Emerging surface characterization techniques for carbon steel corrosion: a critical brief review

NASA Astrophysics Data System (ADS)

Dwivedi, D.; Lepkova, K.; Becker, T.

2017-03-01

Carbon steel is a preferred construction material in many industrial and domestic applications, including oil and gas pipelines, where corrosion mitigation using film-forming corrosion inhibitor formulations is a widely accepted method. This review identifies surface analytical techniques that are considered suitable for analysis of thin films at metallic substrates, but are yet to be applied to analysis of carbon steel surfaces in corrosive media or treated with corrosion inhibitors. The reviewed methods include time of flight-secondary ion mass spectrometry, X-ray absorption spectroscopy methods, particle-induced X-ray emission, Rutherford backscatter spectroscopy, Auger electron spectroscopy, electron probe microanalysis, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission electron microscopy, low-energy electron diffraction, small-angle neutron scattering and neutron reflectometry, and conversion electron Moessbauer spectrometry. Advantages and limitations of the analytical methods in thin-film surface investigations are discussed. Technical parameters of nominated analytical methods are provided to assist in the selection of suitable methods for analysis of metallic substrates deposited with surface films. The challenges associated with the applications of the emerging analytical methods in corrosion science are also addressed.

Emerging surface characterization techniques for carbon steel corrosion: a critical brief review

PubMed Central

Dwivedi, D.; Becker, T.

2017-01-01

Carbon steel is a preferred construction material in many industrial and domestic applications, including oil and gas pipelines, where corrosion mitigation using film-forming corrosion inhibitor formulations is a widely accepted method. This review identifies surface analytical techniques that are considered suitable for analysis of thin films at metallic substrates, but are yet to be applied to analysis of carbon steel surfaces in corrosive media or treated with corrosion inhibitors. The reviewed methods include time of flight-secondary ion mass spectrometry, X-ray absorption spectroscopy methods, particle-induced X-ray emission, Rutherford backscatter spectroscopy, Auger electron spectroscopy, electron probe microanalysis, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission electron microscopy, low-energy electron diffraction, small-angle neutron scattering and neutron reflectometry, and conversion electron Moessbauer spectrometry. Advantages and limitations of the analytical methods in thin-film surface investigations are discussed. Technical parameters of nominated analytical methods are provided to assist in the selection of suitable methods for analysis of metallic substrates deposited with surface films. The challenges associated with the applications of the emerging analytical methods in corrosion science are also addressed. PMID:28413351

Vibrational relaxation and internal conversion in the overlapped optically-allowed 1Bu+ and optically-forbidden 1Bu- or 3Ag- vibronic levels of carotenoids: Effects of diabatic mixing as determined by Kerr-gate fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kakitani, Yoshinori; Miki, Takeshi; Koyama, Yasushi; Nagae, Hiroyoshi; Nakamura, Ryosuke; Kanematsu, Yasuo

2009-07-01

The time constants of the vibrational relaxation, υ = 2 → υ = 1 and υ = 1 → υ = 0, in the 1Bu+ manifold and those of internal conversion from the 1Bu+(0) level, which is isoenergetic (so-called 'diabatic') with the 1Bu- vibronic levels in neurosporene and spheroidene and with the 3Ag- vibronic levels in lycopene and anhydrorhodovibrin, were determined by Kerr-gate fluorescence spectroscopy. The time constants of the vibrational relaxation were in the ˜1:2 ratio, and those of internal conversion agreed with the lifetimes of the diabatic counterparts, i.e., the 1Bu- and 3Ag- electronic states, respectively.

Effect of pretreatment on a platinized tin oxide catalyst used for low-temperature CO-oxidation

NASA Technical Reports Server (NTRS)

Drawdy, Jean E.; Hoflund, Gar B.; Gardner, Steven D.; Yngvadottir, Eva; Schryer, David R.

1990-01-01

A commercial platinized tin oxide catalyst used for low-temperature CO oxidation has been characterized using ion scattering spectroscopy (ISS), Auger electron spectroscopy (AES) and Electron Spectroscopy for Chemical Analysis (ESCA) before and after reduction in 40 Torr of CO for 1 hour at various temperatures from 75 to 175 C. The reduction results in loss of surface oxygen, formation of metallic tin, conversion of platinum oxides to Pt-O-Sn and Pt(OH)2 and a small amount of metallic Pt which alloys with the tin. These results should be useful in understanding how the pretreatment temperature affects the catalytic activity of platinized tin oxide toward CO oxidation.

Monitoring long-range electron transfer pathways in proteins by stimulated attosecond broadband X-ray Raman spectroscopy

DOE PAGES

Zhang, Yu; Biggs, Jason D.; Govind, Niranjan; ...

2014-10-09

In this study, long-range electron transfer (ET) plays a key role in many biological energy conversion and synthesis processes. We show that nonlinear spectroscopy with attosecond X-ray pulses provides a real time movie of the evolving oxidation states and electron densities around atoms, and can probe these processes with high spatial and temporal resolution. This is demonstrated in a simulation study of the stimulated X-ray Raman (SXRS) signals in Re-modified azurin, which had long served as a benchmark for long-range ET in proteins. Nonlinear SXRS signals are sensitive to the local electronic structure and should offer a novel window formore » long-range ET.« less

Comparative studies of thin film growth on aluminium by AFM, TEM and GDOES characterization

NASA Astrophysics Data System (ADS)

Qi, Jiantao; Thompson, George E.

2016-07-01

In this present study, comparative studies of trivalent chromium conversion coating formation, associated with aluminium dissolution process, have been investigated using atomic force microscopy (AFM), transmission electron microscopy (TEM) and glow-discharge optical emission spectroscopy (GDOES). High-resolution electron micrographs revealed the evident and uniform coating initiation on the whole surface after conversion treatment for only 30 s, although a network of metal ridges was created by HF etching pre-treatment. In terms of conversion treatment process on electropolished aluminium, constant kinetics of coating growth, ∼0.30 ± 0.2 nm/s, were found after the prolonged conversion treatment for 600 s. The availability of electrolyte anions for coating deposition determined the growth process. Simultaneously, a proceeding process of aluminium dissolution during conversion treatment, of ∼0.11 ± 0.02 nm/s, was found for the first time, indicating constant kinetics of anodic reactions. The distinct process of aluminium consumption was assigned with loss of corrosion protection of the deposited coating material as evidenced in the electrochemical impedance spectroscopy. Based on the present data, a new mechanism of coating growth on aluminium was proposed, and it consisted of an activation period (0-30 s), a linear growth period (0.30 nm/s, up for 600 s) and limited growth period (0.17 nm/s, 600-1200 s). In addition, the air-drying post-treatment and a high-vacuum environment in the microscope revealed a coating shrinkage, especially in the coatings after conversion treatments for longer time.

Characterization of Molybdate Conversion Coatings for Aluminum Alloys by Electrochemical Impedance Spectroscopy

NASA Technical Reports Server (NTRS)

Calle, Luz Marina

2000-01-01

Electrochemical impedance spectroscopy (EIS) was used to investigate the corrosion inhibiting properties of newly developed proprietary molybdate conversion coatings on aluminum alloy 2024-T3 under immersion in aerated 5% (w/w) NaCl. Corrosion potential and EIS measurements were gathered for six formulations of the coating at several immersion times for two weeks. Nyquist as well as Bode plots of the data were obtained. The conversion-coated alloy panels showed an increase in the corrosion potential during the first 24 hours of immersion that later subsided and approached a steady value. Corrosion potential measurements indicated that formulations A, D, and F exhibit a protective effect on aluminum 2024-T3. The EIS spectra of the conversion-coated alloy were characterized by an impedance that is higher than the impedance of the bare alloy at all the immersion times. The low frequency impedance, Z(sub lf) (determined from the value at 0.05 Hz) for the conversion-coated alloy was higher at all the immersion times than that of the bare panel. This indicates improvement of corrosion resistance with addition of the molybdate conversion coating. Scanning electron microscopy (SEM) revealed the presence of cracks in the coating and the presence of cubic crystals believed to be calcium carbonate. Energy dispersive spectroscopy (EDS) of the test panels revealed the presence of high levels of aluminum, oxygen, and calcium but did not detect the presence of molybdenum on the test panels. X-ray photoelectron spectroscopy (XPS) indicated the presence of less than 0.01 atomic percent molybdenum on the surface of the coating.

Formation Mechanism of Discoloration on Die-Cast AZ91D Components Surface After Chemical Conversion

NASA Astrophysics Data System (ADS)

Liu, Bao-sheng; Wei, Ying-hui; Hou, Li-feng

2013-01-01

A notebook (NB) computer component was manufactured from AZ91D Mg alloy by a die-casting process. After chemical conversion treatment, a discoloration was noted on the component surface. The source of this discoloration has been studied in detail by scanning electron microscopy, energy dispersive spectroscopy, and spark atomic absorption spectroscopy. The corrosion resistance was also measured by potentiodynamic polarization, hydrogen evolution and salt spray testing. The formation mechanism for the discoloration which was caused by the residue left behind by excess mold release agent sprayed during the die-casting was discussed in detail. After chemical conversion treatment, the residual-baked mold release agent was apparent on the component surface as "white ash." Consequently, it degraded seriously both the appearance and the corrosion resistance of the manufactured component.

An Avalanche Diode Electron Detector for Observing NEET

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

Kishimoto, Shunji

2004-05-12

Nuclear excitation by electron transition (NEET) occurs in atomic inner-shell ionization if the nuclear excitation and the electron transition have nearly the same energy and a common multipolarity. We successfully observed the NEET on 197Au and on 193Ir using a silicon avalanche diode electron detector. The detector was used to find internal conversion electrons emitted from excited nuclei in time spectroscopy with a time gate method. Some nuclear resonant levels, including 8.410 keV on 169Tm and 80.577 keV on 166Er, were also observed with the detector.

Ultrafast photophysics of transition metal complexes.

PubMed

Chergui, Majed

2015-03-17

The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of interest. With the emergence of new instruments such as X-ray free electron lasers (XFELs), it is now possible to perform ultrafast laser pump/X-ray emission probe experiments. In this case, one probes the density of occupied states. These core-level spectroscopies and other emerging ones, such as photoelectron spectroscopy of solutions, are delivering a hitherto unseen degree of detail into the photophysics of metal-based molecular complexes. In this Account, we will give examples of applications of the various methods listed above to address specific photophysical processes.

A Black Phosphate Conversion Coating on Steel Surface Using Antimony(III)-Tartrate as an Additive

NASA Astrophysics Data System (ADS)

Li, Feng; Wang, Guiping

2016-05-01

A novel black phosphate conversion coating was formed on steel surface through a Zn-Mn phosphating bath containing mainly ZnO, H3PO4, Mn(H2PO4)2, and Ca(NO3)2, where antimony(III)-tartrate was used as the blackening agent of phosphatization. The surface morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersion spectroscopy, and x-ray photoelectron spectroscopy. Corrosion resistance of the coating was studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy. The pH value of the solution had significant influence on the formation and corrosion resistance of the coating. The experimental results indicated that the Sb plays a vital role in the blackening of phosphate conversion coating. The optimal concentration of antimony(III)-tartrate in the phosphating bath used in this experiment was 1.0 g L-1, as higher values reduced the corrosion resistance of the coating. In addition, by saponification and oil seals, the corrosion duration of the black phosphate coating in a copper sulfate spot test can be as long as 20 min.

Spectroscopic and microscopic characterization of silver nanoparticles synthesized using Justicia adhatoda flower

NASA Astrophysics Data System (ADS)

Singh, Tej; Shekhawat, Dharmender Singh; Jyoti, Kumari

2018-05-01

The synthesis of silver nanoparticles (SNPs) by chemical and physical methods produce harmful products which may cause various environmental problems, thus, there is an increasing demand to use ecofriendly methods. Therefore, biosynthesis of SNPs using Justicia adhatoda flower extract is demonstrated in the present study. The biosynthesized SNPs were characterized by UV-visible spectroscopy, Fourier transform-infrared spectroscopy (FTIR), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and atomic force microscopy (AFM) analysis. The result of UV-visible spectroscopy peaked at 417 nm corresponding to the plasmon absorbance of SNPs. The TEM and SAED result reveals the crystalline nature of SNPs. FTIR spectroscopy used to identify the possible biomolecules responsible for the conversion of silver ions to SNPs. The study concluded that Justicia adhatoda flower extract act as an excellent reducing agent and the green synthesized SNPs are safer to the environment.

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

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

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

DOE PAGES

Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.; ...

2017-06-22

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrummore » at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. Furthermore, high-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.« less

Spectroscopic Studies of Melanin.

DTIC Science & Technology

1986-01-01

operation of the laser optics; Mr. Thomas Haw; Dr. James Gallas; Ms. Christine L. Noah- Cooper for stimulating and useful conversations; and Lottie B...168B. 14. Kozikowski SD, Wolfram LJ, Alfano RR. Fluorescence spectroscopy of eumelanins. IEEE J Quant Electron 1984;OE20:1379-1382. 15. Slawinski J

Structure-processing-property correlations in thin films of conjugated polymer nanocomposites and blends

NASA Astrophysics Data System (ADS)

Sreeram, Arvind

Conjugated polymers have found several applications in recent years, in energy conversion and storage devices such as organic light emitting diodes, solar cells, batteries, and super capacitors. Thin films of polymers used for these applications need to be mechanically and thermally stable to withstand the harsh operating conditions. Although there is significant information on the optoelectronic properties of many of these polymers, there are only few studies on their mechanical properties. There is little information in the literature on how processing of these films influence mechanical properties. In the first part of this study, poly(p-phenylene vinylene) (PPV) films were prepared by thermolytic conversion of poly[p -phenylene (tetrahydrothiophenium)ethylene chloride] precursor films, at different temperatures and the kinetics of reaction was investigated using thermogravimetry and Fourier transform infrared (FTIR) spectroscopy. The mechanical properties of the films, studied using nanoindentation, showed a dependence on the extent of conversion and chemical composition of the films. The presence of chemical defects (e.g., carbonyl groups, detected using FTIR spectroscopy), was also found to have a noticeable effect on the modulus and hardness of the films. The storage modulus, E', and plasticity decreased with an increase in conversion, whereas the loss modulus, E", showed the opposite trend. Both the precursor and the fully-converted PPV films were found to have significantly lower E" than E', consistent with the glassy nature of the polymers at room temperature. In the second part of the study, polyacetylene films were synthesized by acid-catalyzed dehydration reaction of poly(vinyl alcohol) (PVA) precursor films. The kinetics of this reaction was monitored by thermogravimetry. The chemical structure of the conjugated polymer films was characterized by Raman and IR spectroscopy. Polyacetylene films incorporated with 1-propyl-3-methylimidazolium ionic liquid (IL) could be obtained in a single step reaction. The incorporation of IL in the film, not only greatly improved its mechanical properties, by acting as a plasticizer, but also imparted a dual mechanism of charge transport. The segments of conjugated double bonds imparted electronic conductivity to the films, and the IL resulted in ionic conductivity. The presence of both electronic and ionic conduction pathways in the films was confirmed by electrochemical impedance spectroscopy (EIS). These IL-imbibed conjugated polymer films are promising as materials for electrochemical energy conversion and storage. In the third part of this work, conjugated polymer films containing multiwalled carbon nanotubes (MWNT) and graphene nanoplatelets (GNP) were synthesized and characterized. PPV--MWNT nanocomposite films and PA--GNP nanocomposite films were characterized using a variety of analytical techniques including transmission electron microscopy, quasistatic and dynamic nanoindentaiton, electrochemical impedance spectroscopy, and cyclic voltammetry. Potential application of these films is in electrochemical supercapacitors.

An investigation on the photoelectrochemical properties of dye-sensitized solar cells based on graphene-TiO2 composite photoanodes

NASA Astrophysics Data System (ADS)

Zhu, Menghua; Li, Xin; Liu, Weiwei; Cui, Ying

2014-09-01

The graphene-TiO2 nanocomposite has been prepared by mixing graphene oxide (GO) and tetra-n-butyl titanate (TBT) followed by the facile hydrothermal process when the reduction of GO to reduced graphene oxide (RGO) and the hydrolysis of TBT to TiO2 happen. Characterization of the graphene-TiO2 nanostructures is investigated in detail by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. A dye-sensitized solar cell (DSSC) based on graphene-TiO2 composite photoelectrode exhibits a high energy conversion efficiency of 4.28%, compared with a DSSC based on pure TiO2 photoelectrode (3.11%), accompanied by an increment in both short-circuit photocurrent density and open-circuit voltage. The significant enhancement in performance of DSSC is investigated through intensity-modulated photovoltage spectroscopy, intensity-modulated photocurrent spectroscopy, and electrochemical impedance spectroscopy. It is found that the incorporation of two-dimensional graphene nanosheets in the TiO2 electrodes is the key factor leading to the improved photogenerated electron transfer ability and reduced charge recombination.

