH2)2/ZnSO4 solutions at pH of about 10. The film samples were annealed at temperatures ranging from 373 K–473 K and the concentration of the film samples vary from 0.1 M–0.7 M. Post deposition annealing and concentration played an important role on the optical parameters investigated which includes absorbance, transmittance, reflectance, absorption coefficient, band gap, refractive index and extinction coefficient. The optical parameters were found to vary with post deposition annealing in one direction and concentration of Zn2+ in the reverse direction. For instance, post deposition annealing increases the band gap from 3.65 eV for as-deposited to 3.70 eV, 3.75 eV and 3.85 eV for annealed at 373 K, 423 K and 473 K respectively whereas concentration of Zn2+ decreases the band gap from 3.95 eV at 0.1 M to 3.90 eV, 3.85 eV and 3.80 eV at 0.3 M, 0.5 M and 0.7 M respectively. The fundamental absorption edge of ZnS thin films shifted toward the highest photon energies (blue shift) after annealing and shifted toward the lowest photon energies (red shift) with increasing Zn ions concentration. A linear relation between band gap energy and Urbach energy was found. After annealing, the Urbach energy increases form 3.10 eV to 3.50 eV and decreases from 3.40 eV to 3.10 eV at varying Zn2+ concentration. The property of wide band gap makes ZnS suitable for buffer layer of film solar cells, permitting more light especially the short wavelength light into absorber layer.

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.

PubMed

Frank, Patrick; Szilagyi, Robert K; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O

2017-02-06

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II (itao)(SO 4 )(H 2 O) 0,1 ] (M = Co, Ni, Cu) and [Cu(Me 6 tren)(SO 4 )] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal-sulfur bond, while the XAS preedge of [Zn(itao)(SO 4 )] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4 )] but not of [Cu(Me 6 tren)(SO 4 )] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II (SO 4 )(H 2 O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5-2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a hydrogen-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. This electronic structure feature provides a direct spectroscopic confirmation of the through-bond electron-transfer mechanism of redox-active metalloproteins.

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

DOE PAGES

Frank, Patrick; Szilagyi, Robert K.; Gramlich, Volker; ...

2017-01-09

Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II(itao)(SO 4)(H 2O) 0,1] (M = Co, Ni, Cu) and [Cu(Me 6tren)(SO 4)] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal–sulfur bond, while the XAS preedge of [Zn(itao)(SO 4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4)] but not of [Cu(Me 6tren)(SO 4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II(SO 4)(Hmore » 2O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5–2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal–absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which extends across a hydrogen-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. In conclusion, this electronic structure feature provides a direct spectroscopic confirmation of the through-bond electron-transfer mechanism of redox-active metalloproteins.« less

Bond length variation in Zn substituted NiO studied from extended X-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Singh, S. D.; Poswal, A. K.; Kamal, C.; Rajput, Parasmani; Chakrabarti, Aparna; Jha, S. N.; Ganguli, Tapas

2017-06-01

Bond length behavior for Zn substituted NiO is determined through extended x-ray absorption fine structure (EXAFS) measurements performed at ambient conditions. We report bond length value of 2.11±0.01 Å for Zn-O of rock salt (RS) symmetry, when Zn is doped in RS NiO. Bond length for Zn substituted NiO RS ternary solid solutions shows relaxed behavior for Zn-O bond, while it shows un-relaxed behavior for Ni-O bond. These observations are further supported by first-principles calculations. It is also inferred that Zn sublattice remains nearly unchanged with increase in lattice parameter. On the other hand, Ni sublattice dilates for Zn compositions up to 20% to accommodate increase in the lattice parameter. However, for Zn compositions more than 20%, it does not further dilate. It has been attributed to the large disorder that is incorporated in the system at and beyond 20% of Zn incorporation in the cubic RS lattice of ternary solid solutions. For these large percentages of Zn incorporation, the Ni and the Zn atoms re-arrange themselves microscopically about the same nominal bond length rather than systematically increase in magnitude to minimize the energy of the system. This results in an increase in the Debye-Waller factor with increase in the Zn concentration rather than a systematic increase in the bond lengths.

Geochemical control on the reduction of U(VI) to mononuclear U(IV) species in lacustrine sediments

NASA Astrophysics Data System (ADS)

Stetten, L.; Mangeret, A.; Brest, J.; Seder-Colomina, M.; Le Pape, P.; Ikogou, M.; Zeyen, N.; Thouvenot, A.; Julien, A.; Alcalde, G.; Reyss, J. L.; Bombled, B.; Rabouille, C.; Olivi, L.; Proux, O.; Cazala, C.; Morin, G.

2018-02-01

Contaminated systems in which uranium (U) concentrations slightly exceed the geochemical background are of particular interest to identify natural processes governing U trapping and accumulation in Earth's surface environments. For this purpose, we examined the role of early diagenesis on the evolution of U speciation and mobility in sediments from an artificial lake located downstream from a former mining site. Sediment and pore water chemistry together with U and Fe solid state speciation were analyzed in sediment cores sampled down to 50 cm depth at four locations in the lake. These organic-rich sediments (∼12% organic C) exhibited U concentrations in the 40-80 mg kg-1 range. The sediment columns were anoxic 2-3 mm below the sediment-water interface and pore waters pH was circumneutral. Pore water chemistry profiles showed that organic carbon mineralization was associated with Fe and Mn reduction and was correlated with a decrease in dissolved U concentration with depth. Immobilization of U in the sediment was correlated with the reduction of U(VI) to U(IV) at depth, as shown by U LIII-edge XANES spectroscopic analysis. XANES and EXAFS spectroscopy at the Fe K-edge showed the reduction of structural Fe(III) to Fe(II) in phyllosilicate minerals with depth, coincident with U(VI) to U(IV) reduction. Thermodynamic modeling suggests that Fe(II) could act as a major reducing agent for U(VI) during early diagenesis of these sediments, leading to complete U reduction below ∼30 cm depth. Shell-by-shell and Cauchy-Wavelet analysis of U LIII-EXAFS spectra indicates that U(VI) and U(IV) are mainly present as mononuclear species bound to C, P or Si ligands. Chemical extractions confirmed that ∼60-80% of U was present as non-crystalline species, which emphasizes that such species should be considered when evaluating the fate of U in lacustrine environments and the efficiency of sediment remediation strategies.

Soft X-ray spectromicroscopy study of mineral-organic matter associations in pasture soil clay fractions.

PubMed

Chen, Chunmei; Dynes, James J; Wang, Jian; Karunakaran, Chithra; Sparks, Donald L

2014-06-17

There is a growing acceptance that associations with soil minerals may be the most important overarching stabilization mechanism for soil organic matter. However, direct investigation of organo-mineral associations has been hampered by a lack of methods that can simultaneously characterize organic matter (OM) and soil minerals. In this study, STXM-NEXAFS spectroscopy at the C 1s, Ca 2p, Fe 2p, Al 1s, and Si 1s edges was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope. Bulk techniques including C and N NEXAFS, Fe K-edge EXAFS spectroscopy, and XRD were applied to provide additional information. Results demonstrated that C was associated with Ca, Fe, Al, and Si with no separate phase in soil clay particles. In soil clay particles, the pervasive C forms were aromatic C, carboxyl C, and polysaccharides with the relative abundance of carboxyl C and polysaccharides varying spatially at the submicrometer scale. Only limited regions in the soil clay particles had aliphatic C. Good C-Ca spatial correlations were found for soil clay particles with no CaCO3, suggesting a strong role of Ca in organo-mineral assemblage formation. Fe EXAFS showed that about 50% of the total Fe in soils was contained in Fe oxides, whereas Fe-bearing aluminosilicates (vermiculite and Illite) accounted for another 50%. Fe oxides in the soil were mainly crystalline goethite and hematite, with lesser amounts of poorly crystalline ferrihydrite. XRD revealed that soil clay aluminosilicates were hydroxy-interlayered vermiculite, Illite, and kaolinite. C showed similar correlation with Fe to Al and Si, implying a similar association of Fe oxides and aluminosilicates with organic matter in organo-mineral associations. These direct microscopic determinations can help improve understanding of organo-mineral interactions in soils.

Growth of GaN- and ZnO-Based Nanorod Compound Structures

DTIC Science & Technology

2013-08-16

parallel with or forming a 60o tilted angle with respect to the two parallel lateral sides of individual NRs. In the edge-to-edge pattern, the shortest...kV and a probe forming lens of Cs = 1.2 mm. 3. SEM and TEM Observations Figures 2(a)-2(f) show the plan-view SEM images of samples I-VI... angle annular dark field (HAADF) image in TEM observation of an InGaN/GaN QW NR of sample I. In this image, the three almost vertical bright lines

Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra

NASA Astrophysics Data System (ADS)

Aquilanti, Giuliana; Giorgetti, Marco; Dominko, Robert; Stievano, Lorenzo; Arčon, Iztok; Novello, Nicola; Olivi, Luca

2017-02-01

X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

Energy dispersive-EXAFS of Pd nucleation at a liquid/liquid interface

NASA Astrophysics Data System (ADS)

Chang, S.-Y.; Booth, S. G.; Uehara, A.; Mosselmans, J. F. W.; Cibin, G.; Pham, V.-T.; Nataf, L.; Dryfe, R. A. W.; Schroeder, S. L. M.

2016-05-01

Energy dispersive extended X-ray absorption fine structure (EDE) has been applied to Pd nanoparticle nucleation at a liquid/liquid interface under control over the interfacial potential and thereby the driving force for nucleation. Preliminary analysis focusing on Pd K edge-step height determination shows that under supersaturated conditions the concentration of Pd near the interface fluctuate over a period of several hours, likely due to the continuous formation and dissolution of sub-critical nuclei. Open circuit potential measurements conducted ex-situ in a liquid/liquid electrochemical cell support this view, showing that the fluctuations in Pd concentration are also visible as variations in potential across the liquid/liquid interface. By decreasing the interfacial potential through inclusion of a common ion (tetraethylammonium, TEA+) the Pd nanoparticle growth rate could be slowed down, resulting in a smooth nucleation process. Eventually, when the TEA+ ions reached an equilibrium potential, Pd nucleation and particle growth were inhibited.

In situ spectroscopic characterization of Ni 1-xZn x/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.

2015-10-30

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. N₀̣̣₈₅ Zn₀̣̣₁₅O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni 1-xZn x, at ~400 °C with x increasingmore » with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β₁-NiZn formation at ~550 °C. In comparison to a Ni/SiO₂ catalyst, Ni/ZnO necessitates a higher temperature for the reduction of Ni II to Ni⁰, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO₂. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H–D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO₂.These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.« less

Origin of luminescence from ZnO/CdS core/shell nanowire arrays

NASA Astrophysics Data System (ADS)

Wang, Zhiqiang; Wang, Jian; Sham, Tsun-Kong; Yang, Shaoguang

2014-07-01

Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the BGE of CdS and defect emission (DE, zinc vacancies) of ZnO; the IR luminescence is attributed to the DE (bulk defect related to the S site) of CdS; ZnS contributes little to the luminescence of the ZnO/CdS NW arrays. Interestingly, the BGE and DE from oxygen vacancies of ZnO in the ZnO/CdS nano-composites are almost entirely quenched, while DE from zinc vacancies changes little.Chemical imaging, electronic structure and optical properties of ZnO/CdS nano-composites have been investigated using scanning transmission X-ray microscopy (STXM), X-ray absorption near-edge structure (XANES) and X-ray excited optical luminescence (XEOL) spectroscopy. STXM and XANES results confirm that the as-prepared product is ZnO/CdS core/shell nanowires (NWs), and further indicate that ZnS was formed on the surface of ZnO NWs as the interface between ZnO and CdS. The XEOL from ZnO/CdS NW arrays exhibits one weak ultraviolet (UV) emission at 375 nm, one strong green emission at 512 nm, and two broad infrared (IR) emissions at 750 and 900 nm. Combining XANES and XEOL, it is concluded that the UV luminescence is the near band gap emission (BGE) of ZnO; the green luminescence comes from both the BGE of CdS and defect emission (DE, zinc vacancies) of ZnO; the IR luminescence is attributed to the DE (bulk defect related to the S site) of CdS; ZnS contributes little to the luminescence of the ZnO/CdS NW arrays. Interestingly, the BGE and DE from oxygen vacancies of ZnO in the ZnO/CdS nano-composites are almost entirely quenched, while DE from zinc vacancies changes little. Electronic supplementary information (ESI) available: PL spectra of the ZnO NW arrays before/after CdS coating. S K-edge XANES spectra of the ZnO/CdS core/shell NW arrays. See DOI: 10.1039/c4nr02231a

Glutathione Complex Formation With Mercury(Ii) in Aqueous Solution at Physiological Ph

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mah, V.; Jalilehvand, F.; /SLAC

2012-08-23

The mercury(II) complexes formed in neutral aqueous solution with glutathione (GSH, here denoted AH{sub 3} in its triprotonated form) were studied using Hg L{sub III}-edge extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy, complemented with electrospray ionization mass spectrometric (ESI-MS) analyses. The [Hg(AH){sub 2}]{sup 2-} complex, with the Hg-S bond distances at 2.325 {+-} 0.01 {angstrom} in linear S-Hg-S coordination, and the {sup 199}Hg NMR chemical shift at -984 ppm, dominates except at high excess of glutathione. In a series of solutions with C{sub Hg(II)} {approx} 17 mM and GSH/Hg(II) mole ratios rising from 2.4 to 11.8,more » the gradually increasing mean Hg-S bond distance corresponds to an increasing amount of the [Hg(AH){sub 3}]{sup 4-} complex. ESI-MS peaks appear at -m/z values of 1208 and 1230 corresponding to the [Na{sub 4}Hg(AH){sub 2}(A)]{sup -} and [Na{sub 5}Hg(AH)(A){sub 2}]{sup -} species, respectively. In another series of solutions at pH 7.0 with CHg(II) 50 mM and GSH/Hg(II) ratios from 2.0 to 10.0, the Hg L{sub III}-edge EXAFS and {sup 199}Hg NMR spectra show that at high excess of glutathione (0.35 M) about 70% of the total mercury(II) concentration is present as the [Hg(AH){sub 3}]4- complex, with the average Hg-S bond distance 2.42 {+-} 0.02 {angstrom} in trigonal HgS{sub 3} coordination. The proportions of HgSn species, n = 2, 3, and 4, quantified by fitting linear combinations of model EXAFS oscillations to the experimental EXAFS data in our present and previous studies were used to obtain stability constants for the [Hg(AH){sub 3}]{sup 4-} complex and also for the [Hg(A){sub 4}]{sup 10-} complex that is present at high pH. For Hg(II) in low concentration at physiological conditions (pH 7.4, C{sub GSH} = 2.2 mM), the relative amounts of the HgS{sub 2} species [Hg(AH){sub 2}]{sup 2-}, [Hg(AH)(A)]{sup 3-}, and the HgS{sub 3} complex [Hg(AH){sub 3}]{sup 4-} were calculated to be 95:2:3. Our results are not consistent with the formation of dimeric Hg(II)-GSH complexes proposed in a recent EXAFS study.« less

Silver binding in argentiferous manganese oxide minerals investigated by synchrotron radiation X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Fan, Chenzi; Li, Qiaoying; Chu, Binbin; Lu, Guohui; Gao, Yuhong; Xu, Lingxiao

2018-02-01

The knowledge of the nature of silver occurrence and sites in argentiferous manganese oxides is significant for developing better process to extract silver from manganese-silver ores. Synchrotron radiation has been used to collect Ag K-edge X-ray absorption spectroscopy of three natural and five synthetic samples of silver-containing manganese oxide, basically in the phases of tunnel-type cryptomelane or todorokite and layer-type birnessite or chalcophanite. Data were also gathered on five standards including Ag foil, Ag2O, Ag2SO4, Ag2CO3, and AgNO3 to compare the local environments of Ag atoms with the samples. Ag K-edge XANES studies show that Ag is present in most of the samples in Ag+ oxidation state, except in the Ag-Tod sample through annealing step in the form of Ag0 nanoparticles which are also identified by TEM. The natural samples from Xiangguang manganese-silver ores exhibit similar coordination distances as the corresponding tunnel or layer structured synthetic samples. In the argentiferous cryptomelanes, silver cations do not occupy the tunnel centers like K+, but rather place on the common face sites of the cubic cage formed by MnO6 octahedra, coordinated with about four oxygen anions at 2.4 Å bond distances proved by the EXAFS results. In the silver-exchanged birnessites or natural argentiferous chalcophanite, silver cations probably occupy a tetrahedral coordination to interlayer O atoms and a position located above or below the vacant cavities in the Mn octahedra layers.

Local structural environments of Ge doped in eutectic Sb-Te film before and after crystallization

NASA Astrophysics Data System (ADS)

Shin, Sang Yeol; Cheong, Byung-ki; Choi, Yong Gyu

2018-06-01

Electrical phase change device using the Ge-doped eutectic Sb-Te (e.g., Ge1Sb8Te2) film is known to exhibit improved energy efficiency thanks to lowered threshold voltage as well as decreased power consumption for the reset operation, as compared with Ge2Sb2Te5 film. Ge K-edge EXAFS analysis is employed in this study in an effort to elucidate such merits of Ge1Sb8Te2 film in connection with its local atomic arrangements. It is then verified that a Ge atom is four-fold coordinated in its nearest-neighboring shell both in the as-deposited and in the annealed films. It needs to be highlighted that approximately two Sb atoms constitute the Ge tetrahedral units in its amorphous state; however, after being crystallized, heteropolar Ge-Sb bonds hardly exist in this Ge1Sb8Te2 film. It has been known that crystallization temperature and activation energy for crystallization of this Ge1Sb8Te2 composition are greater than those of Ge2Sb2Te5 composition. In addition, these two phase change materials exhibit distinctly different crystallization mechanisms, i.e., nucleation-dominant for Ge2Sb2Te5 film but growth-dominant for Ge1Sb8Te2 film. These discrepancies in the crystallization-related properties are delineated in terms of the local structural changes verified from the present EXAFS analysis.

Long-range electron transfer in porphyrin-containing [2]-rotaxanes: tuning the rate by metal cation coordination.

PubMed

Andersson, Mikael; Linke, Myriam; Chambron, Jean-Claude; Davidsson, Jan; Heitz, Valérie; Hammarström, Leif; Sauvage, Jean-Pierre

2002-04-24

A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP*+-AuP* charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2x10(10) x s(-1) were obtained over a 15-17 A edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced superexchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)22+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron- and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2+ (k = 5.1x10(9) x s(-1)) that proceeded in competition with electron transfer to AuP+ and was followed by a quantitative energy transfer to give the 3ZnP state (k = 1.5x10(9) x s(-1)).

Doping induced modifications in the electronic structure and magnetism of ZnO films: Valence band and conduction band studies

NASA Astrophysics Data System (ADS)

Katba, Savan; Jethva, Sadaf; Udeshi, Malay; Trivedi, Priyanka; Vagadia, Megha; Shukla, D. K.; Choudhary, R. J.; Phase, D. M.; Kuberkar, D. G.

2017-11-01

The electronic structure of Pulsed Laser Deposited (PLD) ZnO, Zn0.95Fe0.05O (ZFO), Zn0.98Al0.02O (ZAO) and Zn0.93Fe0.05Al0.02O (ZFAO) films were investigated by Photoelectron spectroscopy and X-ray absorption spectroscopy. X-ray diffraction and ϕ-scan measurements show epitaxial c-directional growth of the films. Temperature dependent magnetization and M-H loop measurements show the presence of room temperature magnetic ordering in all the films. Fittings of Fe 2p XPS and Fe L3,2 -edge XAS of ZFO and ZFAO films show the presence of Fe, in both, Fe+2 and Fe+3 states in tetrahedral symmetry. Valence band spectra in resonance mode show resonance photon energy at 56 eV showing the presence of Fe2+ state (∼2 eV) near the Fermi level. A significant effect of Fe and Al doping on the spectral shape of O K-edge XAS was observed. Results of the Spectroscopic studies reveal that, ferromagnetism in the films is due to the contribution of oxygen deficiency which increases the number of charge carriers that take part in the exchange interaction. Al co-doping with Fe (in ZFAO) results in the enhancement of saturation magnetization by increase in the carrier-mediated ferromagnetic exchange interaction.

Synchrotron X-ray micro-beam studies of ancient Egyptian make-up

NASA Astrophysics Data System (ADS)

Martinetto, P.; Anne, M.; Dooryhée, E.; Drakopoulos, M.; Dubus, M.; Salomon, J.; Simionovici, A.; Walter, Ph.

2001-07-01

Vases full of make-up are most often present in the burial furniture of Egyptian tombs dated from the pharaonic period. The powdered cosmetics made of isolated grains are analysed to identify their trace element signature. From this signature we identify the provenance of the mineral ingredients in the make-up and we observe different impurities in products, which have been demonstrated as synthetic substances by previous works. Focused X-ray micro-beam ( 2×5 μm2) is successively tuned at 11 keV, below the L III absorption edge of Pb, and 31.8 keV for global characterisation of the metal impurities. The fluorescence signal integrated over each single grain is detected against the X-ray micro-diffraction pattern collected in transmission with a bi-dimensional detector. Furthermore, for galena grains rich in Zn, the XANES signal at the K-absorption edge of Zn shows its immediate nearest-neighbour environment.

Photoinduced Effects in the ZnO Luminescence Spectra

NASA Astrophysics Data System (ADS)

Akopyan, I. Kh.; Labzovskaya, M. E.; Novikov, B. V.; Lisachenko, A. A.; Serov, A. Yu.; Filosofov, N. G.

2018-02-01

The effect of intense UV irradiation on the photoluminescence (PL) spectra of ZnO powders and nanocrystalline films obtained by atomic layer deposition (ALD) was investigated. At room temperature, the behavior of the spectra under continuous UV irradiation in multiple vacuum-atmosphere cycles was studied. The changes in the intensities of exciton radiation and radiation in the "green" band region, associated with the phenomena of oxygen photodesorption and photoadsorption, are discussed. In the temperature range of 5-300 K, the effect of strong UV irradiation on the near-edge luminescence spectrum of ZnO films was studied. The nature of a new line arising in the photoluminescence spectra of an irradiated film in the region of emission of bound excitons is discussed.

Surface and cut-edge corrosion behavior of Zn-Mg-Al alloy-coated steel sheets as a function of the alloy coating microstructure

NASA Astrophysics Data System (ADS)

Oh, Min-Suk; Kim, Sang-Heon; Kim, Jong-Sang; Lee, Jae-Won; Shon, Je-Ha; Jin, Young-Sool

2016-01-01

The effects of Mg and Al content on the microstructure and corrosion resistance of hot-dip Zn-Mg-Al alloycoated steel sheets were investigated. Pure Zn and Zn-based alloy coatings containing Mg (0-5 wt%) and Al (0.2-55 wt%) were produced by a hot-dip galvanizing method. Mg and Al addition induced formation of intermetallic microstructures, like primary Zn, Zn/MgZn2 binary eutectic, dendric Zn/Al eutectoid, and Zn/Al/MgZn2/ternary eutectic structures in the coating layer. MgZn2-related structures (Zn/MgZn2, Zn/Al/MgZn2, MgZn2) played an important role in increasing the corrosion resistance of Zn-Mg-Al alloy-coated steel sheets. Zn-3%Mg-2.5%Al coating layer containing a large volume of lamellar-shaped Zn/MgZn2 binary eutectic structures showed the best cut-edge corrosion resistance. The analysis indicated that Mg dissolved from MgZn2 in the early stage of corrosion and migrated to the cathodic region of steel-exposed cut-edge area to form dense and ordered protective corrosion products, leading to prolonged cathodic protection of Zn-Mg-Al alloy-coated steel sheets.

Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study.

PubMed

Cui, Jinli; Jing, Chuanyong; Che, Dongsheng; Zhang, Jianfeng; Duan, Shuxuan

2015-06-01

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5mg/L Ca(ClO)2. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water. Copyright © 2015. Published by Elsevier B.V.

The effects of redox fluctuation on iron-organic matter interactions in wet tropical soils

NASA Astrophysics Data System (ADS)

Bhattacharyya, A.; Campbell, A.; Lin, Y.; Nico, P. S.; Silver, W. L.; Pett-Ridge, J.

2016-12-01

Two-thirds of the C in the terrestrial biosphere is stored as soil organic C, and much of this is stabilized via iron (Fe) mineral-organic matter (OM) associations that are susceptible to redox effects. The rapid C cycling typical of wet tropical ecosystems- driven by ample moisture and temperature- may also be fueled by a characteristically dynamic redox environment. Yet the net result of altered tropical soil climate and fluctuating soil redox regimes on Fe-organic matter associations is poorly understood. In this study, we hypothesized that the timing of redox transitions (frequency of O2 introduction and ferrous iron (Fe2+) generation) will lead to differences in Fe (oxyhydr)oxide mineral crystallinity and C degradation rates and alter the proportion of organic C associated with iron minerals. Surface soils from a humid tropical forest in Puerto Rico were incubated for 44 days under four redox regimes: (1) static anoxic, (2) static oxic, (3) 4 days anoxic, 4 days oxic, and (4) 4 days anoxic, 8 days oxic. Replicate microcosms were harvested at multiple time points, including before and after a redox switch (oxic to anoxic or vice versa). Selective chemical extractions, bulk Fe K-edge EXAFS and STXM/NEXAFS spectromicroscopy were used to comprehensively probe treatment effects on Fe and C speciation. Static redox conditions had a significant effect on Fe2+ and dissolved organic carbon (DOC) concentrations, and prolonged anoxia promoted reductive dissolution of Fe-oxides and an increase in amorphous or short-range ordered (SRO) Fe oxides. Preferential dissolution of this less-crystalline Fe pool was more prominent during rapid redox switches from oxic to anoxic conditions, and coincided with increased DOC. Bulk Fe K-edge EXAFS spectroscopy identified Fe3+ as the dominant Fe species in all treatments and indicated O/N atoms in the first Fe co-ordination sphere and features similar to SRO Fe-oxide phases (e.g. ferrihydrite or nano-goethite) in the second co-ordination sphere. STXM/NEXAFS analyses indicated an increase in lignin-like biomolecules under static anoxic conditions, and a potential role of Fe-lignin interactions under strong reducing conditions. Our current findings highlight the necessity to explore natural redox-dynamic systems in greater detail in order to develop a better model for climate change.

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I. Effects of pH

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) as a function of pH has been combined with Hg L III-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density ??=0.39-0.42 ??mol/m2) and bayerite (??=0.39-0.44 ??mol/m2), while sorbing more weakly to ??-alumina (??=0.04-0.13 ??mol/m 2). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the ??-Al2O3 sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments. ?? 2003 Elsevier Inc. All rights reserved.

Influence of C or In buffer layer on photoluminescence behaviour of ultrathin ZnO film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saravanan, K., E-mail: saravanan@igcar.gov.in; Jayalakshmi, G.; Krishnan, R.

We study the effect of the indium or carbon buffer layer on the photoluminescence (PL) property of ZnO ultrathin films deposited on a Si(100) substrate. The surface morphology of the films obtained using scanning tunnelling microscopy shows spherical shaped ZnO nanoparticles of size ∼8 nm in ZnO/C/Si and ∼22 nm in ZnO/Si samples, while the ZnO/In/Si sample shows elliptical shaped ZnO particles. Further, the ZnO/C/Si sample shows densely packed ZnO nanoparticles in comparison with other samples. Strong band edge emission has been observed in the presence of In or C buffer layer, whereas the ZnO/Si sample exhibits poor PL emission. The influencemore » of C and In buffer layers on the PL behaviour of ZnO films is studied in detail using temperature dependent PL measurements in the range of 4 K–300 K. The ZnO/C/Si sample exhibits a multi-fold enhancement in the PL emission intensity with well-resolved free and bound exciton emission lines. Our experimental results imply that the ZnO films deposited on the C buffer layer showed higher particle density and better exciton emission desired for optoelectronic applications.« less

Structure and properties of ZnSxSe1-x thin films deposited by thermal evaporation of ZnS and ZnSe powder mixtures

NASA Astrophysics Data System (ADS)

Valeev, R. G.; Romanov, E. A.; Vorobiev, V. L.; Mukhgalin, V. V.; Kriventsov, V. V.; Chukavin, A. I.; Robouch, B. V.

2015-02-01

Interest to ZnSxSe1-x alloys is due to their band-gap tunability varying S and Se content. Films of ZnSxSe1-x were grown evaporating ZnS and ZnSe powder mixtures onto SiO2, NaCl, Si and ITO substrates using an original low-cost method. X-ray diffraction patterns and Raman spectroscopy, show that the lattice structure of these films is cubic ZnSe-like, as S atoms replace Se and film compositions have their initial S/Se ratio. Optical absorption spectra show that band gap values increase from 2.25 to 3 eV as x increases, in agreement with the literature. Because S atomic radii are smaller than Se, EXAFS spectra confirm that bond distances and Se coordination numbers decrease as the Se content decreases. The strong deviation from linearity of ZnSe coordination numbers in the ZnSxSe1-x indicate that within this ordered crystal structure strong site occupation preferences occur in the distribution of Se and S ions. The behavior is quantitatively confirmed by the strong deviation from the random Bernoulli distribution of the three sight occupation preference coefficients of the strained tetrahedron model. Actually, the ternary ZnSxSe1-x system is a bi-binary (ZnS+ZnSe) alloy with evanescent formation of ternary configurations throughout the x-range.

A new detector for sub-millisecond EXAFS spectroscopy at the European Synchrotron Radiation Facility.

PubMed

Kantor, Innokenty; Labiche, Jean-Claude; Collet, Emmanuel; Siron, Laurent; Thevenin, Jean-Jacques; Ponchut, Cyril; Borrel, Jacques; Mairs, Trevor; Marini, Carlo; Strohm, Cornelius; Mathon, Olivier; Pascarelli, Sakura

2014-11-01

A new FReLoN (Fast-Readout Low-Noise) high-frame-rate detector adopted for the fast continuous collection of X-ray absorption spectra is presented. The detector is installed on the energy-dispersive X-ray absorption beamline ID24 at the ESRF and is capable of full time-resolved EXAFS spectra collection with over 4 kHz repetition rate and 0.2 ms exposure time. An example of the in situ kinetic study of the high-temperature oxidation of metallic iron is presented.

Luminescence dynamics of bound exciton of hydrogen doped ZnO nanowires

DOE PAGES

Yoo, Jinkyoung; Yi, Gyu -Chul; Chon, Bonghwan; ...

2016-04-11

In this study, all-optical camera, converting X-rays into visible photons, is a promising strategy for high-performance X-ray imaging detector requiring high detection efficiency and ultrafast detector response time. Zinc oxide is a suitable material for all-optical camera due to its fast radiative recombination lifetime in sub-nanosecond regime and its radiation hardness. ZnO nanostructures have been considered as proper building blocks for ultrafast detectors with spatial resolution in sub-micrometer scale. To achieve remarkable enhancement of luminescence efficiency n-type doping in ZnO has been employed. However, luminescence dynamics of doped ZnO nanostructures have not been thoroughly investigated whereas undoped ZnO nanostructures havemore » been employed to study their luminescence dynamics. Here we report a study of luminescence dynamics of hydrogen doped ZnO nanowires obtained by hydrogen plasma treatment. Hydrogen doping in ZnO nanowires gives rise to significant increase in the near-band-edge emission of ZnO and decrease in averaged photoluminescence lifetime from 300 to 140 ps at 10 K. The effects of hydrogen doping on the luminescent characteristics of ZnO nanowires were changed by hydrogen doping process variables.« less

Origin of magnetic properties in carbon implanted ZnO nanowires.

PubMed

Wang, Y F; Shao, Y C; Hsieh, S H; Chang, Y K; Yeh, P H; Hsueh, H C; Chiou, J W; Wang, H T; Ray, S C; Tsai, H M; Pao, C W; Chen, C H; Lin, H J; Lee, J F; Wu, C T; Wu, J J; Chang, Y M; Asokan, K; Chae, K H; Ohigashi, T; Takagi, Y; Yokoyama, T; Kosugi, N; Pong, W F

2018-05-17

Various synchrotron radiation-based spectroscopic and microscopic techniques are used to elucidate the room-temperature ferromagnetism of carbon-doped ZnO-nanowires (ZnO-C:NW) via a mild C + ion implantation method. The photoluminescence and magnetic hysteresis loops reveal that the implantation of C reduces the number of intrinsic surface defects and increases the saturated magnetization of ZnO-NW. The interstitial implanted C ions constitute the majority of defects in ZnO-C:NW as confirmed by the X-ray absorption spectroscopic studies. The X-ray magnetic circular dichroism spectra of O and C K-edge respectively indicate there is a reduction in the number of unpaired/dangling O 2p bonds in the surface region of ZnO-C:NW and the C 2p-derived states of the implanted C ions strongly affect the net spin polarization in the surface and bulk regions of ZnO-C:NW. Furthermore, these findings corroborate well with the first-principles calculations of C-implanted ZnO in surface and bulk regions, which highlight the stability of implanted C for the suppression and enhancement of the ferromagnetism of the ZnO-C:NW in the surface region and bulk phase, respectively.

Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

PubMed

Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

2012-01-16

Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukerjee, S.; Ziegelbauer, J; Arruda, T

Over the last few decades, researchers have made significant developments in producing more advanced electrocatalytic materials for power generation applications. For example, traditional fuel cell catalysts often involve high-priced precious metals such as Pt. However, in order for fuel cells to become commercially viable, there is a need to reduce or completely remove precious metal altogether. As a result, a myriad of novel, unconventional materials have been explored such as chalcogenides, porphyrins, and organic-metal-macrocycles for low/medium temperature fuel cells as well as enzymatic and microbial fuel cells. As these materials increasingly become more complex, researchers often find themselves in searchmore » of new characterization methods, especially those which are allow in situ and operando measurements with element specificity. One such method that has received much attention for analysis of electrocatalytic materials is X-ray absorption spectroscopy (XAS). XAS is an element specific, core level absorption technique which yields structural and electronic information. As a core electron method, XAS requires an extremely bright source, hence a synchrotron. The resulting intensity of synchrotron radiation allow for experiments to be conducted in situ, under electrochemically relevant conditions. Although a bulk-averaging technique requiring rigorous mathematical manipulation, XAS has the added benefit that it can probe materials which possess no long range order. This makes it ideal to characterize nano-scale electrocatalysts. XAS experiments are conducted by ramping the X-ray photon energy while measuring absorption of the incident beam the sample or by counting fluorescent photons released from a sample due to subsequent relaxation. Absorption mode XAS follows the Beer-Lambert Law, {mu}x = log(I{sub 0}/I{sub t}) (1) where {mu} is the absorption coefficient, x is the sample thickness and I{sub 0} and I{sub t} are the intensities of the incident and transmission beams respectively. When the energy of the incident X-rays exceed the electron binding energy (E{sub 0}) of the element under investigation, the electron is ejected from the core to available excited states in the form of a photoelectron with kinetic energy: E{sub k} = h? - E{sub 0} (2) with, E{sub k} being the kinetic energy of the released photoelectron and h? the energy of the incident beam. In general, the X-ray absorption spectrum is broken down into two distinct energy regions: the X-ray absorption near-edge structure or XANES (-50eV {le} E{sub 0} {le} 50eV) and the extended X-ray absorption fine-structure or EXAFS (50eV {le} E{sub 0} {le} {approx}1000eV). The XANES region is dominated by low-energy photoelectrons which undergo multiple scattering events. As such, it can reveal information about oxidation state, local symmetry, electronic structure, and the extent of oxidation of a material. Due to this complex multiple scattering, there is no simple XANES equation to describe it quantitatively. However, recent advancements in computers and the evolution of numerical methods such as the FEFF code have made possible reliable XANES simulations. Photoelectrons in the EXAFS region have high enough E{sub k} to undergo primarily single back-scattering events. These back-scattered photoelectrons interfere with the outgoing photoelectrons, causing the oscillations in the absorption spectrum. Using the previously developed EXAFS equations it is now possible to model EXAFS data to determine coordination numbers, bond distances, and mean-square disorder (commonly referred to as Debye-Waller factor). EXAFS data is often shown by Fourier Transforming KSpace into distance, r, space where the total magnitude is plotted against the radial coordinates. This allow for easy qualitative comparison of samples. Employing EXAFS on nanoscale materials has the added advantage that it can quantitatively illustrate changes in atom-atom coordination, which can be related to particle size or morphology. Overall this technique enables the measurement of both bulk and surface adsorbed species with element specificity under actual electrochemical operating conditions. Thus this represents the one of the most powerful methods to understand the exact role of the reaction center and degradation processes such as sintering and corrosion.« less

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

USGS Publications Warehouse

Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

2005-01-01

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

Zinc speciation in proximity to phosphate application points in a lead/zinc smelter-contaminated soil.

PubMed

Baker, Lucas R; Pierzynski, Gary M; Hettiarachchi, Ganga M; Scheckel, Kirk G; Newville, Matthew

2012-01-01

The use of P to immobilize Pb in contaminated soils has been well documented. However, the influence of P on Zn speciation in soils has not been extensively examined, and these two metals often occur as co-contaminants. We hypothesized that additions of P to a Pb/Zn-contaminated soil would induce Zn phosphate mineral formation and fluid P sources would be more effective than granular P amendments. A combination of different synchrotron-based techniques, namely, spatially resolved micro-X-ray fluorescence (μ-XRF), micro-extended X-ray absorption fine structure spectroscopy (μ-EXAFS), and micro-X-ray diffraction (μ-XRD), were used to speciate Zn at two incubation times in the proximity of application points (0 to 4 mm) for fluid and granular P amendments in a Pb/Zn smelter-contaminated soil. Phosphate rock (PR), triple super phosphate (TSP), monoammonium phosphate (MAP), and fluid ammonium polyphosphate induced Zn phosphate formation. Ammonium polyphosphate was more effective at greater distances (up to 3.7 mm) from the point of P application. Phosphoric acid increased the presence of soluble Zn species because of increased acidity. Soluble Zn has implications with respect to Zn bioavailability, which may negatively impact vegetation and other sensitive organisms. Although additions of P immobilize Pb, this practice needs close monitoring due to potential increases in Zn solubility in a Pb/Zn smelter-contaminated soil. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu2ZnSnSe4

NASA Astrophysics Data System (ADS)

Zhu, Yingcai; Liu, Yong; Tan, Xing; Ren, Guangkun; Yu, Meijuan; Hu, Tiandou; Marcelli, Augusto; Xu, Wei

2018-04-01

Quaternary chalcogenide Cu2ZnSnSe4 (CZTSe) is a promising wide band-gap p-type thermoelectric material. The structure and thermoelectric properties of lead substituted Cu2ZnSn1-xPbxSe4 are investigated. Lead primarily exists in the framework of PbSe as demonstrated by x-ray diffraction and calculation of x-ray absorption near-edge structure spectroscopy. The second phase distributes at the boundaries of CZTSe with thickness in several hundreds of nanometer. With appropriate grain boundary engineering, the enhancement of power factor and a decrease of thermal conductivity can be achieved simultaneously. As a result, a maximum figure of merit zT of 0.45 is obtained for the sample with x=0.02 at 723K.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jamieson-Hanes, Julia H.; Shrimpton, Heather K.; Veeramani, Harish

A flow-through cell experiment was conducted to evaluate Zn isotope fractionation during ZnS precipitation under microbially-mediated sulfate-reducing conditions. Synthetic groundwater containing 0.90 mM Zn was pumped through a cell containing creek sediment that was biostimulated to promote sulfate reducing conditions. Real-time, in situ X-ray absorption spectroscopy (XAS) was applied at the Zn K-edge to collect spectra via a Kapton® window in the front of the cell over the course of the experiment. Aqueous effluent samples were collected and analysed to determine concentrations of anions and cations, and Zn isotope ratios. The flow rate was increased step-wise during the experiment tomore » modify the residence time and produce changes in the extent of sulfate reduction, which in turn controlled the extent of ZnS precipitation. Greater enrichment in the heavier isotope in the aqueous phase relative to the input solution was associated with more extensive Zn removal. A Rayleigh curve was fit to the isotope data, where ε = -0.27 ± 0.06‰ (2σ). Evaluation of Zn isotope fractionation under controlled flow conditions is critical to improve the efficacy of this powerful analytical technique when applied to natural systems or remediation projects in the field.« less

Development of ZnO:Ga as an Ultrafast Scintillator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourret-Courchesne, E.D.; Derenzo, S.E.; Weber, M.J.

We report on several methods for synthesizing the ultra-fast scintillator ZnO(Ga), and measurements of the resulting products. This material has characteristics that make it an excellent alpha detector for tagging the time and direction of individual neutrons produced by t-d and d-d neutron generators (associated particle imaging). The intensity and decay time are strongly dependent on the method used for dopant incorporation. We compare samples made by diffusion of Ga metal to samples made by solid state reaction between ZnO and Ga2O3 followed by reduction in hydrogen. The latter is much more successful and has a pure, strong near-band-edge fluorescencemore » and an ultra-fast decay time of the x-ray-excited luminescence. The luminescence increases dramatically as the temperature is reduced to 10K. We also present results of an alternate low-temperature synthesis that produces luminescent particles with a more uniform size distribution. We examine possible mechanisms for the bright near-band-edge scintillation and favor the explanation that it is due to the recombination of Ga3+ donor electrons with ionization holes trapped on H+ ion acceptors.« less

Nanoparticulate mackinawite formation; a stopped and continuous flow XANES and EXAFS investigation

NASA Astrophysics Data System (ADS)

Butler, I. B.; Bell, A. M.; Charnock, J. M.; Rickard, D.; Vaughan, D. J.; Oldroyd, A.

2009-12-01

The sequestration of sulfur and iron within sedimentary iron sulfides, and ultimately as pyrite, is a major sink in global biogeochemical cycles of those elements and has impacts on global carbon and oxygen cycles. The formation of the metastable black iron (II) monosulfide mackinawite is a key process because mackinawite forms in aqueous solutions where the Fe(II) and S(-II) IAP exceeds mackinawite’s Ksp. Mackinawite is the first formed iron sulfide phase, a consequence of Ostwald’s step rule and is a reactant phase during the formation of thermodynamically stable sedimentary iron sulfide minerals such as pyrite. The reaction of dissolved Fe(II) and sulfide is extremely fast and reactions in the environmentally significant near-neutral pH range tend to completion in <1 second. We have combined stopped and continuous flow techniques with X-ray absorption spectroscopy to evaluate the products of the fast precipitation kinetics of mackinawite over millisecond timescales. EXAFS spectra and data collected during flow experiments were compared with those from a well characterised freeze-dried nanoparticulate mackinawite standard and with published data. Published work has used Rietveld crystal structure refinement to determine bond distances of 2.2558 and 2.5976Å for Fe-S and Fe-Fe respectively. In our experiments Fe K edge XANES is consistent with tetrahedrally coordinated Fe in the precipitated sulfide phase. EXAFS data show that local Fe-S and Fe-Fe coordination and interatomic distances (Fe-S = 2.24Å; Fe-Fe = 2.57Å) are consistent with those determined for the standard mackinawite and published data. The coordination and spacing are developed in the precipitated phase after <10ms reaction at pH5, and considerably faster in experiments at near neutral to alkaline pH. No evidence for phases structurally intermediate between hexaqua Fe(II) and precipitated mackinawite was observed. Aqueous FeS° cluster complexes previously identified as intermediates during mackinawite formation and iron sulfide mineral transformations did not contribute significantly to the EXAFS spectra collected. For environmental, geological and biogeochemical applications, the precipitation of the mineral mackinawite can be considered to proceed rapidly from aqueous Fe(II) and S(-II) ions to the nanoparticulate crystalline mineral. The materials labelled “disordered mackinawite”, or “amorphous FeS” phase which have been widely quoted in the iron sulfide literature do not form at any stage of the precipitation of mackinawite from aqueous solutions. Physical and chemical properties previously ascribed to an amorphous or disordered structure are a consequence of the nanoparticulate form of the first precipitated solid.

XAS Study at Mo and Co K-Edges of the Sulfidation of a CoMo / Al2O3 Hydrotreating Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pichon, C.; Gandubert, A. D.; Legens, C.

2007-02-02

Because of its impact on environment, the removal of sulfur is an indispensable step, called hydrotreatment, in the refining of petroleum. One of the most commonly used hydrotreating catalysts is CoMo-type catalyst which is composed of molybdenum disulfide slabs promoted by cobalt atoms (CoMoS phase) and well dispersed on a high specific area alumina. As far as the highest sulfur content allowed in gasoline and diesel is continually decreasing, more and more efficient and active hydrotreating catalysts are required. In order to optimize the reactivity of the CoMo-type catalyst in hydrotreatment, a better understanding of the processes used to producemore » the active phase (CoMoS slabs) of the catalyst is necessary. The study reported here deals with the sulfiding mechanism of the slabs and the influence of temperature on the phenomenon. Ex situ X-ray absorption spectroscopy (XANES and EXAFS) was used to study the evolution of the structure of CoMo-type catalyst sulfided at various temperatures (from 293 to 873 K). XAS analysis was performed at both molybdenum and cobalt K-edges to obtain a cross-characterization of the sulfidation of the slabs. It evidenced the formation of various compounds, including two molybdenum oxides, MoS3 (or MoS3-like compound) and Co9S8, at specific steps of the sulfiding process. It showed the role of intermediate played by MoS3 (or MoS3-like compound) during the formation of the slabs and the competition between the appearance of promoted slabs (CoMoS phase) and Co9S8. At last, it leaded to the proposal of a mechanism for the sulfidation of the catalyst.« less

Effects of zinc toxicity on sugar beet (Beta vulgaris L.) plants grown in hydroponics.

PubMed

Sagardoy, R; Morales, F; López-Millán, A-F; Abadía, A; Abadía, J

2009-05-01

The effects of high Zn concentration were investigated in sugar beet (Beta vulgaris L.) plants grown in a controlled environment in hydroponics. High concentrations of Zn sulphate in the nutrient solution (50, 100 and 300 microm) decreased root and shoot fresh and dry mass, and increased root/shoot ratios, when compared to control conditions (1.2 microm Zn). Plants grown with excess Zn had inward-rolled leaf edges and a damaged and brownish root system, with short lateral roots. High Zn decreased N, Mg, K and Mn concentrations in all plant parts, whereas P and Ca concentrations increased, but only in shoots. Leaves of plants treated with 50 and 100 microm Zn developed symptoms of Fe deficiency, including decreases in Fe, chlorophyll and carotenoid concentrations, increases in carotenoid/chlorophyll and chlorophyll a/b ratios and de-epoxidation of violaxanthin cycle pigments. Plants grown with 300 microm Zn had decreased photosystem II efficiency and further growth decreases but did not have leaf Fe deficiency symptoms. Leaf Zn concentrations of plants grown with excess Zn were high but fairly constant (230-260 microg.g(-1) dry weight), whereas total Zn uptake per plant decreased markedly with high Zn supply. These data indicate that sugar beet could be a good model to investigate Zn homeostasis mechanisms in plants, but is not an efficient species for Zn phytoremediation.

Local thermal expansions and lattice strains in Elinvar and stainless steel alloys

NASA Astrophysics Data System (ADS)

Yokoyama, Toshihiko; Koide, Akihiro; Uemura, Yohei

2018-02-01

Local thermal expansions and lattice strains in the Elinvar alloy Fe49.66Ni42.38Cr5.49Ti2.47 (Ni Span C) and the stainless steel SUS304 Fe71.98Ni9.07Cr18.09Mn0.86 (AISI304) were investigated by the temperature-dependent Cr, Fe, and Ni K -edge extended x-ray absorption fine-structure (EXAFS) measurements, combined with the path-integral effective classical potential Monte Carlo (PIECP MC) theoretical simulations. From the EXAFS analysis of the Elinvar alloy, the local thermal expansion around Fe is found to be considerably smaller than the ones around Ni and Cr. This observation can be understood simply because Fe in the Elinvar alloy exhibit an incomplete Invar-like effect. Moreover, in both the Elinvar and SUS304 alloys, the local thermal expansions and the lattice strains around Cr are found to be larger than those around Fe and Ni. From the PIECP MC simulations of both the alloys, the first-nearest neighbor Cr-Fe pair shows extraordinarily large thermal expansion, while the Cr-Cr pair exhibits quite small or even negative thermal expansion. These findings consequently indicate that the lattice strains in both the Elinvar and SUS304 alloys are concentrated predominantly on the Cr atoms. Although the role of Cr in stainless steel has been known to inhibit corrosion by the formation of surface chromium oxide, the present investigation may interestingly suggest that the Cr atoms in the bulk play a hidden new role of absorbing inevitable lattice strains in the alloys.

Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2013-10-15

The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

Activation of an intense near band edge emission from ZnTe/ZnMgTe core/shell nanowires grown on silicon.

PubMed

Wojnar, P; Szymura, M; Zaleszczyk, W; Kłopotowski, L; Janik, E; Wiater, M; Baczewski, L T; Kret, S; Karczewski, G; Kossut, J; Wojtowicz, T

2013-09-13

The absence of luminescence in the near band edge energy region of Te-anion based semiconductor nanowires grown by gold catalyst assisted molecular beam epitaxy has strongly limited their applications in the field of photonics. In this paper, an enhancement of the near band edge emission intensity from ZnTe/ZnMgTe core/shell nanowires grown on Si substrates is reported. A special role of the use of Si substrates instead of GaAs substrates is emphasized, which results in an increase of the near band edge emission intensity by at least one order of magnitude accompanied by a simultaneous reduction of the defect related luminescence. A possible explanation of this effect relies on the presence of Ga-related deep level defects in structures grown on GaAs substrates, which are absent when Si substrates are used. Monochromatic mapping of the cathodoluminescence clearly confirms that the observed emission originates, indeed, from the ZnTe/ZnMgTe core/shell nanowires, whereas individual objects are studied by means of microphotoluminescence.

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater constituents in our data suggest that arsenic is released due to the reductive dissolution of arsenic laden-hydrous ferric oxides, however, further work is required to fully evaluate the mode of arsenic release.

Structural alteration of hexagonal birnessite by aqueous Mn(II): Impacts on Ni(II) sorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lefkowitz, Joshua P.; Elzinga, Evert J.

We studied the impacts of aqueous Mn(II) (1 mM) on the sorption of Ni(II) (200 μM) by hexagonal birnessite (0.1 g L- 1) at pH 6.5 and 7.5 with batch experiments and XRD, ATR-FTIR and Ni K-edge EXAFS analyses. In the absence of Mn(II)aq, sorbed Ni(II) was coordinated predominantly as triple corner-sharing complexes at layer vacancies at both pH values. Introduction of Mn(II)aq into Ni(II)-birnessite suspensions at pH 6.5 caused Ni(II) desorption and led to the formation of edge-sharing Ni(II) complexes. This was attributed to competitive displacement of Ni(II) from layer vacancies by either Mn(II) or by Mn(III) formed throughmore » interfacial Mn(II)-Mn(IV) comproportionation, and/or incorporation of Ni(II) into the birnessite lattice promoted by Mn(II)-catalyzed recrystallization of the sorbent. Similar to Mn(II)aq, the presence of HEPES or MES caused the formation of edge-sharing Ni(II) sorption complexes in Ni(II)-birnessite suspensions, which was attributed to partial reduction of the sorbent by the buffers. At pH 7.5, interaction with aqueous Mn(II) caused reductive transformation of birnessite into secondary feitknechtite that incorporated Ni(II), enhancing removal of Ni(II) from solution. These results demonstrate that reductive alteration of phyllomanganates may significantly affect the speciation and solubility of Ni(II) in anoxic and suboxic environments.« less

Spectroscopic and Mechanistic Studies of Heterodimetallic Forms of Metallo-β-lactamase NDM-1

PubMed Central

2015-01-01

In an effort to characterize the roles of each metal ion in metallo-β-lactamase NDM-1, heterodimetallic analogues (CoCo-, ZnCo-, and CoCd-) of the enzyme were generated and characterized. UV–vis, 1H NMR, EPR, and EXAFS spectroscopies were used to confirm the fidelity of the metal substitutions, including the presence of a homogeneous, heterodimetallic cluster, with a single-atom bridge. This marks the first preparation of a metallo-β-lactamase selectively substituted with a paramagnetic metal ion, Co(II), either in the Zn1 (CoCd-NDM-1) or in the Zn2 site (ZnCo-NDM-1), as well as both (CoCo-NDM-1). We then used these metal-substituted forms of the enzyme to probe the reaction mechanism, using steady-state and stopped-flow kinetics, stopped-flow fluorescence, and rapid-freeze-quench EPR. Both metal sites show significant effects on the kinetic constants, and both paramagnetic variants (CoCd- and ZnCo-NDM-1) showed significant structural changes on reaction with substrate. These changes are discussed in terms of a minimal kinetic mechanism that incorporates all of the data. PMID:24754678

New frontiers in water purification: highly stable amphopolycarboxyglycinate-stabilized Ag-AgCl nanocomposite and its newly discovered potential

NASA Astrophysics Data System (ADS)

Krutyakov, Yurii A.; Zherebin, Pavel M.; Kudrinskiy, Alexey A.; Zubavichus, Yan V.; Presniakov, Mikhail Yu; Yapryntsev, Alexey D.; Karabtseva, Anastasia V.; Mikhaylov, Dmitry M.; Lisichkin, Georgii V.

2016-09-01

A simple synthetic procedure for high-stable dispersions of porous composite Ag/AgCl nanoparticles stabilized with amphoteric surfactant sodium tallow amphopolycarboxyglycinate has been proposed for the first time. The prepared samples were characterized by UV-vis spectroscopy, x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy, small area electron diffraction (SAED), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electron probe micro-analysis. In addition, measurements (carried out at the Kurchatov synchrotron radiation source stations) of the Ag K-edge extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectra and XRD of the prepared nanoparticles have been performed. The obtained results suggest that small-sized Ag clusters are homogeneously distributed in the mass of the AgCl nanoparticle (~80 nm) formed during the synthesis. The Ag/AgCl dispersion demonstrates photocatalytic activity (with respect to methyl orange) and high bactericidal activity against E. coli. This activity is superior to the activity of both Ag and AgCl nanoparticles stabilized by the same surfactant. Thus, porous composite Ag/AgCl nanoparticles can be used as a multifunctional agent that is able to remove both pollutants and bacterium from water.

Fatigue of LiNi0.8Co0.15Al0.05O2 in commercial Li ion batteries

NASA Astrophysics Data System (ADS)

Kleiner, Karin; Dixon, Ditty; Jakes, Peter; Melke, Julia; Yavuz, Murat; Roth, Christina; Nikolowski, Kristian; Liebau, Verena; Ehrenberg, Helmut

2015-01-01

The degradation of LiNi0.8Co0.15Al0.05O2 (LNCAO), a cathode material in lithium-ion-batteries, was studied using in situ powder diffraction and in situ Ni K edge X-ray absorption spectroscopy (XAS). The fatigued material was taken from a 7 Ah battery which was cycled for 34 weeks under defined durability conditions. Meanwhile, a cell was stored, as reference, under controlled conditions without electrochemical treatment. The fatigued LNCAO used in this study showed a capacity loss of 26% ± 9% compared to the non-cycled material. During charge and discharge the local and the overall structure of LNCAO was investigated by X-ray near edge structure (XANES) analysis, the extended X-ray absorption fine structure (EXAFS) analysis and by using Rietveld refinement of in situ powder diffraction patterns. Both powder diffraction and XAS revealed additional, rhombohedral phases which do not change with electrochemical cycling. Moreover, a phase with the lattice parameters of fully lithiated LNCAO was still present in the fatigued material at high potentials, while it was absent in the non-fatigued reference material. The coexistence of these phases is described by domains within the LNCAO particles, in correlation with the observed fatigue.

Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

NASA Astrophysics Data System (ADS)

Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; Stavitski, Eli; Sadowski, Jerzy T.; Vescovo, Elio; Walter, Andrew; Attenkofer, Klaus; Stacchiola, Darío J.; Liu, Mingzhao

2017-12-01

Zinc oxide (ZnO) nanowire arrays have potential applications for various devices such as ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of the reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.

Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Danhua; Zhang, Wenrui; Cen, Jiajie

Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

Near band edge photoluminescence of ZnO nanowires: Optimization via surface engineering

DOE PAGES

Yan, Danhua; Zhang, Wenrui; Cen, Jiajie; ...

2017-12-04

Zinc oxide (ZnO) nanowire arrays have potential applications for various devices including ultra-violet light emitting diodes and lasers, where photoluminescence of intense near band edge emission without defect emissions is usually desired. Here, we demonstrate, counter-intuitively, that the near band edge emission may become dominant by introducing certain surface defects to ZnO nanowires via surface engineering. Specifically, near band edge emission (NBE) is effectively enhanced after a low pressure O 2 plasma treatment that sputters off surface oxygen species to produce a reduced and oxygen vacancy-rich surface. The effect is attributed to the lowered surface valence band maximum of themore » reduced ZnO surface that creates an accumulative band bending, which screens the photo-generated minority carriers (holes) from reaching or being trapped by the surface defects.« less

X-ray crystallographic and tungsten-183 nuclear magnetic resonance structural studies of the [M4(H2O)2(XW9O34) 2]10- heteropolyanions (M = COII or Zn, X = P or As)

USGS Publications Warehouse

Evans, H.T.; Tourne, C.M.; Tourne, G.F.; Weakley, T.J.R.

1986-01-01

The crystal structures of K10[Co4(H2O)2(PW9O 34)2]??22H2O (1) and isomorphous K10[Zn4(H2O)2(AsW9O 34)2]??23H2O (2) have been determined {Mo-K?? radiation, space group P21/n, Z = 2; (1) a = 15.794(2), b = 21.360(2), c = 12.312(1) A??, ?? = 91.96??, R = 0.084 for 3 242 observed reflections [I ??? 3??(I)]; (2) a = 15.842(4), b = 21.327(5), c = 12.308(4) A??, ?? = 92.42(4)??, R = 0.066 for 4 675 observed reflections [F ??? 3??(F)]}. The anions have crystallographic symmetry 1 and non-crystallographic symmetry very close to 2/m (C2h). Each consists of two [XW9O34]9- moieties [??-B isomers; X = P (1) or As (2)] linked via four CoIIO6 or ZnO6 groups. Two Co or Zn atoms each carry a water ligand. The 183W n.m.r. spectra of the anions [Zn4(H2O)2(XW9O34) 2]10- (X = P or As) confirm that the anions retain 2/m symmetry in aqueous solution. Homonuclear coupling constants between 183W atoms are 5.8-9.0 Hz for adjacent WO6 octahedra sharing edges, and 19.6-25.0 Hz for octahedra sharing corners.

Photoconductive ZnO Films Printed on Flexible Substrates by Inkjet and Aerosol Jet Techniques

NASA Astrophysics Data System (ADS)

Winarski, D. J.; Kreit, E.; Heckman, E. M.; Flesburg, E.; Haseman, M.; Aga, R. S.; Selim, F. A.

2018-02-01

Zinc oxide (ZnO) thin films have remarkable versatility in sensor applications. Here, we report simple ink synthesis and printing methods to deposit ZnO photodetectors on a variety of flexible and transparent substrates, including polyimide (Kapton), polyethylene terephthalate, cyclic olefin copolymer (TOPAS), and quartz. X-ray diffraction analysis revealed the dependence of the film orientation on the substrate type and sintering method, and ultraviolet-visible (UV-Vis) absorption measurements revealed a band edge near 380 nm. van der Pauw technique was used to measure the resistivity of undoped ZnO and indium/gallium-codoped ZnO (IGZO) films. IGZO films showed lower resistivity and larger average grain size compared with undoped ZnO films due to addition of In3+ and Ga3+, which act as donors. A 365-nm light-emitting diode was used to photoirradiate the films to study their photoconductive response as a function of light intensity at 300 K. The results revealed that ZnO films printed by aerosol jet and inkjet techniques exhibited five orders of magnitude photoconductivity, indicating that such films are viable options for use in flexible photodetectors.

XAFS measurements on zinc chloride aqueous solutions from ambient to supercritical conditions using the diamond anvil cell

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

1999-01-01

The structure and bonding properties of metal complexes in subcritical and supercritical fluids are still largely unknown. Conventional high pressure and temperature cell designs impose considerable limitations on the pressure, temperature, and concentration of metal salts required for measurements on solutions under supercritical conditions. In this study, we demonstrate the first application of the diamond anvil cell, specially designed for x-ray absorption studies of first-row transition metal ions in supercritical fluids. Zn K-edge XAFS spectra were measured from aqueous solutions of 1-2m ZnCl2 and up to 6m NaCl, at temperatures ranging from 25-660 ??C and pressures up to 800 MPa. Our results indicate that the ZnCl42- complex is predominant in the 1m ZnCl2/6m NaCl solution, while ZnCl2(H2O)2 is similarly predominant in the 2m ZnCl2 solution, at all temperatures and pressures. The Zn-Cl bond length of both types of chlorozinc(II) complexes was found to decrease at a rate of about 0.01 A??/100 ??C.

Microscopic processes ruling the bioavailability of Zn to roots of Euphorbia pithyusa L. pioneer plant.

PubMed

Medas, Daniela; De Giudici, Giovanni; Casu, Maria Antonietta; Musu, Elodia; Gianoncelli, Alessandra; Iadecola, Antonella; Meneghini, Carlo; Tamburini, Elena; Sprocati, Anna Rosa; Turnau, Katarzyna; Lattanzi, Pierfranco

2015-02-03

Euphorbia pithyusa L. was used in a plant growth-promoting assisted field trial experiment. To unravel the microscopic processes at the interface, thin slices of E. pithyusa roots were investigated by micro-X-ray fluorescence mapping. Roots and rhizosphere materials were examined by X-ray absorption spectroscopy at the Zn K-edge, X-ray diffraction, and scanning electron microscopy. Results indicate some features common to all the investigated samples. (i) In the rhizosphere of E. pithyusa, Zn was found to exist in different phases. (ii) Si and Al are mainly concentrated in a rim at the epidermis of the roots. (iii) Zn is mostly stored in root epidermis and does not appear to be coordinated to organic molecules but mainly occurs in mineral phases such as Zn silicates. We interpreted that roots of E. pithyusa significantly promote mineral evolution in the rhizosphere. Concomitantly, the plant uses Si and Al extracted by soil minerals to build a biomineralization rim, which can capture Zn. This Zn silicate biomineralization has relevant implications for phytoremediation techniques and for further biotechnology development, which can be better designed and developed after specific knowledge of molecular processes ruling mineral evolution and biomineralization processes has been gained.

XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

NASA Astrophysics Data System (ADS)

Vlasenko, Valery G.; Vasilchenko, Igor S.; Pirog, Irina V.; Shestakova, Tatiana E.; Uraev, Ali I.; Burlov, Anatolii S.; Garnovskii, Alexander D.

2007-02-01

Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 Å. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures.

SUT-NANOTEC-SLRI beamline for X-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klysubun, Wantana; Kidkhunthod, Pinit; Tarawarakarn, Pongjakr

2017-04-04

The SUT-NANOTEC-SLRI beamline was constructed in 2012 as the flagship of the SUT-NANOTEC-SLRI Joint Research Facility for Synchrotron Utilization, co-established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate-energy X-ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X-ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10 8to 2 × 10 10 photons s -1(100 mA) -1varying across photon energies. Details of the beamlinemore » and XAS instrumentation are described. To demonstrate the beamline performance,K-edge XANES spectra of MgO, Al 2O 3, S 8, FeS, FeSO 4, Cu, Cu 2O and CuO, and EXAFS spectra of Cu and CuO are presented.« less

Structure of Nano-sized CeO 2 Materials: Combined Scattering and Spectroscopic Investigations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I.

Here, the nature of nano-sized ceria, CeO 2, systems were investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction andtotal pair distribution functions (PDFs) revealed that in all the samples the occupancy of both Ce 4+ and O 2- are very close to the ideal stoichiometry, the analysis using reverse Monte Carlo technique revealedsignificant disorder around oxygen atoms in the nano sized ceria samples in comparison to the highly crystalline NIST standard.In addition, the analysis reveal that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributed to themore » particle size of the CeO 2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L 3– and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, are attributed to differences in particle size.« less

Structure of Nano-sized CeO 2 Materials: Combined Scattering and Spectroscopic Investigations

DOE PAGES

Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I.; ...

2016-08-29

Here, the nature of nano-sized ceria, CeO 2, systems were investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction andtotal pair distribution functions (PDFs) revealed that in all the samples the occupancy of both Ce 4+ and O 2- are very close to the ideal stoichiometry, the analysis using reverse Monte Carlo technique revealedsignificant disorder around oxygen atoms in the nano sized ceria samples in comparison to the highly crystalline NIST standard.In addition, the analysis reveal that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributed to themore » particle size of the CeO 2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L 3– and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, are attributed to differences in particle size.« less

Synthesis and characterization of three-dimensional transition metal ions doped zinc oxide based dilute magnetic semiconductor thin films

NASA Astrophysics Data System (ADS)

Samanta, Kousik

Dilute magnetic semiconductors (DMS), especially 3d-transition metal (TM) doped ZnO based DMS materials are the most promising candidates for optoelectronics and spintronics applications; e.g. in spin light emitting diode (SLED), spin transistors, and spin field effect transistors (SFET), etc. In the present dissertation, thin films of Zn1-xTMxO (TM = Co2+, Cu2+, and Mn2+) were grown on (0001) oriented Al2O3 substrates by pulsed laser deposition (PLD) technique. The films were highly c-axis oriented, nearly single crystalline, and defects free for a limited concentration of the dilution of transition metal ions. In particular, we have obtained single crystalline phases of Zn1-xTMxO thin films for up to 10, 3, and 5 stoichiometric percentages of Co2+, Cu2+, and Mn2+ respectively. Raman micro-probe system was used to understand the structural and lattice dynamical properties at different physical conditions. The confinement of optical phonons in the disorder lattice was explained by alloy potential fluctuation (APF) using a spatial correlation (SC) model. The detailed analysis of the optical phonon behavior in disorder lattice confirmed the substitution of the transition metal ions in Zn 2+ site of the ZnO host lattice. The secondary phases of ZnCo 2O4, CuO, and ZnMn2O4 were detected in higher Co, Cu, and Mn doped ZnO thin films respectively; where as, XRD did not detect these secondary phases in the same samples. Room temperature ferromagnetism was observed in Co2+ and Cu2+ ions doped ZnO thin films with maximum saturation magnetization (Ms) of 1.0 and 0.76 muB respectively. The origin of the observed ferromagnetism in Zn1-xCoxO thin films was tested by the controlled introduction of shallow donors (Al) in Zn0.9-x Co0.1O:Alx (x = 0.005 and 0.01) thin films. The saturation magnetization for the 10% Co-doped ZnO (1.0 muB /Co) at 300K reduced (˜0.25 muB/Co) due to Al doping. The observed ferromagnetism and the reduction due to Al doping can be explained by the Bound Magnetic Polaron (BMP) model. The Resistivity of ZCO sample (˜ 103 O-cm) dropped by 5 orders of magnitude (0.02 O-cm) in Co, Al co-doped samples and the carrier concentrations increases 4 orders of magnitude (˜ 1019/cm3). The Cu2+ doped ZnO thin films showed the ferromagnetic property at 300K. The p-d orbital mixing of high spin Cu2+ (d9) state with the nearest neighbor oxygen p-orbital can explain the origin of RTFM in Zn 1-xCuxO thin films. The optical transmission spectroscopy and the photoluminescence spectroscopy analysis were used to understand the electronic band structure, near band edge (NBE) transition, and the excitonic behavior in ZnO and Zn1-xTMxO thin films. We have found the reduction of NBE transition at 300K due to the substitution of Co and Cu in ZnO host lattice. This narrowing of the optical band gap (NBE) is due to the sp-d exchange interaction between the d electrons of transition metal ions and the band electrons of ZnO; the strength of this interaction strongly depends on the number of d electrons. The s-d and p-d exchanges give rise to negative and positive corrections to the conduction and valance band edges respectively, leading to the NBE narrowing. We have observed the characteristic inter atomic d-d transitions in Co doped samples; thus confirming the substitution of Co2+ in the tetrahedral site in ZnO. The low temperature (77K) PL spectrum showed the basic excitonic characteristics of pure ZnO in Zn1-xTMxO thin films. The X-ray photoelectron spectroscopy (XPS) showed that the Co and Cu are normally in 2+ oxidation state, but in the case of higher Cu concentrations (>3%), the mixed state of Cu2+ and Cu1+ were detected.