Effect of photoanode thickness on electrochemical performance of dye sensitized solar cell

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

Khatani, Mehboob, E-mail: mkhatani@hotmail.com; Hamid, Nor Hisham, E-mail: hishmid@petronas.com.my; Sahmer, Ahmed Zahrin, E-mail: azclement@yahoo.com

2015-07-22

The thickness of photoanode is crucial as it adsorbed a large amount of dye molecules that provide electrons for generation of electricity in dye sensitized solar cell (DSC). Thus, in order to realize the practical application of DSC, study on various thickness of photoanode need to be carried out to analyze its effect on the electrochemical behavior of dye sensitized solar cell. To enhance the conversion efficiency, an additional layer of TiO{sub 2} using TiCl{sub 4} treatment was deposited prior to the deposition of the photoanode (active area of 1cm{sup 2}) with the thickness of 6, 12, 18, 24, andmore » 30 µm on fluorine doped tin oxide (FTO) glass substrate. The resulting photoanode after the soak in N719 dye for more than 12hrs were used to be assembled in a test cell in combination with liquid electrolyte and counter electrode. The fabricated cells were characterized by solar simulator, ultraviolet-visible spectroscopy (UV-VIS), and electrochemical impedance spectroscopy (EIS). Scanning electron microscopy (SEM) was used to approximate the thickness of photoanode. An optimum power conversion efficiency of 4.54% was obtained for the cell fabricated with 18 µm photoanode thickness. This is attributed to the reduced resistance related to electron transport in the TiO{sub 2}/dye/electrolyte interface as proven by the EIS result. This led to the reduction of internal resistance, the increase in the electron life time and the improvement in the conversion efficiency.« less

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

DOE PAGES

Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

2016-08-25

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN –) ligands and one 2,2'-bipyridine (bpy) ligand. This enablesmore » MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN) 4(bpy)] 2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN) 4(bpy)] 2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine) 3] 2+ by more than two orders of magnitude.« less

Cocrystals Strategy towards Materials for Near-Infrared Photothermal Conversion and Imaging.

PubMed

Wang, Yu; Zhu, Weigang; Du, Wenna; Liu, Xinfeng; Zhang, Xiaotao; Dong, Huanli; Hu, Wenping

2018-04-03

A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near-infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self-assemble into new cocrystals through non-covalent interactions. The strong D-A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest-lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency (η=18.8 %), which is due to the active non-radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

TiO₂ Nanowire Networks Prepared by Titanium Corrosion and Their Application to Bendable Dye-Sensitized Solar Cells.

PubMed

Jin, Saera; Shin, Eunhye; Hong, Jongin

2017-10-12

TiO₂ nanowire networks were prepared, using the corrosion of Ti foils in alkaline (potassium hydroxide, KOH) solution at different temperatures, and then a further ion-exchange process. The prepared nanostructures were characterized by field emission scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The wet corroded foils were utilized as the photoanodes of bendable dye-sensitized solar cells (DSSCs), which exhibited a power conversion efficiency of 1.11% under back illumination.

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Ultrafast Solvation Dynamics and Vibrational Coherences of Halogenated Boron-Dipyrromethene Derivatives Revealed through Two-Dimensional Electronic Spectroscopy.

PubMed

Lee, Yumin; Das, Saptaparna; Malamakal, Roy M; Meloni, Stephen; Chenoweth, David M; Anna, Jessica M

2017-10-18

Boron-dipyrromethene (BODIPY) chromophores have a wide range of applications, spanning areas from biological imaging to solar energy conversion. Understanding the ultrafast dynamics of electronically excited BODIPY chromophores could lead to further advances in these areas. In this work, we characterize and compare the ultrafast dynamics of halogenated BODIPY chromophores through applying two-dimensional electronic spectroscopy (2DES). Through our studies, we demonstrate a new data analysis procedure for extracting the dynamic Stokes shift from 2DES spectra revealing an ultrafast solvent relaxation. In addition, we extract the frequency of the vibrational modes that are strongly coupled to the electronic excitation, and compare the results of structurally different BODIPY chromophores. We interpret our results with the aid of DFT calculations, finding that structural modifications lead to changes in the frequency, identity, and magnitude of Franck-Condon active vibrational modes. We attribute these changes to differences in the electron density of the electronic states of the structurally different BODIPY chromophores.

Spin conversion of positronium in NiO/Al2O3 catalysts observed by coincidence Doppler broadening technique

NASA Astrophysics Data System (ADS)

Zhang, H. J.; Chen, Z. Q.; Wang, S. J.; Kawasuso, A.; Morishita, N.

2010-07-01

High-purity NiO/Al2O3 catalysts were prepared by mixing NiO and γ-Al2O3 nanopowders. X-ray diffraction patterns were measured to characterize the grain size and crystalline phase of the nanopowders. Positron-annihilation spectroscopy was used to study the microstructure and surface properties of the pores inside the NiO/Al2O3 catalysts. The positron lifetime spectrum comprises two short and two long lifetime components. The two long lifetimes τ3 and τ4 correspond to ortho-positronium (o-Ps) annihilated in microvoids and large pores, respectively. With increasing NiO content in the NiO/Al2O3 catalysts, both τ4 and its intensity I4 show continuous decrease. Meanwhile, the para-positronium (p-Ps) intensity, obtained from coincidence Doppler broadening spectra, increases gradually with NiO content. The different variation in o-Ps and p-Ps intensity suggests the ortho-para conversion of positronium in NiO/Al2O3 catalysts. X-ray photoelectron spectroscopy shows that Ni mainly exists in the form of NiO. The electron-spin-resonance measurements reveal that the ortho-para conversion of Ps is induced by the unpaired electrons of the paramagnetic centers of NiO.

Effect of Few-Layered Graphene-Based CdO Nanocomposite-Enhanced Power Conversion Efficiency of Dye-Sensitized Solar Cell

NASA Astrophysics Data System (ADS)

Bykkam, Satish; Kalagadda, Bikshalu; Kalagadda, Venkateswara Rao; Ahmadipour, Mohsen; Chakra, Ch. Shilpa; Rajendar, V.

2018-01-01

A few-layered graphene (FLG)/cadmium oxide (CdO) nanocomposite was sucessfully prepared through ultrasonic-assisted synthesis. The morphology of FLG (1.0 wt.%, 2.0 wt.%, and 3.0 wt.%)/CdO nanocomposites were characterized using high-resolution transmission electron microscopy and field emission scanning electron microscopy techniques. The optical properties were studied with the help of UV-Vis diffuse reflectance spectroscopy and Raman spectroscopy, while the crystalline phases were analyzed using x-ray diffraction. The doctor blade method was used to deposit FLG/CdO nanocomposites on fluorine-doped tin oxide conductive glass substrates. The effect of FLG weight percentage (1.0 wt.%, 2.0 wt.%, and 3.0 wt.%) was studied on the power conversion efficiency of dye-sensitized solar cell applications. The photovoltaic characteristics, current density-voltage curves were measured with ruthenium (II)-based dye under air mass condition 1.5G, 100 m W m-2 of a solar simulator. The results showed that higher power conversion efficiency of 3.54% was achieved at the appropriate weight percentage of FLG (1.0 wt.%)/CdO nanocomposite, compared to the CdO and other nanocomposite working electrodes FLG (2.0 wt.%, and 3.0 wt.%)/CdO.

Role of the Cu-ZrO 2 Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO 2 and H 2 [The Role of the Cu-ZrO 2 Interfacial Sites for Ethanol Conversion to Ethyl Acetate and Methanol Synthesis from CO 2 and H 2

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

Ro, Insoo; Liu, Yifei; Ball, Madelyn R.

Well-defined Cu catalysts containing different amounts of zirconia were synthesized by controlled surface reactions (CSRs) and atomic layer deposition methods and studied for the selective conversion of ethanol to ethyl acetate and for methanol synthesis. Selective deposition of ZrO 2 on undercoordinated Cu sites or near Cu nanoparticles via the CSR method was evidenced by UV–vis absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The concentrations of Cu and Cu-ZrO 2 interfacial sites were quantified using a combination of subambient CO Fourier transform infrared spectroscopy and reactive N 2O chemisorption measurements. The oxidation states ofmore » the Cu and ZrO 2 species for these catalysts were determined using X-ray absorption near edge structure measurements, showing that these species were present primarily as Cu 0 and Zr 4+, respectively. Here, it was found that the formation of Cu-ZrO 2 interfacial sites increased the turnover frequency by an order of magnitude in both the conversion of ethanol to ethyl acetate and the synthesis of methanol from CO 2 and H 2.« less

Role of the Cu-ZrO 2 Interfacial Sites for Conversion of Ethanol to Ethyl Acetate and Synthesis of Methanol from CO 2 and H 2 [The Role of the Cu-ZrO 2 Interfacial Sites for Ethanol Conversion to Ethyl Acetate and Methanol Synthesis from CO 2 and H 2

DOE PAGES

Ro, Insoo; Liu, Yifei; Ball, Madelyn R.; ...

2016-09-06

Well-defined Cu catalysts containing different amounts of zirconia were synthesized by controlled surface reactions (CSRs) and atomic layer deposition methods and studied for the selective conversion of ethanol to ethyl acetate and for methanol synthesis. Selective deposition of ZrO 2 on undercoordinated Cu sites or near Cu nanoparticles via the CSR method was evidenced by UV–vis absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The concentrations of Cu and Cu-ZrO 2 interfacial sites were quantified using a combination of subambient CO Fourier transform infrared spectroscopy and reactive N 2O chemisorption measurements. The oxidation states ofmore » the Cu and ZrO 2 species for these catalysts were determined using X-ray absorption near edge structure measurements, showing that these species were present primarily as Cu 0 and Zr 4+, respectively. Here, it was found that the formation of Cu-ZrO 2 interfacial sites increased the turnover frequency by an order of magnitude in both the conversion of ethanol to ethyl acetate and the synthesis of methanol from CO 2 and H 2.« less

Characteristics and corrosion studies of vanadate conversion coating formed on Mg-14 wt%Li-1 wt%Al-0.1 wt%Ce alloy

NASA Astrophysics Data System (ADS)

Ma, Yibin; Li, Ning; Li, Deyu; Zhang, Milin; Huang, Xiaomei

2012-11-01

Mg-14Li-1Al-0.1Ce alloy is immersed in NH4VO3 + K3(Fe(CN)6) solutions with different NH4VO3 and/or K3(Fe(CN)6) concentrations, and different immersion time. The surface morphology and composition of the vanadate coating are then characterized by scanning electron microscopy with energy dispersion spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), and the corrosion behavior of the conversion coating is studied by polarization technique and electrochemical impedance spectroscopy (EIS). The experimental results indicate that the vanadate film with better corrosion resistance forms on Mg-Li-Al-Ce surface after the sample is immersed in 30 g L-1 NH4VO3 + 3.75 g L-1 K3(Fe(CN)6) solution at 80 °C for 10 min. The coating consists of V2O5, Li2O and Mg(OH)2.

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface.

PubMed

Sykes, Matthew E; Stewart, Jon W; Akselrod, Gleb M; Kong, Xiang-Tian; Wang, Zhiming; Gosztola, David J; Martinson, Alex B F; Rosenmann, Daniel; Mikkelsen, Maiken H; Govorov, Alexander O; Wiederrecht, Gary P

2017-10-17

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers, which we propose arise from anisotropic electron-electron scattering within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold, whereas the quantum process of hot electron generation takes place in both components. Our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.The creation of energetic electrons through plasmon excitation has implications in optical energy conversion and ultrafast nanophotonics. Here, the authors find evidence for three subpopulations of nonthermal carriers which arise from anisotropic electron-electron scattering near the Fermi surface.

Xe isotope detection and discrimination using beta spectroscopy with coincident gamma spectroscopy

NASA Astrophysics Data System (ADS)

Reeder, P. L.; Bowyer, T. W.

1998-02-01

Beta spectroscopic techniques show promise of significant improvements for a beta-gamma coincidence counter that is part of a system for analyzing Xe automatically separated from air. The previously developed counting system for 131mXe, 133mXe, 133gXe, and 135gXe can be enhanced to give additional discrimination between these Xe isotopes by using the plastic scintillation sample cell as a beta spectrometer to resolve the conversion electron peaks. The automated system will be a key factor in monitoring the Comprehensive Test Ban Treaty.

Efficient mechanochemical bifunctional nanocatalysts for the conversion of isoeugenol to vanillin

NASA Astrophysics Data System (ADS)

Ostovar, Somayeh; Franco, Ana; Puente-Santiago, Alain R.; Pinilla-de Dios, María; Rodríguez-Padrón, Daily; Shaterian, Hamid R.; Luque, Rafael

2018-04-01

A novel highly functionalized nanocatalyst composed of iron containing SBA-15 material modified with sulfonic acid groups was synthesized by a mechanochemical approach. A full characterization of the obtained nanoreactor was performed by N2 physisorption isotherms analysis, transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and Fourier-Infrared Spectroscopy (FT-IR). The mechanochemically synthesized nanocatalyst displays a high isoeugenol conversion to vanillin under mild conditions using H2O2 as oxidizing agent. Interestingly, this conversion resulted to be higher than that one obtained with the same material synthesized by an impregnation method. Additionally, the nanoreactor showed excellent reusability over four successive runs under the studied reaction conditions.

Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

PubMed Central

Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

2016-01-01

A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

PubMed Central

2013-01-01

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO2 nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO2 DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO2 electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO2 nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6 wt.% rutile) TiO2 nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3 mA cm−2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO2 nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies. PMID:23286741

n-type conversion of SnS by isovalent ion substitution: Geometrical doping as a new doping route

PubMed Central

Ran, Fan-Yong; Xiao, Zewen; Toda, Yoshitake; Hiramatsu, Hidenori; Hosono, Hideo; Kamiya, Toshio

2015-01-01

Tin monosulfide (SnS) is a naturally p-type semiconductor with a layered crystal structure, but no reliable n-type SnS has been obtained by conventional aliovalent ion substitution. In this work, carrier polarity conversion to n-type was achieved by isovalent ion substitution for polycrystalline SnS thin films on glass substrates. Substituting Pb2+ for Sn2+ converted the majority carrier from hole to electron, and the free electron density ranged from 1012 to 1015 cm−3 with the largest electron mobility of 7.0 cm2/(Vs). The n-type conduction was confirmed further by the position of the Fermi level (EF) based on photoemission spectroscopy and electrical characteristics of pn heterojunctions. Density functional theory calculations reveal that the Pb substitution invokes a geometrical size effect that enlarges the interlayer distance and subsequently reduces the formation energies of Sn and Pb interstitials, which results in the electron doping. PMID:26020855

Complementary Characterization of Cu(In,Ga)Se₂ Thin-Film Photovoltaic Cells Using Secondary Ion Mass Spectrometry, Auger Electron Spectroscopy, and Atom Probe Tomography.

PubMed

Jang, Yun Jung; Lee, Jihye; Jeong, Jeung-Hyun; Lee, Kang-Bong; Kim, Donghwan; Lee, Yeonhee

2018-05-01

To enhance the conversion performance of solar cells, a quantitative and depth-resolved elemental analysis of photovoltaic thin films is required. In this study, we determined the average concentration of the major elements (Cu, In, Ga, and Se) in fabricated Cu(In,Ga)Se2 (CIGS) thin films, using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and wavelengthdispersive electron probe microanalysis. Depth profiling results for CIGS thin films with different cell efficiencies were obtained using secondary ion mass spectrometry and Auger electron spectroscopy to compare the atomic concentrations. Atom probe tomography, a characterization technique with sub-nanometer resolution, was used to obtain three-dimensional elemental mapping and the compositional distribution at the grain boundaries (GBs). GBs are identified by Na increment accompanied by Cu depletion and In enrichment. Segregation of Na atoms along the GB had a beneficial effect on cell performance. Comparative analyses of different CIGS absorber layers using various analytical techniques provide us with understanding of the compositional distributions and structures of high efficiency CIGS thin films in solar cells.

Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters.

PubMed

Compel, W Scott; Wong, O Andrea; Chen, Xi; Yi, Chongyue; Geiss, Roy; Häkkinen, Hannu; Knappenberger, Kenneth L; Ackerson, Christopher J

2015-12-22

We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen-gold interactions. Close spatial coupling allows electron delocalization between the nanoparticle cores. The resulting assemblies thus possess optical and electronic properties that emerge as a result of assembly.

New insight into the mechanism of peroxymonosulfate activation by sulfur-containing minerals: Role of sulfur conversion in sulfate radical generation.

PubMed

Zhou, Yang; Wang, Xiaolei; Zhu, Changyin; Dionysiou, Dionysios D; Zhao, Guangchao; Fang, Guodong; Zhou, Dongmei

2018-06-04

Peroxymonosulfate (PMS) or persulfate activation by sulfur-containing minerals has been applied extensively for the degradation of contaminants; however, the role of sulfur conversion in this process has not been fully explored. In this study, pyrite (FeS 2 )-based PMS activation process was developed for diethyl phthalate (DEP) degradation, and its underlying mechanisms were elucidated. PMS was found to be efficiently activated by FeS 2 for DEP degradation and mineralization, achieving 58.9% total organic carbon removal using 0.5 g/L FeS 2 and 2.0 mM PMS. Sulfides were the dominant electron donor for PMS activation, and mediated Fe(II) regeneration to activate PMS on the surface of FeS 2 particles. Meanwhile, different sulfur conversion intermediates, such as S 5 2- , S 8 0 , S 2 O 3 2- , and SO 3 2- , were formed from the oxidation of sulfides by Fe(III) and PMS, and determined by X-ray photoelectron spectroscopy and in-situ attenuated total reflectance Fourier transform infrared spectroscopy analysis. SO 3 2- was the dominant sulfur species responsible for sulfate radicals (SO 4 - ) generation by activating PMS directly or activating Fe(III) to initiate a radical chain reaction, which was supported by the electron paramagnetic resonance results. This study highlights the important role of sulfur conversion in PMS activation by pyrite and provides new insights into the mechanism of oxidant activation by sulfur-containing minerals. Copyright © 2018. Published by Elsevier Ltd.

Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques.

PubMed

Somorjai, Gabor A; Frei, Heinz; Park, Jeong Y

2009-11-25

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ("green chemistry") and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

2D black phosphorous nanosheets as a hole transporting material in perovskite solar cells

NASA Astrophysics Data System (ADS)

Muduli, Subas Kumar; Varrla, Eswaraiah; Kulkarni, Sneha Avinash; Han, Guifang; Thirumal, Krishnamoorthy; Lev, Ovadia; Mhaisalkar, Subodh; Mathews, Nripan

2017-12-01

We demonstrate for the first-time liquid exfoliated few layers of 2D Black phosphorus (BP) nanosheets as a hole transporting material (HTM) for perovskite based solar cells. The photoelectron spectroscopy in air (PESA) measurements confirm the low laying valence band level of BP nanosheets (-5.2 eV) favourable for hole injection from CH3NH3PbI3 (MAPbI3). Our results show that ∼25% improvement in power conversion efficiency (PCE) of η = 16.4% for BP nanosheets + Spiro-OMeTAD as an HTM as compared to spiro-OMeTAD (η = 13.1%). When BP nanosheets are exclusively utilised as an HTM, a PCE of η = 7.88% is noted, an improvement over the 4% PCE values observed for HTM free devices. Photoluminescence (PL) quenching of MAPbI3 and impedance measurements further confirm the charge extraction ability of BP nanosheets. The structural and optical characterization of liquid exfoliated BP nanosheets is discussed in detail with the aid of transmission electron microscopy, Raman spectroscopy, absorption spectroscopy and photo-electron spectroscopy.

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

Ledbetter, Rhesa N.; Garcia Costas, Amaya M.; Lubner, Carolyn E.

The biological reduction of dinitrogen (N 2) to ammonia (NH 3) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled tomore » reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered ..delta..rnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Altogether, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.« less

Auger electron spectroscopy and depth profile study of oxidation of modified 440C steel

NASA Technical Reports Server (NTRS)

Ferrante, J.

1974-01-01

Auger electron spectroscopy (AES) and sputtering were used to study selective oxidation of modified 440C steel. The sample was polycrystalline. Oxidation was performed on initially clean surfaces for pressures ranging from 1 x 10 to the minus 7th power to 1 x 10 to the minus 5th power torr and temperatures ranging from room temperature to 800 C. AES traces were taken during oxidation. In situ sputtering depth profiles are also obtained. A transition temperature is observed in the range 600 to 700 C for which the composition of the outer surface oxide changed from iron oxide to chromium oxide. Heating in vacuum about 5 x 10 to the minus 10 power torr to 700 C causes conversion of the iron oxide surface to chromium oxide.

Thermal Conversion of Pine Wood Char to Carbon Nanomaterials in the Presence of Iron Nanoparticles

Treesearch

Sung Phil Mun; Zhiyong Cai; Fumiya Watanabe; Umesh P. Agarwal; Jilei Zhang

2012-01-01

Southern yellow pine (Pinus taeda) wood char powder was thermally treated at 1,000:C in the presence of a 25-nm-size Fe nanoparticle catalyst. The thermally treated carbon materials were analyzed by Raman spectroscopy and high-resolution transmission electron microscopy. Well-aligned graphitic carbon structures with 15 to 17 layers on...

Protonation/reduction dynamics at the [4Fe-4S] cluster of the hydrogen-forming cofactor in [FeFe]-hydrogenases.

PubMed

Senger, Moritz; Mebs, Stefan; Duan, Jifu; Shulenina, Olga; Laun, Konstantin; Kertess, Leonie; Wittkamp, Florian; Apfel, Ulf-Peter; Happe, Thomas; Winkler, Martin; Haumann, Michael; Stripp, Sven T

2018-01-31

The [FeFe]-hydrogenases of bacteria and algae are the most efficient hydrogen conversion catalysts in nature. Their active-site cofactor (H-cluster) comprises a [4Fe-4S] cluster linked to a unique diiron site that binds three carbon monoxide (CO) and two cyanide (CN - ) ligands. Understanding microbial hydrogen conversion requires elucidation of the interplay of proton and electron transfer events at the H-cluster. We performed real-time spectroscopy on [FeFe]-hydrogenase protein films under controlled variation of atmospheric gas composition, sample pH, and reductant concentration. Attenuated total reflection Fourier-transform infrared spectroscopy was used to monitor shifts of the CO/CN - vibrational bands in response to redox and protonation changes. Three different [FeFe]-hydrogenases and several protein and cofactor variants were compared, including element and isotopic exchange studies. A protonated equivalent (HoxH) of the oxidized state (Hox) was found, which preferentially accumulated at acidic pH and under reducing conditions. We show that the one-electron reduced state Hred' represents an intrinsically protonated species. Interestingly, the formation of HoxH and Hred' was independent of the established proton pathway to the diiron site. Quantum chemical calculations of the respective CO/CN - infrared band patterns favored a cysteine ligand of the [4Fe-4S] cluster as the protonation site in HoxH and Hred'. We propose that proton-coupled electron transfer facilitates reduction of the [4Fe-4S] cluster and prevents premature formation of a hydride at the catalytic diiron site. Our findings imply that protonation events both at the [4Fe-4S] cluster and at the diiron site of the H-cluster are important in the hydrogen conversion reaction of [FeFe]-hydrogenases.

Titanium composite conversion coating formation on CRS In the presence of Mo and Ni ions: Electrochemical and microstructure characterizations

NASA Astrophysics Data System (ADS)

Eivaz Mohammadloo, H.; Sarabi, A. A.

2016-11-01

There have been an increasing interest in finding a replacement for the chromating process due to environmental and health concerns. Hence, in this study Chrome-free chemical conversion coatings were deposited on the surface of cold-rolled steel (CRS) on the basis of Titanium (TiCC), Titanium-Nickel (TiNiCC) and titanium-molybdate (TiMoCC) based conversion coating solutions. The surface characterization was performed by field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measuring device. Also, the corrosion behavior was assessed by the means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. FESEM and AFM study show that the TiNiCC is denser and more uniform than that TiCC and TiMoCC since, TiMoCC conversion coating presents network feature, and there were abundant micro-cracks on the surface of the coating. XPS results confirmed the precipitation of Ti and Ni oxide/hydroxide, Mn dioxide/trioxide on the surface of different Ti-based conversion coatings. Electrochemical results revealed that all Ti-based conversion coatings have better anti-corrosion properties than bare CRS. Moreover, TiNiCC treatment inhibited the corrosion of CRS to a significant degree (polarization resistance (Rp) = 5510 Ω cm2) in comparison with TiCC (Rp = 2705 Ω cm2) and TiMoCC (Rp = 805 Ω cm2).

Mesomeric Effects of Graphene Modified with Diazonium Salts: Substituent Type and Position Influence its Properties.

PubMed

Bouša, Daniel; Jankovský, Ondřej; Sedmidubský, David; Luxa, Jan; Šturala, Jiří; Pumera, Martin; Sofer, Zdeněk

2015-12-01

In the last decade, graphene and graphene derivatives have become some of the most intensively studied materials. Tuning of the electronic and electrochemical properties of graphene is of paramount importance. In this study, six diazonium-modified graphenes containing different functional groups according to the diazonium salt precursor were investigated. These diazonium moieties have a strong mesomeric (resonance) effect and act as either electron-donating or -withdrawing species. Different graphene precursors, such as thermally and chemically reduced graphenes were studied. All the products were characterized in detail by elemental combustion analysis, FTIR spectroscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. Resistivity and zeta potential measurements were consistent with theoretical (DFT) calculations. The results show that chemical modification of graphene by diazotation strongly influences its properties, creating a huge application potential in microelectronics, energy storage and conversion devices, and electrocatalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron silicide formation at different layers of (Fe/Si)3 multilayered structures determined by conversion electron Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Badía-Romano, L.; Rubín, J.; Magén, C.; Bürgler, D. E.; Bartolomé, J.

2014-07-01

The morphology and the quantitative composition of the Fe-Si interface layer forming at each Fe layer of a (Fe/Si)3 multilayer have been determined by means of conversion electron Mössbauer spectroscopy (CEMS) and high-resolution transmission electron microscopy (HRTEM). For the CEMS measurements, each layer was selected by depositing the Mössbauer active 57Fe isotope with 95% enrichment. Samples with Fe layers of nominal thickness dFe = 2.6 nm and Si spacers of dSi = 1.5 nm were prepared by thermal evaporation onto a GaAs(001) substrate with an intermediate Ag(001) buffer layer. HRTEM images showed that Si layers grow amorphous and the epitaxial growth of the Fe is good only for the first deposited layer. The CEMS spectra show that at all Fe/Si and Si/Fe interfaces a paramagnetic c-Fe1-xSi phase is formed, which contains 16% of the nominal Fe deposited in the Fe layer. The bottom Fe layer, which is in contact with the Ag buffer, also contains α-Fe and an Fe1-xSix alloy that cannot be attributed to a single phase. In contrast, the other two layers only comprise an Fe1-xSix alloy with a Si concentration of ≃0.15, but no α-Fe.

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

Moosakhani, S.; Color and Polymer Research Center; Sabbagh Alvani, A.A., E-mail: sabbagh_alvani@aut.ac.ir

Highlights: • We have demonstrated AgI sensitized solar cell for the first time. • Obtained mesoporous titania powders possessed small crystallite size, high purity and surface area, and developed mesopores with a narrow pore size distribution. • Photovoltaic measurements revealed the electron injection from AgI to TiO{sub 2}. • The assembled AgI-QD solar cells yielded a power conversion efficiency of 0.64% under one sun illumination. • AgI may be a suitable candidate material for use as a non-toxic sensitizer in QDSSC. - Abstract: The present study reports the performance of a new photosensitizer -AgI quantum dots (QDs)- and mesoporous titaniamore » (TiO{sub 2}) nanocrystals synthesized by sol–gel (SG) method for solar cells. Furthermore, the effects of n-heptane on the textural properties of TiO{sub 2} nanocrystals were comprehensively investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N{sub 2} adsorption–desorption measurements, and UV–vis spectroscopy. TiO{sub 2} powders exhibited an anatase-type mesoporous structure with a high surface area of 89.7 m{sup 2}/g. Afterwards, the QDs were grown on mesoporous TiO{sub 2} surface to fabricate a TiO{sub 2}/AgI electrode by a successive ionic layer adsorption and reaction (SILAR) deposition route. Current–voltage characteristics and electrochemical impedance spectroscopy (EIS) data demonstrated that the injection of photoexcited electrons from AgI QDs into the TiO{sub 2} matrix produces photocurrents. The assembled AgI-QD solar cells yielded a power conversion efficiency of 0.64% and a short-circuit current of 2.13 mA/cm{sup 2} under one sun illumination.« less

Watching the dynamics of electrons and atoms at work in solar energy conversion.

PubMed

Canton, S E; Zhang, X; Liu, Y; Zhang, J; Pápai, M; Corani, A; Smeigh, A L; Smolentsev, G; Attenkofer, K; Jennings, G; Kurtz, C A; Li, F; Harlang, T; Vithanage, D; Chabera, P; Bordage, A; Sun, L; Ott, S; Wärnmark, K; Sundström, V

2015-01-01

The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.

The Electron Bifurcating FixABCX Protein Complex from Azotobacter vinelandii: Generation of Low-Potential Reducing Equivalents for Nitrogenase Catalysis.

PubMed

Ledbetter, Rhesa N; Garcia Costas, Amaya M; Lubner, Carolyn E; Mulder, David W; Tokmina-Lukaszewska, Monika; Artz, Jacob H; Patterson, Angela; Magnuson, Timothy S; Jay, Zackary J; Duan, H Diessel; Miller, Jacquelyn; Plunkett, Mary H; Hoben, John P; Barney, Brett M; Carlson, Ross P; Miller, Anne-Frances; Bothner, Brian; King, Paul W; Peters, John W; Seefeldt, Lance C

2017-08-15

The biological reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled to reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered Δrnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Overall, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.

The Electron Bifurcating FixABCX Protein Complex from Azotobacter vinelandii: Generation of Low-Potential Reducing Equivalents for Nitrogenase Catalysis

DOE PAGES

Ledbetter, Rhesa N.; Garcia Costas, Amaya M.; Lubner, Carolyn E.; ...

2017-07-13

The biological reduction of dinitrogen (N 2) to ammonia (NH 3) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled tomore » reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered ..delta..rnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Altogether, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.« less

NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb.

PubMed

Xu, Chi; Liu, Jian; Zhao, Zhen; Yu, Fei; Cheng, Kai; Wei, Yuechang; Duan, Aijun; Jiang, Guiyuan

2015-05-01

Selective catalytic reduction technology using NH3 as a reducing agent (NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Raman and Hydrogen temperature-programmed reduction (H2-TPR). The catalytic activities of V5CexSby/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5CexSby/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400°C, the V5CexSby/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210°C, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased. Copyright © 2015. Published by Elsevier B.V.

Multifunctional organized mesoporous tin oxide films templated by graft copolymers for dye-sensitized solar cells.

PubMed

Park, Jung Tae; Ahn, Sung Hoon; Roh, Dong Kyu; Lee, Chang Soo; Kim, Jong Hak

2014-07-01

The synthesis of organized mesoporous SnO2 films with high porosity, larger pores, and good interconnectivity, obtained by sol-gel templating with an amphiphilic graft copolymer, poly(vinyl chloride)-graft-poly(oxyethylene methacrylate), is reported. An improved performance of dye-sensitized solar cells (DSSCs) is demonstrated by the introduction of a 400 nm thick organized mesoporous SnO2 interfacial (om-SnO2 IF) layer between nanocrystalline TiO2 (nc-TiO2 ) and a fluorine-doped tin oxide substrate. To elucidate the improved efficiency, the structural, optical, and electrochemical properties of the devices were characterized by SEM, UV/Vis spectroscopy, noncontact 3D surface profilometry, intensity-modulated photocurrent/voltage spectroscopy, incident photon-to-electron conversion efficiency, and electrochemical impedance spectroscopy measurements. The energy-conversion efficiency of the solid polymerized ionic liquid based DSSC fabricated with the om-SnO2 IF/nc-TiO2 photoanode reached 5.9% at 100 mW cm(-2) ; this is higher than those of neat nc-TiO2 (3.5%) and organized mesoporous TiO2 interfacial/nc-TiO2 layer (5.4%) photoanodes. The improved efficiency is attributed to the antireflective property, cascadal energy band gap, good interconnectivity, and high electrical conductivity of the om-SnO2 IF layer, which results in enhanced light harvesting, increased electron transport, reduced charge recombination, and decreased interfacial/internal resistance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Multivariate Accelerated Corrosion Test Protocol

DTIC Science & Technology

2014-10-01

atmospheric, accelerated, AA2024-T3, AA6061-T6, AA7075-T3, 1010 steel, AgCl, rare earth conversion coat, magnesium rich primer, polyurethane , Eyring, Monte...morphology and elemental analysis by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and electrochemical determinations of...in the FT-IR analysis; degradation of the components of the high performance polyurethane coatings exposed in the UV/ozone chamber were more

State-Resolved Metal Nanoparticle Dynamics Viewed through the Combined Lenses of Ultrafast and Magneto-optical Spectroscopies.