Ti-doped ZnO Thin Films Prepared at Different Ambient Conditions: Electronic Structures and Magnetic Properties

PubMed Central

Yong, Zhihua; Liu, Tao; Uruga, Tomoya; Tanida, Hajime; Qi, Dongchen; Rusydi, Andrivo; Wee, Andrew T. S.

2010-01-01

We present a comprehensive study on Ti-doped ZnO thin films using X-ray Absorption Fine Structure (XAFS) spectroscopy. Ti K edge XAFS spectra were measured to study the electronic and chemical properties of Ti ions in the thin films grown under different ambient atmospheres. A strong dependence of Ti speciation, composition, and local structures upon the ambient conditions was observed. The XAFS results suggest a major tetrahedral coordination and a 4+ valence state. The sample grown in a mixture of 80% Ar and 20% O2 shows a portion of precipitates with higher coordination. A large distortion was observed by the Ti substitution in the ZnO lattice. Interestingly, the film prepared in 80% Ar, 20% O2 shows the largest saturation magnetic moment of 0.827 ± 0.013 µB/Ti.

Micro-, to nano-structural relationships in natural serpentines, derived from cationic substitutions.

NASA Astrophysics Data System (ADS)

Munoz, M.; Farges, F.; Andreani, M.; Ulrich, M.; Marcaillou, C.; Mathon, O.

2014-12-01

The understanding of the crystal chemistry of serpentine minerals (incl. antigorite, lizardite and chrysotile) is fundamental since serpentinization processes concern very large scientific domains: e.g., natural abiotic hydrogen production (Marcaillou et al., 2011), origins of life (Russell et al., 2010), fluid properties and mobility of metals in subduction zones (Kelley and Cottrell, 2009). This study aims at characterizing relations between the micro-, and nano-structures of the most abundant serpentine polytypes in the oceanic crust. Serpentine theoretical formula is Mg3Si2O5(OH)4 but several natural substitutions are possible and the formula may be written such as: (Mg,Fe2+,Fe3+,Al)3(Si,Al,Fe3+)2O5(OH)4; showing that Fe and Al may play an important role in the crystallization of serpentines. Preliminary crystal chemistry studies, suggest that, 1) the Al content alone cannot be directly correlated to serpentine polytypes (Andreani et al., 2008), 2) the amounts of tetrahedral iron can be significant in the presence of ferric iron (Marcaillou et al., 2011). Because magnetite is usually associated to serpentine, the Fe-speciation characterization of serpentine is delicate. Here, we provide the study of 33 magnetite-free serpentines containing various amounts of Fe and Al. The samples were characterized by SEM, Raman, XRF, as well as XANES, pre-edge, and EXAFS spectroscopy at the Fe K-edge. XANES experimental data were crosschecked and interpreted thanks to ab initio calculations and EXAFS shell-fitting. Also, preliminary 27Al-RMN data is presented. Results suggest relationships between the type and amount of substitution of trivalent cations in minerals, and the microstructures observed. Chrysotile incorporates less trivalent cations than other varieties, which tends to preserve the so-called misfit between the TO layers, and therefore the tubular structure of the mineral. Lizardites mainly involve Fe/Al Tschermak-type substitutions, while M-site vacancy charge-compensation mechanisms could be favored for antigorite crystals. ReferencesAndréani et al., 2008, European Journal of Mineralogy, 20, 159-171. Kelley and Cottrell, 2009, Science, 325, 605-607. Marcaillou et al., 2011, Earth And Planetary Science Letters, 303, 281-290. Russell et al., 2010, Geobiology, 8, 355-371.

Development of XAFS Into a Structure Determination Technique

NASA Astrophysics Data System (ADS)

Stern, E. A.

After the detection of diffraction of x-rays by M. Laue in 1912, the technique was soon applied to structure determination by Bragg within a year. On the other hand, although the edge steps in X-Ray absorption were discovered even earlier by Barkla and both the near edge (XANES) and extended X-Ray fine structure (EXAFS) past the edge were detected by 1929, it still took over 40 years to realize the structure information contained in this X-Ray absorption fine structure (XAFS). To understand this delay a brief historical review of the development of the scientific ideas that transformed XAFS into the premiere technique for local structure determination is given. The development includes both advances in theoretical understanding and calculational capabilities, and in experimental facilities, especially synchrotron radiation sources. The present state of the XAFS technique and its capabilities are summarized.

[Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing

NASA Astrophysics Data System (ADS)

Frank, Patrick; Benfatto, Maurizio; Qayyum, Munzarin

2018-05-01

High resolution (k = 18 Å-1 or k = 17 Å-1) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)]2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×Oeq = 1.97 Å, Oax1 = 2.22 Å, and Oax2 = 2.34 Å, plus a second-shell of 4×Owater = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)]2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H2O = 1.95 Å and 1×H2O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H2O = 1.94 ± 0.04 Å and H2Oax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H2O = 1.94, H2Oax1 = 2.14 Å, and H2Oax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H2O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)]2+ in 1,5-P prior to freezing revealed the same structures as previously found in aqueous 1M HClO4, which have become axially compressed in the frozen glasses. [Cu(aq)]2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu-O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the dx2-y2, dz2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)]2+ should thus be abandoned in favor of square pyramidal [Cu(H2O)5]2+. The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. The plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.

Role of the node in controlling traffic of cadmium, zinc, and manganese in rice

PubMed Central

Yamaguchi, Noriko; Ishikawa, Satoru; Abe, Tadashi; Baba, Koji; Terada, Yasuko

2012-01-01

Heavy metals are transported to rice grains via the phloem. In rice nodes, the diffuse vascular bundles (DVBs), which enclose the enlarged elliptical vascular bundles (EVBs), are connected to the panicle and have a morphological feature that facilitates xylem-to-phloem transfer. To find a mechanism for restricting cadmium (Cd) transport into grains, the distribution of Cd, zinc (Zn), manganese (Mn), and sulphur (S) around the vascular bundles in node I (the node beneath the panicle) of Oryza sativa ‘Koshihikari’ were compared 1 week after heading. Elemental maps of Cd, Zn, Mn, and S in the vascular bundles of node I were obtained by synchrotron micro-X-ray fluorescence spectrometry and electron probe microanalysis. In addition, Cd K-edge microfocused X-ray absorption near-edge structure analyses were used to identify the elements co-ordinated with Cd. Both Cd and S were mainly distributed in the xylem of the EVB and in the parenchyma cell bridge (PCB) surrounding the EVB. Zn accumulated in the PCB, and Mn accumulated around the protoxylem of the EVB. Cd was co-ordinated mainly with S in the xylem of the EVB, but with both S and O in the phloem of the EVB and in the PCB. The EVB in the node retarded horizontal transport of Cd toward the DVB. By contrast, Zn was first stored in the PCB and then efficiently transferred toward the DVB. Our results provide evidence that transport of Cd, Zn, and Mn is differentially controlled in rice nodes, where vascular bundles are functionally interconnected. PMID:22291135

New CVD-based method for the growth of high-quality crystalline zinc oxide layers

NASA Astrophysics Data System (ADS)

Huber, Florian; Madel, Manfred; Reiser, Anton; Bauer, Sebastian; Thonke, Klaus

2016-07-01

High-quality zinc oxide (ZnO) layers were grown using a new chemical vapour deposition (CVD)-based low-cost growth method. The process is characterized by total simplicity, high growth rates, and cheap, less hazardous precursors. To produce elementary zinc vapour, methane (CH4) is used to reduce a ZnO powder. By re-oxidizing the zinc with pure oxygen, highly crystalline ZnO layers were grown on gallium nitride (GaN) layers and on sapphire substrates with an aluminum nitride (AlN) nucleation layer. Using simple CH4 as precursor has the big advantage of good controllability and the avoidance of highly toxic gases like nitrogen oxides. In photoluminescence (PL) measurements the samples show a strong near-band-edge emission and a sharp line width at 5 K. The good crystal quality has been confirmed in high resolution X-ray diffraction (HRXRD) measurements. This new growth method has great potential for industrial large-scale production of high-quality single crystal ZnO layers.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.

K-Shell Photoabsorption and Photoionisation of Trace Elements I. Isoelectronic Sequences With Electron Number 3< or = N < or = 11

NASA Technical Reports Server (NTRS)

Palmeri, P.; Quinet, P.; Mendoza, C.; Bautista, M. A.; Witthoeft, M. C.; Kallman, T. R.

2016-01-01

Context. With the recent launching of the Hitomi X-ray space observatory, K lines and edges of chemical elements with low cosmic abundances, namely F, Na, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu and Zn, can be resolved and used to determine important properties of supernova remnants, galaxy clusters and accreting black holes and neutron stars.Aims. The second stage of the present ongoing project involves the computation of the accurate photoabsorption and photoionisation cross sections required to interpret the X-ray spectra of such trace elements.Methods. Depending on target complexity and computer tractability, ground-state cross sections are computed either with the close-coupling Breit-Pauli R-matrix method or with the autostructure atomic structure code in the isolated-resonance approximation. The intermediate-coupling scheme is used whenever possible. In order to determine a realistic K-edge behaviour for each species, both radiative and Auger dampings are taken into account, the latter being included in the R-matrix formalism by means of an optical potential.Results. Photoabsorption and total and partial photoionisation cross sections are reported for isoelectronic sequences with electron numbers 3< or = N< or = 11. The Na sequence (N=11) is used to estimate the contributions from configurations with a 2s hole (i.e. [2s]) and those containing 3d orbitals, which will be crucial when considering sequences with N 11.Conclusions. It is found that the [2s/u] configurations must be included in the target representations of species with N> 11 as they contribute significantly to the monotonic background of the cross section between the L and K edges. Configurations with 3d orbitals are important in rendering an accurate L edge, but they can be practically neglected in the K-edge region.

An EXAFS study on the so-called {open_quotes}Co-Mo-S{close_quotes} phase in Co/C and CoMo/C, compared with a Moessbauer emission spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Craje, M.W.J.; Kraan, A.M. van der; Louwers, S.P.A.

1992-06-25

EXAFS was used in this paper to study 4 sulfided catalysts that have the same structure as their {sup 57}Co counterparts characterized by Mossbauer emission spectroscopy. The {open_quotes}Co-Mo-S{close_quotes} phase in Co/C is similar to CoMo/C due to a very highly dispersed Co species. Without Mo, the sulfidic Co results in a Co{sub 9}S{sub 8} phase during sulfidation at 673K, Mo prevents Co sintering in CoMo/C. 37 refs., 6 figs., 2 tabs.

Nicotianamine forms complexes with Zn(II) in vivo.

PubMed

Trampczynska, Aleksandra; Küpper, Hendrik; Meyer-Klaucke, Wolfram; Schmidt, Holger; Clemens, Stephan

2010-01-01

The non-proteinogenic amino acid nicotianamine (NA) is a major player in plant metal homeostasis. It is known to form complexes with different transition metals in vitro. Available evidence associates NA with translocation of Fe, and possibly other micronutrients, to and between different plant cells and tissues. To date, however, it is still extremely challenging to detect metal-ligand complexes in vivo because tissue disruption immediately changes the chemical environment and thereby the availability of binding partners. In order to overcome this limitation we used various Schizosaccharomyces pombe strains expressing a plant NAS gene to study formation of metal-NA complexes in vivo. Tolerance, accumulation and competition data clearly indicated formation of Zn(ii)-NA but not of Cu(ii)-NA complexes. Zn(ii)-NA was then identified by X-ray absorption spectroscopy (XAS). About half of the cellular Zn was found to be bound by NA in NAS-expressing cells while no NA-like ligands were detected by XAS in control cells not expressing NAS. Given the high conservation of eukaryotic metal homeostasis components, these results strongly suggest the possible existence of Zn(ii)-NA complexes also in planta. Reported observations implicating NA in plant Zn homeostasis would then indeed be attributable to direct interaction of Zn(ii) with NA rather than only indirectly to perturbations in Fe metabolism. Re-evaluation of extended X-ray absorption fine structure (EXAFS) spectra for the Zn hyperaccumulator Thlaspi caerulescens showed that NA is as expected not a major storage ligand for Zn. Instead it is hypothesized to be involved in efficient translocation of Zn to above-ground tissues in hyperaccumulators.

Many-particle-effects in the theory of the extended X-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Tran Thoai, D. B.; Ekardt, W.

1981-10-01

The Lee-Beni-procedure for the calculation of the extended X-ray absorption fine structure (EXAFS) is extended so as to include the effects of the electronic charge density outside the localized muffin-tin potentials. In our scheme EXAFS is caused by back-scattering of an elementary excitation of a homogeneous electron gas by localized energy dependent many-particle muffin-tin potentials. The difference between the two schemes is negligible at large k's, as expected from physical grounds. However, at small and intermediate k-values the difference is quite large. The effect of the outer electrons as compared to the Lee-Beni-model is twofold. First, they renormalize the scattered electron in the usual way. Second, they are missing within the scattering muffin-tins. Hence, we avoid to count some of the electrons twice. Results are presented for Cu as an example.

Determination of copper binding in Pseudomonas putida CZ1 by chemical modifications and X-ray absorption spectroscopy.

PubMed

Chen, XinCai; Shi, JiYan; Chen, YingXu; Xu, XiangHua; Chen, LiTao; Wang, Hui; Hu, TianDou

2007-03-01

Previously performed studies have shown that Pseudomonas putida CZ1 biomass can bind an appreciable amount of Cu(II) and Zn(II) ions from aqueous solutions. The mechanisms of Cu- and Zn-binding by P. putida CZ1 were ascertained by chemical modifications of the biomass followed by Fourier transform infrared and X-ray absorption spectroscopic analyses of the living or nonliving cells. A dramatic decrease in Cu(II)- and Zn(II)-binding resulted after acidic methanol esterification of the nonliving cells, indicating that carboxyl functional groups play an important role in the binding of metal to the biomaterial. X-ray absorption spectroscopy was used to determine the speciation of Cu ions bound by living and nonliving cells, as well as to elucidate which functional groups were involved in binding of the Cu ions. The X-ray absorption near-edge structure spectra analysis showed that the majority of the Cu was bound in both samples as Cu(II). The fitting results of Cu K-edge extended X-ray absorption fine structure spectra showed that N/O ligands dominated in living and nonliving cells. Therefore, by combining different techniques, our results indicate that carboxyl functional groups are the major ligands responsible for the metal binding in P. putida CZ1.

An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

PubMed Central

Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

1982-01-01

Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

Deep-Ultraviolet Luminescence of Rocksalt-Structured Mg x Zn1-x O (x > 0.5) Films on MgO Substrates

NASA Astrophysics Data System (ADS)

Kaneko, Kentaro; Tsumura, Keiichi; Ishii, Kyohei; Onuma, Takayoshi; Honda, Tohru; Fujita, Shizuo

2018-04-01

Rocksalt-structured Mg x Zn1-x O films with Mg composition x of 0.47, 0.57, and 0.64 were grown on (100)-oriented MgO substrates using mist chemical vapor deposition. Cathodoluminescence measurements showed deep ultraviolet (DUV) emission peaking at 4.88 eV (254 nm), 5.15 eV (241 nm), and 5.21 eV (238 nm), respectively, at 12 K. The peak energies were lower than the band gap energies by ca. 1 eV, suggesting that the deep ultraviolet (DUV) emission may be recognized as near band edge luminescence but is associated with impurities, defects, or band fluctuations. The use of carbon-free precursors in the growth is suggested to eliminate carbon impurities and to improve the optical properties of Mg x Zn1-x O.

Detection of uranium and chemical state analysis of individual radioactive microparticles emitted from the Fukushima nuclear accident using multiple synchrotron radiation X-ray analyses.

PubMed

Abe, Yoshinari; Iizawa, Yushin; Terada, Yasuko; Adachi, Kouji; Igarashi, Yasuhito; Nakai, Izumi

2014-09-02

Synchrotron radiation (SR) X-ray microbeam analyses revealed the detailed chemical nature of radioactive aerosol microparticles emitted during the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, resulting in better understanding of what occurred in the plant during the early stages of the accident. Three spherical microparticles (∼2 μm, diameter) containing radioactive Cs were found in aerosol samples collected on March 14th and 15th, 2011, in Tsukuba, 172 km southwest of the FDNPP. SR-μ-X-ray fluorescence analysis detected the following 10 heavy elements in all three particles: Fe, Zn, Rb, Zr, Mo, Sn, Sb, Te, Cs, and Ba. In addition, U was found for the first time in two of the particles, further confirmed by U L-edge X-ray absorption near-edge structure (XANES) spectra, implying that U fuel and its fission products were contained in these particles along with radioactive Cs. These results strongly suggest that the FDNPP was damaged sufficiently to emit U fuel and fission products outside the containment vessel as aerosol particles. SR-μ-XANES spectra of Fe, Zn, Mo, and Sn K-edges for the individual particles revealed that they were present at high oxidation states, i.e., Fe(3+), Zn(2+), Mo(6+), and Sn(4+) in the glass matrix, confirmed by SR-μ-X-ray diffraction analysis. These radioactive materials in a glassy state may remain in the environment longer than those emitted as water-soluble radioactive Cs aerosol particles.

Sorption of Ferric Iron from Ferrioxamine B to Synthetic and Biogenic Layer Type Manganese Oxides

NASA Astrophysics Data System (ADS)

Duckworth, O.; John, B.; Sposito, G.

2006-12-01

Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effects of predominantly Mn(IV) oxides, we studied the sorption reaction of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(III, IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over at pH 8. After 72 hours equilibration time, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the EXAFS spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to into the mineral structure at multiple sites with no evidence of DFOB complexation, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron in marine and terrestrial environments.

Removal of Ca 2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn 4O 5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

DOE PAGES

Lohmiller, Thomas; Shelby, Megan L.; Long, Xi; ...

2015-05-19

We studied Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4O 5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1') and S 2 (S 2') states, the S 2'Y Z• state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mnmore » K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z• (D1-Tyr161).« less

Removal of Ca(2+) from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study.

PubMed

Lohmiller, Thomas; Shelby, Megan L; Long, Xi; Yachandra, Vittal K; Yano, Junko

2015-10-29

Ca(2+)-depleted and Ca(2+)-reconstituted spinach photosystem II was studied using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca(2+) ion in the Mn4O5Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca(2+)-depleted S1 (S1') and S2 (S2') states, the S2'YZ(•) state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca(2+)-reconstituted S1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca(2+)-depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca(2+)-containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca(2+) ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca(2+) ion in the OEC is not critical for structural maintenance of the cluster, at least in the S1 and S2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca(2+) removal are discussed, attributing to the Ca(2+) ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to YZ(•) (D1-Tyr161).

Photoluminescence and positron annihilation spectroscopic investigation on a H+ irradiated ZnO single crystal

NASA Astrophysics Data System (ADS)

Sarkar, A.; Chakrabarti, Mahuya; Sanyal, D.; Bhowmick, D.; Dechoudhury, S.; Chakrabarti, A.; Rakshit, Tamita; Ray, S. K.

2012-08-01

Low temperature photoluminescence and room temperature positron annihilation spectroscopy have been employed to investigate the defects incorporated by 6 MeV H+ ions in a hydrothermally grown ZnO single crystal. Prior to irradiation, the emission from donor bound excitons is at 3.378 eV (10 K). The irradiation creates an intense and narrow emission at 3.368 eV (10 K). The intensity of this peak is nearly four times that of the dominant near band edge peak of the pristine crystal. The characteristic features of the 3.368 eV emission indicate its origin as a ‘hydrogen at oxygen vacancy’ type defect. The positron annihilation lifetime measurement reveals a single component lifetime spectrum for both the unirradiated (164 ± 1 ps) and irradiated crystal (175 ± 1 ps). It reflects the fact that the positron lifetime and intensity of the new irradiation driven defect species are a little higher compared to those in the unirradiated crystal. However, the estimated defect concentration, even considering the high dynamic defect annihilation rate in ZnO, comes out to be ˜4 × 1017 cm-3 (using SRIM software). This is a very high defect concentration compared to the defect sensitivity of positron annihilation spectroscopy. A probable reason is the partial filling of the incorporated vacancies (positron traps), which in ZnO are zinc vacancies. The positron lifetime of ˜175 ps (in irradiated ZnO) is consistent with recent theoretical calculations for partially hydrogen-filled zinc vacancies in ZnO. Passivation of oxygen vacancies by hydrogen is also reflected in the photoluminescence results. A possible reason for such vacancy filling (at both Zn and O sites) due to irradiation has also been discussed.

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

Solvation structure of the halides from x-ray absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

2016-07-28

Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

NASA Astrophysics Data System (ADS)

Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

2009-04-01

Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of trioctahedral Mg-clay minerals. Alternative models assuming other elements (Ni, Al, Fe) in addition to Mg in the second shell could not be fitted successfully. Aqueous concentration data were used to calculate the speciation of the leaching solutions. Saturation index (SI) calculations indicate undersaturation with respect to NiCO 3 and NiSO 4·7H 2O, but oversaturation with respect to β-Ni(OH) 2. The latter result is probably due to the omission of Ni borate and Ni silicate complexes in the speciation calculations, for which formation constants are not available. With the help of estimation techniques, we could infer that such complexes would dominate the Ni speciation and consequently reduce the SI below the saturation of β-Ni(OH) 2. The μ-XRF maps show that Cs is uniformly distributed in the MW glass, since no region with high Cs concentration could be detected. The Cs L III-edge μ-XAS spectra were all very similar independently of the degree of alteration, indicating similar coordination environments of Cs in the core regions of the glass as well as in the secondary clays. These spectra largely differ from that measured for pollucite (a potential secondary Cs-phase in altered glasses) implying that the coordination environments of Cs in the MW glass and in pollucite are fundamentally different. The present study shows that μ-XRF and μ-XAS are essential tools in determining the fate and the retention mechanisms of radionuclides released from nuclear waste during aqueous alteration. Our spectroscopic analyses allowed us to exclude formation of specific Ni and Cs secondary solids (e.g. nepouite, β-Ni(OH) 2, pollucite) during the aqueous alteration. Ni and Cs are instead distributed as trace elements in the alteration phases formed by major elements during the leaching process. Our results imply that solid solution and/or adsorption equilibria, rather than pure phase solubility equilibria, are the adequate chemical models to determine Ni and Cs aqueous concentrations in performance assessments for radioactive waste repositories.

ZnO Nanoparticles Affect Bacillus subtilis Cell Growth and Biofilm Formation.

PubMed

Hsueh, Yi-Huang; Ke, Wan-Ju; Hsieh, Chien-Te; Lin, Kuen-Song; Tzou, Dong-Ying; Chiang, Chao-Lung

2015-01-01

Zinc oxide nanoparticles (ZnO NPs) are an important antimicrobial additive in many industrial applications. However, mass-produced ZnO NPs are ultimately disposed of in the environment, which can threaten soil-dwelling microorganisms that play important roles in biodegradation, nutrient recycling, plant protection, and ecological balance. This study sought to understand how ZnO NPs affect Bacillus subtilis, a plant-beneficial bacterium ubiquitously found in soil. The impact of ZnO NPs on B. subtilis growth, FtsZ ring formation, cytosolic protein activity, and biofilm formation were assessed, and our results show that B. subtilis growth is inhibited by high concentrations of ZnO NPs (≥ 50 ppm), with cells exhibiting a prolonged lag phase and delayed medial FtsZ ring formation. RedoxSensor and Phag-GFP fluorescence data further show that at ZnO-NP concentrations above 50 ppm, B. subtilis reductase activity, membrane stability, and protein expression all decrease. SDS-PAGE Stains-All staining results and FT-IR data further demonstrate that ZnO NPs negatively affect exopolysaccharide production. Moreover, it was found that B. subtilis biofilm surface structures became smooth under ZnO-NP concentrations of only 5-10 ppm, with concentrations ≤ 25 ppm significantly reducing biofilm formation activity. XANES and EXAFS spectra analysis further confirmed the presence of ZnO in co-cultured B. subtilis cells, which suggests penetration of cell membranes by either ZnO NPs or toxic Zn+ ions from ionized ZnO NPs, the latter of which may be deionized to ZnO within bacterial cells. Together, these results demonstrate that ZnO NPs can affect B. subtilis viability through the inhibition of cell growth, cytosolic protein expression, and biofilm formation, and suggest that future ZnO-NP waste management strategies would do well to mitigate the potential environmental impact engendered by the disposal of these nanoparticles.

ZnO Nanoparticles Affect Bacillus subtilis Cell Growth and Biofilm Formation

PubMed Central

Hsueh, Yi-Huang; Ke, Wan-Ju; Hsieh, Chien-Te; Lin, Kuen-Song; Tzou, Dong-Ying; Chiang, Chao-Lung

2015-01-01

Zinc oxide nanoparticles (ZnO NPs) are an important antimicrobial additive in many industrial applications. However, mass-produced ZnO NPs are ultimately disposed of in the environment, which can threaten soil-dwelling microorganisms that play important roles in biodegradation, nutrient recycling, plant protection, and ecological balance. This study sought to understand how ZnO NPs affect Bacillus subtilis, a plant-beneficial bacterium ubiquitously found in soil. The impact of ZnO NPs on B. subtilis growth, FtsZ ring formation, cytosolic protein activity, and biofilm formation were assessed, and our results show that B. subtilis growth is inhibited by high concentrations of ZnO NPs (≥ 50 ppm), with cells exhibiting a prolonged lag phase and delayed medial FtsZ ring formation. RedoxSensor and Phag-GFP fluorescence data further show that at ZnO-NP concentrations above 50 ppm, B. subtilis reductase activity, membrane stability, and protein expression all decrease. SDS-PAGE Stains-All staining results and FT-IR data further demonstrate that ZnO NPs negatively affect exopolysaccharide production. Moreover, it was found that B. subtilis biofilm surface structures became smooth under ZnO-NP concentrations of only 5–10 ppm, with concentrations ≤ 25 ppm significantly reducing biofilm formation activity. XANES and EXAFS spectra analysis further confirmed the presence of ZnO in co-cultured B. subtilis cells, which suggests penetration of cell membranes by either ZnO NPs or toxic Zn+ ions from ionized ZnO NPs, the latter of which may be deionized to ZnO within bacterial cells. Together, these results demonstrate that ZnO NPs can affect B. subtilis viability through the inhibition of cell growth, cytosolic protein expression, and biofilm formation, and suggest that future ZnO-NP waste management strategies would do well to mitigate the potential environmental impact engendered by the disposal of these nanoparticles. PMID:26039692

Unoccupied states in Cu and Zn octaethyl-porphyrin and phthalocyanine.

PubMed

Cook, Peter L; Yang, Wanli; Liu, Xiaosong; García-Lastra, Juan María; Rubio, Angel; Himpsel, F J

2011-05-28

Copper and zinc phthalocyanines and porphyrins are used in organic light emitting diodes and dye-sensitized solar cells. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Cu 2p and Zn 2p edges, the unoccupied valence states at the Cu and Zn atoms are probed and decomposed into 3d and 4s contributions with the help of density functional calculations. A comparison with the N 1s edge provides the 2p states of the N atoms surrounding the metal, and a comparison with inverse photoemission provides a combined density of states. © 2011 American Institute of Physics

Analytical electron microscopy as a powerful tool in plant cell biology: examples using electron energy loss spectroscopy and X-ray microanalysis.

PubMed

Lichtenberger, O; Neumann, D

1997-08-01

Energy filtering transmission electron microscopy in combination with energy dispersive X-ray analysis (EDX) and quantumchemical calculations opens new possibilities for elemental and bone analysis at the ultrastructural level. The possibilities and limitations of these methods, applied to botanical samples, are discussed and some examples are given. Ca-oxalate crystals in plant cell vacuoles show a specific C K-edge in the electron energy loss spectrum (EELS), which allows a more reliable identification than light microscopical or cytochemical methods. In some dicots crystalline inclusions can be observed in different cell compartments, which are identified as silicon dioxide or calcium silicate by the fine structure of the Si L2,3-edge. Their formation is discussed on the basis of EEL-spectra and quantumchemical calculations. Examples concerning heavy metal detoxification are given for some tolerant plants. In Minuartia Zn is bound as Zn-silicate in cell walls; Armeria accumulates Cu in leaf idioblasts by chelation with phenolic compounds and Cd is precipitated as CdS/phytochelatin-complexes in tomato.

The molecular structure of the isopoly complex ion, decavanadate (V10O286-)

USGS Publications Warehouse

Evans, H.T.

1966-01-01

The structure of the decavanadate ion V10O286- has been found by a determination of the crystal structure of K2Zn2V10O28?? 16H2O. The soluble, orange crystals are triclinic with space group P1 and have a unit cell with a = 10.778 A, b = 11.146 A, c = 8.774 A, ?? = 104?? 57???, ?? = 109?? 3???', and ?? = 65?? 0??? (Z = 1). The structure was solved from a three-dimensional Patterson map based on 5143 Weissenberg-film data. The full-matrix, least-squares refinement gave R = 0.094 and ?? for V-O bond lengths of 0.008 A. The unit cell contains one V10O286- unit, two Zn(H2O)62+ groups, two K+ ions, and four additional water molecules. The decavanadate ion is an isolated group of ten condensed VO6 octahedra, six in a rectangular 2 x 3 array sharing edges, and four more, two fitted in above and two below by sharing sloping edges. The structure, which is based on a sodium-chloride-like arrangement of V and O atoms, has a close relationship to other isopoly complex molybdates, niobates, and tantalates. Strong distortions in the VO6 octahedra are analogous to square-pyramid and other special coordination features known in other vanadate structures.

Composition and hydrophilicity control of Mn-doped ferrite (MnxFe3-xO4) nanoparticles induced by polyol differentiation.

PubMed

Vamvakidis, Kosmas; Katsikini, Maria; Vourlias, George; Angelakeris, Mavroeidis; Paloura, Eleni C; Dendrinou-Samara, Catherine

2015-03-28

Manganese doped ferrite (MnxFe3-xO4) nanoparticles with x = 0.29-0.77 were prepared under solvothermal conditions in the presence solely of a polyol using the trivalent manganese and iron acetylacetonates as precursors. In this facile approach, a variety of polyols such as polyethylene glycol (PEG 8000), tetraethylene glycol (TEG), propylene glycol (PG) and a mixture of TEG and PG (1 : 1) were utilized in a triple role as a solvent, a reducing agent and a surface-functionalizing agent. The composition of the fine cubic-spinel structures was found to be related to the reductive ability of each polyol, while determination of structural characteristics plus the inversion parameter (i = 0.18-0.38) were provided by X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy at both the Fe and Mn K-edges. The saturation magnetization increased up to 80 emu g(-1) when x = 0.35 and i = 0.22. In addition, the as-prepared nanocrystals coated with PEG, PG and PG&TEG showed excellent colloidal stability in water, while the TEG-coated particles were not water dispersible and converted to hydrophilic when were extra PEGylated. Measurements of the (1)H NMR relaxation in water were carried out and the nanoprobes were evaluated as potential contrast agents.

Trichomes of Tobacco Excrete Zinc as Zinc-Substituted Calcium Carbonate and Other Zinc-Containing Compounds1[W

PubMed Central

Sarret, Géraldine; Harada, Emiko; Choi, Yong-Eui; Isaure, Marie-Pierre; Geoffroy, Nicolas; Fakra, Sirine; Marcus, Matthew A.; Birschwilks, Mandy; Clemens, Stephan; Manceau, Alain

2006-01-01

Tobacco (Nicotiana tabacum L. cv Xanthi) plants were exposed to toxic levels of zinc (Zn). Zn exposure resulted in toxicity signs in plants, and these damages were partly reduced by a calcium (Ca) supplement. Confocal imaging of intracellular Zn using Zinquin showed that Zn was preferentially accumulated in trichomes. Exposure to Zn and Zn + Ca increased the trichome density and induced the production of Ca/Zn mineral grains on the head cells of trichomes. These grains were aggregates of submicrometer-sized crystals and poorly crystalline material and contained Ca as major element, along with subordinate amounts of Zn, manganese, potassium, chlorine, phosphorus, silicon, and magnesium. Micro x-ray diffraction revealed that the large majority of the grains were composed essentially of metal-substituted calcite (CaCO3). CaCO3 polymorphs (aragonite and vaterite) and CaC2O4 (Ca oxalate) mono- and dihydrate also were identified, either as an admixture to calcite or in separate grains. Some grains did not diffract, although they contained Ca, suggesting the presence of amorphous form of Ca. The presence of Zn-substituted calcite was confirmed by Zn K-edge micro-extended x-ray absorption fine structure spectroscopy. Zn bound to organic compounds and Zn-containing silica and phosphate were also identified by this technique. The proportion of Zn-substituted calcite relative to the other species increased with Ca exposure. The production of Zn-containing biogenic calcite and other Zn compounds through the trichomes is a novel mechanism involved in Zn detoxification. This study illustrates the potential of laterally resolved x-ray synchrotron radiation techniques to study biomineralization and metal homeostasis processes in plants. PMID:16731580

Model for determination of mid-gap states in amorphous metal oxides from thin film transistors

NASA Astrophysics Data System (ADS)

Bubel, S.; Chabinyc, M. L.

2013-06-01

The electronic density of states in metal oxide semiconductors like amorphous zinc oxide (a-ZnO) and its ternary and quaternary oxide alloys with indium, gallium, tin, or aluminum are different from amorphous silicon, or disordered materials such as pentacene, or P3HT. Many ZnO based semiconductors exhibit a steep decaying density of acceptor tail states (trap DOS) and a Fermi level (EF) close to the conduction band energy (EC). Considering thin film transistor (TFT) operation in accumulation mode, the quasi Fermi level for electrons (Eq) moves even closer to EC. Classic analytic TFT simulations use the simplification EC-EF> `several'kT and cannot reproduce exponential tail states with a characteristic energy smaller than 1/2 kT. We demonstrate an analytic model for tail and deep acceptor states, valid for all amorphous metal oxides and include the effect of trap assisted hopping instead of simpler percolation or mobility edge models, to account for the observed field dependent mobility.

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

NASA Technical Reports Server (NTRS)

Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

2001-01-01

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(sub x)V(sub 1-x) alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(sub x)V(sub 1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(sub x)Te(sub 1-x) and ZnSe(sub y)Te(sub 1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(sub y)Te(sub 1-y) alloys in the entire composition range, y between 0 and 1. The samples used in this study are bulk ZnSe(sub y)Te(sub 1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between localized Se states and the conduction band. On the other hand we show that the large band gap reduction observed on the Se-rich side of the alloy system is a result of an interaction between the localized Te level and the valence bands. This interaction leads to the formation of a Te-like valence band edge that strongly interacts with the light hole valence band. Calculations based on a modified k(sup dot)p model account for the reduction of the band gap and the large increase of the spin-orbit splitting observed in Se-rich ZnSe(sub y)Te(sub 1-y) alloys. We will also discuss the importance of these new results for understanding of the electronic structure and band offsets in other highly mismatched alloy systems.

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

NASA Technical Reports Server (NTRS)

Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Ramdas, A.; Su, Ching-Hua; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(x)V(1-x), alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(x),V(1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(x)Te(l-x) and ZnSe(Y)Te(1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(y)Te(1-y) alloys in the entire composition range, 0 less than or equal to y less than or equal to 1. The samples used in this study are bulk ZnSe(y)Te(1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between localized Se states and the conduction band. On the other hand we show that the large band gap reduction observed on the Se-rich side of the alloy system is a result of an interaction between the localized Te level and the valence bands. This interaction leads to the formation of a Te-like valence band edge that strongly interacts with the light hole valence band. Calculations based on a modified k p model account for the reduction of the band gap and the large increase of the spin-orbit splitting observed in Se-rich ZnSe(y)Te(l-y) alloys. We will also discuss the importance of these new results for understanding of the electronic structure and band offsets in other highly mismatched alloy systems.

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

NASA Astrophysics Data System (ADS)

Juillot, Farid; Maréchal, Chloe; Morin, Guillaume; Jouvin, Delphine; Cacaly, Sylvain; Telouk, Philipe; Benedetti, Marc F.; Ildefonse, Philippe; Sutton, Steve; Guyot, François; Brown, Gordon E., Jr.

2011-05-01

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ 66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2 σ) to +0.34 ± 0.17‰ (2 σ) at the lowest horizons and from +0.38 ± 0.45‰ (2 σ) to +0.76 ± 0.14‰ (2 σ) near the surface. The δ 66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ 66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe 2O 4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ 66Zn values of +0.81 ± 0.20‰ (2 σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ 66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ 66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.

Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

USGS Publications Warehouse

Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

2001-01-01

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

PubMed

Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

2013-06-01

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy.

PubMed

Laurencin, Danielle; Wong, Alan; Chrzanowski, Wojciech; Knowles, Jonathan C; Qiu, Dong; Pickup, David M; Newport, Robert J; Gan, Zhehong; Duer, Melinda J; Smith, Mark E

2010-02-07

Despite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by (31)P and (1)H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both (43)Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The (43)Ca delta(iso) in HB and CT is found to correlate with the average Ca-O bond distance measured by Ca K-edge EXAFS, and the (43)Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, (23)Na MAS NMR, high resolution 3Q-MAS NMR, as well as (23)Na{(31)P} REDOR and (1)H{(23)Na} R(3)-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA).

Ultrathin ZnO interfacial passivation layer for atomic layer deposited ZrO2 dielectric on the p-In0.2Ga0.8As substrate

NASA Astrophysics Data System (ADS)

Liu, Chen; Lü, Hongliang; Yang, Tong; Zhang, Yuming; Zhang, Yimen; Liu, Dong; Ma, Zhenqiang; Yu, Weijian; Guo, Lixin

2018-06-01

Interfacial and electrical properties were investigated on metal-oxidesemiconductor capacitors (MOSCAPs) fabricated with bilayer ZnO/ZrO2 films by atomic layer deposition (ALD) on p-In0.2Ga0.8As substrates. The ZnO passivated In0.2Ga0.8As MOSCAPs have exhibited significantly improved capacitance-voltage (C-V) characteristics with the suppressed "stretched out" effect, increased accumulation capacitance and reduced accumulation frequency dispersion as well as the lower gate leakage current. In addition, the interface trap density (Dit) estimated by the Terman method was decreased dramatically for ZnO passivated p-In0.2Ga0.8As. The inherent mechanism is attributed to the fact that an ultrathin ZnO IPL employed by ALD prior to ZrO2 dielectric deposition can effectively suppress the formation of defect-related low-k oxides and As-As dimers at the interface, thus effectively improving the interface quality by largely removing the border traps aligned near the valence band edge of the p-In0.2Ga0.8As substrate.

Mechanisms of lichen resistance to metallic pollution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarret, C.; Manceau, A.; Eybert-Berard, L.

1998-11-01

Some lichens have a unique ability to grow in heavily contaminated areas due to the development of adaptative mechanisms allowing a high tolerance to metals. Here the authors report on the chemical forms of Pb and Zn in the metal hyperaccumulator Diploschistes muscorum and of Pb in the metal tolerant lichen Xanthoria parietina. The speciation of Zn and Pb has been investigated by powder X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy using the advanced third-generation synchrotron radiation source of the European synchrotron radiation facility (ESRF in Grenoble). This study reveals that in both lichens cells aremore » protected from toxicity by complexation of heavy metals, but the strategies differ: in D. muscorum, Pb and Zn are accumulated through an enhanced synthesis of oxalate, which precipitates toxic elements as insoluble salts, whereas in X. parietina, Pb is complexed to carboxylic groups of the fungal cell walls. The authors conclude that hyperaccumulation of metals results from a reactive mechanism of organic acid production, whereas metallo-tolerance is achieved by a passive complexation to existing functional groups.« less

Direct deconvolution of two-state pump-probe X-ray absorption spectra and the structural changes in a 100 ps transient of Ni(II)-tetramesitylporphyrin.

PubMed

Della-Longa, S; Chen, L X; Frank, P; Hayakawa, K; Hatada, K; Benfatto, M

2009-05-04

Full multiple scattering (FMS) Minuit XANES (MXAN) has been combined with laser pump-probe K-edge X-ray absorption spectroscopy (XAS) to determine the structure of photoexcited Ni(II)tetramesitylporphyrin, Ni(II)TMP, in dilute toluene solution. It is shown that an excellent simulation of the XANES spectrum is obtained, excluding the lowest-energy bound-state transitions. In ground-state Ni(II)TMP, the first-shell and second-shell distances are, respectively, d(Ni-N) = (1.93 +/- 0.02) A and d(Ni-C) = (2.94 +/- 0.03) A, in agreement with a previous EXAFS result. The time-resolved XANES difference spectrum was obtained (1) from the spectra of Ni(II)TMP in its photoexcited T(1) state and its ground state, S(0). The XANES difference spectrum has been analyzed to obtain both the structure and the fraction of the T(1) state. If the T(1) fraction is kept fixed at the value (0.37 +/- 0.10) determined by optical transient spectroscopy, a 0.07 A elongation of the Ni-N and Ni-C distances [d(Ni-N) and d(Ni-C)] is found, in agreement with the EXAFS result. However, an evaluation of both the distance elongation and the T(1) fraction can also be obtained using XANES data only. According to experimental evidence, and MXAN simulations, the T(1) fraction is (0.60 +/- 0.15) with d(Ni-N) = (1.98 +/- 0.03) A (0.05 A elongation). The overall uncertainty of these results depends on the statistical correlation between the distances and T(1) fraction, and the chemical shift of the ionization energy because of subtle changes of metal charge between the T(1) and S(0) states. The T(1) excited-state structure results, independently obtained without the excited-state fraction from optical transient spectroscopy, are still in agreement with previous EXAFS investigations. Thus, full multiple scattering theory applied through the MXAN formalism can be used to provide structural information, not only on the ground-state molecules but also on very short-lived excited states through differential analysis applied to transient photoexcited species from time-resolved experiments.

Quantitative and simultaneous analysis of the polarity of polycrystalline ZnO seed layers and related nanowires grown by wet chemical deposition.

PubMed

Guillemin, Sophie; Parize, Romain; Carabetta, Joseph; Cantelli, Valentina; Albertini, David; Gautier, Brice; Brémond, Georges; Fong, Dillon D; Renevier, Hubert; Consonni, Vincent

2017-03-03

The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscale-engineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol-gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 10 7 nano-objects both on the macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscale-engineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.

Quantitative and simultaneous analysis of the polarity of polycrystalline ZnO seed layers and related nanowires grown by wet chemical deposition

NASA Astrophysics Data System (ADS)

Guillemin, Sophie; Parize, Romain; Carabetta, Joseph; Cantelli, Valentina; Albertini, David; Gautier, Brice; Brémond, Georges; Fong, Dillon D.; Renevier, Hubert; Consonni, Vincent

2017-03-01

The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscale-engineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol-gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 107 nano-objects both on the macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscale-engineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.

Quantitative and simultaneous analysis of the polarity of polycrystalline ZnO seed layers and related nanowires grown by wet chemical deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guillemin, Sophie; Parize, Romain; Carabetta, Joseph

The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscaleengineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol–gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 107 nano-objects both on themore » macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscaleengineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.« less

Synthesis of ZnS films on Si(100) wafers by using chemical bath deposition assisted by the complexing agent ethylenediamine

NASA Astrophysics Data System (ADS)

Zhu, He-Jie; Wang, Xue-Mei; Gao, Xiao-Yong

2015-07-01

Low-cost synthesis of high-quality ZnS films on silicon wafers is of much importance to the ZnSbased heterojunction blue light-emitting device integrated with silicon. Thus, a series of ZnS films were chemically synthesized at low cost on Si(100) wafers at 353 K under a mixed acidic solution with a pH of 4 with zinc acetate and thioacetamide as precursors and with ethylenediamine and hydrochloric acid as the complexing agent and the pH value modifier, respectively. The effects of the ethylenediamine concentration on the crystallization, surface morphology, and optical properties of the ZnS films were investigated by using X-ray diffractometry, scanning electron microscopy, spectrophotometry, and fluorescence spectroscopy. A mechanism for the formation of ZnS film under an acidic condition was also proposed. All of the ZnS films were polycrystalline in nature, with a dominant cubic phase and a small amounts of hexagonal phases. The crystallization and the surface pattern of the films were clearly improved with increasing ethylenediamine concentration due to its enhanced complexing role. The absorption edge of the films almost underwent a blue shift with increasing ethylenediamine concentration, which was largely attributed to the quantum confinement effects caused by the small particle size of the polycrystalline ZnS films. Defect species and the corresponding strengths of the ZnS films were strongly affected by the ethylenediamine concentration.

Optical absorption edge of ZnO thin films: The effect of substrate

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1997-05-01

The optical absorption edge and the near-absorption edge characteristics of undoped ZnO films grown by laser ablation on various substrates have been investigated. The band edge of films on C [(0001)] and R-plane [(1102)] sapphire, 3.29 and 3.32 eV, respectively, are found to be very close to the single crystal value of ZnO (3.3 eV) with the differences being accounted for in terms of the thermal mismatch strain using the known deformation potentials of ZnO. In contrast, films grown on fused silica consistently exhibit a band edge ˜0.1 eV lower than that predicted using the known deformation potential and the thermal mismatch strains. This behavior is attributed to the small grain size (50 nm) realized in these films and the effect of electrostatic potentials that exist at the grain boundaries. Additionally, the spread in the tail (E0) of the band edge for the different films is found to be very sensitive to the defect structure in the films. For films grown on sapphire substrates, values of E0 as low as 30 meV can be achieved on annealing in air, whereas films on fused silica always show a value >100 meV. We attribute this difference to the substantially higher density of high-angle grain boundaries in the films on fused silica.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO 2 solids, suggesting that oxidized U is distributed between the interior of the UO 2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO 2 oxidation rate constants determined here relative to prior studies. In conclusion, our results suggest that the natural presence or addition of Ca and PO 4 in groundwater could slow the rates of U IV oxidation, but that the rates are still fast enough to cause complete oxidation of U IV within days under fully oxygenated conditions.« less

Problems with the thermogravimetric determination of oxygen stoichiometries in pure and rare-earth substituted La2RuO5

NASA Astrophysics Data System (ADS)

Riegg, S.; Müller, T.; Ebbinghaus, S. G.

2013-06-01

The oxygen stoichiometries of pure and rare-earth substituted La2RuO5 have been investigated by thermogravimetry (TG) in reducing atmosphere. Assuming that the observed total weight loss is caused by the reduction of Ru4+ to Ru-metal, remarkable oxygen deficiencies were calculated. These would correspond to ruthenium oxidation states significantly lower than the ones experimentally observed by XANES. To explain this discrepancy we investigated the reduction products by X-ray absorption spectroscopy (XAS). EXAFS measurements at the Ru-K edge revealed the presence of an X-ray amorphous ruthenium oxide, indicating an incomplete reduction. The apparent oxygen deficiencies obtained for pure and rare-earth substituted samples correlate with the amount of remaining ruthenium oxide. The presence of a ruthenium oxide species was furthermore verified by Ru-LIII XANES investigations. Our results show that the determination of oxygen contents by thermogravimetry might fail even for the easily reducable nobel metal oxides and therefore has to be applied with caution if the reaction products cannot be identified unambiguously.

X-ray absorption spectroscopic studies on gold nanoparticles in mesoporous and microporous materials.

PubMed

Akolekar, Deepak B; Foran, Garry; Bhargava, Suresh K

2004-05-01

Au L(3)-edge X-ray absorption spectroscopic measurements were carried out over a series of mesoporous and microporous materials containing gold nanoparticles to investigate the effects of the host matrix and preparation methods on the properties of gold nanoparticles. The materials of structure type MCM-41, ZSM-5, SAPO-18 and LSX with varying framework composition containing low concentrations of gold nanoparticles were prepared and characterized. In these materials the size of the gold nanoparticles varied in the range approximately 1 to 4 nm. A series of gold nanoparticles within different mesoporous and microporous materials have been investigated using X-ray absorption fine structure (XANES, EXAFS) and other techniques. Information such as atomic distances, bonding and neighbouring environment obtained from XAFS measurements was useful in elucidating the nature and structure of gold nanoparticles on these catalytic materials. The influence of the high-temperature (823, 1113, 1273 K) treatment on gold nanoparticles inside the mesoporous matrix was investigated using the XAFS technique. The XAFS and XANES results confirm various characteristics of gold nanoparticles in these materials suitable for catalysis, fabrication of nanodevices and other applications.

Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment.

PubMed

Hayes, Sarah M; O'Day, Peggy A; Webb, Sam M; Maier, Raina M; Chorover, Jon

2011-09-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.

Contrast enhancement of biological nanoporous materials with zinc oxide infiltration for electron and X-ray nanoscale microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ocola, L. E.; Sampathkumar, V.; Kasthuri, N.

Here, we show that using infiltration of ZnO metal oxide can be useful for high resolution imaging of biological samples in electron and X-ray microscopy. This method is compatible with standard fixation techniques that leave the sample dry, such as finishing with super critical CO 2 drying, or simple vacuum drying at 95°C. We demonstrate this technique can be applied on tooth and brain tissue samples. We also show that high resolution X-ray tomography can be performed on biological systems using Zn K edge (1s) absorption to enhance internal structures, and obtained the first nanoscale 10 KeV X-ray absorption imagesmore » of the interior regions of a tooth.« less

Contrast enhancement of biological nanoporous materials with zinc oxide infiltration for electron and X-ray nanoscale microscopy

DOE PAGES

Ocola, L. E.; Sampathkumar, V.; Kasthuri, N.; ...

2017-07-19

Here, we show that using infiltration of ZnO metal oxide can be useful for high resolution imaging of biological samples in electron and X-ray microscopy. This method is compatible with standard fixation techniques that leave the sample dry, such as finishing with super critical CO 2 drying, or simple vacuum drying at 95°C. We demonstrate this technique can be applied on tooth and brain tissue samples. We also show that high resolution X-ray tomography can be performed on biological systems using Zn K edge (1s) absorption to enhance internal structures, and obtained the first nanoscale 10 KeV X-ray absorption imagesmore » of the interior regions of a tooth.« less

In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

DOE PAGES

Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

2015-10-23

We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

DOE PAGES

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; ...

2016-01-18

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO 2 + and AmO 2 2+ with only a small amount AmO 2 present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties ofmore » the AmO 2 + and AmO 2 2+ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).« less

In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

PubMed

Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

2015-02-17

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Cam-driven monochromator for QEXAFS

NASA Astrophysics Data System (ADS)

Caliebe, W. A.; So, I.; Lenhard, A.; Siddons, D. P.

2006-11-01

We have developed a cam-drive for quickly tuning the energy of an X-ray monochromator through an X-ray absorption edge for quick extended X-ray absorption spectroscopy (QEXAFS). The data are collected using a 4-channel, 12-bit multiplexed VME analog to digital converter and a VME angle encoder. The VME crate controller runs a real-time operating system. This system is capable of collecting 2 EXAFS-scans in 1 s with an energy stability of better than 1 eV. Additional improvements to increase the speed and the energy stability are under way.

Anomalous Rayleigh scattering with dilute concentrations of elements of biological importance

NASA Astrophysics Data System (ADS)

Hugtenburg, Richard P.; Bradley, David A.

2004-01-01

The anomalous scattering factor (ASF) correction to the relativistic form-factor approximation for Rayleigh scattering is examined in support of its utilization in radiographic imaging. ASF corrected total cross-section data have been generated for a low resolution grid for the Monte Carlo code EGS4 for the biologically important elements, K, Ca, Mn, Fe, Cu and Zn. Points in the fixed energy grid used by EGS4 as well as 8 other points in the vicinity of the K-edge have been chosen to achieve an uncertainty in the ASF component of 20% according to the Thomas-Reiche-Kuhn sum rule and an energy resolution of 20 eV. Such data is useful for analysis of imaging with a quasi-monoenergetic source. Corrections to the sampled distribution of outgoing photons, due to ASF, are given and new total cross-section data including that of the photoelectric effect have been computed using the Slater exchange self-consistent potential with the Latter tail. A measurement of Rayleigh scattering in a dilute aqueous solution of manganese (II) was performed, this system enabling determination of the absolute cross-section, although background subtraction was necessary to remove K β fluorescence and resonant Raman scattering occurring within several 100 eV of the edge. Measurements confirm the presence of below edge bound-bound structure and variation in the structure due to the ionic state that are not currently included in tabulations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Pingping; Siddiqi, Georges; Vining, William C.

Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs withmore » increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.« less

The BALDER Beamline at the MAX IV Laboratory

NASA Astrophysics Data System (ADS)

Klementiev, K.; Norén, K.; Carlson, S.; Sigfridsson Clauss, K. G. V.; Persson, I.

2016-05-01

X-ray absorption spectroscopy (XAS) includes well-established methods to study the local structure around the absorbing element - extended X-ray absorption fine structure (EXAFS), and the effective oxidation number or to quantitatively determine the speciation of an element in a complex matrix - X-ray absorption near-edge structure (XANES). The increased brilliance and intensities available at the new generation of synchrotron light sources makes it possible to study, in-situ and in-operando, much more dilute systems with relevance for natural systems, as well as the micro-scale variability and dynamics of chemical reactions on the millisecond time-scale. The design of the BALDER beamline at the MAX IV Laboratory 3 GeV ring has focused on a high flux of photons in a wide energy range, 2.4-40 keV, where the K-edge is covered for the elements S to La, and the L 3-edge for all elements heavier than Sb. The overall design of the beamline will allow large flexibility in energy range, beam size and data collection time. The other focus of the beamline design is the possibility to perform multi-technique analyses on samples. Development of sample environment requires focus on implementation of auxiliary methods in such a way that techniques like Fourier transform infrared (FTIR) spectroscopy, UV-Raman spectroscopy, X-ray diffraction and/or mass spectrometry can be performed simultaneously as the XAS study. It will be a flexible system where different instruments can be plugged in and out depending on the needs for the particular investigation. Many research areas will benefit from the properties of the wiggler based light source and the capabilities to perform in-situ and in-operando measurements, for example environmental and geochemical sciences, nuclear chemistry, catalysis, materials sciences, and cultural heritage.

Changes in zinc speciation with mine tailings acidification in a semi-arid weathering environment

PubMed Central

Hayes, Sarah M.; O’Day, Peggy A.; Webb, Sam M.; Maier, Raina M.; Chorover, Jon

2011-01-01

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semi-arid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6,000 to 450 mg kg−1) and plant-available (590 to 75 mg kg−1) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and micro-focused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn0.8talc), Zn sorbed to ferrihydrite (ZnadsFeOx), and zinc sulfate (ZnSO4·7H2O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly-crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Micro-scale analyses identified hetaerolite (ZnMn2O4), hemimorphite (Zn4Si2O7(OH)2·H2O) and sphalerite (ZnS) as minor phases. Bulk and micro-focused spectroscopy complement the chemical extraction results and highlight the importance of using a multi-method approach to interrogate complex tailings systems. PMID:21761897

Local environments and transport properties of heavily doped strontium barium niobates Sr0.5Ba0.5Nb2O6

NASA Astrophysics Data System (ADS)

Ottini, Riccardo; Tealdi, Cristina; Tomasi, Corrado; Tredici, Ilenia G.; Soffientini, Alessandro; Burriel, Ramón; Palacios, Elías; Castro, Miguel; Anselmi-Tamburini, Umberto; Ghigna, Paolo; Spinolo, Giorgio

2018-02-01

Undoped as well as K-doped (40%), Y-doped (40%), Zr-doped (10%), and Mo-doped (12.5%) strontium barium niobate Sr0.5Ba0.5Nb2O6 (SBN50) materials have been investigated to explore the effect of heavy doping on the structural and functional properties (thermo-power, thermal and electrical conductivities) both in the as prepared (oxidized) and reduced states. For all materials, the EXAFS spectra at the Nb - K edge can be consistently analyzed with the same model of six shells around the Nb sites. Doping mostly gives a simple size effect on the structural parameters, but doping on the Nb sites weakens the Nb-O bond regardless of dopant size and charge. Shell sizes and Debye-Waller factors are almost unaffected by temperature and oxidation state, and the disorder is of static nature. The functional effects of heavy doping do not agree with a simple model of hole or electron injection by aliovalent substitutions on a large band gap semiconductor. With respect to the undoped samples, doping with Mo depresses the thermal conductivity by 30%, Y doping enhances the electrical conductivity by an order of magnitude, while Zr doping increases the Seebeck coefficient by a factor of 2-3. Globally, the ZT efficiency factor of the K-, Y-, and Zr-doped samples is enhanced at least by one order of magnitude with respect to the undoped or Mo-doped materials.

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

Probing the Li Insertion Mechanism of ZnFe 2O 4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe 2O 4 in Li ion batteries: A combined XRD, EXAFS, and DFT study

DOE PAGES

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; ...

2017-04-24

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe 2O 4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn 2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Limore » + ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn 2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe 2O 3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe 2O 4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.« less

High covalence in CuSO4 and the radicalization of sulfate: an X-ray absorption and density functional study.

PubMed

Szilagyi, Robert K; Frank, Patrick; DeBeer George, Serena; Hedman, Britt; Hodgson, Keith O

2004-12-27

Sulfur K-edge X-ray absorption spectroscopy (XAS) of anhydrous CuSO(4) reveals a well-resolved preedge transition feature at 2478.8 eV that has no counterpart in the XAS spectra of anhydrous ZnSO(4) or copper sulfate pentahydrate. Similar but weaker preedge features occur in the sulfur K-edge XAS spectra of [Cu(itao)SO(4)] (2478.4 eV) and [Cu[(CH(3))(6)tren]SO(4)] (2477.7 eV). Preedge features in the XAS spectra of transition metal ligands are generally attributed to covalent delocalization of a metal d-orbital hole into a ligand-based orbital. Copper L-edge XAS of CuSO(4) revealed that 56% of the Cu(II) 3d hole is delocalized onto the sulfate ligand. Hybrid density functional calculations on the two most realistic models of the covalent delocalization pathways in CuSO(4) indicate about 50% electron delocalization onto the sulfate oxygen-based 2p orbitals; however, at most 14% of that can be found on sulfate sulfur. Both experimental and computational results indicated that the high covalence of anhydrous CuSO(4) has made sulfate more like the radical monoanion, inducing an extensive mixing and redistribution of sulfur 3p-based unoccupied orbitals to lower energy in comparison to sulfate in ZnSO(4). It is this redistribution, rather than a direct covalent interaction between Cu(II) and sulfur, that is the origin of the observed sulfur XAS preedge feature. From pseudo-Voigt fits to the CuSO(4) sulfur K-edge XAS spectrum, a ground-state 3p character of 6% was quantified for the orbital contributing to the preedge transition, in reasonable agreement with the DFT calculation. Similar XAS fits indicated 2% sulfur 3p character for the preedge transition orbitals in [Cu(itao)SO(4)] and [Cu[(CH(3))(6)tren]SO(4)]. The covalent radicalization of ligands similar to sulfate, with consequent energy redistribution of the virtual orbitals, represents a new mechanism for the induction of ligand preedge XAS features. The high covalence of the Cu sites in CuSO(4) was found to be similar to that of Cu sites in oxidized cupredoxins, including its anistropic nature, and can serve as the simplest inorganic examples of intramolecular electron-transfer processes.

Oxygen vacancy induced by La and Fe into ZnO nanoparticles to modify ferromagnetic ordering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verma, Kuldeep Chand, E-mail: kuldeep0309@yahoo.co.in; Kotnala, R.K., E-mail: rkkotnala@gmail.com

We reported long-range ferromagnetic interactions in La doped Zn{sub 0.95}Fe{sub 0.05}O nanoparticles that mediated through lattice defects or vacancies. Zn{sub 0.92}Fe{sub 0.05}La{sub 0.03}O (ZFLaO53) nanoparticles were synthesized by a sol–gel process. X-ray fluorescence spectrum of ZFLaO53 detects the weight percentage of Zn, Fe, La and O. X-ray diffraction shows the hexagonal Wurtzite ZnO phase. The Rietveld refinement has been used to calculate the lattice parameters and the position of Zn, Fe, La and O atoms in the Wurtzite unit cell. The average size of ZFLaO53 nanoparticles is 99 nm. The agglomeration type product due to OH ions with La resultsmore » into ZnO nanoparticles than nanorods that found in pure ZnO and Zn{sub 0.95}Fe{sub 0.05}O sample. The effect of doping concentration to induce Wurtzite ZnO structure and lattice defects has been analyzed by Raman active vibrational modes. Photoluminescence spectra show an abnormal emission in both UV and visible region, and a blue shift at near band edge is formed with doping. The room temperature magnetic measurement result into weak ferromagnetism but pure ZnO is diamagnetic. However, the temperature dependent magnetic measurement using zero-field and field cooling at dc magnetizing field 500 Oe induces long-range ferromagnetic ordering. It results into antiferromagnetic Neel temperature of ZFLaO53 at around 42 K. The magnetic hysteresis is also measured at 200, 100, 50 and 10 K measurement that indicate enhancement in ferromagnetism at low temperature. Overall, the La doping into Zn{sub 0.95}Fe{sub 0.05}O results into enhanced antiferromagnetic interaction as well as lattice defects/vacancies. The role of the oxygen vacancy as the dominant defects in doped ZnO must form Bound magnetic polarons has been described. - Graphical abstract: The long-range ferromagnetic order in Zn{sub 0.92}Fe{sub 0.05}La{sub 0.03}O nanoparticles at low temperature measurements involves oxygen vacancy as the medium of magnetic interactions. - Highlights: • The La and Fe doping into ZnO nanoparticles induce defects in terms of oxygen vacancy. • The La ions in Fe substituted ZnO formed nanoparticles than nanorods. • Antiferromagnetic interactions are observed at room temperature magnetic measurement. • Rietveld analysis evaluated structural deformation in the Wurtzite ZnO lattice.« less

Edge-emitting ultraviolet n-ZnO:Al/i-ZnO/p-GaN heterojunction light-emitting diode with a rib waveguide.

PubMed

Liang, H K; Yu, S F; Yang, H Y

2010-02-15

An edge-emitting ultraviolet n-ZnO:Al/i-ZnO/p-GaN heterojunction light-emitting diode with a rib waveguide is fabricated by filtered cathodic vacuum arc technique at low deposition temperature (approximately 150 degrees C). Electroluminescence with emission peak at 387 nm is observed. Good correlation between electro- and photo- luminescence spectra suggests that the i-ZnO layer of the heterojunction supports radiative excitonic recombination. Furthermore, it is found that the emission intensity can be enhanced by approximately 5 times due to the presence of the rib waveguide. Only fundamental TE and TM polarizations are supported inside the rib waveguide and the intensity of TE polarization is approximately 2.2 time larger than that of TM polarization.

In Situ X-ray Absorption Near-Edge Structure Spectroscopy of ZnO Nanowire Growth During Chemical Bath Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

McPeak, Kevin M.; Becker, Matthew A.; Britton, Nathan G.

2010-12-03

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. Here we report the first use of in situ X-ray absorption spectroscopy during CBD, enabling detailed investigation of both reaction mechanisms and kinetics of ZnO nanowire growth from zinc nitrate and hexamethylenetetramine (HMTA) precursors. Time-resolved X-ray absorption near-edge structure (XANES) spectra were used to quantify Zn(II) speciation in both solution and solid phases. ZnO crystallizes directly from [Zn(H{sub 2}O){sub 6}]{sup 2+} without long-lived intermediates. Using ZnO nanowire deposition as an example,more » this study establishes in situ XANES spectroscopy as an excellent quantitative tool to understand CBD of nanomaterials.« less

Micro and bulk analysis of prostate tissues classified as hyperplasia

NASA Astrophysics Data System (ADS)

Kwiatek, W. M.; Banaś, A.; Banaś, K.; Cinque, G.; Dyduch, G.; Falkenberg, G.; Kisiel, A.; Marcelli, A.; Podgórczyk, M.

2007-07-01

BPH (Benign Prostatic Hyperplasia) is the most common benign neoplasm (non cancerous enlargement of the prostate gland), whose prevalence increases with age. The gland, when increased in size, exerts pressure on the urethra, causing obstruction to urine flow. The latter may result in severe urinary tract and kidney conditions. In this work prostate samples from patients diagnosed with BPH were analyzed using synchrotron radiation. Micro-analysis of the hyperplastic samples was carried out on the L-beam line at HASYLAB, DESY (Germany), while bulk analysis on selected samples was performed at the DRX2 beamline at LNF, Frascati (Italy). Microanalysis with a mono-energetic beam 15 μm in diameter confirmed that concentrations of certain elements, such as S, Mn, Cu, Fe and Zn, are good indicators of pathological disorders in prostate tissue that may be considered effective tracers of developing compliant. The concentrations of Mn, Cu, Fe and Zn are higher in hyperplastic tissues, as compared to normal ones, while for sulphur the opposite is observed. Additionally, Fe and S K-edge XANES (X-ray Absorption Near Edge Structure) spectroscopy experiments were carried out in order to determine the chemical speciation of these elements in our samples.

Photoluminescence and positron annihilation spectroscopic investigation on a H(+) irradiated ZnO single crystal.

PubMed

Sarkar, A; Chakrabarti, Mahuya; Sanyal, D; Bhowmick, D; Dechoudhury, S; Chakrabarti, A; Rakshit, Tamita; Ray, S K

2012-08-15

Low temperature photoluminescence and room temperature positron annihilation spectroscopy have been employed to investigate the defects incorporated by 6 MeV H(+) ions in a hydrothermally grown ZnO single crystal. Prior to irradiation, the emission from donor bound excitons is at 3.378 eV (10 K). The irradiation creates an intense and narrow emission at 3.368 eV (10 K). The intensity of this peak is nearly four times that of the dominant near band edge peak of the pristine crystal. The characteristic features of the 3.368 eV emission indicate its origin as a 'hydrogen at oxygen vacancy' type defect. The positron annihilation lifetime measurement reveals a single component lifetime spectrum for both the unirradiated (164 ± 1 ps) and irradiated crystal (175 ± 1 ps). It reflects the fact that the positron lifetime and intensity of the new irradiation driven defect species are a little higher compared to those in the unirradiated crystal. However, the estimated defect concentration, even considering the high dynamic defect annihilation rate in ZnO, comes out to be ∼4 × 10(17) cm(-3) (using SRIM software). This is a very high defect concentration compared to the defect sensitivity of positron annihilation spectroscopy. A probable reason is the partial filling of the incorporated vacancies (positron traps), which in ZnO are zinc vacancies. The positron lifetime of ∼175 ps (in irradiated ZnO) is consistent with recent theoretical calculations for partially hydrogen-filled zinc vacancies in ZnO. Passivation of oxygen vacancies by hydrogen is also reflected in the photoluminescence results. A possible reason for such vacancy filling (at both Zn and O sites) due to irradiation has also been discussed.