PubMed

Zhao, Tian; Herbert, Patrick J; Zheng, Hongjun; Knappenberger, Kenneth L

2018-06-19

Electronic carrier dynamics play pivotal roles in the functional properties of nanomaterials. For colloidal metals, the mechanisms and influences of these dynamics are structure dependent. The coherent carrier dynamics of collective plasmon modes for nanoparticles (approximately 2 nm and larger) determine optical amplification factors that are important to applied spectroscopy techniques. In the nanocluster domain (sub-2 nm), carrier coupling to vibrational modes affects photoluminescence yields. The performance of photocatalytic materials featuring both nanoparticles and nanoclusters also depends on the relaxation dynamics of nonequilibrium charge carriers. The challenges for developing comprehensive descriptions of carrier dynamics spanning both domains are multifold. Plasmon coherences are short-lived, persisting for only tens of femtoseconds. Nanoclusters exhibit discrete carrier dynamics that can persist for microseconds in some cases. On this time scale, many state-dependent processes, including vibrational relaxation, charge transfer, and spin conversion, affect carrier dynamics in ways that are nonscalable but, rather, structure specific. Hence, state-resolved spectroscopy methods are needed for understanding carrier dynamics in the nanocluster domain. Based on these considerations, a detailed understanding of structure-dependent carrier dynamics across length scales requires an appropriate combination of spectroscopic methods. Plasmon mode-specific dynamics can be obtained through ultrafast correlated light and electron microscopy (UCLEM), which pairs interferometric nonlinear optical (INLO) with electron imaging methods. INLO yields nanostructure spectral resonance responses, which capture the system's homogeneous line width and coherence dynamics. State-resolved nanocluster dynamics can be obtained by pairing ultrafast with magnetic-optical spectroscopy methods. In particular, variable-temperature variable-field (VTVH) spectroscopies allow quantification of transient, excited states, providing quantification of important parameters such as spin and orbital angular momenta as well as the energy gaps that separate electronic fine structure states. Ultrafast two-dimensional electronic spectroscopy (2DES) can be used to understand how these details influence state-to-state carrier dynamics. In combination, VTVH and 2DES methods can provide chemists with detailed information regarding the structure-dependent and state-specific flow of energy through metal nanoclusters. In this Account, we highlight recent advances toward understanding structure-dependent carrier dynamics for metals spanning the sub-nanometer to tens of nanometers length scale. We demonstrate the use of UCLEM methods for arresting interband scattering effects. For sub-nanometer thiol-protected nanoclusters, we discuss the effectiveness of VTVH for distinguishing state-specific radiative recombination originating from a gold core versus organometallic protecting layers. This state specificity is refined further using femtosecond 2DES and two-color methods to isolate so-called superatom state dynamics and vibrationally mediated spin-conversion and emission processes. Finally, we discuss prospects for merging VTVH and 2DES methods into a single platform.

Conversion of Nuclear Waste to Molten Glass: Cold-Cap Reactions in Crucible Tests

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

Xu, Kai; Hrma, Pavel; Rice, Jarrett A.

2016-05-23

The feed-to-glass conversion, which comprises complex chemical reactions and phase transitions, occurs in the cold-cap zone during nuclear waste vitrification. Knowledge of the chemistry and physics of feed-to-glass conversion will help us control the conversion path by changing the melter feed makeup to maximize the glass production rate. To investigate the conversion process, we analyzed heat-treated samples of a simulated high-level waste feed using X-ray diffraction, electron probe microanalysis – wavelength dispersive X-ray spectroscopy, leaching tests, and residual anion analysis. Feed dehydration, gas evolution, and borate phase formation occurred at temperatures below 700 °C before the emerging glass-forming melt wasmore » completely connected. Above 800 °C, intermediate aluminosilicate phases and quartz particles were gradually dissolving in the continuous borosilicate melt, which expanded into transient foam. Knowledge of the chemistry and physics of feed-to-glass conversion will help us control the conversion path by changing the melter feed makeup to maximize the glass production rate.« less

Structure and up-conversion luminescence in sol-gel derived Er 3+-Yb 3+ co-doped SiO 2:PbF 2 nano-glass-ceramics

NASA Astrophysics Data System (ADS)

del-Castillo, J.; Yanes, A. C.; Méndez-Ramos, J.; Tikhomirov, V. K.; Rodríguez, V. D.

2009-11-01

Transparent oxyfluoride nano-glass-ceramics 90(SiO 2)10(PbF 2) co-doped with 0.3 Yb 3+ and 0.1 Er 3+ (mol%) have been prepared by thermal treatment of precursor sol-gel glasses. X-ray diffraction and high resolution transmission electron microscopy analysis pointed out a precipitation of cubic β-PbF 2 nanocrystals of certain diameter in nano-glass-ceramics varying from 10 to 20 nm depending on heat treatment conditions. The incorporation of Yb 3+ and Er 3+ dopants in these nanocrystals has been confirmed by signatures of luminescence spectroscopy. Up-conversion luminescence pumped at 980 nm has been detected. Colour tuneability of up-conversion luminescence varying pump power has been analyzed in terms of standard chromaticity diagram. This tuneability opens applications for up-conversion phosphors and three-dimensional optical recording.

Ru-N-C Hybrid Nanocomposite for Ammonia Dehydrogenation: Influence of N-doping on Catalytic Activity

PubMed Central

Hien, Nguyen Thi Bich; Kim, Hyo Young; Jeon, Mina; Lee, Jin Hee; Ridwan, Muhammad; Tamarany, Rizcky; Yoon, Chang Won

2015-01-01

For application to ammonia dehydrogenation, novel Ru-based heterogeneous catalysts, Ru-N-C and Ru-C, were synthesized via simple pyrolysis of a mixture of RuCl3·6H2O and carbon black with or without dicyandiamide as a nitrogen-containing precursor at 550 °C. Characterization of the prepared Ru-N-C and Ru-C catalysts via scanning transmission electron microscopy, in conjunction with energy dispersive X-ray spectroscopy, indicated the formation of hollow nanocomposites in which the average sizes of the Ru nanoparticles were 1.3 nm and 5.1 nm, respectively. Compared to Ru-C, the Ru-N-C nanocomposites not only proved to be highly active for ammonia dehydrogenation, giving rise to a NH3 conversion of >99% at 550 °C, but also exhibited high durability. X-ray photoelectron spectroscopy revealed that the Ru active sites in Ru-N-C were electronically perturbed by the incorporated nitrogen atoms, which increased the Ru electron density and ultimately enhanced the catalyst activity.

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

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

Hansen, Christopher S., E-mail: csh297@uowmail.edu.au; Trevitt, Adam J., E-mail: adamt@uow.edu.au; Blanksby, Stephen J.

2015-01-07

The S{sub 1}←S{sub 0} electronic transition of the N-pyridinium ion (C{sub 5}H{sub 5}NH{sup +}) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N{sub 2}-tagged complex. Gas-phase N-pyridinium ions photodissociate by the loss of molecular hydrogen (H{sub 2}) in the photon energy range 37 000–45 000 cm{sup −1} with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculationsmore » are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum.« less

Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching.

PubMed

Smeigh, Amanda L; Creelman, Mark; Mathies, Richard A; McCusker, James K

2008-10-29

A combination of femtosecond electronic absorption and stimulated Raman spectroscopies has been employed to determine the kinetics associated with low-spin to high-spin conversion following charge-transfer excitation of a FeII spin-crossover system in solution. A time constant of tau = 190 +/- 50 fs for the formation of the 5T2 ligand-field state was assigned based on the establishment of two isosbestic points in the ultraviolet in conjunction with changes in ligand stretching frequencies and Raman scattering amplitudes; additional dynamics observed in both the electronic and vibrational spectra further indicate that vibrational relaxation in the high-spin state occurs with a time constant of ca. 10 ps. The results set an important precedent for extremely rapid, formally forbidden (DeltaS = 2) nonradiative relaxation as well as defining the time scale for intramolecular optical switching between two electronic states possessing vastly different spectroscopic, geometric, and magnetic properties.

Photoinduced electron transfer in a molecular dyad by nanosecond pump-pump-probe spectroscopy.

PubMed

Ha-Thi, M-H; Pham, V-T; Pino, T; Maslova, V; Quaranta, A; Lefumeux, C; Leibl, W; Aukauloo, A

2018-06-01

The design of robust and inexpensive molecular photocatalysts for the conversion of abundant stable molecules like H2O and CO2 into an energetic carrier is one of the major fundamental questions for scientists nowadays. The outstanding challenge is to couple single photoinduced charge separation events with the sequential accumulation of redox equivalents at the catalytic unit for performing multielectronic catalytic reactions. Herein, double excitation by nanosecond pump-pump-probe experiments was used to interrogate the photoinduced charge transfer and charge accumulation on a molecular dyad composed of a porphyrin chromophore and a ruthenium-based catalyst in the presence of a reversible electron acceptor. An accumulative charge transfer state is unattainable because of rapid reverse electron transfer to the photosensitizer upon the second excitation and the low driving force of the forward photodriven electron transfer reaction. Such a method allows the fundamental understanding of the relaxation mechanism after two sequential photon absorptions, deciphering the undesired electron transfer reactions that limit the charge accumulation efficiency. This study is a step toward the improvement of synthetic strategies of molecular photocatalysts for light-induced charge accumulation and more generally, for solar energy conversion.

INFRARED SPECTROSCOPY: A TOOL FOR DETERMINATION OF THE DEGREE OF CONVERSION IN DENTAL COMPOSITES

PubMed Central

Moraes, Luciene Gonçalves Palmeira; Rocha, Renata Sanches Ferreira; Menegazzo, Lívia Maluf; de AraÚjo, Eudes Borges; Yukimitu, Keizo; Moraes, João Carlos Silos

2008-01-01

Infrared spectroscopy is one of the most widely used techniques for measurement of conversion degree in dental composites. However, to obtain good quality spectra and quantitative analysis from spectral data, appropriate expertise and knowledge of the technique are mandatory. This paper presents important details to use infrared spectroscopy for determination of the conversion degree. PMID:19089207

Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

NASA Astrophysics Data System (ADS)

Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

2016-07-01

The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Sisbnd Osbnd Si and Sisbnd Osbnd M chemical bonds. The optimum corrosion resistance of the coating in the corrosive media is obtained by 25 ml L-1 BTESPT modification. This whole study implies that the cerium conversion coating modified with certain silane agent deserves cautiousness before its application for corrosion resistance.

Enhanced photovoltaic performance of novel TiO2 photoelectrode on TCO substrates for dye-sensitized solar cells.

PubMed

Nam, Jung Eun; Kwon, Soon Jin; Jo, Hyo Jeong; Yi, Kwang Bok; Kim, Dae-Hwan; Kang, Jin-Kyu

2014-12-01

In this study, we report synthesis and growth of rutile-anatase TiO2 thin film on fluorine-doped tin oxide (FTO) glass by a two-step hydrothermal method. The effects of additional treatments (i.e., TiCl4 post-treatment and seed layer formation were also studied. Photocurrent-voltage (I-V) measurement of rutile-anatase TiO2 thin film was performed under 1.5 G light illumination. Photovoltaic performance was investigated by incident photon-to-electron conversion efficiency (IPCE), electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent/photovoltage spectroscopy (IMVS/IMPS) and open-circuit photovoltage decay (OCVD).

Conversion electrons from high-statistics β-decay measurements with the 8π spectrometer at TRIUMF-ISAC

NASA Astrophysics Data System (ADS)

Garrett, P. E.; Jigmeddorj, B.; Radich, A. J.; Andreoiu, C.; Ball, G. C.; Bangay, J. C.; Bianco, L.; Bildstein, V.; Chagnon-Lessard, S.; Cross, D. S.; Demand, G. A.; Diaz Varela, A.; Dunlop, R.; Finlay, P.; Garnsworthy, A. B.; Green, K. L.; Hackman, G.; Hadinia, B.; Leach, K. G.; Michetti-Wilson, J.; Orce, J. N.; Rajabali, M. M.; Rand, E. T.; Starosta, K.; Sumithrarachchi, C.; Svensson, C. E.; Triambak, S.; Wang, Z. M.; Williams, S. J.; Wood, J. L.; Wong, J.; Yates, S. W.; Zganjar, E. F.

2016-09-01

The 8π spectrometer, located at TRIUMF-ISAC, was the world's most powerful spectrometer dedicated to β-decay studies until its decommissioning in early 2014 for replacement with the GRIFFIN array. An integral part of the 8π spectrometer was the Pentagonal Array for Conversion Electron Spectroscopy (PACES) consisting of 5 Si(Li) detectors used for charged-particle detection. PACES enabled both γ - e- and e- - e- coincidence measurements, which were crucial for increasing the sensitivity for discrete e- lines in the presence of large backgrounds. Examples from a 124Cs decay experiment, where the data were vital for the expansion of the 124Cs decay scheme, are shown. With suffcient statistics, measurements of conversion coeffcients can be used to extract the E0 components of Jπ → Jπ transitions for J ≠ 0, which is demonstrated for data obtained in 110In→110Cd decay. With knowledge of the shapes of the states involved, as obtained, for example, from the use of Kumar-Cline shape invariants, the mixing of the states can be extracted.

Vibrational energy flow controls internal conversion in a transition metal complex.

PubMed

Hedley, Gordon J; Ruseckas, Arvydas; Samuel, Ifor D W

2010-09-02

Internal conversion (IC) between excited electronic states is a fundamental photophysical process that is important for understanding protection from UV radiation, energy transfer pathways and electron injection in artificial photosynthetic systems and organic solar cells. We have studied IC between three singlet MLCT states in an iridium complex using femtosecond fluorescence spectroscopy. Very fast IC with a time constant of <20 fs is observed from the highest state and a much slower relaxation to the lowest energy singlet state on a 70 fs time scale. The abrupt slowdown of the relaxation rate occurs when there is >0.6 eV of vibrational energy stored in the complex that has to be dissipated by intramolecular vibrational redistribution before further IC to the lower energy states can occur. These results show that the ability to dissipate vibrational energy can control the relaxation process in this class of materials.

Direct evidence and enhancement of surface plasmon resonance effect on Ag-loaded TiO2 nanotube arrays for photocatalytic CO2 reduction

NASA Astrophysics Data System (ADS)

Low, Jingxiang; Qiu, Shuoqi; Xu, Difa; Jiang, Chuanjia; Cheng, Bei

2018-03-01

Surface plasmon resonance (SPR) effect has been utilized in many solar conversion applications because of its ability to convert visible photons into "hot electron" energy. However, the direct evidence and enhancement of this unique effect are still great challenges, limiting its practical applications. Here we present the direct evidence and enhancement of SPR effect using TiO2 nanotube arrays (TNTAs) loaded with Ag nanoparticles (NPs) as a proof-of-concept example. Particularly, electrochemical deposition method is applied to deposit Ag NPs into the inner space of TNTAs for enhancing SPR effect of Ag NPs, as demonstrated by Raman and light absorption spectroscopies. This enhanced SPR effect is because multi-scattered light within TNTAs can be effectively utilized by Ag NPs in the inner space of TNTAs. Moreover, combining synchronous-illumination X-ray photoelectron and electrochemical impedance spectroscopy characterization, we confirm that the SPR effect of Ag NPs can enhance photocatalytic performance of TNTAs mainly from two aspects: (i) injection of "hot electrons" from Ag NPs to TNTAs and (ii) acceleration of charge carrier migration on the TNTAs through a unique near field effect. The direct evidence and enhancement of SPR effect open new perspectives in design of functional plasmonic nanomaterials with high solar conversion efficiency.

Tuning electronic transport via hepta-alanine peptides junction by tryptophan doping.

PubMed

Guo, Cunlan; Yu, Xi; Refaely-Abramson, Sivan; Sepunaru, Lior; Bendikov, Tatyana; Pecht, Israel; Kronik, Leeor; Vilan, Ayelet; Sheves, Mordechai; Cahen, David

2016-09-27

Charge migration for electron transfer via the polypeptide matrix of proteins is a key process in biological energy conversion and signaling systems. It is sensitive to the sequence of amino acids composing the protein and, therefore, offers a tool for chemical control of charge transport across biomaterial-based devices. We designed a series of linear oligoalanine peptides with a single tryptophan substitution that acts as a "dopant," introducing an energy level closer to the electrodes' Fermi level than that of the alanine homopeptide. We investigated the solid-state electron transport (ETp) across a self-assembled monolayer of these peptides between gold contacts. The single tryptophan "doping" markedly increased the conductance of the peptide chain, especially when its location in the sequence is close to the electrodes. Combining inelastic tunneling spectroscopy, UV photoelectron spectroscopy, electronic structure calculations by advanced density-functional theory, and dc current-voltage analysis, the role of tryptophan in ETp is rationalized by charge tunneling across a heterogeneous energy barrier, via electronic states of alanine and tryptophan, and by relatively efficient direct coupling of tryptophan to a Au electrode. These results reveal a controlled way of modulating the electrical properties of molecular junctions by tailor-made "building block" peptides.

Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface.

PubMed

Lian, Zichao; Sakamoto, Masanori; Matsunaga, Hironori; Vequizo, Junie Jhon M; Yamakata, Akira; Haruta, Mitsutaka; Kurata, Hiroki; Ota, Wataru; Sato, Tohru; Teranishi, Toshiharu

2018-06-13

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

Nuclear structure of 231Ac

NASA Astrophysics Data System (ADS)

Boutami, R.; Borge, M. J. G.; Mach, H.; Kurcewicz, W.; Fraile, L. M.; Gulda, K.; Aas, A. J.; García-Raffi, L. M.; Løvhøiden, G.; Martínez, T.; Rubio, B.; Taín, J. L.; Tengblad, O.

2008-10-01

The low-energy structure of 231Ac has been investigated by means of γ ray spectroscopy following the β decay of 231Ra. Multipolarities of 28 transitions have been established by measuring conversion electrons with a MINI-ORANGE electron spectrometer. The decay scheme of 231Ra → 231Ac has been constructed for the first time. The Advanced Time Delayed βγγ(t) method has been used to measure the half-lives of five levels. The moderately fast B(E1) transition rates derived suggest that the octupole effects, albeit weak, are still present in this exotic nucleus.

Synthesis and Characteristics of ZnS Nanospheres for Heterojunction Photovoltaic Device

NASA Astrophysics Data System (ADS)

Chou, Sheng-Hung; Hsiao, Yu-Jen; Fang, Te-Hua; Chou, Po-Hsun

2015-06-01

The synthesis of ZnS nanospheres produced using the microwave hydrothermal method was studied. The microstructure and surface and optical properties of ZnS nanospheres on glass were characterized using scanning electron microscopy, high-resolution transmission electron microscopy, x-ray diffraction, and ultraviolet-visible spectroscopy. The influence of deposition time on the transmission and photovoltaic performance was determined. The power conversion efficiency of an Al-doped ZnO/ZnS nanosphere/textured p-Si device improved from 0.93 to 1.77% when the thickness of the ZnS nanostructured film was changed from 75 to 150 nm.

Electron impact dissociation of amorphous cis-methyl acetate ice analogs

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Mukherjee, R.; Subramanian, K. P.; Banerjee, S. B.

2014-08-01

We have carried out, for the first time, electron irradiation on methyl acetate (CH3COOCH3) ices grown, under astrochemical condition, at 85 K and the chemical changes were probed by FTIR spectroscopy in the mid-IR region (4000-500 cm-1). Carbon dioxide (CO2), carbon monoxide (CO) molecules were found to be the major products indicating a competing dissociation pathway along with the by-products ethane (C2H6) and dimethyl ether (CH3OCH3), respectively. CH3OH (methyl alcohol) formation showed the possibility of acetate to alcohol conversion by keV electron irradiation. In addition irradiation induced aggregation of CH3COOCH3 molecules is also proposed.

In vitro analysis of riboflavin-modified, experimental, two-step etch-and-rinse dentin adhesive: Fourier transform infrared spectroscopy and micro-Raman studies.

PubMed

Daood, Umer; Swee Heng, Chan; Neo Chiew Lian, Jennifer; Fawzy, Amr S

2015-06-26

To modify two-step experimental etch-and-rinse dentin adhesive with different concentrations of riboflavin and to study its effect on the bond strength, degree of conversion, along with resin infiltration within the demineralized dentin substrate, an experimental adhesive-system was modified with different concentrations of riboflavin (m/m, 0, 1%, 3%, 5% and 10%). Dentin surfaces were etched with 37% phosphoric acid, bonded with respective adhesives, restored with restorative composite-resin, and sectioned into resin-dentin slabs and beams to be stored for 24 h or 9 months in artificial saliva. Micro-tensile bond testing was performed with scanning electron microscopy to analyse the failure of debonded beams. The degree of conversion was evaluated with Fourier transform infrared spectroscopy (FTIR) at different time points along with micro-Raman spectroscopy analysis. Data was analyzed with one-way and two-way analysis of variance followed by Tukey's for pair-wise comparison. Modification with 1% and 3% riboflavin increased the micro-tensile bond strength compared to the control at 24 h and 9-month storage with no significant differences in degree of conversion (P<0.05). The most predominant failure mode was the mixed fracture among all specimens except 10% riboflavin-modified adhesive specimens where cohesive failure was predominant. Raman analysis revealed that 1% and 3% riboflavin adhesives specimens showed relatively higher resin infiltration. The incorporation of riboflavin in the experimental two-step etch-and-rinse adhesive at 3% (m/m) improved the immediate bond strengths and bond durability after 9-month storage in artificial saliva without adversely affecting the degree of conversion of the adhesive monomers and resin infiltration.

In vitro analysis of riboflavin-modified, experimental, two-step etch-and-rinse dentin adhesive: Fourier transform infrared spectroscopy and micro-Raman studies

PubMed Central

Daood, Umer; Swee Heng, Chan; Neo Chiew Lian, Jennifer; Fawzy, Amr S

2015-01-01

To modify two-step experimental etch-and-rinse dentin adhesive with different concentrations of riboflavin and to study its effect on the bond strength, degree of conversion, along with resin infiltration within the demineralized dentin substrate, an experimental adhesive-system was modified with different concentrations of riboflavin (m/m, 0, 1%, 3%, 5% and 10%). Dentin surfaces were etched with 37% phosphoric acid, bonded with respective adhesives, restored with restorative composite–resin, and sectioned into resin–dentin slabs and beams to be stored for 24 h or 9 months in artificial saliva. Micro-tensile bond testing was performed with scanning electron microscopy to analyse the failure of debonded beams. The degree of conversion was evaluated with Fourier transform infrared spectroscopy (FTIR) at different time points along with micro-Raman spectroscopy analysis. Data was analyzed with one-way and two-way analysis of variance followed by Tukey's for pair-wise comparison. Modification with 1% and 3% riboflavin increased the micro-tensile bond strength compared to the control at 24 h and 9-month storage with no significant differences in degree of conversion (P<0.05). The most predominant failure mode was the mixed fracture among all specimens except 10% riboflavin-modified adhesive specimens where cohesive failure was predominant. Raman analysis revealed that 1% and 3% riboflavin adhesives specimens showed relatively higher resin infiltration. The incorporation of riboflavin in the experimental two-step etch-and-rinse adhesive at 3% (m/m) improved the immediate bond strengths and bond durability after 9-month storage in artificial saliva without adversely affecting the degree of conversion of the adhesive monomers and resin infiltration. PMID:25257880

Watching the dynamics of electrons and atoms at work in solar energy conversion

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

Canton, S. E.; Zhang, X.; Liu, Y.

2015-07-06

The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium–cobalt dyads, which belong to the large family of donor–bridge–acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfermore » processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.« less

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

Tong Dongge; Han Xue; Chu Wei

Co-B flowers with mesoporous structure were first prepared via reduction of cobalt acetate by potassium borohydride in the presence of complexing agent ethylenediamine. The as-prepared Co-B flowers were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, N{sub 2} adsorption-desorption, and magnetic performance test. The Co-B flowers exhibited enhanced coercivity, and weakened saturation magnetization and remanet magnetization as compared with the regular Co-B. During the hydrolysis of KBH{sub 4}, the Co-B flowers exhibited higher catalytic activity than the regular Co-B. It is attributed to themore » larger specific surface area and mesoporous channels. During the successive reactions, the conversion of KBH{sub 4} over Co-B flowers was about 97%. The average H{sub 2} generation rate of Co-B flowers was 4620 mL/min/g-catalyst in 1.5 wt% NaOH + 15 wt% KBH{sub 4} solution, which may give a successive H{sub 2} supply for a 748 W polymer electrolyte membrane fuel cell (PEMFC) at 100% H{sub 2} utilization.« less

Modifying surface properties of KIT-6 zeolite with Ni and V for enhancing catalytic CO methanation

NASA Astrophysics Data System (ADS)

Cao, Hong-Xia; Zhang, Jun; Guo, Cheng-Long; Chen, Jingguang G.; Ren, Xiang-Kun

2017-12-01

The surface of the KIT-6 zeolite was modified with different amounts of Ni and V to promote the catalytic properties for CO methanation. A series of xNi-yV/KIT-6 with various Ni and V contents were prepared by the incipient-wetness impregnation method. The modified surfaces were characterized using N2 adsorption-desorption, Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H2-TPR), Fourier transformed infrared spectroscopy (FT-IR), Raman, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and energy-dispersive X-ray spectroscopy (EDX), respectively. The characterization results illustrated that the modification of V species was able to significantly promote low-temperature catalytic performance below 350 °C compared to that of unmodified Ni/KIT-6, which was likely due to an increase in the H2 uptake accompanied by enhanced CO dissociation derived from stronger electron transfer from V species to Ni0. Correspondingly, the xNi-yV/KIT-6 catalysts exhibited a distinct enhancement in CO conversion, CH4 selectivity and CH4 yield over unmodified Ni/KIT-6. Among all catalysts, 20Ni-2V/KIT-6 showed the best catalytic performance, corresponding to nearly 100% CO conversion and 85% CH4 yield at a low temperature of 300 °C. Furthermore, 20Ni-2V/KIT-6 presented enhanced coking-resistant and anti-sintering properties during a 60h-lifetime test at 500 °C and 1 atm with a high weight hourly space velocity (WHSV) of 60000 ml/g/h.

Biomimetic synthesis of selenium nanoparticles by Pseudomonas aeruginosa ATCC 27853: An approach for conversion of selenite.

PubMed

Kora, Aruna Jyothi; Rastogi, Lori

2016-10-01

A facile and green method for the reduction of selenite was developed using a Gram-negative bacterial strain Pseudomonas aeruginosa, under aerobic conditions. During the process of bacterial conversion, the elemental selenium nanoparticles were produced. These nanoparticles were systematically characterized using various analytical techniques including UV-visible spectroscopy, XRD, Raman spectroscopy, SEM, DLS, TEM and FTIR spectroscopy techniques. The generation of selenium nanoparticles was confirmed from the appearance of red colour in the culture broth and broad absorption peaks in the UV-vis. The synthesized nanoparticles were spherical, polydisperse, ranged from 47 to 165 nm and the average particle size was about 95.9 nm. The selected-area electron diffraction, XRD patterns; and Raman spectroscopy established the amorphous nature of the fabricated nanoparticles. The IR data demonstrated the bacterial protein mediated selenite reduction and capping of the produced nanoparticles. The selenium removal was assessed at different selenite concentrations using ICP-OES and the results showed that the tested bacterial strain exhibited significant selenite reduction activity. The results demonstrate the possible application of P. aeruginosa for bioremediation of waters polluted with toxic and soluble selenite. Moreover, the potential metal reduction capability of the bacterial strain can function as green method for aerobic generation of selenium nanospheres. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reducing exciton binding energy by increasing thin film permittivity: an effective approach to enhance exciton separation efficiency in organic solar cells.

PubMed

Leblebici, Sibel Y; Chen, Teresa L; Olalde-Velasco, Paul; Yang, Wanli; Ma, Biwu

2013-10-23

Photocurrent generation in organic solar cells requires that excitons, which are formed upon light absorption, dissociate into free carriers at the interface of electron acceptor and donor materials. The high exciton binding energy, arising from the low permittivity of organic semiconductor films, generally causes low exciton separation efficiency and subsequently low power conversion efficiency. We demonstrate here, for the first time, that the exciton binding energy in B,O-chelated azadipyrromethene (BO-ADPM) donor films is reduced by increasing the film permittivity by blending the BO-ADPM donor with a high dielectric constant small molecule, camphoric anhydride (CA). Various spectroscopic techniques, including impedance spectroscopy, photon absorption and emission spectroscopies, as well as X-ray spectroscopies, are applied to characterize the thin film electronic and photophysical properties. Planar heterojunction solar cells are fabricated with a BO-ADPM:CA film as the electron donor and C60 as the acceptor. With an increase in the dielectric constant of the donor film from ∼4.5 to ∼11, the exciton binding energy is reduced and the internal quantum efficiency of the photovoltaic cells improves across the entire spectrum, with an ∼30% improvement in the BO-ADPM photoactive region.

Investigation of the {Fe}/{Si} interface and its phase transformations

NASA Astrophysics Data System (ADS)

Fanciulli, M.; Degroote, S.; Weyer, G.; Langouche, G.

1997-04-01

Thin 57Fe films (3-10 Å) have been grown by molecular beam epitaxy (MBE) on (7 × 7) reconstructed Si(111) and (2 × 1) reconstructed Si(001) surfaces and by e-gun evaporation on an H-terminated Si(111) surface. Conversion electron Mössbauer spectroscopy (CEMS) with high statistical accuracy and resolution allowed a detailed microscopic investigation of the silicide formation mechanism and of the structural phase transformations upon annealing.

Enhancement of the efficiency of dye-sensitized solar cell with multi-wall carbon nanotubes/polypyrrole composite counter electrodes prepared by electrophoresis/electrochemical polymerization

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

Luo, Jun; Niu, Hai-jun; Wen, Hai-lin

2013-03-15

Graphical abstract: The overall energy conversion efficiency of the DSSC employing the MWCNT/PPy CE reached 3.78%. Compared with a reference DSSC using single MWCNT film CE with efficiency of 2.68%, the energy conversion efficiency was increased by 41.04%. Highlights: ► MWCNT/PPy composite film prepared by electrodeposition layer by layer was used as counter electrode in DSSC. ► The overall energy conversion efficiency of the DSSC was 3.78% by employing the composite film. ► The energy conversion efficiency increased by 41.04% compared with efficiency of 2.68% by using the single MWCNT film. ► We analyzed the mechanism and influence factor ofmore » electron transfer in the composite electrode by EIS. - Abstract: For the purpose of replacing the precious Pt counter electrode in dye-sensitized solar cells (DSSCs) with higher energy conversion efficiency, multi-wall carbon nanotube (MWCNT)/polypyrrole (PPy) double layers film counter electrode (CE) was fabricated by electrophoresis and cyclic voltammetry (CV) layer by layer. Atom force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscope (TEM) demonstrated the morphologies of the composite electrode and Raman spectroscopy verified the PPy had come into being. The overall energy conversion efficiency of the DSSC employing the MWCNT/PPy CE reached 3.78%. Compared with a reference DSSC using single MWCNT film CE with efficiency of 2.68%, the energy conversion efficiency was increased by 41.04%. The result of impedance showed that the charge transfer resistance R{sub ct} of the MWCNT/PPy CE had the lowest value compared to that of MWCNT or PPy electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for I{sub 3}{sup −} reduction can potentially be used as the CE in a high-performance DSSC.« less

Charge-transfer-to-solvent reactions from I{sup −} to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

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

Okuyama, Haruki; Karashima, Shutaro; Suzuki, Toshinori, E-mail: suzuki@kuchem.kyoto-u.ac.jp

The charge-transfer-to-solvent (CTTS) reactions from iodide (I{sup −}) to H{sub 2}O, D{sub 2}O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H{sub 2}O and D{sub 2}O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field createdmore » for I{sup −}. The photoelectron spectra for CTTS in H{sub 2}O and D{sub 2}O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I{sup −*} (CTTS) state are less than 10%, while alcohols provide 2–3 times greater yields of internal conversion from I{sup −*}. The overall geminate recombination yields are found to be in the order of H{sub 2}O > D{sub 2}O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.« less

23327Enhanced photoelectric conversion efficiency of dye-sensitized solar cells by the incorporation of flower-like Bi2S3:Eu3+ sub-microspheres.

PubMed

Xu, Bingyu; Wang, Guofeng; Fu, Honggang

2016-03-21

In this paper, TiO2-Bi2S3 and TiO2-Bi2S3:Eu(3+) composite photoanodes were successfully designed, which can not only fully absorb visible light but also transfer the electron from Bi2S3 to TiO2 conduction band due to the narrow band gap and high conduction band of Bi2S3. Compared to pure TiO2 cell, the photoelectric conversion efficiencies of TiO2-Bi2S3 and TiO2-Bi2S3:Eu(3+) composite cells were increased significantly. In addition, the efficiency of TiO2-Bi2S3:Eu(3+) composite cells were higher than that of TiO2-Bi2S3 cell which could be attributed to the larger BET surface area of Bi2S3:Eu(3+). The electron transport and interfacial recombination kinetics were investigated by the electrochemical impedance spectroscopy and intensity-modulated photocurrent/photovoltage spectroscopy. The results indicated that the interfacial resistance of the TiO2-dye|I3(-)/I(-) electrolyte interface of TiO2-Bi2S3:Eu(3+) composite cell was much bigger than that of pure TiO2 cell. In addition, the TiO2-Bi2S3:Eu(3+) cell has longer electron recombination time and longer electron transport time than pure TiO2 cell. The charge collection efficiency of TiO2-Bi2S3:Eu(3+) composite cell was higher than that of pure TiO2 cell.

Advanced characterization study of commercial conversion and electrocoating structures on magnesium alloys AZ31B and ZE10A

DOE PAGES

Brady, Michael P.; Leonard, Donovan N.; Meyer, III, Harry M.; ...

2016-03-31

The local metal-coating interface microstructure and chemistry formed on commercial magnesium alloys Mg–3Al–1Zn (AZ31B) and Mg–1Zn–0.25Zr–<0.5Nd (ZE10A, ZEK100 type) were analyzed as-chemical conversion coated with a commercial hexafluoro-titanate/zirconate type + organic polymer based treatment (Bonderite® 5200) and a commercial hexafluoro-zirconate type + trivalent chromium Cr3 + type treatment (Surtec® 650), and after the same conversion coatings followed by electrocoating with an epoxy based coating, Cathoguard® 525. Characterization techniques included scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and cross-section scanning transmission electron microscopy (STEM). Corrosion behavior was assessed in room temperature saturated aqueous Mg(OH)2 solution with 1 wt.% NaCl. Themore » goal of the effort was to assess the degree to which substrate alloy additions become enriched in the conversion coating, and how the conversion coating was impacted by subsequent electrocoating. Key findings included the enrichment of Al from AZ31B and Zr from ZE10A, respectively, into the conversion coating, with moderate corrosion resistance benefits for AZ31B when Al was incorporated. Varying degrees of increased porosity and modification of the initial conversion coating chemistry at the metal-coating interface were observed after electrocoating. These changes were postulated to result in degraded electrocoating protectiveness. As a result, these observations highlight the challenges of coating Mg, and the need to tailor electrocoating in light of potential degradation of the initial as-conversion coated Mg alloy surface.« less

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

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

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

Size dependent behavior of Fe 3O 4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

DOE PAGES

Bock, David C.; Pelliccione, Christopher J.; Zhang, Wei; ...