Unusual heme iron-lipid acyl chain coordination in Escherichia coli flavohemoglobin.

PubMed

D'Angelo, Paola; Lucarelli, Debora; della Longa, Stefano; Benfatto, Maurizio; Hazemann, Jean Louis; Feis, Alessandro; Smulevich, Giulietta; Ilari, Andrea; Bonamore, Alessandra; Boffi, Alberto

2004-06-01

Escherichia coli flavohemoglobin is endowed with the notable property of binding specifically unsaturated and/or cyclopropanated fatty acids both as free acids or incorporated into a phospholipid molecule. Unsaturated or cyclopropanated fatty acid binding to the ferric heme results in a spectral change observed in the visible absorption, resonance Raman, extended x-ray absorption fine spectroscopy (EXAFS), and x-ray absorption near edge spectroscopy (XANES) spectra. Resonance Raman spectra, measured on the flavohemoglobin heme domain, demonstrate that the lipid (linoleic acid or total lipid extracts)-induced spectral signals correspond to a transition from a five-coordinated (typical of the ligand-free protein) to a hexacoordinated, high spin heme iron. EXAFS and XANES measurements have been carried out both on the lipid-free and on the lipid-bound protein to assign the nature of ligand in the sixth coordination position of the ferric heme iron. EXAFS data analysis is consistent with the presence of a couple of atoms in the sixth coordination position at 2.7 A in the lipid-bound derivative (bonding interaction), whereas a contribution at 3.54 A (nonbonding interaction) can be singled out in the lipid-free protein. This last contribution is assigned to the CD1 carbon atoms of the distal LeuE11, in full agreement with crystallographic data on the lipid-free protein at 1.6 A resolution obtained in the present work. Thus, the contributions at 2.7 A distance from the heme iron are assigned to a couple of carbon atoms of the lipid acyl chain, possibly corresponding to the unsaturated carbons of the linoleic acid.

XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

NASA Astrophysics Data System (ADS)

Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.

2016-08-01

X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

PubMed

Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

2018-04-25

We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tetrahedrally Coordinated Fe3+ in Silicate Glasses: A Mossbauer, Iron K-edge XANES and Raman Spectroscopies Study

NASA Astrophysics Data System (ADS)

Cochain, B.; Neuville, D. R.; McCammon, C.; Henderson, G. S.; de Ligny, D.; Pinet, O.; Richet, P.

2009-05-01

In natural or industrial glasses, iron is the most abundant transition metal. A good knowledge of its redox equilibrium is important to better understand the chemical and structural evolution of magmas (crystallization, viscosity), and also to optimize vitrification processes and properties of iron-bearing glasses. To study the role of iron in silicate glasses and melts, we have used in a consistent manner the Mössbauer, iron K-edge XANES and Raman spectroscopies to investigate several series of silicate glasses as a function of redox state. The samples were selected to cover a wide composition range and to investigate the interactions of iron with two network forming cations, namely, Al3+ and B3+. The glasses investigated were synthesized at high temperature under various conditions of oxygen fugacity to achieve different redox ratios for each composition. Therefore, the iron redox state was varied from the most oxidized to the most reduced. Iron redox ratios were first determined by wet chemical analysis and in some cases by room temperature Mossbauer spectroscopy. This experimental method was also used to determine the local structure of iron of some of the investigated glasses. These results where compared to iron K-edge XANES/EXAFS spectroscopy results, which lead to the iron redox state and indicate that Fe2+ is in octahedral coordination whereas Fe3+ is in tetrahedral coordination. In addition, Raman spectroscopy gave us information on the network polymerization of glasses. Clearly changes in Raman spectra are visible with the evolution of iron redox ratio. For a given composition, we observed systematically, in the 800-1200 cm-1 envelope, which is sensitive to the environment of tetrahedrally coordinated cations, the growth of a band with the iron content and the oxidation state of the sample. The peak area of this band, which we attribute to vibrational modes involving tetrahedrally coordinated Fe3+, increases with the oxidation of the sample. This evolution leads us to establish a calibration procedure for a given composition. Calibration curves can be followed to investigate in situ kinetics of redox reactions. We present here results on the role of iron and its interactions with the silicate network for several compositions as pyroxene based glasses and iron bearing alkali alumino-borosilicate glasses.

MAX: Multiplatform Applications for XAFS

NASA Astrophysics Data System (ADS)

Alain, Michalowicz; Jacques, Moscovici; Diane, Muller-Bouvet; Karine, Provost

2009-11-01

MAX is a new EXAFS and XANES analysis package, replacing our old "EXAFS pour le Mac" software suite. The major improvement is the ability to work with strictly the same code, compiled at once for Microsoft Windows, Apple MacOSX and LINUX systems, justifying the title "Multiplatform Applications for XAFS". It is organized as four modules: ABSORBIX (X-ray absorbance and fluorescence self-absorption calculations), CHEROKEE (EXAFS and XANES data treatment), ROUNDMIDNIGHT (EXAFS modeling and fit) and CRYSTALFFREV (from crystal structures and molecular modeling to FEFF EXAFS and XANES theoretical calculations). Most features developed in "EXAFS pour le Mac" are still available, but with much improvements in the user's interface, data treatment algorithms and new functionalities.

Effect of an Electrochemically Oxidized ZnO Seed Layer on ZnO Nanorods Grown by using Electrodeposition

NASA Astrophysics Data System (ADS)

Jeon, Woosung; Leem, Jae-Young

2018-05-01

ZnO nanorods were prepared on a Si substrate with and without a ZnO seed layer formed by electro-oxidation to investigate the effect of the seed layer on their growth. The ZnO nanorods grown on the ZnO seed layer had top surfaces that were flat whereas those grown without it had rough top surfaces, as observed in field-emission scanning electron microscopy images. In the Xray diffraction analysis, all ZnO nanorods showed preferential orientation with the (002) plane. In the case of ZnO nanorods prepared with a ZnO seed layer, the residual stress decreased, and the full width at half maximum of the ZnO (002) plane peak decreased. The photoluminescence spectra show a strong and narrow near-band-edge emission peak and high near-band-edge emission to deep-level emission peak ratio for the ZnO nanorods prepared with the seed layer. With respect to the photoresponse properties, the ZnO nanorods grown with the ZnO seed layer showed higher responsivity and faster rise/decay curves than those grown without it. Thus, the ZnO seed layer formed by electro-oxidation improves the structural, optical, and photoresponse properties of the ZnO nanorods formed on it. This method could serve as a new route for improving the properties of optoelectronic devices.

Growth of ternary CdxZn1-xO thin films in oxygen ambient using pulsed laser deposition

NASA Astrophysics Data System (ADS)

Sharma, Sugandha; Saini, Basant; Kaur, Ravinder; Gupta, Vinay; Tomar, Monika; Kapoor, Avinashi

2018-05-01

This study reports the growth of cadmium alloyed zinc (CdxZn1-xO) oxide thin films using pulsed laser deposition. The films are deposited on Corning glass substrates at different oxygen pressures of 5, 20, and 40 mTorr. High resolution X-ray diffraction studies reveal mixed phase (hexagonal and cubic) for films deposited at 20 and 40 mTorr, while a cubic phase for film deposited at 5 mTorr pressure. Optical transmittance studies indicate red-shifting of transmission edge as oxygen pressure decreases to 5 mTorr from 20 mTorr, hinting at a possible increase in cadmium content in thin films. Minimum band gap energy is obtained at growth pressure of 5 mTorr. Resistivity measurements have been performed using Hall effect measurement set up at 298 K.

Variability in Chemical Vapor Deposited Zinc Sulfide: Assessment of Legacy and International CVD ZnS Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCloy, John S.; Korenstein, Ralph

2009-10-06

Samples of CVD ZnS from the United States, Germany, Israel, and China were evaluated using transmission spectroscopy, x-ray diffraction, photoluminescence, and biaxial flexure testing. Visible and near-infrared scattering, 6 μm absorption, and ultraviolet cut-on edge varied substantially in tested materials. Crystallographic hexagonality and texture was determined and correlated with optical scattering. Transmission cut-on (ultraviolet edge) blue-shifts with annealing and corresponds to visible color but not the 6 μm absorption. Photoluminescence results suggest that CVD ZnS exhibits a complex suite of electronic bandgap defects. All CVD ZnS tested with biaxial flexure exhibit similar fracture strength values and Weibull moduli. This surveymore » suggests that technical understanding of the structure and optical properties CVD ZnS is still in its infancy.« less

Rational Design, Synthesis and Evaluation of First Generation Inhibitors of the Giardia lamblia Fructose-1,6-biphosphate Aldolase

PubMed Central

Li, Zhimin; Liu, Zhengang; Cho, Dae Won; Zou, Jiwen; Gong, Maozhen; Breece, Robert M.; Galkin, Andrey; Li, Ling; Zhao, Hong; Maestas, Gabriel D.; Tierney, David L.; Herzberg, Osnat; Dunaway-Mariano, Debra; Mariano, Patrick S.

2011-01-01

Inhibitors of the Giardia lamblia fructose 1,6-bisphosphate aldolase (GlFBPA), which transforms fructose 1,6-bisphosphate (FBP) to dihydroxyacetone phosphate and glyceraldehyde 3-phosphate, were designed based on 3-hydroxy-2-pyridone and 1,2-dihydroxypyridine scaffolds that position two negatively charged tetrahedral groups for interaction with substrate phosphate binding residues, a hydrogen bond donor to the catalytic Asp83, and a Zn2+ binding group. The inhibition activities for the GlFBPA catalyzed reaction of FBP of the prepared alkyl phosphonate/phosphate substituted 3-hydroxy-2-pyridinones and a dihydroxypyridine were determined. The 3-hydroxy-2-pyridone inhibitor 8 was found to bind to GlFBPA with an affinity (Ki = 14 μM) that is comparable to that of FBP (Km = 2 μM) or its inert analog TBP (Ki = 1 μM). The X-ray structure of the GlFBPA-inhibitor 8 complex (2.3 Å) shows that 8 binds to the active site in the manner predicted by in silico docking with the exception of coordination with Zn2+. The observed distances and orientation of the pyridone ring O=C-C-OH relative to Zn2+ are not consistent with a strong interaction. To determine if Zn2+coordination occurs in the GlFBPA-inhibitor 8 complex in solution, EXAFS spectra were measured. A four coordinate geometry comprised of the three enzyme histidine ligands and an oxygen atom from the pyridone ring O=C-C-OH was indicated. Analysis of the Zn2+ coordination geometries in recently reported structures of class II FBPAs suggests that strong Zn2+ coordination is reserved for the enediolate-like transition state, accounting for minimal contribution of Zn2+ coordination to binding of 8 to GlFBPA. PMID:21333622

Ir/KLTL zeolites: Structural characterization and catalysis on n-hexane reforming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Gates, B.C.

Ir/KLTL zeolite catalysts were prepared by incipient wetness impregnation of LTL zeolites with [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2}. The catalysts were characterized by extended X-ray absorption fine structure (EX-AFS) spectroscopy, infrared spectroscopy, and H{sub 2} chemisorption. EXAFS data show that the average Ir cluster size (after treatment at 300{degrees}C in H{sub 2}) increased from about 7 to 20 {Angstrom} as the zeolite K:Al atomic ratio increased from 0.34 to 1.56. Infrared spectra of adsorbed CO show that the electron donation to the Ir increased as the K:Al ratio increased. In contrast to the performance reported for Pt/KLTL zeolites with metal clustersmore » as small as those observed in the present experiments, the Ir/KLTL catalyst has a low selectivity for dehydrocyclization of n-hexane at 440-480{degrees}C and 1 atm with a H{sub 2}: n-hexane feed molar ratio of 6. Instead, the catalysts are selective for hydrogenolysis. The selectivity is insensitive to the K:Al ratio, but the activity for dehydrocyclization is a maximum at a K:Al atomic ratio of about 1. The results show that even the smallest Ir clusters to which electron donation is significant still behave essentially like metallic Ir in the catalytic reactions. 49 refs., 4 figs., 7 tabs.« less

Effects of Zn, macronutrients, and their interactions through foliar applications on winter wheat grain nutritional quality.

PubMed

Wang, Shaoxia; Li, Meng; Liu, Ke; Tian, Xiaohong; Li, Shuo; Chen, Yanlong; Jia, Zhou

2017-01-01

Although application of Zn combined with macronutrients (K, P, and N) can be used to fortify wheat grain with Zn, little is known about their interactions when foliar application is employed or the influences of common soil fertility management practices (e.g. N and straw management) on their efficiency. Therefore, the effects of foliar-applied Zn and N, P, or K on grain nutritional quality (especially Zn) were investigated in wheat grown under different soil N rates at two sites with (Sanyuan) or without (Yangling) employing straw return. A 4-year-long field experiment was also conducted to evaluate the environmental stability of the foliar formulations. Across 6 site-years, foliar Zn application alone or combined with N, P, or K fertilizers resulted in 95.7%, 101%, 67.9% and 121% increases in grain Zn concentration, respectively. In terms of increasing grain Zn concentration, foliar-applied Zn positively interacted with N (at Sanyuan) and K (at Yangling), but negatively interacted with P at any condition tested, suggesting depressive effects of foliarly-applied P on physiological availability of Zn. Although these interaction effects were the major factor that governing the efficiency of foliar-applied Zn combined with N, P, or K on grain Zn concentration, the magnitude of the increase/decrease in grain Zn (-3.96~5.71 mg kg-1) due to these interactions was much less than the average increases following Zn+K (31.3), Zn+P (18.7), and Zn+N (26.5 mg kg-1) treatments relative to that observed in foliar Zn-only treatment. The combined foliar application of Zn with N, P, or K did not cause any adverse impact on grain yield and other nutritional quality and in some cases slightly increased grain yield and macronutrient concentrations. Grain phytic acid:Zn molar ratios were respectively 52.0%, 53.1%, 43.4% and 63.5% lower in the foliar Zn, Zn+N, Zn+P and Zn+K treatments than in the control treatment. These effects were consistent over four years and across three soil N rates. Overall, combined foliar application of Zn with N, P, or K can successfully fortify wheat grain with Zn (above 40 mg kg-1), and including Zn in foliar N or K application are preferred for practically increasing dietary Zn intake.

Effects of Zn, macronutrients, and their interactions through foliar applications on winter wheat grain nutritional quality

PubMed Central

Liu, Ke; Tian, Xiaohong; Li, Shuo; Chen, Yanlong; Jia, Zhou

2017-01-01

Although application of Zn combined with macronutrients (K, P, and N) can be used to fortify wheat grain with Zn, little is known about their interactions when foliar application is employed or the influences of common soil fertility management practices (e.g. N and straw management) on their efficiency. Therefore, the effects of foliar-applied Zn and N, P, or K on grain nutritional quality (especially Zn) were investigated in wheat grown under different soil N rates at two sites with (Sanyuan) or without (Yangling) employing straw return. A 4-year-long field experiment was also conducted to evaluate the environmental stability of the foliar formulations. Across 6 site-years, foliar Zn application alone or combined with N, P, or K fertilizers resulted in 95.7%, 101%, 67.9% and 121% increases in grain Zn concentration, respectively. In terms of increasing grain Zn concentration, foliar-applied Zn positively interacted with N (at Sanyuan) and K (at Yangling), but negatively interacted with P at any condition tested, suggesting depressive effects of foliarly-applied P on physiological availability of Zn. Although these interaction effects were the major factor that governing the efficiency of foliar-applied Zn combined with N, P, or K on grain Zn concentration, the magnitude of the increase/decrease in grain Zn (–3.96~5.71 mg kg-1) due to these interactions was much less than the average increases following Zn+K (31.3), Zn+P (18.7), and Zn+N (26.5 mg kg-1) treatments relative to that observed in foliar Zn-only treatment. The combined foliar application of Zn with N, P, or K did not cause any adverse impact on grain yield and other nutritional quality and in some cases slightly increased grain yield and macronutrient concentrations. Grain phytic acid:Zn molar ratios were respectively 52.0%, 53.1%, 43.4% and 63.5% lower in the foliar Zn, Zn+N, Zn+P and Zn+K treatments than in the control treatment. These effects were consistent over four years and across three soil N rates. Overall, combined foliar application of Zn with N, P, or K can successfully fortify wheat grain with Zn (above 40 mg kg-1), and including Zn in foliar N or K application are preferred for practically increasing dietary Zn intake. PMID:28746402

Augmentation of Quick-EXAFS measurement facility at the energy scanning EXAFS beamline at INDUS-2 SRS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poswal, A. K., E-mail: poswalashwini@gmail.com; Agrawal, Ankur; Bhattachryya, D.

2015-06-24

In this paper implementation of Quick-EXAFS data acquisition facility at the Energy Scanning EXAFS beamline(BL-09) at INDUS-2 synchrotron source, Indore is presented. By adopting a continuous-scan mode in the Double Crystal monochromator (DCM), a high signal-to-noise ratio is maintained and the acquisition time is reduced to few seconds. The quality of spectra and repeatability is checked by measuring standards. The present mode of data acquisition would enable EXAFS measurement for in-situ studies even in fluorescence mode.

Emission intensity of the λ = 1.54 μm line in ZnO films grown by magnetron sputtering, diffusion doped with Ce, Yb, Er

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mezdrogina, M. M., E-mail: margeret.m@mail.ioffe.ru; Eremenko, M. V.; Smirnov, A. N.

2015-08-15

The effect of the Er{sup 3+}-ion excitation type on the photoluminescence spectra of crystalline ZnO(ZnO〈Ce, Yb, Er〉) films is determined in the cases of resonant (λ = 532 nm, Er{sup 3+}-ion transition from {sup 4}S{sub 3/2}, {sup 2}H{sub 11/2} levels to {sup 4}I{sub 15/2}) and non-resonant (λ = 325 nm, in the region near the ZnO band-edge emission) excitation. It is shown that resonant excitation gives rise to lines with various emission intensities, characteristic of the Er{sup 3+}-ion intracenter 4f transition with λ = 1535 nm when doping crystalline ZnO films with three rare-earth ions (REIs, Ce, Yb, Er) ormore » with two impurities (Ce, Er) or (Er, Yb), independently of the measurement temperature (T = 83 and 300 K). The doping of crystalline ZnO films with rare-earth impurities (Ce, Yb, Er) leads to the efficient transfer of energy to REIs, a consequence of which is the intense emission of an Er{sup 3+} ion in the IR spectral region at λ{sub max} = 1535 nm. The kick-out diffusion mechanism is used upon the sequential introduction of impurities into semiconductor matrices and during the postgrowth annealing of the ZnO films under study. The crystalline ZnO films doped with Ce, Yb, Er also exhibit intense emission in the visible spectral region at room temperature, which makes them promising materials for optoelectronics.« less

Near band edge emission characteristics of sputtered nano-crystalline ZnO films

NASA Astrophysics Data System (ADS)

Kunj, Saurabh; Sreenivas, K.

2016-05-01

Sputtered zinc oxide (ZnO) thin films deposited on unheated glass substrate under different sputtering gas mixtures (Ar+O2) have been investigated using X-ray diffraction and photo luminescence spectroscopy. Earlier reported studies on ZnO films prepared by different techniques exhibit either a sharp/broad near band edge (NBE) emission peak depending on the crystalline quality of the film. In the present study zinc oxide films, grown on unheated substrates, are seen to possess a preferred (002) orientation with a microstructure consisting of clustered nano-sized crystallites. The splitting in the near band edge emission (NBE) into three characteristic peaks is attributed to quantum confinement effect, and is observed specifically under an excitation of 270 nm. Deep level emission (DLE) in the range 400 to 700 nm is not observed indicating absence of deep level radiative defects.

Dual-Color Emission in Hybrid III-Nitride/ZnO Light Emitting Diodes

NASA Astrophysics Data System (ADS)

Namkoong, Gon; Trybus, Elaissa; Cheung, Maurice C.; Doolittle, W. Alan; Cartwright, Alexander N.; Ferguson, Ian; Seong, Tae-Yeon; Nause, Jeff

2010-02-01

We report dual-color production of the blue and green regions using hybrid nitride/ZnO light emitting diode (LED) structures grown on ZnO substrates. The blue emission is ascribed to the near-band edge transition in InGaN while green emission is related to Zn-related defect levels formed by the unintentional interdiffusion of Zn into the InGaN active layer from the ZnO substrates.

XANES Identification of Plutonium Speciation in RFETS Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

LoPresti, V.; Conradson, S.D.; Clark, D.L.

2009-06-03

Using primarily X-ray absorption near edge spectroscopy (XANES) with standards run in tandem with samples, probable plutonium speciation was determined for 13 samples from contaminated soil, acid-splash or fire-deposition building interior surfaces, or asphalt pads from the Rocky Flats Environmental Technology Site (RFETS). Save for extreme oxidizing situations, all other samples were found to be of Pu(IV) speciation, supporting the supposition that such contamination is less likely to show mobility off site. EXAFS analysis conducted on two of the 13 samples supported the validity of the XANES features employed as determinants of the plutonium valence.

XAS Studies of Arsenic in the Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

Cr(VI) removal by FeS-coated alumina, silica, and natural sand

NASA Astrophysics Data System (ADS)

Park, M.; Lee, S.; Jeong, H. Y.

2014-12-01

Removal of Cr(VI) was investigated using mackinawite (FeS)-coated mineral sorbents under anoxic conditions. The sorbents included alumina (Al), silica (WS), and natural sand (NS). By analysis of both solution and solid phases, all FeS-coated sorbents were found to reduce Cr(VI) into Cr(III). The sorption extent and mechanism of Cr(VI) strongly depended on the pH conditions. Only at pH 4.5, significant amounts of the dissolved Cr remained in the solution. Titration of dissolved Cr(III) and Fe(III) by NaOH solutions indicated that no bulk-phase precipitation occurred at pH 4.5. Also, the removal of Cr(VI) at pH 4.5 was the greatest by FeS-coated NS. Consistent with these, Cr-K edge EXAFS revealed that Cr was removed by FeS-coated NS via surface precipitation, and that it was immobilized by FeS-coated WS and Al by forming surface clusters. Regardless of FeS-coated sorbents, at pH 7.0 and pH 9.5, the initially added Cr(VI) was quantitatively removed from the solution phase. By EXAFS analysis, the Cr sorption by FeS-coated Al was mainly due to the bulk-phase precipitation of Cr(OH)3(s) or [Cr, Fe](OH)3(s). In case of FeS-coated WS and NS, the short Cr-Cr distance (~2.6 Å) at pH 7.0 and pH 9.5 was not simply accounted for by the bulk precipitation as either hydroxide (rCr-Cr ~ 3.0 Å), and it would rather result from the surface precipitation. Such a difference in the coordination structure among FeS-coated sorbents was likely due to in the lower surface area of the former available for the surface precipitation.

Effect of K-doping on structural and optical properties of ZnO thin films

NASA Astrophysics Data System (ADS)

Xu, Linhua; Li, Xiangyin; Yuan, Jun

2008-09-01

In this work, K-doped ZnO thin films were prepared by a sol-gel method on Si(111) and glass substrates. The effect of different K-doping concentrations on structural and optical properties of the ZnO thin films was studied. The results showed that the 1 at.% K-doped ZnO thin film had the best crystallization quality and the strongest ultraviolet emission ability. When the concentration of K was above 1 at.%, the crystallization quality and ultraviolet emission ability dropped. For the K-doped ZnO thin films, there was not only ultraviolet emission, but also a blue emission signal in their photoluminescent spectra. The blue emission might be connected with K impurity or/and the intrinsic defects (Zn interstitial and Zn vacancy) of the ZnO thin films.

Study of cobalt effect on structural and optical properties of Dy doped ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Pawan; Pandey, Praveen C.

2018-05-01

The present study has been carried out to investigate the effect of Co doping on structural and optical properties of Dy doped ZnO nanoparticles. We have prepared pure Zinc oxide, Dy (1%) doped ZnO and Dy (1%) doped ZnO co-doped with Co(2%) with the help of simple sol-gel combustion method. The structural analysis carried out using X-ray diffraction spectra (XRD) indicates substitution of Dy and Co at Zn site of ZnO crystal structure and hexagonal crystal structure without any secondary phase formation in all the samples. The surface morphology was analyzed by transmission electron microscopy (TEM). Absorption study indicates that Dy doping causes a small shift in band edge, while Co co-doping results significant change is absorption edge as well as introduce defect level absorption in the visible region. The band gap of samples decreases due to Dy and Co doping, which can be attributed to defect level formation below the conduction band in the system.

EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms

NASA Astrophysics Data System (ADS)

Richmann, Michael K.; Reed, Donald T.; Kropf, A. Jeremy; Aase, Scott B.; Lewis, Michele A.

2001-09-01

A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.

A structural study of bone changes in knee osteoarthritis by synchrotron-based X-ray fluorescence and X-ray absorption spectroscopy techniques

NASA Astrophysics Data System (ADS)

Sindhupakorn, Bura; Thienpratharn, Suwittaya; Kidkhunthod, Pinit

2017-10-01

Osteoarthritis (OA) is characterized by degeneration of articular cartilage and thickening of subchondral bone. The present study investigated the changing of biochemical components of cartilage and bone compared between normal and OA people. Using Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniquesincluding X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were employed for the bone changes in kneeosteoarthritisstudies. The bone samples were collected from various osteoarthritis patients with both male and female in the ages range between 20 and 74 years old. SR-XRF results excited at 4240 eV for Ca elements show a majority three main groups, based on their XRF intensities, 20-36 years, 40-60 years and over 70 years, respectively. By employing XAS techniques, XANES features can be used to clearly explain in term of electronic transitions occurring in bone samples which are affected from osteoarthritis symptoms. Moreover, a structural change around Ca ions in bone samples is obviously obtained by EXAFS results indicating an increase of Ca-amorphous phase when the ages increase.

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.

PubMed

Pacławski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K

2010-11-11

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

Multifunctional synchrotron spectrometer of the National Research Center "Kurchatov Institute": I. EXAFS in dispersive mode

NASA Astrophysics Data System (ADS)

Aksenov, V. L.; Tyutyunnikov, S. I.; Shalyapin, V. N.; Belyaev, A. D.; Artemiev, A. N.; Artemiev, N. A.; Kirillov, B. F.; Kovalchiuk, M. V.; Demkiv, A. A.; Knyazev, G. A.

2017-01-01

The improved X-ray optical scheme, the system of registration, and the measurement procedure of the multifunctional synchrotron radiation spectrometer in the dispersive EXAFS mode are described. The results of the spectrometer energy resolution measurements are given. The advantages and disadvantages of traditional and dispersive EXAFS spectrometers are analyzed. Examples of EXAFS spectra measured in the dispersive mode are given.

Growth and characterization of Hg(1-x)Zn(x)Se

NASA Technical Reports Server (NTRS)

Andrews, R. N.

1986-01-01

Hg sub 1-xZn sub xSe alloys of composition x=0.10 were grown in a Bridgman-Stockbarger growth furnace at translation rates of 0.3 and 0.1 micron sec. The axial and radial composition profiles were determined using precision density measurements and IR transmission-edge-mapping, respectively. A more radially homogeneous alloy was produced at the slower growth rate, while the faster growth rate produced more axially homogeneous alloys. A determination of the electrical properties of the Hg sub 1-xZn sub xSe samples in the temperature range 300K-20K was also made. Typical carrier concentrations were on the order of magnitude of 10 to the 18th power cu/cm, and remained fairly constant as a function of temperature. A study was also made of the temperature dependence of the resistivity and Hall mobility. The effect of annealing in a selenium vapor on both the IR transmission and the electrical properties was determined. Annealing was effective in reducing the number of native donor defects and at the resulting lower carrier concentrations, charge carrier concentration was shown to be a function of temperature. Annealing caused the mobility to increase, primarily at the lower temperature, and the room temperature resistivity to increase. Annealing was also observed to greatly enhance the % IR transmittance of the samples. This was due primarily to the effect of annealing on decreasing the charge carrier concentration.

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite.

PubMed

Voegelin, Andreas; Jacquat, Olivier; Pfister, Sabina; Barmettler, Kurt; Scheinost, Andreas C; Kretzschmar, Ruben

2011-01-01

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.

Biotransformation of copper oxide nanoparticles by the pathogenic fungus Botrytis cinerea.

PubMed

Kovačec, Eva; Regvar, Marjana; van Elteren, Johannes Teun; Arčon, Iztok; Papp, Tamás; Makovec, Darko; Vogel-Mikuš, Katarina

2017-08-01

Two plant pathogenic fungi, Botrytis cinerea and Alternaria alternata, isolated from crop plants, were exposed to Cu in ionic (Cu 2+ ), microparticulate (MP, CuO) or nanoparticulate (NP, Cu or CuO) form, in solid and liquid culturing media in order to test fungal response and toxic effects of the mentioned compounds for the potential use as fungicides. B. cinerea has shown pronounced growth and lower levels of lipid peroxidation compared to A. alternata. Its higher resistance/tolerance is attributed mainly to biotransformation of CuO and Cu NPs and CuO MPs into a blue compound at the fungal/culturing media interface, recognized by Cu K-edge EXAFS analysis as Cu-oxalate complex. The pronounced activity of catechol-type siderophores and organic acid secretion in B. cinerea induce leaching and mobilization of Cu ions from the particles and their further complexation with extracellularly secreted oxalic acid. The ability of pathogenic fungus to biotransform CuO MPs and NPs hampers their use as fungicides. However the results show that B. cinerea has a potential to be used in degradation of Cu(O) nanoparticles in environment, copper extraction and purification techniques. Copyright © 2017 Elsevier Ltd. All rights reserved.

Triggering of spin-flipping-modulated exchange bias in FeCo nanoparticles by electronic excitation

PubMed Central

Sarker, Debalaya; Bhattacharya, Saswata; Srivastava, Pankaj; Ghosh, Santanu

2016-01-01

The exchange coupling between ferromagnetic (FM)-antiferromagnetic (AF) interfaces is a key element of modern spintronic devices. We here introduce a new way of triggering exchange bias (EB) in swift heavy ion (SHI) irradiated FeCo-SiO2 films, which is a manifestation of spin-flipping at high irradiation fluence. The elongation of FeCo nanoparticles (NPs) in SiO2 matrix gives rise to perpendicular magnetic anisotropy at intermediate fluence. However, a clear shift in hysteresis loop is evident at the highest fluence. This reveals the existence of an AF exchange pinning domain in the NPs, which is identified not to be oxide shell from XANES analysis. Thermal spike calculations along with first-principles based simulations under the framework of density functional theory (DFT) demonstrate that spin flipping of 3d valence electrons is responsible for formation of these AF domains inside the FM NPs. EXAFS experiments at Fe and Co K-edges further unravel that spin-flipping in highest fluence irradiated film results in reduced bond lengths. The results highlight the possibility of miniaturization of magnetic storage devices by using irradiated NPs instead of conventionally used FM-AF multilayers. PMID:27991552

Structure and spectroscopic study of aqueous Fe(III)-As(V) complexes using UV-Vis, XAS and DFT-TDDFT.

PubMed

Chai, Liyuan; Yang, Jinqin; Zhang, Ning; Wu, Pin-Jiun; Li, Qingzhu; Wang, Qingwei; Liu, Hui; Yi, Haibo

2017-09-01

Aqueous complexes between ferric (Fe(III)) and arsenate (As(V)) are indispensable for understanding the mobility of arsenic (As) in Fe(III)-As(V)-rich systems. In this study, aqueous Fe(III)-As(V) complexes, FeH 2 AsO 4 2+ and FeHAsO 4 + , were postulated based on the qualitative analysis of UV-Vis spectra in both Fe(III)-As(V)-HClO 4 and Fe(III)-As(V)-H 2 SO 4 systems. Subsequently, monodentate structures were evidenced by Fe K-edge EXAFS and modeled as [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + by DFT. The feature band at ∼280 nm was verified as electron excitation chiefly from Fe-As-bridged O atoms to d-orbital of Fe in [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + . The structural and spectral information of Fe(III)-As(V) complexes will enable future speciation analysis in Fe(III)-As(V)-rich system. Copyright © 2017. Published by Elsevier Ltd.

Highly Efficient Defect Emission from ZnO:Zn and ZnO:S Powders

NASA Astrophysics Data System (ADS)

Everitt, Henry

2013-03-01

Bulk Zinc Oxide (ZnO) is a wide band gap semiconductor with an ultraviolet direct band gap energy of 3.4 eV and a broad, defect-related visible wavelength emission band centered near 2 eV. We have shown that the external quantum efficiency can exceed 50% for this nearly white emission band that closely matches the human dark-adapted visual response. To explore the potential of ZnO as a rare earth-free white light phosphor, we investigated the mechanism of efficient defect emission in three types of ZnO powders: unannealed, annealed, and sulfur-doped. Annealing and sulfur-doping of ZnO greatly increase the strength of defect emission while suppressing the UV band edge emission. Continuous wave and ultrafast one- and two-photon excitation spectroscopy are used to examine the defect emission mechanism. Low temperature photoluminescence (PL) and PL excitation (PLE) spectra were measured for all three compounds, and it was found that bound excitons mediate the defect emission. Temperature-dependent PLE spectra for the defect and band edge emission were measured to estimate trapping and activation energies of the bound excitons and clarify the role they play in the defect emission. Time-resolved techniques were used to ascertain the role of exciton diffusion, the effects of reabsorption, and the spatial distributions of radiative and non-radiative traps. In unannealed ZnO we find that defect emission is suppressed and UV band edge emission is inefficient (< 2%) because of reabsorption and non-radiative recombination due to a high density of non-radiative bulk traps. By annealing ZnO, bulk trap densities are reduced, and a high density of defects responsible for the broad visible emission are created near the surface. Interestingly, nearly identical PLE spectra are found for both the band edge and the defect emission, one of many indications that the defect emission is deeply connected to bound excitons. Quantum efficiency, also measured as a function of excitation wavelength, closely mirrors the PLE spectra for both emission bands. Sulfur-doped ZnO exhibits additional PLE and X-ray features indicative of a ZnS-rich surface shell that correlates with even more efficient defect emission. The results presented here offer hope that engineering defects in ZnO materials may significantly improve the quantum efficiency for white light phosphor applications. This work was supported by the Army's in-house laboratory innovative research program.