2017-07-17

Here, the iron oxide magnetite, Fe 3O 4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe 3O 4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe 3O 4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during themore » electrochemical (de)lithiation reaction in Fe 3O 4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe 3O 4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe 3O 4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li + diffusion length in larger crystals results in conversion to Fe 0 metal while insertion of Li + into spinel-Fe 3O 4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.« less

CdSe quantum dot-fullerene hybrid nanocomposite for solar energy conversion: electron transfer and photoelectrochemistry.

PubMed

Bang, Jin Ho; Kamat, Prashant V

2011-12-27

The development of organic/inorganic hybrid nanocomposite systems that enable efficient solar energy conversion has been important for applications in solar cell research. Nanostructured carbon-based systems, in particular C(60), offer attractive strategies to collect and transport electrons generated in a light harvesting assembly. We have assembled CdSe-C(60) nanocomposites by chemically linking CdSe quantum dots (QDs) with thiol-functionalized C(60). The photoinduced charge separation and collection of electrons in CdSe QD-C(60) nanocomposites have been evaluated using transient absorption spectroscopy and photoelectrochemical measurements. The rate constant for electron transfer between excited CdSe QD and C(60) increased with the decreasing size of the CdSe QD (7.9 × 10(9) s(-1) (4.5 nm), 1.7 × 10(10) s(-1) (3.2 nm), and 9.0 × 10(10) s(-1) (2.6 nm)). Slower hole transfer and faster charge recombination and transport events were found to dominate over the forward electron injection process, thus limiting the deliverance of maximum power in CdSe QD-C(60)-based solar cells. The photoinduced charge separation between CdSe QDs and C(60) opens up new design strategies for developing light harvesting assemblies.

A 4 π dilepton spectrometer: PEPSI

NASA Astrophysics Data System (ADS)

Buda, A.; Bacelar, J. C. S.; Bałanda, A.; van Klinken, J.; Sujkowski, Z.; van der Woude, A.

1993-11-01

A novel positron-electron pair spectroscopy instrument (PEPSI) was designed to measure transitions in the energy region 10-40 MeV. It consists of Nd 2Fe 14B permanent magnets forming a compact 4 π magnetic filter consisting of 12 positron and 20 electron mini-orange-like spectrometers. The response function of PEPSI has been measured with mono-energetic beams of electrons from 5 to 20 MeV. The PEPSI spectrometer was used for measuring the internal pair conversion coefficient ( απ) of the 15.1 MeV M1 transition from a Jπ = 1 + state to the ground state in 12C. Our experimental value of απ = (3.3 ± 0.5) × 10 -3 is in good agreement with theoretical estimates.

Titanium conversion coatings on the aluminum foil AA 8021 used for lithium-ion battery package

NASA Astrophysics Data System (ADS)

Xia, Xu-Feng; Gu, Ying-Ying; Xu, Shi-Ai

2017-10-01

In this study, an environment-friendly titanium (Ti) conversion coating was successfully deposited on the aluminum foil AA 8021 in the solution containing hexafluorotitanic acid (H2TiF6), and its morphology, composition, growth process, hydrophilicity and corrosion resistance were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), X-ray photoelectric spectroscopy (XPS), contact-angle measurements (CAM) and salt spray exposure. The peeling strength between the Ti treated Al foil and the modified polypropylene (PP) film (PP grafted with maleic anhydride, PP-g-MAH) (Al/PP-g-MAH) was measured by T-peeling test. The results show that the Ti conversion coating is a multi-component coating composed primarily of metal oxides (TiO2 and Al2O3) and metal fluoride (AlF3). Ti treated Al foil shows better corrosion resistance than untreated and alkali-cleaned Al foils. The peeling strength of PP-g-MAH film with Ti treated Al foils is approximately 30 times higher than that with untreated Al foils. Thus, Ti treatment is a promising approach to improve the corrosion resistance and peeling strength of aluminum/polymer composite film (Al/P) used in the lithium-ion battery package.

Patterned low temperature copper-rich deposits using inkjet printing

NASA Astrophysics Data System (ADS)

Rozenberg, Gregor G.; Bresler, Eric; Speakman, Stuart P.; Jeynes, Chris; Steinke, Joachim H. G.

2002-12-01

A PZT piezoelectric ceramic research drop-on-demand inkjet print head operating in bend mode was used as a means of delivering a copper precursor, vinyltrimethylsilane copper (+1) hexafluoroacetylacetonate, in a controlled and placement accurate fashion. The reagent disproportionates at low temperature (<200 °C), to deposit copper on glass. These deposits are shown to be more than 90% copper by weight by electron probe microanalysis and microbeam Rutherford backscattering spectroscopy. Microscopy shows a deposit diameter and three-dimensional profile that suggests a complex deposition and conversion mechanism. Our findings represent an important step towards the manufacture of electronic devices by entirely nonlithographic means.

Fragmentation mechanism of UV-excited peptides in the gas phase

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

Zabuga, Aleksandra V., E-mail: aleksandra.zabuga@epfl.ch; Kamrath, Michael Z.; Boyarkin, Oleg V.

We present evidence that following near-UV excitation, protonated tyrosine- or phenylalanine–containing peptides undergo intersystem crossing to produce a triplet species. This pathway competes with direct dissociation from the excited electronic state and with dissociation from the electronic ground state subsequent to internal conversion. We employ UV-IR double-resonance photofragment spectroscopy to record conformer-specific vibrational spectra of cold peptides pre-excited to their S{sub 1} electronic state. The absorption of tunable IR light by these electronically excited peptides leads to a drastic increase in fragmentation, selectively enhancing the loss of neutral phenylalanine or tyrosine side-chain, which are not the lowest dissociation channels inmore » the ground electronic state. The recorded IR spectra evolve upon increasing the time delay between the UV and IR pulses, reflecting the dynamics of the intersystem crossing on a timescale of ∼80 ns and <10 ns for phenylalanine- and tyrosine-containing peptides, respectively. Once in the triplet state, phenylalanine-containing peptides may live for more than 100 ms, unless they absorb IR photons and undergo dissociation by the loss of an aromatic side-chain. We discuss the mechanism of this fragmentation channel and its possible implications for photofragment spectroscopy and peptide photostability.« less

Mössbauer effect study of corrosion products from a Brazilian oil refinery

NASA Astrophysics Data System (ADS)

da Costa, M. I.; Kunrath, J. I.; Moro, J. T.; da Cunha, J. B. M.; Englert, G.; Comparsi, L. U.; Muller, I. L.

1993-04-01

Corrosion of an oil refining plant in southern Brazil is controlled by placing metallic coupons in strategic places of the unit. The amount of the corrosion products formed after two months of exposure of the coupons is then obtained by weight loss measurements. To have a better insight of these products an analysis by Conversion Electron and transmission Mössbauer spectroscopies was done on some of the coupons. This paper reports some of the findings.

Science and Technology Text Mining: Electrochemical Power

DTIC Science & Technology

2003-07-14

X-RAY DIFFRACTION, TRANSMISSION ELECTRON MICROSCOPY, X- RAY PHOTOELECTRON SPECTROSCOPY, ELECTROCHEMICAL MEASUREMENTS, THERMOGRAVIMETRIC ANALYSIS ...0 -0 0 -0 0 -0 0 -0 -0 -0 0 0 thermogravimetric analysis -0 -0 0 -0 0 0 -0 -0 -0 0 0 0 -0 0 -0 0 -0 0 -0 -0 0 SEM 0 -0 0 0 -0 -0 -0 -0 0 -0 0 -0 -0 0...Capacitors; Energy Production; Power Production; Energy Conversion; Energy Storage; Citation Analysis ; Scientometrics; Military Requirements REPORT

Self-repairing vanadium-zirconium composite conversion coating for aluminum alloys

NASA Astrophysics Data System (ADS)

Zhong, Xin; Wu, Xiaosong; Jia, Yuyu; Liu, Yali

2013-09-01

In this paper, new self-repairing vanadium-zirconium composite conversion coating was prepared and investigated by Electrochemical impedance spectra (EIS), Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. EIS results showed that V-Zr conversion coating with hydrogen peroxide modified (VZO) revealed an increasing corrosion resistance in corrosive media which meant a certain self-repairing effect. SEM comparison photos also disclosed that VZO treated with scratches was gradually ameliorated from the initial cracked configuration to fewer cracks and more fillers through an immersion of 3.5% NaCl solution. XPS results demonstrated that the content of vanadium on VZO increased and zirconium declined when immersed in the corrosive solution. This explained further that the self-repairing ability could be related to vanadium. From the above results, we inferred possible structures of VZO and proposed that self-repairing effect was achieved through a hydrolysis condensation polymerization process of vanadate in the localized corrosion area.

Ultra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium

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

Maiuri, Margherita; Department of Chemistry, Princeton University, Washington Road, Princeton, New Jersey 08544; Réhault, Julien

We investigate the excitation energy transfer (EET) pathways in the photosynthetic light harvesting 1 (LH1) complex of purple bacterium Rhodospirillum rubrum with ultra-broadband two-dimensional electronic spectroscopy (2DES). We employ a 2DES apparatus in the partially collinear geometry, using a passive birefringent interferometer to generate the phase-locked pump pulse pair. This scheme easily lends itself to two-color operation, by coupling a sub-10 fs visible pulse with a sub-15-fs near-infrared pulse. This unique pulse combination allows us to simultaneously track with extremely high temporal resolution both the dynamics of the photoexcited carotenoid spirilloxanthin (Spx) in the visible range and the EET betweenmore » the Spx and the B890 bacterio-chlorophyll (BChl), whose Q{sub x} and Q{sub y} transitions peak at 585 and 881 nm, respectively, in the near-infrared. Global analysis of the one-color and two-color 2DES maps unravels different relaxation mechanisms in the LH1 complex: (i) the initial events of the internal conversion process within the Spx, (ii) the parallel EET from the first bright state S{sub 2} of the Spx towards the Q{sub x} state of the B890, and (iii) the internal conversion from Q{sub x} to Q{sub y} within the B890.« less

In situ synthesis of CdS/CdWO4/WO3 heterojunction films with enhanced photoelectrochemical properties

NASA Astrophysics Data System (ADS)

Zhan, Faqi; Li, Jie; Li, Wenzhang; Yang, Yahui; Liu, Wenhua; Li, Yaomin

2016-09-01

CdS/CdWO4/WO3 heterojunction films on fluorine-doped tin oxide (FTO) substrates are for the first time prepared as an efficient photoanode for photoelectrochemical (PEC) hydrogen generation by an in situ conversion process. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet visible spectrometry (UV-vis) and X-ray photoelectron spectroscopy (XPS). The CdS hollow spheres (∼80 nm) sensitized WO3 plate film with a CdWO4 buffer-layer exhibits increased visible light absorption and a significantly improved photoelectrochemical performance. The photocurrent density at 0 V (vs. Ag/AgCl) of the CdS/CdWO4/WO3 anode is ∼3 times higher than that of the CdWO4/WO3 anode, and ∼9 times higher than that of pure WO3 under illumination. The highest incident-photon-to-current-efficiency (IPCE) value increased from 16% to 63% when the ternary heterojunction was formed. This study demonstrates that the synthesis of ternary composite photocatalysts by the in situ conversion process may be a promising approach to achieve high photoelectric conversion efficiency.

Segregation of chlorine in n-type tin monosulfide ceramics: Actual chlorine concentration for carrier-type conversion

NASA Astrophysics Data System (ADS)

Iguchi, Yuki; Sugiyama, Taiki; Inoue, Kazutoshi; Yanagi, Hiroshi

2018-05-01

Tin monosulfide (SnS) is an attractive material for photovoltaic cells because of its suitable band-gap energy, high absorption coefficient, and non-toxic and abundant constituent elements. The primary drawback of this material is the lack of n-type SnS. We recently demonstrated n-type SnS by doping with Cl. However, the Cl-doped n-type SnS bulk ceramics exhibited an odd behavior in which carrier-type conversion but not electron carrier concentration depended on the Cl concentration. In this study, the electron probe microanalysis (EPMA) elemental mapping of Cl-doped SnS revealed continuous homogeneous regions with a relatively low Cl concentration along with the islands of high Cl concentration in which Sn/S is far from unity. The difference between the Cl concentration in the homogeneous region (determined by EPMA) and the bulk Cl concentration (determined by wavelength-dispersive X-ray fluorescence spectroscopy) increased with the increasing Cl doping amount. The carrier concentration and the Hall coefficient clearly depended on the Cl concentration in the homogeneous region. Carrier-type conversion was observed at the Cl concentration of 0.26 at. % (in the homogeneous region).

The effect of chromic sulfate concentration and immersion time on the structures and anticorrosive performance of the Cr(III) conversion coatings on aluminum alloys

NASA Astrophysics Data System (ADS)

Chen, Wei-Kun; Bai, Ching-Yuan; Liu, Chung-Ming; Lin, Chao-Sung; Ger, Ming-Der

2010-06-01

The main purpose of this study is to develop trivalent chromium, Cr(III), conversion coatings on aluminum alloys. The influence of Cr(III) concentration and immersion time on structures and anticorrosive performance of the coatings has been investigated. Corrosion behaviors of the coatings were evaluated in a 0.5 M H 2SO 4 aqueous solution at room temperature using potentiodynamic polarization. The structure and valence state of the coatings were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The addition of Cr(III) ions to the conversion bath considerably changes structures and compositions of the coatings. The coatings with Cr oxides possess a denser and thinner structure. Moreover, the corrosion resistance of Cr(III) coatings tends to decline with increasing immersion time due to the dissolution of coatings in the dipping period. According to XPS analysis, the Cr(III) conversion coatings are composed of Cr 2O 3, Cr(OH) 3, Al 2O 3, Al(OH) 3, ZrO 2, Zr(OH) 4, AlF 3, and ZrF 4, but no hexavalent chromium component in the coatings. The result indicates that the coatings prepared in the solution with 0.01 M Cr(III) for 5 min have the smoothest and densest structure and the best anticorrosive performance among all of conversion coatings in this work.

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2016-08-02

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

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

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Development of Zirconium-based Conversion Coatings for the Pretreatment of AZ91D Magnesium Alloy Prior to Electrocoating

NASA Astrophysics Data System (ADS)

Reck, James; Wang, Yar-Ming; Kuo, Hong-Hsiang Harry

This work examines the use of hexafluorozirconic acid based solutions at concentrations from 0.025 M to 0.100 M and pH values of 2.0 to 4.0 for the creation of a zirconia-based conversion coating less than 1 micron thick to protect magnesium alloy AZ91D. Similar coatings have been found to give excellent protection for steel and aluminum alloys, but little research has been conducted on its application to magnesium. Work was performed to gain an understanding of the film formation mechanisms and related kinetics using x-ray photo-electron spectroscopy, scanning electron microscopy, and open circuit potential monitoring techniques. A design of experiments approach was taken to determine the effects of acid concentration, pH, and soak time on the corrosion properties both as-deposited and with an application of electrocoat. It was found that the application of the zirconia-based coating significantly increased corrosion resistance, and allowed for an acceptable e-coat application with excellent adherence.

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface

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

Sykes, Matthew E.; Stewart, Jon W.; Akselrod, Gleb M.

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers which we propose arise from anisotropic electron-electron scatteringmore » within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold whereas the quantum process of hot electron generation takes place in both components. As a result, our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.« less

Enhanced generation and anisotropic Coulomb scattering of hot electrons in an ultra-broadband plasmonic nanopatch metasurface

DOE PAGES

Sykes, Matthew E.; Stewart, Jon W.; Akselrod, Gleb M.; ...

2017-10-17

The creation of energetic electrons through plasmon excitation of nanostructures before thermalization has been proposed for a wide number of applications in optical energy conversion and ultrafast nanophotonics. However, the use of "nonthermal" electrons is primarily limited by both a low generation efficiency and their ultrafast decay. We report experimental and theoretical results on the use of broadband plasmonic nanopatch metasurfaces comprising a gold substrate coupled to silver nanocubes that produce large concentrations of hot electrons, which we measure using transient absorption spectroscopy. We find evidence for three subpopulations of nonthermal carriers which we propose arise from anisotropic electron-electron scatteringmore » within sp-bands near the Fermi surface. The bimetallic character of the metasurface strongly impacts the physics, with dissipation occurring primarily in the gold whereas the quantum process of hot electron generation takes place in both components. As a result, our calculations show that the choice of geometry and materials is crucial for producing strong ultrafast nonthermal electron components.« less

Effects for rapid conversion from abalone shell to hydroxyapaptite nanosheets by ionic surfactants.

PubMed

Zhong, Shengnan; Wen, Zhenliang; Chen, Jingdi; Li, Qian; Shi, Xuetao; Ding, Shinnjyh; Zhang, Qiqing

2017-08-01

Hydroxyapatite (HAP) has been widely used for repairing or substituting human hard tissues. In this paper, two typical ionic surfactants, cation hexadecyltrimethylammonium bromide (CTAB) and anion sodium dodecyl sulfate (SDS), were used for rapid conversion of HAP from abalone shell. From field emission scanning electron microscopy (FESEM), the prepared HAP is flake-like structure. From X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal analysis, these samples contain a small amount of calcium carbonate whose content gradually increases by increasing the surfactants. The results showed that the HAP formed fast on the layer of abalone shell powder with the assistance of CTAB and SDS. Copyright © 2017 Elsevier B.V. All rights reserved.

Gradient doping - a case study with Ti-Fe2O3 towards an improved photoelectrochemical response.

PubMed

Srivastav, Anupam; Verma, Anuradha; Banerjee, Anamika; Khan, Saif A; Gupta, Mukul; Satsangi, Vibha Rani; Shrivastav, Rohit; Dass, Sahab

2016-12-07

The present study investigates the effect of gradient doping on modifying the photoelectrochemical response of Ti-doped Fe 2 O 3 photoanodes for their use in sunlight based water splitting for hydrogen evolution. The deposition of a thin film over the ITO (tin doped indium oxide) substrate was carried out using a spray pyrolysis method. The concentration of dopant was varied from 0.5-8.0 at% and two sets of samples were also prepared with low to high (0.5-8%) and high to low (8-0.5%) dopant concentrations in the direction towards the substrate. The prepared thin films were characterized using X-ray Diffractometry (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX) Spectroscopy, Secondary Ion Mass Spectroscopy (SIMS), X-ray Photoelectron Spectroscopy (XPS) and UV-visible Spectroscopy. The photoelectrochemical studies revealed that the deposition of dopant layers with a low to high concentration towards the substrate exhibited a highly improved photoresponse (200 times) in comparison to the pristine sample and a two fold enhancement in comparison to 2% Ti-doped Fe 2 O 3 . The improvement in the photoresponse has been attributed to the values of a high flat band potential, low resistance, high open circuit voltage, carrier separation efficiency, applied bias photon-to-current conversion efficiency (ABPE), and incident photon-to-current conversion efficiency (IPCE). A reduced charge transfer resistance has been demonstrated with Nyquist plots.

Precision Muonium Spectroscopy

NASA Astrophysics Data System (ADS)

Jungmann, Klaus P.

2016-09-01

The muonium atom is the purely leptonic bound state of a positive muon and an electron. It has a lifetime of 2.2 µs. The absence of any known internal structure provides for precision experiments to test fundamental physics theories and to determine accurate values of fundamental constants. In particular ground state hyperfine structure transitions can be measured by microwave spectroscopy to deliver the muon magnetic moment. The frequency of the 1s-2s transition in the hydrogen-like atom can be determined with laser spectroscopy to obtain the muon mass. With such measurements fundamental physical interactions, in particular quantum electrodynamics, can also be tested at highest precision. The results are important input parameters for experiments on the muon magnetic anomaly. The simplicity of the atom enables further precise experiments, such as a search for muonium-antimuonium conversion for testing charged lepton number conservation and searches for possible antigravity of muons and dark matter.

Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO2 Conversion to CO.

PubMed

Porosoff, Marc D; Baldwin, Jeffrey W; Peng, Xi; Mpourmpakis, Giannis; Willauer, Heather D

2017-06-09

The high concentration of CO 2 bound in seawater represents a significant opportunity to extract and use this CO 2 as a C 1 feedstock for synthetic fuels. Using an existing process, CO 2 and H 2 can be concurrently extracted from seawater and then catalytically reacted to produce synthetic fuel. Hydrogenating CO 2 directly into liquid hydrocarbons is exceptionally difficult, but by first identifying a catalyst for selective CO production through the reverse water-gas shift (RWGS) reaction, CO can then be hydrogenated to fuel through Fischer-Tropsch (FT) synthesis. Results of this study demonstrate that potassium-promoted molybdenum carbide supported on γ-Al 2 O 3 (K-Mo 2 C/γ-Al 2 O 3 ) is a low-cost, stable, and highly selective catalyst for RWGS over a wide range of conversions. These findings are supported by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elucidation of the Conversion Reaction of CoMnFeO4 Nanoparticles in Lithium Ion Battery Anode via Operando Studies.

PubMed

Permien, Stefan; Indris, Sylvio; Hansen, Anna-Lena; Scheuermann, Marco; Zahn, Dirk; Schürmann, Ulrich; Neubüser, Gero; Kienle, Lorenz; Yegudin, Eugen; Bensch, Wolfgang

2016-06-22

Conversion reactions deliver much higher capacities than intercalation/deintercalation reactions of commercial Li ion batteries. However, the complex reaction pathways of conversion reactions occurring during Li uptake and release are not entirely understood, especially the irreversible capacity loss of Mn(III)-containing oxidic spinels. Here, we report for the first time on the electrochemical Li uptake and release of Co(II)Mn(III)Fe(III)O4 spinel nanoparticles and the conversion reaction mechanisms elucidated by combined operando X-ray diffraction, operando and ex-situ X-ray absorption spectroscopy, transmission electron microscopy, (7)Li NMR, and molecular dynamics simulation. The combination of these techniques enabled uncovering the pronounced electronic changes and structural alterations on different length scales in a unique way. The spinel nanoparticles undergo a successive phase transition into a mixed monoxide caused by a movement of the reduced cations from tetrahedral to octahedral positions. While the redox reactions Fe(3+) ↔ Fe(0) and Co(2+) ↔ Co(0) occur for many charge/discharge cycles, metallic Mn nanoparticles formed during the first discharge can only be oxidized to Mn(2+) during charge. This finding explains the partial capacity loss reported for Mn(III)-based spinels. Furthermore, the results of the investigations evidence that the reaction mechanisms on the nanoscale are very different from pathways of microcrystalline materials.

Electronic Structure of Low-Temperature Solution-Processed Amorphous Metal Oxide Semiconductors for Thin-Film Transistor Applications

PubMed Central

Socratous, Josephine; Banger, Kulbinder K; Vaynzof, Yana; Sadhanala, Aditya; Brown, Adam D; Sepe, Alessandro; Steiner, Ullrich; Sirringhaus, Henning

2015-01-01

The electronic structure of low temperature, solution-processed indium–zinc oxide thin-film transistors is complex and remains insufficiently understood. As commonly observed, high device performance with mobility >1 cm2 V−1 s−1 is achievable after annealing in air above typically 250 °C but performance decreases rapidly when annealing temperatures ≤200 °C are used. Here, the electronic structure of low temperature, solution-processed oxide thin films as a function of annealing temperature and environment using a combination of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and photothermal deflection spectroscopy is investigated. The drop-off in performance at temperatures ≤200 °C to incomplete conversion of metal hydroxide species into the fully coordinated oxide is attributed. The effect of an additional vacuum annealing step, which is beneficial if performed for short times at low temperatures, but leads to catastrophic device failure if performed at too high temperatures or for too long is also investigated. Evidence is found that during vacuum annealing, the workfunction increases and a large concentration of sub-bandgap defect states (re)appears. These results demonstrate that good devices can only be achieved in low temperature, solution-processed oxides if a significant concentration of acceptor states below the conduction band minimum is compensated or passivated by shallow hydrogen and oxygen vacancy-induced donor levels. PMID:26190964

Interactions between photoexcited NIR emitting CdHgTe quantum dots and graphene oxide

NASA Astrophysics Data System (ADS)

Jagtap, Amardeep M.; Varade, Vaibhav; Konkena, Bharathi; Ramesh, K. P.; Chatterjee, Abhijit; Banerjee, Arup; Pendyala, Naresh Babu; Koteswara Rao, K. S. R.

2016-02-01

Hydrothermally grown mercury cadmium telluride quantum dots (CdHgTe QDs) are decorated on graphene oxide (GO) sheets through physisorption. The structural change of GO through partial reduction of oxygen functional groups is observed with X-ray photoelectron spectroscopy in GO-QDs composites. Raman spectroscopy provides relatively a small change (˜1.1 times) in D/G ratio of band intensity and red shift in G band from 1606 cm-1 to 1594 cm-1 in GO-CdHgTe QDs (2.6 nm) composites, which indicates structural modification of GO network. Steady state and time resolved photoluminescence (PL) spectroscopy shows the electronic interactions between photoexcited near infrared emitting CdHgTe QDs and GO. Another interesting observation is PL quenching in the presence of GO, and it is quite effective in the case of smaller size QDs (2.6 nm) compared to the larger size QDs (4.2 nm). Thus, the observed PL quenching is attributed to the photogenerated electron transfer from QDs to GO. The photoexcited electron transfer rate decreases from 2.2 × 109 to 1.5 × 108 s-1 with increasing particle size from 2.6 to 4.2 nm. Photoconductivity measurements on QDs-GO composite devices show nearly 3 fold increase in the current density under photo-illumination, which is a promising aspect for solar energy conversion and other optoelectronic applications.

Electronic Structure of Low-Temperature Solution-Processed Amorphous Metal Oxide Semiconductors for Thin-Film Transistor Applications.

PubMed

Socratous, Josephine; Banger, Kulbinder K; Vaynzof, Yana; Sadhanala, Aditya; Brown, Adam D; Sepe, Alessandro; Steiner, Ullrich; Sirringhaus, Henning

2015-03-25

The electronic structure of low temperature, solution-processed indium-zinc oxide thin-film transistors is complex and remains insufficiently understood. As commonly observed, high device performance with mobility >1 cm 2 V -1 s -1 is achievable after annealing in air above typically 250 °C but performance decreases rapidly when annealing temperatures ≤200 °C are used. Here, the electronic structure of low temperature, solution-processed oxide thin films as a function of annealing temperature and environment using a combination of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and photothermal deflection spectroscopy is investigated. The drop-off in performance at temperatures ≤200 °C to incomplete conversion of metal hydroxide species into the fully coordinated oxide is attributed. The effect of an additional vacuum annealing step, which is beneficial if performed for short times at low temperatures, but leads to catastrophic device failure if performed at too high temperatures or for too long is also investigated. Evidence is found that during vacuum annealing, the workfunction increases and a large concentration of sub-bandgap defect states (re)appears. These results demonstrate that good devices can only be achieved in low temperature, solution-processed oxides if a significant concentration of acceptor states below the conduction band minimum is compensated or passivated by shallow hydrogen and oxygen vacancy-induced donor levels.

Comparative study of the anchorage and the catalytic properties of nanoporous TiO2 films modified with ruthenium (II) and rhenium (I) carbonyl complexes

NASA Astrophysics Data System (ADS)

Oyarzún, Diego P.; Chardon-Noblat, Sylvie; Linarez Pérez, Omar E.; López Teijelo, Manuel; Zúñiga, César; Zarate, Ximena; Shott, Eduardo; Carreño, Alexander; Arratia-Perez, Ramiro

2018-02-01

In this article we study the anchoring of cis-[Ru(bpyC4pyr)(CO)2(CH3CN)2]2+, cis-[Ru(bpy)2(CO)2]2+ and cis-[Ru(bpyac)(CO)2Cl2], onto nanoporous TiO2 employing electropolymerization, electrostatic interaction and chemical bonding. Also, the [Re(bpyac)(CO)3Cl] rhenium(I) complex for chemical anchorage was analyzed. The characterization of TiO2/Ru(II) and TiO2/Re(I) nanocomposite films was performed by field emission scanning electron microscopy (FESEM), electron dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. In addition, for the more stable nanocomposites obtained, the catalytic properties (solar energy conversion and CO2 reduction) were evaluated. The efficiency improvement in redox process derived from the (photo)electrochemical evidence indicates that modified nanoporous TiO2 structures enhance the rate of charge transfer reactions.

Improving the Optoelectronic Properties of Mesoporous TiO2 by Cobalt Doping for High-Performance Hysteresis-free Perovskite Solar Cells.

PubMed

Sidhik, Siraj; Cerdan Pasarán, Andrea; Esparza, Diego; López Luke, Tzarara; Carriles, Ramón; De la Rosa, Elder

2018-01-31

We for the first time report the incorporation of cobalt into a mesoporous TiO 2 electrode for application in perovskite solar cells (PSCs). The Co-doped PSC exhibits excellent optoelectronic properties; we explain the improvements by passivation of electronic trap or sub-band-gap states arising due to the oxygen vacancies in pristine TiO 2 , enabling faster electron transport and collection. A simple postannealing treatment is used to prepare the cobalt-doped mesoporous electrode; UV-visible spectroscopy, X-ray photoemission spectroscopy, space charge-limited current, photoluminescence, and electrochemical impedance measurements confirm the incorporation of cobalt, enhanced conductivity, and the passivation effect induced in the TiO 2 . An optimized doping concentration of 0.3 mol % results in the maximum power conversion efficiency of 18.16%, 21.7% higher than that of a similar cell with an undoped TiO 2 electrode. Also, the device shows negligible hysteresis and higher stability, retaining 80.54% of the initial efficiency after 200 h.

Reversible mechanical protection: building a 3D “suit” around a T-shaped benzimidazole axle† †Electronic supplementary information (ESI) available: Synthetic details and full characterisation of all new compounds. CCDC 1533271 and 1533272. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00790f Click here for additional data file. Click here for additional data file.

PubMed Central

Baggi, Giorgio; Vukotic, V. Nicholas

2017-01-01

The T-shaped benzimidazolium/crown ether recognition motif was used to prepare suit[1]anes. These novel mechanically interlocked molecules (MIMs) were fully characterized by 1H and 13C NMR spectroscopy, single-crystal X-ray diffraction, UV-vis absorption and fluorescence spectroscopy. By conversion to a suit[1]ane, a simple benzimidazole was shown to be protected from deprotonation by strong base. Moreover, it was demonstrated that this unique three-dimensional encapsulation can be made reversible, thus introducing the concept of “reversible mechanical protection”; a protecting methodology that may have potential applications in synthetic organic chemistry and the design of molecular machinery. PMID:28626559

Coupling Nuclear Induced Phonon Propagation with Conversion Electron Moessbauer Spectroscopy

DTIC Science & Technology

2015-06-18

penetrating and a small detector with low density will be insensitive to the gammas. Thus, a small gas proportional counter is ideal for this application ...and Materials Science Vol. 1. Plenum: New York, 1993. 16. Long, G. J. and Stevens, J. G., eds. (1986) " Industrial applications of the Mössbauer...proportional gas detector attached to left side of 1” diameter stainless steel type-310 bar, phonon source encased in a mounting device attached to the right

Built-in potential shift and Schottky-barrier narrowing in organic solar cells with UV-sensitive electron transport layers.

PubMed

Li, Cheng; Credgington, Dan; Ko, Doo-Hyun; Rong, Zhuxia; Wang, Jianpu; Greenham, Neil C

2014-06-28

The performance of organic solar cells incorporating solution-processed titanium suboxide (TiOx) as electron-collecting layers can be improved by UV illumination. We study the mechanism of this improvement using electrical measurements and electroabsorption spectroscopy. We propose a model in which UV illumination modifies the effective work function of the oxide layer through a significant increase in its free electron density. This leads to a dramatic improvement in device power conversion efficiency through several mechanisms - increasing the built-in potential by 0.3 V, increasing the conductivity of the TiOx layer and narrowing the interfacial Schottky barrier between the suboxide and the underlying transparent electrode. This work highlights the importance of considering Fermi-level equilibration when designing multi-layer transparent electrodes.

X-ray spectroscopic study of amorphous and polycrystalline PbO films, α-PbO, and β-PbO for direct conversion imaging.

PubMed

Qamar, A; LeBlanc, K; Semeniuk, O; Reznik, A; Lin, J; Pan, Y; Moewes, A

2017-10-13

We investigated the electronic structure of Lead Oxide (PbO) - one of the most promising photoconductor materials for direct conversion x-ray imaging detectors, using soft x-ray emission and absorption spectroscopy. Two structural configurations of thin PbO layers, namely the polycrystalline and the amorphous phase, were studied, and compared to the properties of powdered α-PbO and β-PbO samples. In addition, we performed calculations within the framework of density functional theory and found an excellent agreement between the calculated and the measured absorption and emission spectra, which indicates high accuracy of our structural models. Our work provides strong evidence that the electronic structure of PbO layers, specifically the width of the band gap and the presence of additional interband and intraband states in both conduction and valence band, depend on the deposition conditions. We tested several model structures using DFT simulations to understand what the origin of these states is. The presence of O vacancies is the most plausible explanation for these additional electronic states. Several other plausible models were ruled out including interstitial O, dislocated O and the presence of significant lattice stress in PbO.

Moessbauer spectroscopy study on the corrosion resistance of plasma nitrided ASTM F138 stainless steel in chloride solution

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

Souza, S.D. de; Olzon-Dionysio, M., E-mail: dmod@df.ufscar.br; Basso, R.L.O.