Optimization of the K-edge imaging for vulnerable plaques using gold nanoparticles and energy-resolved photon counting detectors: a simulation study

PubMed Central

Alivov, Yahya; Baturin, Pavlo; Le, Huy Q.; Ducote, Justin; Molloi, Sabee

2014-01-01

We investigated the effect of different imaging parameters such as dose, beam energy, energy resolution, and number of energy bins on image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. Maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of plaque's inflammation. The simulations studies used a single slice parallel beam CT geometry with an X-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33x24 cm2) phantom, where both phantoms contained tissue, calcium, and gold. In the simulation studies GNP quantification and background (calcium and tissue) suppression task were pursued. The X-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% FWHM energy resolution) implementations of photon counting detector were simulated. The simulations were performed for the CdZnTe detector with pixel pitch of 0.5-1 mm, which corresponds to the performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the X-ray beam energy (kVp) to achieve the highest signal-to-noise ratio (SNR) with respect to patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at 125 kVp X-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 μmol/mL (0.21 mg/mL) for an ideal detector and about 2.5 μmol/mL (0.49 mg/mL) for more realistic (12% FWHM) detector. The studies show the optimal imaging parameters at lowest patient dose using an energy resolved photon counting detector to image GNP in an atherosclerotic plaque. PMID:24334301

Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

NASA Technical Reports Server (NTRS)

Paerels, Frits; Weisskopf, Martin C.; Tennant, Allyn F.; ODell, Stephen L.; Swartz, Douglas A.; Kahn, Steven M.; Behar, Ehud; Becker, Werner; Whitaker, Ann F. (Technical Monitor)

2001-01-01

We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

Isochronal annealing effects on local structure, crystalline fraction, and undamaged region size of radiation damage in Ga-stabilized δ-Pu

DOE PAGES

Olive, D. T.; Booth, C. H.; Wang, D. L.; ...

2016-07-19

The effects on the local structure due to self-irradiation damage of Ga stabilized δ-Pu stored at cryogenic temperatures have been examined using extended x-ray absorption fine structure (EXAFS) experiments. Extensive damage, seen as a loss of local order, was evident after 72 days of storage below 15 K. The effect was observed from both the Pu and the Ga sites, although less pronounced around Ga. Isochronal annealing was performed on this sample to study the annealing processes that occur between cryogenic and room temperature storage conditions, where damage is mostly reversed. Damage fractions at various points along the annealing curvemore » have been determined using an amplitude-ratio method, a standard EXAFS fitting, and a spherical crystallite model, and provide information complementary to the previous electrical resistivity- and susceptibility-based isochronal annealing studies. The use of a spherical crystallite model accounts for the changes in EXAFS spectra using just two parameters, namely, the crystalline fraction and the particle radius. Altogether, these results are discussed in terms of changes to the local structure around Ga and Pu throughout the annealing process and highlight the unusual role of Ga in the behavior of the lowest temperature anneals.« less

Isochronal annealing effects on local structure, crystalline fraction, and undamaged region size of radiation damage in Ga-stabilized δ-Pu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olive, D. T.; Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545; Wang, D. L.

2016-07-21

The effects on the local structure due to self-irradiation damage of Ga stabilized δ-Pu stored at cryogenic temperatures have been examined using extended x-ray absorption fine structure (EXAFS) experiments. Extensive damage, seen as a loss of local order, was evident after 72 days of storage below 15 K. The effect was observed from both the Pu and the Ga sites, although less pronounced around Ga. Isochronal annealing was performed on this sample to study the annealing processes that occur between cryogenic and room temperature storage conditions, where damage is mostly reversed. Damage fractions at various points along the annealing curve havemore » been determined using an amplitude-ratio method, a standard EXAFS fitting, and a spherical crystallite model, and provide information complementary to the previous electrical resistivity- and susceptibility-based isochronal annealing studies. The use of a spherical crystallite model accounts for the changes in EXAFS spectra using just two parameters, namely, the crystalline fraction and the particle radius. Together, these results are discussed in terms of changes to the local structure around Ga and Pu throughout the annealing process and highlight the unusual role of Ga in the behavior of the lowest temperature anneals.« less

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

PubMed

Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

2007-05-14

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

Heat capacities and entropies at 298.15 K of MgTiO3 (geikielite), ZnO (zincite), and ZnCO3 (smithsonite)

USGS Publications Warehouse

Robie, R.A.; Haselton, H.T.; Hemingway, B.S.

1989-01-01

Heat capacities of synthetic MgTiO3 (geikielite), ZnO (zincite), and natural crystals of smithsonite (ZnCO3) were measured between 9 and 366 K using an automatic adiabatically shielded calorimeter. At 298.15 K the standard molar entropies Smo of MgTiO3, ZnO, and ZnCO3 are (74.64 ?? 0.15), (43.16 ?? 0.09), and (81.19 ?? 0.16) J??K-1??mol-1, respectively. Debye temperatures for MgTiO3 and ZnO calculated from our Cp, mo values below 20 K are (900 ?? 20) K and (440 ?? 25) K respectively. Heat capacities for MgTiO3 and ZnO were combined with enthalpy increments from the literature to derive heat-capacity equations for these phases from 260 to about 1800 K. The heat capacities of MgTiO3 between 260 and 1720 K were fitted with an average deviation of 0.3 per cent by the equation: C??p,m/(J??K-1??mol-1) = 222.5-0.05274(T/K)-6.092x105(T/K)-1-1874.6(T/K) -1/2+1.878x10-5(T/K)2 and for ZnO the equation: C??p,m/(J??K-1??mol-1) = 53.999+7.851x10-4(T/K)-5.868x105(T/K)-2 -127.50(T/K)-:1/2+1.9376x10-6(T/K)2 fits the heat capacities in the temperature interval of 250 to 1800 K with an average deviation of 0.7 per cent. ?? 1989.

Electrostatic redesign of the [myoglobin, cytochrome b5] interface to create a well-defined docked complex with rapid interprotein electron transfer.

PubMed

Xiong, Peng; Nocek, Judith M; Griffin, Amanda K K; Wang, Jingyun; Hoffman, Brian M

2009-05-27

Cyt b(5) is the electron-carrier "repair" protein that reduces met-Mb and met-Hb to their O(2)-carrying ferroheme forms. Studies of electron transfer (ET) between Mb and cyt b(5) revealed that they react on a "Dynamic Docking" (DD) energy landscape on which binding and reactivity are uncoupled: binding is weak and involves an ensemble of nearly isoenergetic configurations, only a few of which are reactive; those few contribute negligibly to binding. We set the task of redesigning the surface of Mb so that its reaction with cyt b(5) instead would occur on a conventional "simple docking" (SD) energy landscape, on which a complex exhibits a well-defined (set of) reactive binding configuration(s), with binding and reactivity thus no longer being decoupled. We prepared a myoglobin (Mb) triple mutant (D44K/D60K/E85K; Mb(+6)) substituted with Zn-deuteroporphyrin and monitored cytochrome b(5) (cyt b(5)) binding and electron transfer (ET) quenching of the (3)ZnMb(+6) triplet state. In contrast, to Mb(WT), the three charge reversals around the "front-face" heme edge of Mb(+6) have directed cyt b(5) to a surface area of Mb adjacent to its heme, created a well-defined, most-stable structure that supports good ET pathways, and apparently coupled binding and ET: both K(a) and k(et) are increased by the same factor of approximately 2 x 10(2), creating a complex that exhibits a large ET rate constant, k(et) = 10(6 1) s(-1), and is in slow exchange (k(off) < k(et)). In short, these mutations indeed appear to have created the sought-for conversion from DD to simple docking (SD) energy landscapes.

Zinc complexation in chloride-rich hydrothermal fluids (25-600 °C): A thermodynamic model derived from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Mei, Yuan; Sherman, David M.; Liu, Weihua; Etschmann, Barbara; Testemale, Denis; Brugger, Joël

2015-02-01

The solubility of zinc minerals in hydrothermal fluids is enhanced by chloride complexation of Zn2+. Thermodynamic models of these complexation reactions are central to models of Zn transport and ore formation. However, existing thermodynamic models, derived from solubility measurements, are inconsistent with spectroscopic measurements of Zn speciation. Here, we used ab initio molecular dynamics simulations (with the PBE exchange-correlation functional) to predict the speciation of Zn-Cl complexes from 25 to 600 °C. We also obtained in situ XAS measurements of Zn-Cl solutions at 30-600 °C. Qualitatively, the simulations reproduced the main features derived from in situ XANES and EXAFS measurements: octahedral to tetrahedral transition with increasing temperature and salinity, stability of ZnCl42- at high chloride concentration up to ⩾500 °C, and increasing stability of the trigonal planar [ZnCl3]- complex at high temperature. Having confirmed the dominant species, we directly determined the stability constants for the Zn-Cl complexes using thermodynamic integration along constrained Zn-Cl distances in a series of MD simulations. We corrected our stability constants to infinite dilution using the b-dot model for the activity coefficients of the solute species. In order to compare the ab initio results with experiments, we need to re-model the existing solubility data using the species we identified in our MD simulations. The stability constants derived from refitting published experimental data are in reasonable agreement with those we obtained using ab initio MD simulations. Our new thermodynamic model accurately predicts the experimentally observed changes in ZnO(s) and ZnCO3(s) solubility as a function of chloride concentration from 200 (Psat) to 600 °C (2000 bar). This study demonstrates that metal speciation and geologically useful stability constants can be derived for species in hydrothermal fluids from ab initio MD simulations even at the generalized gradient approximation for exchange-correlation. We caution, however, that simulations are mostly reliable at high T where ligand exchange is fast enough to yield thermodynamic averages over the timescales of the simulations.

Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

PubMed

Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

2009-02-28

The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type. Preliminary studies in CO and H(2) oxidation were made in a DRIFTS flow reactor with on-line MS, and their activities and selectivities were compared against skeletal Ru and Cu controls, Ru/Al(2)O(3), and Au/Fe(2)O(3). All samples were active in CO oxidation above approximately 50 degrees C, showing light-off temperatures in the range 60-70 degrees C. Ru(22)Cu(7) and Ru(17)Cu(12.5) also showed good selectivities (vs. H(2) oxidation), attributed tentatively to Ru-modified Cu surfaces of varying thickness. These compositions are promising candidates to test in a (PROX) fuel processor to supply purified (CO-free) H(2) to a PEM fuel cell.

UV light induced insulator-metal transition in ultra-thin ZnO/TiOx stacked layer grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Saha, D.; Misra, P.; Joshi, M. P.; Kukreja, L. M.

2016-08-01

In the present study, atomic layer deposition has been used to grow a series of Ti incorporated ZnO thin films by vertically stacking different numbers (n = 1-7) of ZnO/TiOx layers on (0001) sapphire substrates. The effects of defect states mediated chemisorption of O2 and/OH groups on the electrical properties of these films have been investigated by illuminating the samples under UV light inside a high vacuum optical cryostat. The ultra-thin film having one stacked layer (n = 1) did not show any change in its electrical resistance upon UV light exposure. On the contrary, marginal drop in the electrical resistivity was measured for the samples with n ≥ 3. Most surprisingly, the sample with n = 2 (thickness ˜ 12 nm) showed an insulator to metal transition upon UV light exposure. The temperature dependent electrical resistivity measurement on the as grown film (n = 2) showed insulating behaviour, i.e., diverging resistivity on extrapolation to T→ 0 K. However, upon UV light exposure, it transformed to a metallic state, i.e., finite resistivity at T → 0 K. Such an insulator-metal transition plausibly arises due to the de-trapping of conduction electrons from the surface defect sites which resulted in an upward shift of the Fermi level above the mobility edge. The low-temperature electron transport properties on the insulating film (n = 2) were investigated by a combined study of zero field electrical resistivity ρ(T) and magnetoresistance (MR) measurements. The observed negative MR was found to be in good agreement with the magnetic field induced suppression of quantum interference between forward-going paths of tunnelling electrons. Both ρ(T) and MR measurements provided strong evidence for the Efros-Shklovskii type variable range hopping conduction in the low-temperature (≤40 K) regime. Such studies on electron transport in ultra-thin n-type doped ZnO films are crucial to achieve optimum functionality with long term reliability of ZnO based transparent conducting oxides.

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

1996-04-01

The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

K-shell photoabsorption and photoionization of trace elements. II. Isoelectronic sequences with electron number 12 ≤N ≤ 18

NASA Astrophysics Data System (ADS)

Mendoza, C.; Bautista, M. A.; Palmeri, P.; Quinet, P.; Witthoeft, M. C.; Kallman, T. R.

2017-08-01

Context. We are concerned with improving the diagnostic potential of the K lines and edges of elements with low cosmic abundances, namely F, Na, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu, and Zn, that are observed in the X-ray spectra of supernova remnants, galaxy clusters, and accreting black holes and neutron stars. Aims: Since accurate photoabsorption and photoionization cross sections are needed in their spectral models, they have been computed for isoelectronic sequences with electron number 12 ≤ N ≤ 18 using a multi-channel method. Methods: Target representations are obtained with the atomic structure code autostructure, and ground-state cross sections are computed with the Breit-Pauli R-matrix method (bprm) in intermediate coupling, including damping (radiative and Auger) effects. Results: Following the findings in our earlier work on sequences with 2 ≤ N ≤ 11, the contributions from channels associated with the 2s-hole [2s] μ target configurations and those containing 3d orbitals are studied in the Mg (N = 12) and Ar (N = 18) isoelectronic sequences. Cross sections for the latter ions are also calculated in the isolated-resonance approximation as implemented in autostructure and compared with bprm to test their accuracy. Conclusions: It is confirmed that the collisional channels associated with the [2s] μ target configurations must be taken into account owing to significant increases in the monotonic background cross section between the L and K edges. Target configurations with 3d orbitals give rise to fairly conspicuous unresolved transition arrays in the L-edge region, but to a much lesser extent in the K-edge that is our main concern; therefore, they have been neglected throughout owing to their computationally intractable channel inventory, thus allowing the computation of cross sections for all the ions with 12 ≤ N ≤ 18 in intermediate coupling with bprm. We find that the isolated-resonance approximations performs satisfactorily and will be our best choice to tackle the systems with ground configuration 3p63dm (3 ≤ m ≤ 8) in isoelectronic sequences with N> 20.

Heterostructured nanohybrid of zinc oxide-montmorillonite clay.

PubMed

Hur, Su Gil; Kim, Tae Woo; Hwang, Seong-Ju; Hwang, Sung-Ho; Yang, Jae Hun; Choy, Jin-Ho

2006-02-02

We have synthesized heterostructured zinc oxide-aluminosilicate nanohybrids through a hydrothermal reaction between the colloidal suspension of exfoliated montmorillonite nanosheets and the sol solution of zinc acetate. According to X-ray diffraction, N2 adsorption-desorption isotherm, and field emission-scanning electron microscopic analyses, it was found that the intercalation of zinc oxide nanoparticles expands the basal spacing of the host montmorillonite clay, and the crystallites of the nanohybrids are assembled to form a house-of-cards structure. From UV-vis spectroscopic investigation, it becomes certain that calcined nanohybrid contains two kinds of the zinc oxide species in the interlayer space of host lattice and in mesopores formed by the house-of-cards type stacking of the crystallites. Zn K-edge X-ray absorption near-edge structure/extended X-ray absorption fine structure analyses clearly demonstrate that guest species in the nanohybrids exist as nanocrystalline zinc oxides with wurzite-type structure.

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials.

PubMed

Németh, Károly; Chapman, Karena W; Balasubramanian, Mahalingam; Shyam, Badri; Chupas, Peter J; Heald, Steve M; Newville, Matt; Klingler, Robert J; Winans, Randall E; Almer, Jonathan D; Sandi, Giselle; Srajer, George

2012-02-21

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials. © 2012 American Institute of Physics

Nanoporous structures on ZnO thin films

NASA Astrophysics Data System (ADS)

Gür, Emre; Kılıç, Bayram; Coşkun, C.; Tüzemen, S.; Bayrakçeken, Fatma

2010-01-01

Porous structures were formed on ZnO thin films which were grown by an electrochemical deposition (ECD) method. The growth processes were carried out in a solution of dimethylsulfoxide (DMSO) zinc perchlorate, Zn(ClO 4) 2, at 120 ∘C on indium tin oxide (ITO) substrates. Optical and structural characterizations of electrochemically grown ZnO thin films have shown that the films possess high (0002) c-axis orientation, high nucleation, high intensity and low FWHM of UV emission at the band edge region and a sharp UV absorption edge. Nanoporous structures were formed via self-assembled monolayers (SAMs) of hexanethiol (C 6SH) and dodecanethiol (C 12SH). Scanning electron microscope (SEM) measurements showed that while a nanoporous structure (pore radius 20 nm) is formed on the ZnO thin films by hexanathiol solution, a macroporous structure (pore radius 360 nm) is formed by dodecanethiol solution. No significant variation is observed in X-ray diffraction (XRD) measurements on the ZnO thin films after pore formation. However, photoluminescence (PL) measurements showed that green emission is observed as the dominant emission for the macroporous structures, while no variation is observed for the thin film nanoporous ZnO sample.

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

Effects of Na Doping on Structural, Optical, and Electronic Properties of ZnO Thin Films Fabricated by Sol-Gel Technique

NASA Astrophysics Data System (ADS)

Fan, Heliang; Yao, Zhen; Xu, Cheng; Wang, Xinqiang; Yu, Zhichao

2018-04-01

Undoped and Na-doped ZnO thin films were fabricated by sol-gel technique on quartz glass substrates and annealed at 500°C for 1 h. The structural properties of the films were characterized using x-ray diffraction analysis, which revealed hexagonal wurtzite structure with no peaks corresponding to Na2O or other Na phases being found. Surface morphology observations by scanning electron microscopy revealed that the crystallite size and topographical properties of the ZnO films were influenced by the Na doping concentration. X-ray photoelectron spectra revealed presence of Na+ in ZnO regime. The transmittance spectra indicated that the average transmittance of Na-doped ZnO film was above 80% in the visible range, superior to that of the undoped film. There was a blue-shift in the ultraviolet absorption edge with increase of the Na content. Photoluminescence spectra illustrated two peaks, corresponding to ultraviolet near-band-edge and visible emission.

Energy Scaling of Nanosecond Gain-Switched Cr2+:ZnSe Lasers

DTIC Science & Technology

2011-01-01

outcoupler or absorption from the lightly-doped active ions. Additionally, the edges of the crystals are cut at the Brewster angle , which raises...experiments we used Brewster cut Cr:ZnSe gain elements with a chromium concentration of 8x1018 cm-3. Under Cr:Tm:Ho:YAG pumping, the first Cr:ZnSe laser...the energy scaling of nanosecond gain-switched Cr:ZnSe lasers is optimization of the gain medium. In this study we used Brewster cut Cr:ZnSe gain

Ag@ZnO core-shell nanoparticles study by first principle: The structural, magnetic and optical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Hai-Xia; Wang, Xiao-Xu; Beijing Computing Center, Beijing 100094

Ag@ZnO core-shell nanoparticles of around 72 atoms have been investigated by the density functional theory, revealing proving for the first time that the core-shell structure exhibits a shrinkage phenomenon from outer shell in agreement with the other studies in literatures. Our calculations predict that the Ag@ZnO core-shell structure is a ferromagnetic spin polarized state, and the magnetism mainly stems from the spin splitting of 2p electrons of O atoms. In addition, the total and partial DOS of Ag@ZnO indicate that the nanostructure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. Furthermore, the optical properties calculations showmore » that the absorption edge of Ag@ZnO have a red shift and good photocatalysis compare to that of the bulk ZnO. These results of the Ag@ZnO core-shell structure obtain a well agreement with the experimental measurement. - Graphical abstract: Geometric structure of (a) Ag@ZnO core-shell nanostructure; (b) the core of Ag; (c) the shell of ZnO The core-shell nanoparticle Ag@ZnO contains Ag inner core of radius of 4 Å and ZnO outer shell with thickness of 2 Å. Ag@ZnO core-shell nanoparticles of around 72 atoms have been proved for the first time that the core-shell structure exhibit a shrinkage phenomenon from outer shell. Our calculations predict that the Ag@ZnO core-shell structure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. The absorption edge of Ag@ZnO have a red shift and get good photo-catalysis compare to that of the bulk ZnO.« less

Effect of heavy metals on seed germination and seedling growth of common ragweed and roadside ground cover legumes.

PubMed

Bae, Jichul; Benoit, Diane L; Watson, Alan K

2016-06-01

In southern Québec, supplement roadside ground covers (i.e. Trifolium spp.) struggle to establish near edges of major roads and thus fail to assist turf recruitment. It creates empty niches vulnerable to weed establishment such as common ragweed (Ambrosia artemisiifolia). We hypothesized that heavy metal stresses may drive such species shifts along roadside edges. A growth chamber experiment was conducted to assess effects of metals (Zn, Pb, Ni, Cu, and Cd) on germination and seedling behaviors of roadside weed (A. artemisiifolia) and ground cover legumes (Coronilla varia, Lotus corniculatus, and Trifolium arvense). All metals inhibited T. arvense germination, but the effect was least on A. artemisiifolia. Low levels of Pb and Ni promoted germination initiation of A. artemisiifolia. Germination of L. corniculatus was not affected by Zn, Pb, and Ni, but inhibited by Cu and Cd. Germination of C. varia was decreased by Ni, Cu, and Cd and delayed by Zn and Pb. Metal additions hindered seedling growth of all test species, and the inhibitory effect on the belowground growth was greater than on the aboveground growth. Seedling mortality was lowest in A. artemisiifolia but highest in T. arvense when exposed to the metal treatments. L. corniculatus and C. varia seedlings survived when subjected to high levels of Zn, Pb, and Cd. In conclusion, the successful establishment of A. artemisiifolia along roadside edges can be associated with its greater tolerance of heavy metals. The findings also revealed that L. corniculatus is a potential candidate for supplement ground cover in metal-contaminated roadside edges in southern Québec, especially sites contaminated with Zn and Pb. Copyright © 2015 Elsevier Ltd. All rights reserved.

Relationship between dislocation and the visible luminescence band observed in ZnO epitaxial layers grown on c-plane p-GaN templates by chemical vapor deposition technique

NASA Astrophysics Data System (ADS)

Saroj, Rajendra K.; Dhar, S.

2016-08-01

ZnO epitaxial layers are grown on c-plane GaN (p-type)/sapphire substrates using a chemical vapor deposition technique. Structural and luminescence properties of these layers have been studied systematically as a function of various growth parameters. It has been found that high quality ZnO epitaxial layers can indeed be grown on GaN films at certain optimum conditions. It has also been observed that the growth temperature and growth time have distinctly different influences on the screw and edge dislocation densities. While the growth temperature affects the density of edge dislocations more strongly than that of screw dislocations, an increase of growth duration leads to a rapid drop in the density of screw dislocation, whereas the density of edge dislocation hardly changes. Densities of both edge and screw dislocations are found to be minimum at a growth temperature of 500 °C. Interestingly, the defect related visible luminescence intensity also shows a minimum at the same temperature. Our study indeed suggests that the luminescence feature is related to threading edge dislocation. A continuum percolation model, where the defects responsible for visible luminescence are considered to be formed under the influence of the strain field surrounding the threading edge dislocations, is proposed. The theory explains the observed variation of the visible luminescence intensity as a function of the concentration of the dislocations.

How Langmuir-Blodgett trilayers act as templates for directed self-assembly of nanoparticles

NASA Astrophysics Data System (ADS)

Mukherjee, Smita; Datta, Alokmay; Biswas, Nupur; Giglia, Angelo; Nannarone, Stefano

2014-04-01

Atomic force microscopy (AFM) shows that Langmuir-Blodgett (LB) deposition of dissimilar metal stearates (MSt, M = Co, Zn, Cd) on templates of Co-stearate (Co-T) and Cd-stearate (Cd-T) results in self-assembly of MSts into nanocrystalline grains having clear and consistent morphological habits. The grains are better formed and well separated on Cd-T than on Co-T. Fourier transform infrared spectroscopy (FTIR) results show that the headgroup coordination of the overlayer is tuned by the coordination of the Cd-T template and remains unaffected by that of the Co-T template. They also indicate co-existence of a different kind of headgroup structure that is close to the undissociated fatty acid headgroup but differing more in the two types of carbon-oxygen bonds, suggesting an inter-headgroup bonding such as hydrogen bond that may exist on a nanocrystal surface. Results of synchrotron x-ray diffraction at C K-edge, of ZnSt on Cd-T (ZnSt/Cd-T) and Co-T (ZnSt/Co-T), point to a non-closed packed structure for ZnSt/Cd-T and a closed-packed structure for ZnSt/Co-T, with significant superlattice order in the former. The presence of crystalline phases of ZnSt in the nanometer scale, on LB templates, in contrast to the the presence of lamellar phase in bulk ZnSt, is attributed to the the presence of unidentate metal-carboxylate coordination in the former and absence of it in the latter, creating different gradients of dipolar forces at template overlayer interface. Relative strength of this long-range force over short-range intermolecular forces in the templates qualitatively explains better crystallinity and higher ordering in ZnSt/Cd-T compared to ZnSt/Co-T. We propose that the role of dipole moment gradient between template and overlayer in tuning of these metal-organic nanoparticles may be somewhat similar to structural and optical tunability of semiconductor nanocrystals by thermal and self-equilibrium strain.

Sub-Micrometer Scale Minor Element Mapping in Interplanetary Dust Particles: A Test for Stratospheric Contamination

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.; Sutton, S. R.

2004-01-01

Combined X-ray microprobe (XRM), energy dispersive x-ray fluorescence using a Transmission Electron Microscope (TEM), and electron microprobe measurements have determined that the average bulk chemical composition of the interplanetary dust particles (IDPs) collected from the Earth s stratosphere is enriched relative to the CI meteorite composition by a factor of 2 to 4 for carbon and for the moderately volatile elements Na, K, P, Mn, Cu, Zn, Ga, Ge, and Se, and enriched to approximately 30 times CI for Br. However, Jessberger et al., who have reported similar bulk enrichments using Proton Induced X-ray Emission (PIXE), attribute the enrichments to contamination by meteor-derived atmospheric aerosols during the several weeks these IDPs reside in the Earth s atmosphere prior to collection. Using scanning Auger spectroscopy, a very sensitive surface analysis technique, Mackinnon and Mogk have observed S contamination on the surface of IDPs, presumably due to the accretion of sulfate aerosols during stratospheric residence. But the S-rich layer they detected was so thin (approximately 100 angstroms thick) that the total amount of S on the surface was too small to significantly perturb the bulk S-content of a chondritic IDP. Stephan et al. provide support for the contamination hypothesis by reporting the enrichment of Br on the edges of the IDPs using Time-of-Flight Secondary-Ion Mass-Spectrometry (TOFSIMS), but TOF-SIMS is notorious for producing false edge-effects, particularly on irregularly-shaped samples like IDPs. Sutton et al. mapped the spatial distribution of Fe, Ni, Zn, Br, and Sr, at the approximately 2 m scale, in four IDPs using element-specific x-ray fluorescence (XRF) computed microtomography. They found the moderately volatile elements Zn and Br, although spatially inhomogeneous, were not concentrated on the surface of any of the IDPs they examined, suggesting that the Zn and the Br enrichments in the IDPs are not due to contamination during stratospheric residence.

[Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

PubMed

Shen, Ya-Ting

2014-03-01

In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.

Zinc oxide nanoring embedded lacey graphene nanoribbons in symmetric/asymmetric electrochemical capacitive energy storage

NASA Astrophysics Data System (ADS)

Sahu, Vikrant; Goel, Shubhra; Sharma, Raj Kishore; Singh, Gurmeet

2015-12-01

This article describes the synthesis and characterization of ZnO nanoring embedded graphene nanoribbons. Patterned holes (mesopore dia.) in graphene nanoribbons are chemically generated, leading to a high density of the edge planes. These planes carry negatively charged surface groups (like -COOH and -OH) and therefore anchor the metal ions in a cordial fashion forming a string of metal ions along the edge planes. These strings of imbibed metal ions precipitate as tiny ZnO nanorings over lacey graphene nanoribbons. The thus obtained graphene nanoribbon (GNR) based hierarchical ZnO mesoporous structures are three dimensionally accessible to the electrolyte and demonstrate high performance in capacitive energy storage. The ZnO/GNR nanocomposite electrode in an asymmetric supercapacitor device with lacey reduced graphene oxide nanoribbons (LRGONRs) as a negative electrode exhibits a 2.0 V potential window in the aqueous electrolyte and an ultra-short time constant (0.08 s). The wide potential window consequently increased the energy density from 6.8 Wh kg-1 (ZnO/GNR symmetric) to 9.4 Wh kg-1 (ZnO/GNR||LRGONR asymmetric). The relaxation time constant obtained for the asymmetric supercapacitor device was three orders of magnitude less compared to the ZnO (symmetric, 33 s) supercapacitor device. The high cycling stability of ZnO/GNR||LRGONR up to 96.7% capacitance retention, after 5000 GCD cycles at 2 mA cm-2, paves the way to a high performance aqueous electrochemical supercapacitive energy storage.This article describes the synthesis and characterization of ZnO nanoring embedded graphene nanoribbons. Patterned holes (mesopore dia.) in graphene nanoribbons are chemically generated, leading to a high density of the edge planes. These planes carry negatively charged surface groups (like -COOH and -OH) and therefore anchor the metal ions in a cordial fashion forming a string of metal ions along the edge planes. These strings of imbibed metal ions precipitate as tiny ZnO nanorings over lacey graphene nanoribbons. The thus obtained graphene nanoribbon (GNR) based hierarchical ZnO mesoporous structures are three dimensionally accessible to the electrolyte and demonstrate high performance in capacitive energy storage. The ZnO/GNR nanocomposite electrode in an asymmetric supercapacitor device with lacey reduced graphene oxide nanoribbons (LRGONRs) as a negative electrode exhibits a 2.0 V potential window in the aqueous electrolyte and an ultra-short time constant (0.08 s). The wide potential window consequently increased the energy density from 6.8 Wh kg-1 (ZnO/GNR symmetric) to 9.4 Wh kg-1 (ZnO/GNR||LRGONR asymmetric). The relaxation time constant obtained for the asymmetric supercapacitor device was three orders of magnitude less compared to the ZnO (symmetric, 33 s) supercapacitor device. The high cycling stability of ZnO/GNR||LRGONR up to 96.7% capacitance retention, after 5000 GCD cycles at 2 mA cm-2, paves the way to a high performance aqueous electrochemical supercapacitive energy storage. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06083d

Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

PubMed

Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

2011-07-04

The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on the (CN)(4)Pt-Tl(dmso)(5)(+) system by using DFT calculations (B3LYP model) provide bond distances in excellent agreement with the EXAFS data. The four cyanide ligands are located in a square around the Pt atom, while the Tl atom is coordinated in a distorted octahedral fashion with the metal being located 0.40 Å above the equatorial plane described by four oxygen atoms of dmso ligands. The four equatorial Tl-O bonds and the four cyano ligands around the Pt atom are arranged in an alternate geometry. The coordination environment around Pt may be considered as being square pyramidal, where the apical position is occupied by the Tl atom. The optimized geometry of (CN)(4)Pt-Tl(dmso)(5)(+) is asymmetrical (C(1) point group). This low symmetry might be responsible for the unusually large NMR linewidths observed due to intramolecular chemical exchange processes. The nature of the Pt-Tl bond has been studied by MO analysis. The metal-metal bond formation in (CN)(4)Pt-Tl(dmso)(5)(+) can be simply interpreted as the result of a Pt(5d(z(2)))(2) → Tl(6s)(0) donation. This bonding scheme may rationalize the smaller thermodynamic stability of this adduct compared to the related complexes with (CN)(5)Pt-Tl entity, where the linear C-Pt-Tl unit constitutes a very stable bonding system. © 2011 American Chemical Society

EXAFS study of some coordination polymers of copper

NASA Astrophysics Data System (ADS)

Deshpande, A. P.

1995-02-01

The EXAFS spectra for (1) azelaic acid bis phenyl hydrazide, (2) azelaic acid bis 2,4 dinitro phenyl hydrazide and (3) sebacic acid bis phenyl hydrazide coordination polymers of copper were obtained using the EXAFS facility of the Daresbury Laboratory. The EXAFS analysis revealed that copper is surrounded by four nitrogen and two oxygen atoms in the first coordination shell, while the second coordination shell consists of two carbon atoms. This information suggests the octahedral geometry for the repeating units of polymeric complexes, in contrast to the square planar geometry previously proposed.

An extended X-Ray absorption fine structure (exafs) study of copper (II) sulphate pentahydrate

NASA Astrophysics Data System (ADS)

Joyner, Richard W.

1980-05-01

The EXAFS spectrum of copper (II) sulphate pentahydrate has been measured using synchrotron radiation. Comparison with the results of ab initio calculation gives a mean copper-oxygen distance of 1.95 Å, in reasonable agreement with the known value of 1.97 Å. The relation between the EXAFS Debye-Waller factor and thermal parameters measured by neutron diffraction is discussed. Absence in the EXAFS spectrum of evidence for the second-nearest neighbour oxygen atoms, at Cu-O ≈ 2.4 Å, is discussed.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

The low temperature synthesis, characterization and properties of ferroelectrics

NASA Astrophysics Data System (ADS)

Xu, Jie

2000-10-01

PZT 50:50 xerogels prepared by two different sol-gel routes crystallized in a similar fashion to give a mixture of tetragonal and rhombohedral at high temperature (1000°C). Both the diffraction and EXAFS data suggest that the compositional inhomogeneity of the samples prepared by the two routes is similar. The crystallization of CZT gels is complicated. Crystalline CaCO 3 was always detected in the dry gels regardless of the sample composition and preparation methods. At intermediate temperatures a fluorite related phase was always formed and it transformed to perovskite at higher temperatures. The EXAFS data suggest that perovskite CZT samples prepared using alkoxide sol-gel chemistry may not be random solid solutions. All the solution processed ZrTiO4 materials crystallized in the range 600--700°C. The KTN samples prepared using a conventional alkoxide sol-gel route crystallized completely to perovskite at lower temperatures than those prepared using prehydrolyzed precursors. The EXAFS data for the KTN samples prepared using a conventional alkoxide sol-gel route are consistent with a random distribution of tantalum and niobium in the solid solution. However, materials prepared using the inhomogeneous sol-gel route and by the direct reaction of mixed oxides were shown to be compositionally inhomogeneous. The heterogeneity could not be removed by regrinding and heating the mixed oxide samples several times. K2Ta4-xNbxO11 (x = 0, 2, 4) samples were prepared using alkoxide sol-gel chemistry and their crystallization was examined by powder X-ray diffraction. A Rietveld structure analysis of the pyrochlore formed from a gel with bulk composition K2Ta 2Nb2O11 indicated that it was rich in potassium relative to the bulk sample. On heating to high temperatures tetragonal tungsten bronzes were formed. A Rietveld analysis was also performed for K2Ta 2Nb2O11 with tetragonal tungsten bronze structure. The defect pyrochlores "AgTaO3" and GaTaO 3 were synthesized by ion-exchange using pyrochlore KTaO3 as a starting material. The structures of the pyrochlores were examined using the Rietveld method. The pyrochlore-to-perovskite transformations were also explored.

Annealing effect on the structural, morphological and electrical properties of TiO2/ZnO bilayer thin films

NASA Astrophysics Data System (ADS)

Khan, M. I.; Imran, S.; Shahnawaz; Saleem, Muhammad; Ur Rehman, Saif

2018-03-01

The effect of annealing temperature on the structural, morphological and electrical properties of TiO2/ZnO (TZ) thin films has been observed. Bilayer thin films of TiO2/ZnO are deposited on FTO glass substrate by spray pyrolysis method. After deposition, these films are annealed at 573 K, 723 K and 873 K. XRD shows that TiO2 is present in anatase phase only and ZnO is present in hexagonal phase. No other phases of TiO2 and ZnO are present. Also, there is no evidence of other compounds like Zn-Ti etc. It also shows that the average grain size of TiO2/ZnO films is increased by increasing annealing temperature. AFM (Atomic force microscope) showed that the average roughness of TiO2/ZnO films is decreased at temperature 573-723 K and then increased at 873 K. The calculated average sheet resistivity of thin films annealed at 573 K, 723 K and 873 K is 152.28 × 102, 75.29 × 102 and 63.34 × 102 ohm-m respectively. This decrease in sheet resistivity might be due to the increment of electron concentration with increasing thickness and the temperature of thin films.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission

NASA Astrophysics Data System (ADS)

Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

2011-08-01

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications. Electronic supplementary information (ESI) available: Representative SEM and TEM images of 700 °C annealed ZnO/MgO core/shell NWs, a TEM image of an individual MgO nanocrystal inside the MgO NTs and SEM images of SnO2 NP chains embedded in MgO NTs and comb-shaped MgO hollow nanostructures. See DOI: 10.1039/c1nr10352k

ZnO films on /001/-cut (110)-propagating GaAs substrates for surface acoustic wave device applications

NASA Technical Reports Server (NTRS)

Hickernell, Frederick S.; Higgins, Robert J.; Jen, Cheng-Kuei; Kim, Yoonkee; Hunt, William D.

1995-01-01

A potential application for piezoelectric films substrates is the monolithic integration of surface acoustic wave (SAW) devices with GaAs electronics. Knowledge of the SAW properties of the layered structure is critical for the optimum and accurate design of such devices. The acoustic properties of ZnO films sputtered on /001/-cut group of (110) zone axes-propagating GaAs substrates are investigated in this article, including SAW velocity, effective piezoelectric coupling constant, propagation loss, diffraction, velocity surface, and reflectivity of shorted and open metallic gratings. The measurements of these essential SAW properties for the frequency range between 180 and 360 MHz have been performed using a knife-edge laser probe for film thicknesses over the range of 1.6-4 micron and with films of different grain sizes. The high quality of dc triode sputtered films was observed as evidenced by high K(sup 2) and low attenuation. The measurements of the velocity surface, which directly affects the SAW diffraction, on the bare and metalized ZnO on SiO2 or Si3N4 on /001/-cut GaAs samples are reported using two different techniques: (1) knife-edge laser probe, (2) line-focus-beam scanning acoustic microscope. It was found that near the group of (110) zone axes propagation direction, the focusing SAW property of the bare GaAs changes into a nonfocusing one for the layered structure, but a reversed phenomenon exists near the (100) direction. Furthermore, to some extent the diffraction of the substrate can be controlled with the film thickness. The reflectivity of shorted and open gratings are also analyzed and measured. Zero reflectivity is observed for a shorted grating. There is good agreement between the measured data and theoretical values.

ZnO Films on {001}-Cut <110>-Propagating GaAs Substrates for Surface Acoustic Wave Device Applications

NASA Technical Reports Server (NTRS)

Kim, Yoonkee; Hunt, William D.; Hickernell, Frederick S.; Higgins, Robert J.; Jen, Cheng-Kuei

1995-01-01

A potential application for piezoelectric films on GaAs substrates is the monolithic integration of surface acoustic wave (SAW) devices with GaAs electronics. Knowledge of the SAW properties of the layered structure is critical for the optimum and accurate design of such devices. The acoustic properties of ZnO films sputtered on {001}-cut <110> -propagating GaAs substrates are investigated in this article, including SAW Velocity effective piezoelectric coupling constant, propagation loss. diffraction, velocity surface, and reflectivity of shorted and open metallic gratings. The measurements of these essential SAW properties for the frequency range between 180 and 360 MHz have been performed using a knife-edge laser probe for film thicknesses over the range of 1.6-4 micron and with films or different grain sizes. The high quality of dc triode sputtered films was observed as evidenced by high K(exp 2) and low attenuation. The measurements of the velocity surface, which directly affects the SAW diffraction, on the bare and metalized ZnO on SiO2, or Si3N4 on {001}-cut GaAs samples are reported using two different techniques: 1) knife-edge laser probe, 2) line-focus-beam scanning acoustic microscope. It was found that near the <110> propagation direction, the focusing SAW property of the bare GaAs changes into a nonfocusing one for the layered structure, but a reversed phenomenon exists near the <100> direction. Furthermore, to some extent the diffraction of the substrate can be controlled with the film thickness. The reflectivity of shorted and open gratings are also analyzed and measured. Zero reflectivity is observed for a shorted grating. There is good agreement between the measured data and theoretical values.

Preferential Zn2+ influx through Ca2+-permeable AMPA/kainate channels triggers prolonged mitochondrial superoxide production

PubMed Central

Sensi, Stefano L.; Yin, Hong Z.; Carriedo, Sean G.; Rao, Shyam S.; Weiss, John H.

1999-01-01

Synaptically released Zn2+ can enter and cause injury to postsynaptic neurons. Microfluorimetric studies using the Zn2+-sensitive probe, Newport green, examined levels of [Zn2+]i attained in cultured cortical neurons on exposure to N-methyl-d-asparte, kainate, or high K+ (to activate voltage-sensitive Ca2+ channels) in the presence of 300 μM Zn2+. Indicating particularly high permeability through Ca2+-permeable α-amino3-hydroxy-5-methyl-4-isoxazolepropionic-acid/kainate (Ca-A/K) channels, micromolar [Zn2+]i rises were observed only after kainate exposures and only in neurons expressing these channels [Ca-A/K(+) neurons]. Further studies using the oxidation-sensitive dye, hydroethidine, revealed Zn2+-dependent reactive oxygen species (ROS) generation that paralleled the [Zn2+]i rises, with rapid oxidation observed only in the case of Zn2+ entry through Ca-A/K channels. Indicating a mitochondrial source of this ROS generation, hydroethidine oxidation was inhibited by the mitochondrial electron transport blocker, rotenone. Additional evidence for a direct interaction between Zn2+ and mitochondria was provided by the observation that the Zn2+ entry through Ca-A/K channels triggered rapid mitochondrial depolarization, as assessed by using the potential-sensitive dye tetramethylrhodamine ethylester. Whereas Ca2+ influx through Ca-A/K channels also triggers ROS production, the [Zn2+]i rises and subsequent ROS production are of more prolonged duration. PMID:10051656

Composition and molecular scale structure of nanophases formed by precipitation of biotite weathering products

NASA Astrophysics Data System (ADS)

Tamrat, Wuhib Zewde; Rose, Jérôme; Grauby, Olivier; Doelsch, Emmanuel; Levard, Clément; Chaurand, Perrine; Basile-Doelsch, Isabelle

2018-05-01

Because of their large surface area and reactivity, nanometric-size soil mineral phases have a high potential for soil organic matter stabilization, contaminant sorption or soil aggregation. In the literature, Fe and Al phases have been the main targets of batch-synthesized nanomineral studies while nano-aluminosilicates (Al and Si phases) have been mainly studied in Andic soils. In the present work, we synthesized secondary nanophases of Fe, Al and Si. To simulate a system as close as possible to soil conditions, we conducted laboratory simulations of the processes of (1) biotite alteration in acidic conditions producing a Al Si Fe Mg K leachate solution and (2) the following neoformation of secondary nanophases by titrating the leachate solution to pH 4.2, 5 and 7. The morphology of the nanophases, their size, crystallinity and chemistry were characterized by TEM-EDX on single particles and their local atomic structure by EXAFS (Extended X-ray Absorption Fine Structure) at the Fe absorption K-edge. The main nanophases formed were amorphous particles 10-60 nm in size whose composition (dominated by Fe and Si) was strongly controlled by the pH conditions at the end of the titration. At pH 4.2 and pH 7, the structure of the nanophases was dominated by the polymerization of Fe, which was hindered by Al, Si, Mg and K. Conversely, at pH 5, the polymerization of Fe was counteracted by precipitation of high amounts of Si. The synthetized nanophases were estimated to be rather analogous to nanophases formed in natural biotite-bearing soils. Because of their small size and potential high surface reactivity, the adsorption capacities of these nanophases with respect to the OM should be revisited in the framework of soil C storage.

Preparation and optical properties of TeO2-BaO-ZnO-ZnF2 fluoro-tellurite glass for mid-infrared fiber Raman laser applications

NASA Astrophysics Data System (ADS)

Li, Jie; Xiao, Xusheng; Gu, Shaoxuan; Xu, Yantao; Zhou, Zhiguang; Guo, Haitao

2017-04-01

A serial of novel fluoro-tellurite glasses with compositions of 60TeO2-20BaO-(20-x)ZnO-xZnF2 (x = 0, 2, 4, 5 and 6 mol%) were prepared. The compositional dependences of glass structural evaluation, Raman gain coefficient, UV-Vis transmission spectrum, IR transmission spectrum, linear refractive index and third-order nonlinearity were analyzed. The results showed that the addition of 6 mol% ZnF2 can further improve the Raman gain coefficient to as well as 52 × 10-11 cm/W and effectively decrease around 73% and 57% absorption coefficients respectively caused by free Osbnd H groups (@3.3 μm) and hydrogen-bonded Osbnd H groups (@4.5 μm) in glass. Addition of ZnF2 does not change the UV-Vis absorption edge, optical band gap energy and infrared region cut-off edge almost, while the linear refraction index and ultrafast third-nonlinearity show unmonotonic changes. These novel fluoro-tellurite glasses may be suitable candidates for using in mid-infrared Raman fiber laser and/or amplifier.

Effect of thermal treatment on Zn nanodisks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acuña-Avila, Pedro E., E-mail: pacunaa004@alumno.uaemex.mx; López, Roberto; Vigueras-Santiago, Enrique

2015-06-15

Metallic Zn nanodisks with hexagonal morphology were obtained onto glass substrate under vacuum thermal evaporation. A thermal characterization of Zn nanodiks showed a lower oxidation temperature than source powder Zn. Different thermal treatment on Zn nanodisks played an important role on the morphology, crystal size and surface vibrational modes of ZnO. The growth of ZnO nanoneedles started at the edge of metallic zinc hexagonal structures according with SEM images, the higher temperature the longer needles were grown. XRD diffractogram confirmed the wurtzite structure of ZnO with metallic nuclei. A wide band between 530 and 580 cm{sup −1} of Raman scatteringmore » corresponded at surface vibrational modes not observed at higher temperature.« less

Opposing effects of stacking faults and antisite domain boundaries on the conduction band edge in kesterite quaternary semiconductors

NASA Astrophysics Data System (ADS)

Park, Ji-Sang; Kim, Sunghyun; Walsh, Aron

2018-01-01

We investigated stability and the electronic structure of extended defects including antisite domain boundaries and stacking faults in the kesterite-structured semiconductors, Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe). Our hybrid density functional theory calculations show that stacking faults in CZTS and CZTSe induce a higher conduction band edge than the bulk counterparts, and thus the stacking faults act as electron barriers. Antisite domain boundaries, however, accumulate electrons as the conduction band edge is reduced in energy, having an opposite role. An Ising model was constructed to account for the stability of stacking faults, which shows the nearest-neighbor interaction is stronger in the case of the selenide.

Effect of substrates and thickness on optical properties in atomic layer deposition grown ZnO thin films

NASA Astrophysics Data System (ADS)

Pal, Dipayan; Singhal, Jaya; Mathur, Aakash; Singh, Ajaib; Dutta, Surjendu; Zollner, Stefan; Chattopadhyay, Sudeshna

2017-11-01

Atomic Layer Deposition technique was used to grow high quality, very low roughness, crystalline, Zinc Oxide (ZnO) thin films on silicon (Si) and fused quartz (SiO2) substrates to study the optical properties. Spectroscopic ellipsometry results of ZnO/Si system, staggered type-II quantum well, demonstrate that there is a significant drop in the magnitudes of both the real and imaginary parts of complex dielectric constants and in near-band gap absorption along with a blue shift of the absorption edge with decreasing film thickness at and below ∼20 nm. Conversely, UV-vis absorption spectroscopy of ZnO/SiO2, thin type-I quantum well, consisting of a narrower-band gap semiconductor grown on a wider-band gap (insulator) substrate, shows the similar thickness dependent blue-shift of the absorption edge but with an increase in the magnitude of near-band gap absorption with decreasing film thickness. Thickness dependent blue shift, energy vs. 1/d2, in two different systems, ZnO/Si and ZnO/SiO2, show a difference in their slopes. The observed phenomena can be consistently explained by the corresponding exciton (or carrier/s) deconfinement and confinement effects at the ZnO/Si and ZnO/SiO2 interface respectively, where Tanguy-Elliott amplitude pre-factor plays the key role through the electron-hole overlap factor at the interface.

The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

NASA Astrophysics Data System (ADS)

Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

2016-05-01

Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

At-edge minima in elastic photon scattering amplitudes for dilute aqueous ions

NASA Astrophysics Data System (ADS)

Bradley, D. A.; Hugtenburg, R. P.; Yusoff, A. L.

2006-11-01

Elastic photon scattering and absorption in the vicinity of core atomic orbital energies give rise to resonances in the elastic photon scattering cross-section. Of interest is whether a dilute-ion aqueous system provides an environment suitable for testing independent particle approximation (IPA) predictions. Predictions of the energy of these resonances have been determined for a Dirac-Slater exchange potential with a Latter tail. At BM28 (ESRF), tuneable X-rays were obtained at eV resolution using a 1 1 1 Si monochromator. From target systems including Cu 2+ and Zn 2+, the X-rays were scattered through high angle from an aqueous medium contained in a thin Perspex cell provided with 8 μm kaplan windows. An energy resolution of ˜500 eV from the HPGe detector was adequate to separate the elastic scattering signal from K α radiation but not from Compton or K β contributions. The Compton contribution from the medium was removed assuming validity of the relativistic impulse approximation. The contribution due to K β fluorescence and the resonant X-ray Raman scattering process were handled by assuming the branching ratio for K α and K β contributions to be constant and to be accurately described by fluorescent yields measured above edge. At ionic concentrations ranging from 0.01 to 0.1 mol/l, resonance structures accord with predictions of elastic scattering cross-sections calculated within IPA. Amplitudes calculated using modified form-factors and anomalous scatter factors computed from a Dirac-Slater exchange potential were convolved with a Lorentzian of several eV (FWHM).

Investigation of magnetic order in SmTr2Zn20 (Tr=Fe ,Co,Ru) and SmTr2Cd20 (Tr=Ni ,Pd)

NASA Astrophysics Data System (ADS)

Yazici, D.; White, B. D.; Ho, P.-C.; Kanchanavatee, N.; Huang, K.; Friedman, A. J.; Wong, A. S.; Burnett, V. W.; Dilley, N. R.; Maple, M. B.

2014-10-01

Single crystals of the "cage compounds" SmTr2Zn20 (Tr=Fe, Co, Ru) and SmTr2Cd20 (Tr=Ni, Pd) have been investigated by means of electrical resistivity, magnetization, and specific-heat measurements. The compounds SmFe2Zn20,SmRu2Zn20, and SmNi2Cd20 exhibit ferromagnetic order with Curie temperatures of TC=47.4, 7.6, and 7.5 K, respectively, whereas SmPd2Cd20 is an antiferromagnet with a Néel temperature of TN=3.4 K. No evidence for magnetic order is observed in SmCo2Zn20 down to 110 mK. The Sommerfeld coefficients γ are found to be 57 mJ /molK2 for SmFe2Zn20,79.5 mJ /molK2 for SmCo2Zn20,258 mJ /molK2 for SmRu2Zn20,165 mJ /molK2 for SmNi2Cd20, and 208 mJ /molK2 for SmPd2Cd20. Enhanced values of γ and a quadratic temperature dependence of the electrical resistivity at low temperature for SmRu2Zn20 and SmPd2Cd20 suggest an enhancement of the quasiparticle masses due to hybridization between localized 4f and conduction electron states.

Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lahariya, Vikas

The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

Investigation of magnetic order in SmTr2Zn20 (Tr = Fe, Co, Ru) and SmTr2Cd20 (Tr = Ni, Pd)

NASA Astrophysics Data System (ADS)

Yazici, Duygu; White, B. D.; Ho, P.-C.; Kanchanavatee, N.; Huang, K.; Dilley, N. R.; Maple, M. B.

2015-03-01

Single crystals of the cage compounds Sm Tr 2Zn20 (Tr = Fe, Co, Ru) and Sm Tr 2Cd20 (Tr = Ni, Pd) have been investigated by means of electrical resistivity, magnetization, and specific heat measurements. The compounds SmFe2Zn20, SmRu2Zn20,andSmNi2Cd20 exhibit ferromagnetic order with Curie temperatures of TC = 47.4 K, 7.6 K, and 7.5 K, respectively, whereas SmPd2Cd20 is an antiferromagnet with a Néel temperature of TN = 3.4 K. No evidence for magnetic order is observed in SmCo2Zn20 down to 110 mK. The Sommerfeld coefficients γ are found to be 57 mJ/mol-K2 for SmFe2Zn20, 79.5 mJ/mol-K2 for SmCo2Zn20, 258 mJ/mol-K2 for SmRu2Zn20, 165 mJ/mol-K2 for SmNi2Cd20, and 208 mJ/mol-K2 for SmPd2Cd20. Enhanced values of Sommerfeld coefficients γ and a quadratic temperature dependence of the electrical resistivity at low temperature for SmRu2Zn20andSmPd2Cd20 suggest an enhancement of the quasiparticle masses due to hybridization between localized 4 f and conduction electron states. Research at UCSD was supported by the U.S. DOE under Grant No. DE-FG02-04-ER46105 and the U.S. NSF under Award Grant No. DMR 1206553. Research at California State University, Fresno was supported by the U.S. NSF under Grant No. DMR 1104544.

Towards a new class of heavy ion doped magnetic semiconductors for room temperature applications

PubMed Central

Lee, Juwon; Subramaniam, Nagarajan Ganapathi; Agnieszka Kowalik, Iwona; Nisar, Jawad; Lee, Jaechul; Kwon, Younghae; Lee, Jaechoon; Kang, Taewon; Peng, Xiangyang; Arvanitis, Dimitri; Ahuja, Rajeev

2015-01-01

The article presents, using Bi doped ZnO, an example of a heavy ion doped oxide semiconductor, highlighting a novel p-symmetry interaction of the electronic states to stabilize ferromagnetism. The study includes both ab initio theory and experiments, which yield clear evidence for above room temperature ferromagnetism. ZnBixO1−x thin films are grown using the pulsed laser deposition technique. The room temperature ferromagnetism finds its origin in the holes introduced by the Bi doping and the p-p coupling between Bi and the host atoms. A sizeable magnetic moment is measured by means of x-ray magnetic circular dichroism at the O K-edge, probing directly the spin polarization of the O(2p) states. This result is in agreement with the theoretical predictions and inductive magnetometry measurements. Ab initio calculations of the electronic and magnetic structure of ZnBixO1−x at various doping levels allow to trace the origin of the ferromagnetic character of this material. It appears, that the spin-orbit energy of the heavy ion Bi stabilizes the ferromagnetic phase. Thus, ZnBixO1−x doped with a heavy non-ferromagnetic element, such as Bi, is a credible example of a candidate material for a new class of compounds for spintronics applications, based on the spin polarization of the p states. PMID:26592564

Metal oxidation states in biological water splitting† †Electronic supplementary information (ESI) available: Additional methodological details and discussion, Tables S1–S10, Fig. S1–S16, spin populations, parameters of optimized structures, experimental details and analysis of 55Mn ENDOR at 2.5 K, analysis of calculated Mn K pre-edge XAS, discussion of reduced S states. See DOI: 10.1039/c4sc03720k Click here for additional data file.

PubMed Central

Krewald, Vera; Retegan, Marius; Cox, Nicholas; Messinger, Johannes; Lubitz, Wolfgang; DeBeer, Serena; Neese, Frank

2015-01-01

A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five Si states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster. PMID:29308133

Molecular investigation on the binding of Cd(II) by the binary mixtures of montmorillonite with two bacterial species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Huihui; Qu, ChenChen; Liu, Jing

Bacteria and phyllosilicate commonly coexist in the natural environment, producing various bacteria–clay complexes that are capable of immobilizing heavy metals, such as cadmium, via adsorption. However, the molecular binding mechanisms of heavy metals on these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive B. subtilis, Gram-negative P. putida and their binary mixtures with montmorillonite (Mont) using the Cd K-edge x-ray absorption spectroscopy (XAS) and isothermal titration calorimetry (ITC). We observed a lower adsorptive capacity for P. putida than B. subtilis, whereas P. putida–Mont and B. subtilis–Mont mixtures showed nearly identical Cd adsorption behaviors. EXAFS fitsmore » and ITC measurements demonstrated more phosphoryl binding of Cd in P. putida. The decreased coordination of C atoms around Cd and the reduced adsorption enthalpies and entropies for the binary mixtures compared to that for individual bacteria suggested that the bidentate Cd-carboxyl complexes in pure bacteria systems were probably transformed into monodentate complexes that acted as ionic bridging structure between bacteria and motmorillonite. This study clarified the binding mechanism of Cd at the bacteria–phyllosilicate interfaces from a molecular and thermodynamic view, which has an environmental significance for predicting the chemical behavior of trace elements in complex mineral–organic systems.« less

Schwertmannite stability in acidified coastal environments

NASA Astrophysics Data System (ADS)

Collins, Richard N.; Jones, Adele M.; Waite, T. David

2010-01-01

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.

A novel approach for arsenic adsorbents regeneration using MgO.

PubMed

Tresintsi, Sofia; Simeonidis, Konstantinos; Katsikini, Maria; Paloura, Eleni C; Bantsis, Georgios; Mitrakas, Manassis

2014-01-30

An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task. Copyright © 2013 Elsevier B.V. All rights reserved.

Zn-VI quasiparticle gaps and optical spectra from many-body calculations.

PubMed

Riefer, A; Weber, N; Mund, J; Yakovlev, D R; Bayer, M; Schindlmayr, Arno; Meier, C; Schmidt, W G

2017-06-01

The electronic band structures of hexagonal ZnO and cubic ZnS, ZnSe, and ZnTe compounds are determined within hybrid-density-functional theory and quasiparticle calculations. It is found that the band-edge energies calculated on the [Formula: see text] (Zn chalcogenides) or GW (ZnO) level of theory agree well with experiment, while fully self-consistent QSGW calculations are required for the correct description of the Zn 3d bands. The quasiparticle band structures are used to calculate the linear response and second-harmonic-generation (SHG) spectra of the Zn-VI compounds. Excitonic effects in the optical absorption are accounted for within the Bethe-Salpeter approach. The calculated spectra are discussed in the context of previous experimental data and present SHG measurements for ZnO.

Optimization of K-edge imaging for vulnerable plaques using gold nanoparticles and energy resolved photon counting detectors: a simulation study.

PubMed

Alivov, Yahya; Baturin, Pavlo; Le, Huy Q; Ducote, Justin; Molloi, Sabee

2014-01-06

We investigated the effect of different imaging parameters, such as dose, beam energy, energy resolution and the number of energy bins, on the image quality of K-edge spectral computed tomography (CT) of gold nanoparticles (GNP) accumulated in an atherosclerotic plaque. A maximum likelihood technique was employed to estimate the concentration of GNP, which served as a targeted intravenous contrast material intended to detect the degree of the plaque's inflammation. The simulation studies used a single-slice parallel beam CT geometry with an x-ray beam energy ranging between 50 and 140 kVp. The synthetic phantoms included small (3 cm in diameter) cylinder and chest (33 × 24 cm(2)) phantoms, where both phantoms contained tissue, calcium and gold. In the simulation studies, GNP quantification and background (calcium and tissue) suppression tasks were pursued. The x-ray detection sensor was represented by an energy resolved photon counting detector (e.g., CdZnTe) with adjustable energy bins. Both ideal and more realistic (12% full width at half maximum (FWHM) energy resolution) implementations of the photon counting detector were simulated. The simulations were performed for the CdZnTe detector with a pixel pitch of 0.5-1 mm, which corresponds to a performance without significant charge sharing and cross-talk effects. The Rose model was employed to estimate the minimum detectable concentration of GNPs. A figure of merit (FOM) was used to optimize the x-ray beam energy (kVp) to achieve the highest signal-to-noise ratio with respect to the patient dose. As a result, the successful identification of gold and background suppression was demonstrated. The highest FOM was observed at the 125 kVp x-ray beam energy. The minimum detectable GNP concentration was determined to be approximately 1.06 µmol mL(-1) (0.21 mg mL(-1)) for an ideal detector and about 2.5 µmol mL(-1) (0.49 mg mL(-1)) for a more realistic (12% FWHM) detector. The studies show the optimal imaging parameters at the lowest patient dose using an energy resolved photon counting detector to image GNP in an atherosclerotic plaque.

Double Q-switch Ho:Sc2SiO5 laser by acousto-optic modulator combined with Cr2+:ZnSe saturable absorber

NASA Astrophysics Data System (ADS)

Yang, Xiao-tao; Zhang, Peng; Xie, Wen-qiang; Li, Lin-jun

2018-01-01

A double Q-switch (DQS) Ho:Sc2SiO5 laser modulated by a acousto-optic modulators (AOM) combined with a Cr2+:ZnSe saturable absorber (SA) was reported for the first time. The actively Q-switch (AQS) and passively Q-switch (PQS) were also studied. For the DQS mode, a maximum average output power of 2.49 W under the incident pump power of 12.5 W was obtained, corresponding to a slope efficiency of 24%. The characteristics of the DQS Ho:SSO laser versus different repetition frequencies (RF) of the AOM were researched. The maximum single-pulse energy of the DQS Ho:SSO laser was calculated to 1.98 mJ. The maximum peak power of the DQS Ho:SSO laser was 49.5 kW. The output beam quality factor M2 of DQS Ho:SSO laser was measured to be 1.15 with the highest peak power by knife-edge method at different positions.

SUNY beamline facilities at the National Synchrotron Light Source (Final Report)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coppens, Philip

2003-06-22

The DOE sponsored SUNY synchrotron project has involved close cooperation among faculty at several SUNY campuses. A large number of students and postdoctoral associates have participated in its operation which was centered at the X3 beamline of the National Synchrotron Light Source at Brookhaven National Laboratory. Four stations with capabilities for Small Angle Scattering, Single Crystal and Powder and Surface diffraction and EXAFS were designed and operated with capability to perform experiments at very low as well as elevated temperatures and under high vacuum. A large amount of cutting-edge science was performed at the facility, which in addition provided excellentmore » training for students and postdoctoral scientists in the field.« less

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Temperature dependent optical properties of ZnO thin film using ellipsometry and photoluminescence

NASA Astrophysics Data System (ADS)

Bouzourâa, M.-B.; Battie, Y.; Dalmasso, S.; Zaïbi, M.-A.; Oueslati, M.; En Naciri, A.

2018-05-01

We report the temperature dependence of the dielectric function, the exciton binding energy and the electronic transitions of crystallized ZnO thin film using spectroscopic ellipsometry (SE) and photoluminescence (PL). ZnO layers were prepared by sol-gel method and deposited on crystalline silicon (Si) by spin coating technique. The ZnO optical properties were determined between 300 K and 620 K. Rigorous study of optical responses was achieved in order to demonstrate the quenching exciton of ZnO as a function of temperature. Numerical technique named constrained cubic splines approximation (CCS), Tauc-Lorentz (TL) and Tanguy dispersion models were selected for the ellipsometry data modeling in order to obtain the dielectric function of ZnO. The results reveals that the exciton bound becomes widely flattening at 470 K on the one hand, and on the other that the Tanguy dispersion law is more appropriate for determining the optical responses of ZnO thin film in the temperature range of 300 K-420 K. The Tauc-Lorentz, for its part, reproduces correctly the ZnO dielectric function in 470 K-620 K temperature range. The temperature dependence of the electronic transition given by SE and PL shows that the exciton quenching was observed in 420 K-∼520 K temperature range. This quenching effect can be explained by the equilibrium between the Coulomb force of exciton and its kinetic energy in the film. The kinetic energy was found to induce three degrees of freedom of the exciton.

Effects of thermal treatment on the Mg{sub x}Zn{sub 1−x}O films and fabrication of visible-blind and solar-blind ultraviolet photodetectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Chunguang; Jiang, Dayong, E-mail: dayongjiangcust@126.com; Tan, Zhendong

Highlights: • Single-phase wurtzite/cubic Mg{sub x}Zn{sub 1−x}O films were grown by RF magnetron sputtering technique. • We focus on the red-shift caused by annealing the Mg{sub x}Zn{sub 1−x}O films. • MSM-structured visible-blind and solar-blind UV photodetectors were fabricated. - Abstract: A series of single-phase Mg{sub x}Zn{sub 1−x}O films with different Mg contents were prepared on quartz substrates by RF magnetron sputtering technique using different MgZnO targets, and annealed under the atmospheric environment. The absorption edges of Mg{sub x}Zn{sub 1−x}O films can cover the whole near ultraviolet and even the whole solar-blind spectra range, and the solar-blind wurtzite/cubic Mg{sub x}Zn{sub 1−x}Omore » films have been realized successfully by the same method. In addition, the absorption edges of annealed films shift to a long wavelength, which is caused by the diffusion of Zn atoms gathering at the surface during the thermal treatment process. Finally, the truly solar-blind metal-semiconductor-metal structured photodetectors based on wurtzite Mg{sub 0.445}Zn{sub 0.555}O and cubic Mg{sub 0.728}Zn{sub 0.272}O films were fabricated. The corresponding peak responsivities are 17 mA/W at 275 nm and 0.53 mA/W at 250 nm under a 120 V bias, respectively.« less

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

Structure and magnetic properties of Fe-doped ZnO prepared by the sol-gel method.

PubMed

Liu, Huilian; Yang, Jinghai; Zhang, Yongjun; Yang, Lili; Wei, Maobin; Ding, Xue

2009-04-08

Zn(0.97)Fe(0.03)O nanoparticles were synthesized by the sol-gel method. X-ray diffraction (XRD) and transmission electron microscope (TEM) analysis revealed that the samples had pure ZnO wurtzite structure and Fe ions were well incorporated into the ZnO crystal lattice. X-ray photoelectron spectroscopy (XPS) showed that both Fe(2+) and Fe(3+) existed in Zn(0.97)Fe(0.03)O. The result of x-ray absorption near-edge structure (XANES) further testified that Fe ions took the place of Zn sites in our samples. Magnetic measurements indicated that Zn(0.97)Fe(0.03)O was ferromagnetic at room temperature.

Size-dependent characterization of embedded Ge nanocrystals: Structural and thermal properties

NASA Astrophysics Data System (ADS)

Araujo, L. L.; Giulian, R.; Sprouster, D. J.; Schnohr, C. S.; Llewellyn, D. J.; Kluth, P.; Cookson, D. J.; Foran, G. J.; Ridgway, M. C.

2008-09-01

A combination of conventional and synchrotron-based techniques has been used to characterize the size-dependent structural and thermal properties of Ge nanocrystals (NCs) embedded in a silica (a-SiO2) matrix. Ge NC size distributions with four different diameters ranging from 4.0 to 9.0 nm were produced by ion implantation and thermal annealing as characterized with small-angle x-ray scattering and transmission electron microscopy. The NCs were well represented by the superposition of bulklike crystalline and amorphous environments, suggesting the formation of an amorphous layer separating the crystalline NC core and the a-SiO2 matrix. The amorphous fraction was quantified with x-ray-absorption near-edge spectroscopy and increased as the NC diameter decreased, consistent with the increase in surface-to-volume ratio. The structural parameters of the first three nearest-neighbor shells were determined with extended x-ray-absorption fine-structure (EXAFS) spectroscopy and evolved linearly with inverse NC diameter. Specifically, increases in total disorder, interatomic distance, and the asymmetry in the distribution of distances were observed as the NC size decreased, demonstrating that finite-size effects govern the structural properties of embedded Ge NCs. Temperature-dependent EXAFS measurements in the range of 15-300 K were employed to probe the mean vibrational frequency and the variation of the interatomic distance distribution (mean value, variance, and asymmetry) with temperature for all NC distributions. A clear trend of increased stiffness (higher vibrational frequency) and decreased thermal expansion with decreasing NC size was evident, confirming the close relationship between the variation of structural and thermal/vibrational properties with size for embedded Ge NCs. The increase in surface-to-volume ratio and the presence of an amorphous Ge layer separating the matrix and crystalline NC core are identified as the main factors responsible for the observed behavior, with the surrounding a-SiO2 matrix also contributing to a lesser extent. Such results are compared to previous reports and discussed in terms of the influence of the surface-to-volume ratio in objects of nanometer dimensions.

Electromechanical coupling coefficient k15 of polycrystalline ZnO films with the c-axes lie in the substrate plane.

PubMed

Yanagitani, Takahiko; Mishima, Natsuki; Matsukawa, Mami; Watanabe, Yoshiaki

2007-04-01

The (1120) textured polycrystalline ZnO films with a high shear mode electromechanical coupling coefficient k15 are obtained by sputter deposition. An over-moded resonator, a layered structure of metal electrode film/(1120) textured ZnO piezoelectric film/metal electrode film/silica glass substrate was used to characterize k15 by a resonant spectrum method. The (1120) textured ZnO piezoelectric films with excellent crystallite c-axis alignment showed an electromechanical coupling coefficient k15 of 0.24. This value was 92% of k15 value in single-crystal (k15 = 0.26).

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Spinel and post-spinel phase assemblages in Zn 2TiO 4: an experimental and theoretical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanyao; Liu, Xi; Shieh, Sean R.

Zn2TiO4 spinel (Zn2TiO4-Sp) was synthesized by a solid-state reaction method (1573 K, room P and 72 h) and quasi-hydrostatically compressed to ~24 GPa using a DAC coupled with a synchrotron X-ray radiation (ambient T). We found that the Zn2TiO4-Sp was stable up to ~21 GPa and transformed to another phase at higher P. With some theoretical simulations, we revealed that this high-P phase adopted the CaTi2O4-type structure (Zn2TiO4-CT). Additionally, the isothermal bulk modulus (KT) of the Zn2TiO4-Sp was experimentally obtained as 156.0(44) GPa and theoretically obtained as 159.1(4) GPa, with its first pressure derivative K'TKT' as 3.8(6) and 4.37(4), respectively.more » The volumetric and axial isothermal bulk moduli of the Zn2TiO4-CT were theoretically obtained as KT = 150(2) GPa (K'TKT' = 5.4(2); for the volume), KT-a = 173(2) GPa (K'T-aKT-a' = 3.9(1); for the a-axis), KT-b = 74(2) GPa (K'T-bKT-b' = 7.0(2); for the b-axis), and KT-c = 365(8) GPa (K'T-cKT-c' = 1.5(4); for the c-axis), indicating a strong elastic anisotropy. The Zn2TiO4-CT was found as ~10.0 % denser than the Zn2TiO4-Sp at ambient conditions. The spinel and post-spinel phase assemblages for the Zn2TiO4 composition at high T have been deduced as Zn2TiO4-Sp, ZnTiO3-ilmenite + ZnO-wurtzite, ZnTiO3-ilmenite + ZnO-rock salt, ZnTiO3-perovskite + ZnO-rock salt, and Zn2TiO4-CT as P increases, which presumably implies a potential stability field for a CT-type Mg2SiO4 at very high P.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saha, D., E-mail: sahaphys@gmail.com, E-mail: pmisra@rrcat.gov.in; Misra, P., E-mail: sahaphys@gmail.com, E-mail: pmisra@rrcat.gov.in; Joshi, M. P.

In the present study, atomic layer deposition has been used to grow a series of Ti incorporated ZnO thin films by vertically stacking different numbers (n = 1–7) of ZnO/TiO{sub x} layers on (0001) sapphire substrates. The effects of defect states mediated chemisorption of O{sub 2} and/OH groups on the electrical properties of these films have been investigated by illuminating the samples under UV light inside a high vacuum optical cryostat. The ultra-thin film having one stacked layer (n = 1) did not show any change in its electrical resistance upon UV light exposure. On the contrary, marginal drop in the electrical resistivity wasmore » measured for the samples with n ≥ 3. Most surprisingly, the sample with n = 2 (thickness ∼ 12 nm) showed an insulator to metal transition upon UV light exposure. The temperature dependent electrical resistivity measurement on the as grown film (n = 2) showed insulating behaviour, i.e., diverging resistivity on extrapolation to T→ 0 K. However, upon UV light exposure, it transformed to a metallic state, i.e., finite resistivity at T → 0 K. Such an insulator-metal transition plausibly arises due to the de-trapping of conduction electrons from the surface defect sites which resulted in an upward shift of the Fermi level above the mobility edge. The low-temperature electron transport properties on the insulating film (n = 2) were investigated by a combined study of zero field electrical resistivity ρ(T) and magnetoresistance (MR) measurements. The observed negative MR was found to be in good agreement with the magnetic field induced suppression of quantum interference between forward-going paths of tunnelling electrons. Both ρ(T) and MR measurements provided strong evidence for the Efros-Shklovskii type variable range hopping conduction in the low-temperature (≤40 K) regime. Such studies on electron transport in ultra-thin n-type doped ZnO films are crucial to achieve optimum functionality with long term reliability of ZnO based transparent conducting oxides.« less

Deep levels due to hydrogen in ZnO single crystals

NASA Astrophysics Data System (ADS)

Parmar, Narendra; Weber, Marc; Lynn, Kelvin

2009-05-01

Hydrogen impurities and oxygen vacancies are involved in the ˜0.7 eV shift of the optical absorption edge of ZnO. Deuterium causes a smaller shift. Titanium metal is used to bind hydrogen as it diffuses out of ZnO. Positron annihilation spectroscopy coupled with other techniques point to the presence of oxygen vacancies. Removing hydrogen followed by annealing in oxygen reduces the carrier concentration.

Time-resolved optical studies of wide-gap II-VI semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Wang, Hong

ZnSe and ZnSe-based quantum well and superlattice structures are potential candidates for light emitting devices and other optical devices such as switches and modulators working in the blue-green wavelength range. Carrier dynamics studies of these structures are important in evaluating device performance as well as understanding the underlying physical processes. In this thesis, a carrier dynamics investigation is conducted for temperature from 77K to 295K on CdZnSSe/ZnSSe single quantum well structure (SQW) and ZnSe/ZnSTe superlattice fabricated by molecular beam epitaxy (MBE). Two experimental techniques with femtosecond time resolution are used in this work: up-conversion technique for time- resolved photoluminescence (PL) and pump-probe technique for time-resolved differential absorption studies. For both heterostructures, the radiative recombination is dominated by exciton transition due to the large exciton binding energy as a result of quantum confinement effect. The measured decay time of free exciton PL in CdZnSSe/ZnSSe SQW increases linearly with increasing temperature which agrees with the theoretical prediction by considering the conservation of momentum requirement for radiative recombination. However, the recombination of free carriers is also observed in CdZnSSe/ZnSSe SQW for the whole temperature range studied. On the other hand, in ZnSe/ZnSTe superlattice structures, the non- radiative recombination processes are non-negligible even at 77K and become more important in higher temperature range. The relaxation processes such as spectral hole burning, carrier thermalization and hot-carrier cooling are observed in ZnSe/ZnSTe superlattices at room temperature (295K) by the femtosecond pump-probe measurements. A rapid cooling of the thermalized hot- carrier from 763K to 450K within 4ps is deduced. A large optical nonlinearity (i.e., the induced absorption change) around the heavy-hole exciton energy is also obtained.

Electron magnetic resonance and magnetooptical studies of nanoparticle-containing borate glasses

NASA Astrophysics Data System (ADS)

Kliava, Janis; Edelman, Irina; Ivanova, Oxana; Ivantsov, Ruslan; Petrakovskaja, Eleonora; Hennet, Louis; Thiaudière, Dominique; Saboungi, Marie-Louise

2011-03-01

We report electron magnetic resonance (EMR) and magnetooptical studies of borate glasses of molar composition 22.5K 2O-22.5Al 2O 3-55B 2O 3 co-doped with low concentrations of Fe 2O 3 and MnO. In as-prepared samples the paramagnetic ions, as a rule, are in diluted state. However, in the case where the ratio of the iron and manganese oxides in the charge is 3/2, magnetic nanoparticles with characteristics close to those of manganese ferrite are formed already at the first stage of the glass preparation, as evidenced by both magnetic circular dichroism (MCD) and EMR. After thermal treatment all glasses show characteristic MCD and EMR spectra, attesting to the presence of magnetic nanoparticles, predominantly including iron ions. Preliminary EXAFS measurements at the Fe K-absorption edge show an emergence of nanoparticles with a structure close to MnFe 2O 4 after annealing the glasses at 560 °C. By computer simulating the EMR spectra at variable temperatures, a superparamagnetic nature of relatively broad size and shape distribution with the average diameter of ca. 3-4 nm. The characteristic temperature-dependent shift of the apparent resonance field is explained by a strong temperature dependence of the magnetic anisotropy in the nanoparticles. The formation of magnetic nanoparticles confers to the potassium-alumina-borate glasses magnetic and magneto-optical properties typical of magnetically ordered substances. At the same time, they remain transparent in a part of the visible and near infrared spectral range and display a high Faraday rotation value.

EXAFS: New tool for study of battery and fuel cell materials

NASA Technical Reports Server (NTRS)

Mcbreen, James; Ogrady, William E.; Pandya, Kaumudi I.

1987-01-01

Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth.

PubMed

Lim, Kipil; Jang, Ho Seong; Woo, Kyoungja

2012-12-07

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth

NASA Astrophysics Data System (ADS)

Lim, Kipil; Jang, Ho Seong; Woo, Kyoungja

2012-12-01

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Photon counting x-ray imaging with K-edge filtered x-rays: A simulation study.

PubMed

Atak, Haluk; Shikhaliev, Polad M

2016-03-01

In photon counting (PC) x-ray imaging and computed tomography (CT), the broad x-ray spectrum can be split into two parts using an x-ray filter with appropriate K-edge energy, which can improve material decomposition. Recent experimental study has demonstrated substantial improvement in material decomposition with PC CT when K-edge filtered x-rays were used. The purpose of the current work was to conduct further investigations of the K-edge filtration method using comprehensive simulation studies. The study was performed in the following aspects: (1) optimization of the K-edge filter for a particular imaging configuration, (2) effects of the K-edge filter parameters on material decomposition, (3) trade-off between the energy bin separation, tube load, and beam quality with K-edge filter, (4) image quality of general (unsubtracted) images when a K-edge filter is used to improve dual energy (DE) subtracted images, and (5) improvements with K-edge filtered x-rays when PC detector has limited energy resolution. The PC x-ray images of soft tissue phantoms with 15 and 30 cm thicknesses including iodine, CaCO3, and soft tissue contrast materials, were simulated. The signal to noise ratio (SNR) of the contrast elements was determined in general and material-decomposed images using K-edge filters with different atomic numbers and thicknesses. The effect of the filter atomic number and filter thickness on energy separation factor and SNR was determined. The boundary conditions for the tube load and halfvalue layer were determined when the K-edge filters are used. The material-decomposed images were also simulated using PC detector with limited energy resolution, and improvements with K-edge filtered x-rays were quantified. The K-edge filters with atomic numbers from 56 to 71 and K-edge energies 37.4-63.4 keV, respectively, can be used for tube voltages from 60 to 150 kVp, respectively. For a particular tube voltage of 120 kVp, the Gd and Ho were the optimal filter materials to achieve highest SNR. For a particular K-edge filter of Gd and tube voltage of 120 kVp, the filter thickness 0.6 mm provided maximum SNR for considered imaging applications. While K-edge filtration improved SNR of CaCO3 and iodine by 41% and 36%, respectively, in DE subtracted images, it did not deteriorate SNR in general images. For x-ray imaging with nonideal PC detector, the positive effect of the K-edge filter was increased when FWHM energy resolution was degraded, and maximum improvement was at 60% FWHM. This study has shown that K-edge filtered x-rays can provide substantial improvements of material selective PC x-ray and CT imaging for nearly all imaging applications using 60-150 kVp tube voltages. Potential limitations such as tube load, beam hardening, and availability of filter material were shown to not be critical.

Roles of K2O on the CaO-ZnO Catalyst and Its Influence on Catalyst Basicity for Biodiesel Production

NASA Astrophysics Data System (ADS)

Buchori, Luqman; Istadi, I.; Purwanto; Marpaung, Louis Claudia; Safitri, Rahmatika Luthfiani

2018-02-01

This research aimed to study the effect of K2O impregnation on the basicity of the CaO-ZnO catalyst and its effect on biodiesel production. The effect of mole ratio of CaO to ZnO catalyst and %wt K2O were also studied. The mole ratio of CaO to ZnO catalyst was varied at 1:1, 1:1.5, 1:2, 1:3, and 3:1, while the %wt K2O was varied at 1, 3, and 5 %. The catalyst basicity was determined by titration method. The basicity of the catalyst increased after the CaO-ZnO catalyst was impregnated with K2O in all mole ratios of CaO-ZnO catalyst. The addition of K2O as a promoter also increase the basicity. The highest basicity was obtained at the CaO-ZnO mole ratio of 3:1 and 5%wt K2O. The tranesterification process was carried out in a batch reactor at a methanol to oil mole ratio of 15:1, a reaction temperature of 60°C, a reaction time of 4 h, and a catalyst loading of 5%wt oil. The FAME yields obtained were 41.33%. These results proved that K2O plays a role in enhancing the catalyst basicity. In addition, K2O also serves as a binding agent to improve the mechanical properties of the catalyst.

The effect of local atomic structure on the optical properties of GeSi self-assembled islands buried in silicon matrix

NASA Astrophysics Data System (ADS)

Demchenko, I. N.; Lawniczak-Jablonska, K.; Kret, S.; Novikov, A. V.; Laval, J.-Y.; Zak, M.; Szczepanska, A.; Yablonskiy, A. N.; Krasilnik, Z. F.

2007-03-01

The local atomic structure of GeSi self-assembled islands buried in a silicon matrix strongly influences the optical properties of such systems. In the present paper this structure was determined by x-ray absorption fine-structure (XAFS) spectroscopy and high resolution transmission electron microscopy (HRTEM) and used to build a schematic description of the band structure model. Quantitative analysis of the extended XAFS (EXAFS) spectrum was performed for three coordination shells around the Ge absorbing atom with multiple scattering taken into account. It was proved that the coordination number of elements in an alloy resulting from EXAFS analysis for all three coordination spheres (i.e. 'mixing degree' parameters) cannot be taken as the concentration of alloy but can be used together with a proper model of the alloy unit cell to calculate a realistic concentration. The fraction of Ge calculated in this way is consistent with HRTEM results. The found model of the unit cell was used to generate a x-ray absorption near edge structure spectrum by ab initio calculations. This approach yielded a spectrum in good agreement with the experimental one. The information gained from XAFS and HRTEM was then used for calculation of the band structure diagram. Results of the calculation are discussed and compared with the experimental photoluminescence spectrum.

Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

PubMed

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

2013-06-25

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

Luminescence properties of In(Zn)P alloy core/ZnS shell quantum dots

NASA Astrophysics Data System (ADS)

Thuy, Ung Thi Dieu; Reiss, Peter; Liem, Nguyen Quang

2010-11-01

Chemically synthesized InP/ZnS core/shell quantum dots (QDs) are studied using time-resolved photoluminescence spectroscopy and x-ray diffraction. Zinc stearate, which is added during the synthesis of the InP core, significantly improves the optical characteristics of the QDs. The luminescence quantum yield (QY) reaches 60%-70% and the emission is tunable from 485 to 586 nm by varying the Zn2+:In3+ molar ratio and growth temperature. The observed increased Stokes shift, luminescence decay time, and QY in the presence of Zn are rationalized by the formation of an In(Zn)P alloy structure that causes band-edge fluctuation to enhance the confinement of the excited carriers.

N doped ZnO and ZnO nanorods based p-n homojunction fabricated by ion implantation

NASA Astrophysics Data System (ADS)

Chakraborty, Mohua; Thangavel, R.; Asokan, K.

2018-05-01

Nitrogen (N) doped and undoped Zinc Oxide (ZnO) nanorod p-n homojunctions were fabricated by ion implantation method. The structural and optical characterizations showed that the N atoms doped into the ZnO crystal lattice. The UV-Vis absorption spectra revealed shift in optical absorption edge towards higher wavelength with ion implantation on ZnO, which attributed N acceptor levels above the valence band. The current-voltage (I-V) measurements exhibit a typical semiconductor rectification characteristic indicating the electrical conductivity of the N-doped ZnO nanorod have p-type conductivity. Moreover, a high photocurrent response has been observed with these p-n homojunctions.

3D highly oriented nanoparticulate and microparticulate array ofmetal oxide materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

2006-09-15

Advanced nano and micro particulate thin films of 3d transition and post-transition metal oxides consisting of nanorods and microrods with parallel and perpendicular orientation with respect to the substrate normal, have been successfully grown onto various substrates by heteronucleation, without template and/or surfactant, from the aqueous condensation of solution of metal salts or metal complexes (aqueous chemical growth). Three-dimensional arrays of iron oxide nanorods and zinc oxide nanorods with parallel and perpendicular orientation are presented as well as the oxygen K-edge polarization dependent x-ray absorption spectroscopy (XAS) study of anisotropic perpendicularly oriented microrod array of ZnO performed at synchrotron radiationmore » source facility.« less

Photoemission and x-ray absorption studies of the isostructural to Fe-based superconductors diluted magnetic semiconductor Ba1 -xKx(Zn1 -yMny)2As2

NASA Astrophysics Data System (ADS)

Suzuki, H.; Zhao, K.; Shibata, G.; Takahashi, Y.; Sakamoto, S.; Yoshimatsu, K.; Chen, B. J.; Kumigashira, H.; Chang, F.-H.; Lin, H.-J.; Huang, D. J.; Chen, C. T.; Gu, Bo; Maekawa, S.; Uemura, Y. J.; Jin, C. Q.; Fujimori, A.

2015-04-01

The electronic and magnetic properties of a new diluted magnetic semiconductor (DMS) Ba1 -xKx (Zn1 -yMny )2As2 , which is isostructural to so-called 122-type Fe-based superconductors, are investigated by x-ray absorption spectroscopy (XAS) and resonance photoemission spectroscopy (RPES). Mn L2 ,3-edge XAS indicates that the doped Mn atoms have a valence 2+ and strongly hybridize with the 4 p orbitals of the tetrahedrally coordinating As ligands. The Mn 3 d partial density of states obtained by RPES shows a peak around 4 eV and is relatively high between 0 and 2 eV below the Fermi level (EF) with little contribution at EF, similar to that of the archetypal DMS Ga1 -xMnxAs . This energy level creates a d5 electron configuration with S =5 /2 local magnetic moments at the Mn atoms. Hole carriers induced by K substitution for Ba atoms go into the top of the As 4 p valence band and are weakly bound to the Mn local spins. The ferromagnetic correlation between the local spins mediated by the hole carriers induces ferromagnetism in Ba1 -xKx (Zn1 -yMny )2As2 .

Characterization of the Cu(Π) and Zn(Π) binding to the Amyloid-β short peptides by both the Extended X-ray Absorption Fine Structure and the Synchrotron Radiation Circular Dichroism spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Zhiyin; Sun, Shuaishuai; Xu, Jianhua; Zhang, Jing; Huang, Yan; Zhang, Bingbing; Tao, Ye

2013-04-01

Alzheimer's disease (AD) is a progressive and devastating neurodegenerative pathology, clinically characterized by dementia, cognitive impairment, personality disorders and memory loss. It is generally accepted that, misfolding of Aβ peptides is the key element in pathogenesis and the secondary structure of Aβ can be changed to major β-strand with reasons unknown yet. Many studies have shown that the misfolding may be linked with some biometals, mainly copper and zinc ions. To characterize interactions of Aβ and metal ions, we utilized both the extended X-ray fine structure spectroscopy (EXAFS) and the synchrotron radiation circular dichroism spectroscopy (SRCD). Aβ (13-22), Aβ (13-21), Aβ (E22G) and Aβ(HH-AA) were selected to study the mechanism of copper and zinc binding to Aβ. We found that Cu interaction with H13 and H14 residues led to the disappearance of the PPΠ, while the Cu binding E22 residue caused a remarkable conformation change to β-sheet enrichment. The Zn ion, in contrast, made little effect on the conformation and it coordinated to only one histidine (H residue) or not.

Reducing radiation dose by application of optimized low-energy x-ray filters to K-edge imaging with a photon counting detector.

PubMed

Choi, Yu-Na; Lee, Seungwan; Kim, Hee-Joung

2016-01-21

K-edge imaging with photon counting x-ray detectors (PCXDs) can improve image quality compared with conventional energy integrating detectors. However, low-energy x-ray photons below the K-edge absorption energy of a target material do not contribute to image formation in the K-edge imaging and are likely to be completely absorbed by an object. In this study, we applied x-ray filters to the K-edge imaging with a PCXD based on cadmium zinc telluride for reducing radiation dose induced by low-energy x-ray photons. We used aluminum (Al) filters with different thicknesses as the low-energy x-ray filters and implemented the iodine K-edge imaging with an energy bin of 34-48 keV at the tube voltages of 50, 70 and 90 kVp. The effects of the low-energy x-ray filters on the K-edge imaging were investigated with respect to signal-difference-to-noise ratio (SDNR), entrance surface air kerma (ESAK) and figure of merit (FOM). The highest value of SDNR was observed in the K-edge imaging with a 2 mm Al filter, and the SDNR decreased as a function of the filter thicknesses. Compared to the K-edge imaging with a 2 mm Al filter, the ESAK was reduced by 66%, 48% and 39% in the K-edge imaging with a 12 mm Al filter for 50 kVp, 70 kVp and 90 kVp, respectively. The FOM values, which took into account the ESAK and SDNR, were maximized for 8, 6 to 8 and 4 mm Al filters at 50 kVp, 70 kVp and 90 kVp, respectively. We concluded that the use of an optimal low-energy filter thickness, which was determined by maximizing the FOM, could significantly reduce radiation dose while maintaining image quality in the K-edge imaging with the PCXD.

Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

PubMed

Serrano, Susana; Vlassopoulos, Dimitri; O'Day, Peggy A

2016-04-01

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO 4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L III - and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca 6 Al 2 (SO 4 ) 3 (OH) 12 . 26H 2 O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20-25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg-Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg-Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.

Super-high color rendering properties of color temperature tunable white LEDs based on high quality InP/ZnS quantum dots via myristic acid passivation and Ag doping

NASA Astrophysics Data System (ADS)

Yang, Wu; Zhang, Wanlu; Zhang, Guilin; Zhu, Jiatao; He, Guoxing; Guo, Ruiqian

2018-07-01

We reported two types of tunable white LEDs (WLEDs) based on high quality the single emissive InP/ZnS quantum dots (QDs) and the dual emissive Ag:InP/ZnS QDs via myristic acid (MA) passivation and Ag doping. The WLEDs with three color InP/ZnS QDs could realize color rendering indices (CRIs) of 97-98, color quality scales (CQSs) of 94-98, and limited luminous efficacies (LLEs) of 238-246 lm/W at correlated color temperatures (CCTs) of 2700 K to 6500 K, and the WLEDs with dual emissive Ag:InP/ZnS and red emissive InP/ZnS QDs could realize CRIs of 90-93, CQSs of 90-93, and LLEs of 223-242 lm/W at CCTs of 2700 K to 4000 K. Finally, their luminous efficacies were estimated.

Microstructure, electronic structure and optical properties of combustion synthesized Co doped ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Srinatha, N.; Nair, K. G. M.; Angadi, Basavaraj

2015-10-01

We report on the microstructure, electronic structure and optical properties of nanocrystalline Zn1-xCoxO (x=0, 0.01, 0.03, 0.05 and 0.07) particles prepared by solution combustion technique using L-Valine as fuel. The detailed structural and micro-structural studies were carried out by XRD, HRTEM and TEM-SAED respectively, which confirms the formation of single phased, nano-sized particles. The electronic structure was determined through NEXAFS and atomic multiplet calculations/simulations performed for various symmetries and valence states of 'Co' to determine the valance state, symmetry and crystal field splitting. The correlations between the experimental NEXAFS spectra and atomic multiplet simulations, confirms that, 'Co' present is in the 2+ valence state and substituted at the 'Zn' site in tetrahedral symmetry with crystal field splitting, 10Dq =-0.6 eV. The optical properties and 'Co' induced defect formation of as-synthesized materials were examined by using diffuse reflectance and Photoluminescence spectroscopy, respectively. Red-shift of band gap energy (Eg) was observed in Zn1-xCoxO samples due to Co (0.58 Å) substitution at Zn (0.60 Å) site of the host ZnO. Also, in PL spectra, a prominent pre-edge peak corresponds to ultraviolet (UV) emission around 360-370 nm was observed with Co concentration along with near band edge emission (NBE) of the wide band gap ZnO and all samples show emission in the blue region.

Computational study of the absorption spectrum of defected ZnS nanoparticles

NASA Astrophysics Data System (ADS)

Michos, F. I.; Sigalas, M. M.

2018-04-01

Energy levels and absorption spectra of defected ZnS nanoparticles (NPs) were calculated with Density Functional Theory (DFT) and Time Dependent DFT. Several types of defects were examined such as vacancies and substitutions. NPs with S vacancies were found to have their absorption spectra moved to lower energies well inside the visible spectrum with significantly high oscillator strength. Also, NPs with substitution of S atoms with Cl, Br, or I showed significant absorption. In general, this type of defect moves the absorption spectra in lower energies, thus bringing the absorption edge into the visible spectrum, while the unperturbed NPs have absorption edges in the UV region. In addition, ZnS NPs are made from more abundant and less toxic elements than the more commonly used CdSe NPs. For that reason, they may find significant applications in solar cells and other photonic applications, as well as in biosensing applications as biomarkers.

Zn influence on the plasticity of Cdo{0.96}Zn{0.04}Te

NASA Astrophysics Data System (ADS)

Imhoff, D.; Zozime, A.; Triboulet, R.

1991-11-01

Compression tests were performed on CdTe and Cd{0.96}Zn{0.04}Te to elucidate the mechanism through which Zn inhibits dislocation formation and motion during CdTe crystal growth, thus leading to a decreasing of the dislocation density. Uniaxial deformation experiments performed with CdTe and CdZnTe at constant strain rate within a wide temperature range (0. 14;T_m le T le 0.87;T_m,;T_m = 1 365; K), have revealed a strong hardening effect of Zn within the whole temperature range. They also showed in CdZnTe a Portevin Le Chatelier effect between 770 K and 920 K confirmed by static strain aging experiments. Critical resolved shear stress (C.R.S.S.) values at T = 195; K and static strain aging results with CdZnTe point to size effect as the dominant interaction between Zn and dislocations. Thermal activation parameters were estimated in both materials. La déformation plastique a été utilisée comme approche des mécanismes par lesquels le zinc entrave le mouvement des dislocations au cours du processus de croissance cristalline de CdTe massif, réduisant ainsi la densité de dislocations. Les expériences de compression uniaxiale à vitesse constante, réalisées dans CdTe et CdZnTe entre 0,14 T_f et 0,87 T_f ont montré que le zinc est responsable d'un fort durcissement sur tout le domaine de températures étudié. Les expériences de déformation dans CdZnTe ont mis en évidence un phénomène du type Portevin Le Chatelier entre 770 K et 920 K, confirmé par des expériences de vieillissement statique. Les valeurs de scission critique tau_c à 195 K et les résultats des expériences de vieillissement statique dans CdZnTe sont compatibles avec un effet de taille dominant pour les interactions Zndislocations. Les paramètres d'activation thermique ont été estimés dans les deux matériaux.

Preparation and optical characteristics of ZnSe nanocrystals doped glass by sol gel in situ crystallization method

NASA Astrophysics Data System (ADS)

Hao, Haiyan; Yao, Xi; Wang, Minqiang

2007-01-01

Homogeneous ZnSe nanocrystals doped SiO 2 glass was successfully prepared by sol-gel in situ crystallization method. The structure of the doped ZnSe nanocrystals was studied by X-ray diffraction (XRD). ZnSe nanocrystals in silica were about 4-10 nm analysed by transmission electron microscopy (TEM), which was consistent with the results of XRD estimated using Scherrer's formular. The quantum size effect in ZnSe nanocrystals was evidenced from the blue-shifts of the optical absorption edge, and the average size of ZnSe nanocrystals was estimated by the magnitude of blue shift according to the L.E. Brus' effective mass model. The size of ZnSe nanocrystals depending on annealing time and temperature was further discussed using XRF.

Electronic structure modifications and band gap narrowing in Zn0.95V0.05O

NASA Astrophysics Data System (ADS)

Ahad, Abdul; Majid, S. S.; Rahman, F.; Shukla, D. K.; Phase, D. M.

2018-04-01

We present here, structural, optical and electronic structure studies on Zn0.95V0.05O, synthesized using solid state method. Rietveld refinement of x-ray diffraction pattern indicates no considerable change in the lattice of doped ZnO. The band gap of doped sample, as calculated by Kubelka-Munk transformed reflectance spectra, has been found reduced compared to pure ZnO. Considerable changes in absorbance in UV-Vis range is observed in doped sample. V doping induced decrease in band gap is supported by x-ray absorption spectroscopy measurements. It is experimentally confirmed that conduction band edge in Zn0.95V0.05O has shifted towards Fermi level than in pure ZnO.

Giant spin splitting in optically active ZnMnTe/ZnMgTe core/shell nanowires.

PubMed

Wojnar, Piotr; Janik, Elżbieta; Baczewski, Lech T; Kret, Sławomir; Dynowska, Elżbieta; Wojciechowski, Tomasz; Suffczyński, Jan; Papierska, Joanna; Kossacki, Piotr; Karczewski, Grzegorz; Kossut, Jacek; Wojtowicz, Tomasz

2012-07-11

An enhancement of the Zeeman splitting as a result of the incorporation of paramagnetic Mn ions in ZnMnTe/ZnMgTe core/shell nanowires is reported. The studied structures are grown by gold-catalyst assisted molecular beam epitaxy. The near band edge emission of these structures, conspicuously absent in the case of uncoated ZnMnTe nanowires, is activated by the presence of ZnMgTe coating. Giant Zeeman splitting of this emission is studied in ensembles of nanowires with various average Mn concentrations of the order of a few percent, as well as in individual nanowires. Thus, we show convincingly that a strong spin sp-d coupling is indeed present in these structures.

ChromAIX2: A large area, high count-rate energy-resolving photon counting ASIC for a Spectral CT Prototype

NASA Astrophysics Data System (ADS)

Steadman, Roger; Herrmann, Christoph; Livne, Amir

2017-08-01

Spectral CT based on energy-resolving photon counting detectors is expected to deliver additional diagnostic value at a lower dose than current state-of-the-art CT [1]. The capability of simultaneously providing a number of spectrally distinct measurements not only allows distinguishing between photo-electric and Compton interactions but also discriminating contrast agents that exhibit a K-edge discontinuity in the absorption spectrum, referred to as K-edge Imaging [2]. Such detectors are based on direct converting sensors (e.g. CdTe or CdZnTe) and high-rate photon counting electronics. To support the development of Spectral CT and show the feasibility of obtaining rates exceeding 10 Mcps/pixel (Poissonian observed count-rate), the ChromAIX ASIC has been previously reported showing 13.5 Mcps/pixel (150 Mcps/mm2 incident) [3]. The ChromAIX has been improved to offer the possibility of a large area coverage detector, and increased overall performance. The new ASIC is called ChromAIX2, and delivers count-rates exceeding 15 Mcps/pixel with an rms-noise performance of approximately 260 e-. It has an isotropic pixel pitch of 500 μm in an array of 22×32 pixels and is tile-able on three of its sides. The pixel topology consists of a two stage amplifier (CSA and Shaper) and a number of test features allowing to thoroughly characterize the ASIC without a sensor. A total of 5 independent thresholds are also available within each pixel, allowing to acquire 5 spectrally distinct measurements simultaneously. The ASIC also incorporates a baseline restorer to eliminate excess currents induced by the sensor (e.g. dark current and low frequency drifts) which would otherwise cause an energy estimation error. In this paper we report on the inherent electrical performance of the ChromAXI2 as well as measurements obtained with CZT (CdZnTe)/CdTe sensors and X-rays and radioactive sources.