2010-10-15

Plasma nitriding of ASTM F138 stainless steel samples has been carried out using dc glow discharge under 80% H{sub 2}-20% N{sub 2} gas mixture, at 673 K, and 2, 4, and 7 h time intervals, in order to investigate the influence of treatment time on the microstructure and the corrosion resistance properties. The samples were characterized by scanning electron microscopy, glancing angle X-ray diffraction and conversion electron Moessbauer spectroscopy, besides electrochemical tests in NaCl aerated solution. A modified layer of about 6 {mu}m was observed for all the nitrided samples, independent of nitriding time. The X-ray diffraction analysis shows broadmore » {gamma}{sub N} phase peaks, signifying a great degree of nitrogen supersaturation. Besides {gamma}{sub N,} the Moessbauer spectroscopy results indicated the occurrence of {gamma}' and {epsilon} phases, as well as some other less important phases. Corrosion measurements demonstrate that the plasma nitriding time affects the corrosion resistance and the best performance is reached at 4 h treatment. It seems that the {epsilon}/{gamma}' fraction ratio plays an important role on the resistance corrosion. Additionally, the Moessbauer spectroscopy was decisive in this study, since it was able to identify and quantify the iron phases that influence the corrosion resistance of plasma nitrided ASTM F138 samples.« less

D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Shaikh, Shoyebmohamad F.; Mane, Rajaram S.; Min, Byoung Koun; Hwang, Yun Jeong; Joo, Oh-Shim

2016-02-01

Using a simple hydrothermal synthesis, the crystal structure of TiO2 nanoparticles was controlled from rutile to anatase using a sugar alcohol, D-sorbitol. Adding small amounts of D-sorbitol to an aqueous TiCl4 solution resulted in changes in the crystal phase, particle size, and surface area by affecting the hydrolysis rate of TiCl4. These changes led to improvements of the solar-to-electrical power conversion efficiency (η) of dye-sensitized solar cells (DSSC) fabricated using these nanoparticles. A postulated reaction mechanism concerning the role of D-sorbitol in the formation of rutile and anatase was proposed. Fourier-transform infrared spectroscopy, 13C NMR spectroscopy, and dynamic light scattering analyses were used to better understand the interaction between the Ti precursor and D-sorbitol. The crystal phase and size of the synthesized TiO2 nanocrystallites as well as photovoltaic performance of the DSSC were examined using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and photocurrent density-applied voltage spectroscopy measurement techniques. The DSSC fabricated using the anatase TiO2 nanoparticles synthesized in the presence of D-sorbitol, exhibited an enhanced η (6%, 1.5-fold improvement) compared with the device fabricated using the rutile TiO2 synthesized without D-sorbitol.

Annealing Behavior of 57Fe Implanted in ZrO2(Y)

NASA Astrophysics Data System (ADS)

Zhang, G. L.; Yu, F. H.; Weng, H. M.; Zhang, H. H.

1998-12-01

Using conversion electron Mossbauer spectroscopy(CEMS) and slow positron beam, the chemical states of the implanted 57Fe (100KeV,3 × 10 16 ions/cm 2) in ZrO2 containing 3 mol% Y 2O 3( ZY 3) and its thermodynamic behavior during annealing process with the temperature from 200 to 500°C were studied. After annealing at 400°C the complex of Fe3+-V has been mostly dissolved, and the prior phase to α-Fe and α-Fe nano-crystalline cluster were present in the sample. Meanwhile the mixed conducting of oxygen-ions and electrons in the ZY3 containing Fe sample appeared.

Coupling EELS/EFTEM Imaging with Environmental Fluid Cell Microscopy

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

Unocic, Raymond R; Baggetto, Loic; Veith, Gabriel M

2012-01-01

Insight into dynamically evolving electrochemical reactions and mechanisms encountered in electrical energy storage (EES) and conversion technologies (batteries, fuel cells, and supercapacitors), materials science (corrosion and oxidation), and materials synthesis (electrodeposition) remains limited due to the present lack of in situ high-resolution characterization methodologies. Electrochemical fluid cell microscopy is an emerging in-situ method that allows for the direct, real-time imaging of electrochemical processes within a fluid environment. This technique is facilitated by the use of MEMS-based biasing microchip platforms that serve the purpose of sealing the highly volatile electrolyte between two electron transparent SiNx membranes and interfacing electrodes to anmore » external potentiostat for controlled nanoscale electrochemislly experiments [!]. In order to elucidate both stmctural and chemical changes during such in situ electrochemical experiments, it is impmtant to first improve upon the spatial resolution by utilizing energy-filtered transmission electron microscopy (EFTEM) (to minimize chromatic aben ation), then to detennine the chemical changes via electron energy loss spectroscopy (EELS). This presents a formidable challenge since the overall thickness through which electrons are scattered through the multiple layers of the cell can be on the order of hundreds of nanometers to microns, scattering through which has the deleterious effect of degrading image resolution and decreasing signal-to noise for spectroscopy [2].« less

Interfacial scanning tunneling spectroscopy (STS) of chalcogenide/metal hybrid nanostructure

NASA Astrophysics Data System (ADS)

Saad, Mahmoud M.; Abdallah, Tamer; Easawi, Khalid; Negm, Sohair; Talaat, Hassan

2015-05-01

The electronic structure at the interface of chalcogenide/metal hybrid nanostructure (CdSe-Au tipped) had been studied by UHV scanning tunneling spectroscopy (STS) technique at room temperature. This nanostructure was synthesized by a phase transfer chemical method. The optical absorption of this hybrid nanostructure was recorded, and the application of the effective mass approximation (EMA) model gave dimensions that were confirmed by the direct measurements using the scanning tunneling microscopy (STM) as well as the high-resolution transmission electron microscope (HRTEM). The energy band gap obtained by STS agrees with the values obtained from the optical absorption. Moreover, the STS at the interface of CdSe-Au tipped hybrid nanostructure between CdSe of size about 4.1 ± 0.19 nm and Au tip of size about 3.5 ± 0.29 nm shows a band bending about 0.18 ± 0.03 eV in CdSe down in the direction of the interface. Such a result gives a direct observation of the electron accumulation at the interface of CdSe-Au tipped hybrid nanostructure, consistent with its energy band diagram. The presence of the electron accumulation at the interface of chalcogenides with metals has an important implication for hybrid nanoelectronic devices and the newly developed plasmon/chalcogenide photovoltaic solar energy conversion.

Improvement of energy conversion efficiency and power generation in direct borohydride-hydrogen peroxide fuel cell: The effect of Ni-M core-shell nanoparticles (M = Pt, Pd, Ru)/Multiwalled Carbon Nanotubes on the cell performance

NASA Astrophysics Data System (ADS)

Hosseini, M. G.; Mahmoodi, R.

2017-12-01

In this study, core@shell nanoparticles with Ni as a core material and Pt, Pd and Ru as shell materials are synthesized on multiwalled carbon nanotube (MWCNT) as catalyst support using the sequence reduction method. The influence of Ni@Pt, Ni@Pd and Ni@Ru core@shell nanoparticles on MWCNT toward borohydride oxidation in alkaline solution is investigated by various three-electrode electrochemical techniques. Also, the impact of these anodic electrocatalysts on the performance of direct borohydride-hydrogen peroxide fuel cell (DBHPFC) is evaluated. The structural and morphological properties of electrocatalysts are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The results of three electrode investigations show that Ni@Pd/MWCNT has excellent catalytic activity since borohydride oxidation current density on Ni@Pd/MWCNT (34773.27 A g-1) is 1.37 and 9.19 times higher than those of Ni@Pt/MWCNT (25347.27 A g-1) and Ni@Ru/MWCNT (3782.83 A g-1), respectively. Also, the energy conversion efficiency and power density of DBHPFC with Ni@Pd/MWCNT (246.82 mW cm-2) increase to 34.27% and 51.53% respect to Ni@Pt/MWCNT (162.24 mW cm-2) and Ni@Ru/MWCNT (119.62 mW cm-2), respectively. This study reveals that Ni@Pd/MWCNT has highest activity toward borohydride oxidation and stability in fuel cell.

Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3–SCR

PubMed Central

Yang, Wenjing; Cui, Shitong; Street, Jason; Luo, Yan

2018-01-01

Ce-Mn/TiO2 catalyst prepared using a simple impregnation method demonstrated a better low-temperature selective catalytic reduction of NO with NH3 (NH3–SCR) activity in comparison with the sol-gel method. The Ce-Mn/TiO2 catalyst loading with 20% Ce had the best low-temperature activity and achieved a NO conversion rate higher than 90% at 140–260°C with a 99.7% NO conversion rate at 180°C. The Ce-Mn/TiO2 catalyst only had a 6% NO conversion rate decrease after 100 ppm of SO2 was added to the stream. When SO2 was removed from the stream, the catalyst was able to recover completely. The crystal structure, morphology, textural properties and valence state of the metals involving the novel catalysts were investigated using X-ray diffraction, N2 adsorption and desorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive spectroscopy, respectively. The decrease of NH3–SCR performance in the presence of 100 ppm SO2 was due to the decrease of the surface area, change of the pore structure, the decrease of Ce4+ and Mn4+ concentration and the formation of the sulfur phase chemicals which blocked the active sites and changed the valence status of the elements. PMID:29657791

Enhanced conversion efficiency of dye-sensitized solar cells using a CNT-incorporated TiO{sub 2} slurry-based photoanode

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

Cai, Jiaoping; Chen, Zexiang, E-mail: zxchen@uestc.edu.cn; Li, Jun

2015-02-15

A new titanium dioxide (TiO{sub 2}) slurry formulation is herein reported for the fabrication of TiO{sub 2} photoanode for use in dye-sensitized solar cells (DSSCs). The prepared TiO{sub 2} photoanode featured a highly uniform mesoporous structure with well-dispersed TiO{sub 2} nanoparticles. The energy conversion efficiency of the resulting TiO{sub 2} slurry-based DSSC was ∼63% higher than that achieved by a DSSC prepared using a commercial TiO{sub 2} slurry. Subsequently, the incorporation of acid-treated multi-walled carbon nanotubes (CNTs) into the TiO{sub 2} slurry was examined. More specifically, the effect of varying the concentration of the CNTs in this slurry on themore » performance of the resulting DSSCs was studied. The chemical state of the CNTs-incorporated TiO{sub 2} photoanode was investigated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. A high energy conversion efficiency of 6.23% was obtained at an optimum CNT concentration of ∼0.06 wt.%. The obtained efficiency corresponds to a 63% enhancement when compared with that obtained from a DSSC based on a commercial TiO{sub 2} slurry. The higher efficiency was attributed to the improvement in the collection and transport of excited electrons in the presence of the CNTs.« less

Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3-SCR

NASA Astrophysics Data System (ADS)

Xu, Quan; Yang, Wenjing; Cui, Shitong; Street, Jason; Luo, Yan

2018-03-01

Ce-Mn/TiO2 catalyst prepared using a simple impregnation method demonstrated a better low-temperature selective catalytic reduction of NO with NH3 (NH3-SCR) activity in comparison with the sol-gel method. The Ce-Mn/TiO2 catalyst loading with 20% Ce had the best low-temperature activity and achieved a NO conversion rate higher than 90% at 140-260°C with a 99.7% NO conversion rate at 180°C. The Ce-Mn/TiO2 catalyst only had a 6% NO conversion rate decrease after 100 ppm of SO2 was added to the stream. When SO2 was removed from the stream, the catalyst was able to recover completely. The crystal structure, morphology, textural properties and valence state of the metals involving the novel catalysts were investigated using X-ray diffraction, N2 adsorption and desorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive spectroscopy, respectively. The decrease of NH3-SCR performance in the presence of 100 ppm SO2 was due to the decrease of the surface area, change of the pore structure, the decrease of Ce4+ and Mn4+ concentration and the formation of the sulfur phase chemicals which blocked the active sites and changed the valence status of the elements.

Comparative study on Ti/Zr/V and chromate conversion treated aluminum alloys: Anti-corrosion performance and epoxy coating adhesion properties

NASA Astrophysics Data System (ADS)

Zhu, Wen; Li, Wenfang; Mu, Songlin; Fu, Nianqing; Liao, Zhongmiao

2017-05-01

In this study, a Ti/Zr/V conversion coating (TZVCC) was deposited on the surface of aluminum alloy 6063 (AA6063) as an alternative of the chromate conversion coating (CCC). Both the TZVCC treated AA6063 (TZVCC/AA6063) and CCC treated AA6063 (CCC/AA6063) were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM) and contact angle measuring device. The anti-corrosion performance of the TZVCC/AA6063 and CCC/AA6063 was evaluated by electrochemical measurements and neutral salt spray tests. It showed that both the surface roughness and surface free energy of the AA6063 were significantly increased after TZVCC treatment. The anti-corrosion performance of TZVCC/AA6063 was superior to that of CCC/AA6063. In addition, the effects of the TZVCC and CCC on the adhesion properties and anti-corrosion performance of epoxy coating applied on samples were examined by pull-off tests and electrochemical impedance spectroscopy (EIS). The dry, wet and recovery adhesive strengths of the epoxy coating on TZVCC treated samples (epoxy coated TZVCC/AA6063) were very close to those of epoxy coating on CCC treated ones (epoxy coated CCC/AA6063). The epoxy coated TZVCC/AA6063 showed better corrosion resistance than the epoxy coated CCC/AA6063 and epoxy coated AA6063.

One-step synthesis of vertically aligned anatase thornbush-like TiO2 nanowire arrays on transparent conducting oxides for solid-state dye-sensitized solar cells.

PubMed

Roh, Dong Kyu; Chi, Won Seok; Ahn, Sung Hoon; Jeon, Harim; Kim, Jong Hak

2013-08-01

Herein, we report a facile synthesis of high-density anatase-phase vertically aligned thornbush-like TiO2 nanowires (TBWs) on transparent conducting oxide glasses. Morphologically controllable TBW arrays of 9 μm in length are generated through a one-step hydrothermal reaction at 200 °C over 11 h using potassium titanium oxide oxalate dehydrate, diethylene glycol (DEG), and water. The TBWs consist of a large number of nanoplates or nanorods, as confirmed by SEM and TEM imaging. The morphologies of TBWs are controllable by adjusting DEG/water ratios. TBW diameters gradually decrease from 600 (TBW600) to 400 (TBW400) to 200 nm (TBW200) and morphologies change from nanoplates to nanorods with an increase in DEG content. TBWs are utilized as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs) and solid-state DSSCs (ssDSSCs). The energy-conversion efficiency of qssDSSCs is in the order: TBW200 (5.2%)>TBW400 (4.5%)>TBW600 (3.4%). These results can be attributed to the different surface areas, light-scattering effects, and charge transport rates, as confirmed by dye-loading measurements, reflectance spectroscopy, and incident photon-to-electron conversion efficiency and intensity-modulated photovoltage spectroscopy/intensity-modulated photocurrent spectroscopy analyses. TBW200 is further treated with a graft-copolymer-directed organized mesoporous TiO2 to increase the surface area and interconnectivity of TBWs. As a result, the energy-conversion efficiency of the ssDSSC increases to 6.7% at 100 mW cm(-2) , which is among the highest values for N719-dye-based ssDSSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transient and stationary spectroscopy of cytochrome c: ultrafast internal conversion controls photoreduction.

PubMed

Löwenich, Dennis; Kleinermanns, Karl; Karunakaran, Venugopal; Kovalenko, Sergey Alexander

2008-01-01

Photoreduction of cytochrome c (Cyt c) has been reinvestigated using femtosecond-to-nanosecond transient absorption and stationary spectroscopy. Femtosecond spectra of oxidized Cyt c, recorded in the probe range 270-1000 nm, demonstrate similar evolution upon 266 or 403 nm excitation: an ultrafast 0.3 ps internal conversion followed by a 4 ps vibrational cooling. Late transient spectra after 20 ps, from the cold ground-state chromophore, reveal a small but measurable signal from reduced Cyt c. The yield phi for Fe3+-->Fe2+ photoreduction is measured to be phi(403) = 0.016 and phi(266) = 0.08 for 403 and 266 nm excitation. These yields lead to a guess of the barrier E(f)(A) = 55 kJ mol(-1) for thermal ground-state electron transfer (ET). Nanosecond spectra initially show the typical absorption from reduced Cyt c and then exhibit temperature-dependent sub-microsecond decays (0.5 micros at 297 K), corresponding to a barrier E(A)(b) = 33 kJ mol(-1) for the back ET reaction and a reaction energy DeltaE = 22 kJ mol(-1). The nanosecond transients do not decay to zero on a second time scale, demonstrating the stability of some of the reduced Cyt c. The yields calculated from this stable reduced form agree with quasistationary reduction yields. Modest heating of Cyt c leads to its efficient thermal reduction as demonstrated by differential stationary absorption spectroscopy. In summary, our results point to ultrafast internal conversion of oxidized Cyt c upon UV or visible excitation, followed by Fe-porphyrin reduction due to thermal ground-state ET as the prevailing mechanism.

Observation of Enhanced Hole Extraction in Br Concentration Gradient Perovskite Materials.

PubMed

Kim, Min-Cheol; Kim, Byeong Jo; Son, Dae-Yong; Park, Nam-Gyu; Jung, Hyun Suk; Choi, Mansoo

2016-09-14

Enhancing hole extraction inside the perovskite layer is the key factor for boosting photovoltaic performance. Realization of halide concentration gradient perovskite materials has been expected to exhibit rapid hole extraction due to the precise bandgap tuning. Moreover, a formation of Br-rich region on the tri-iodide perovskite layer is expected to enhance moisture stability without a loss of current density. However, conventional synthetic techniques of perovskite materials such as the solution process have not achieved the realization of halide concentration gradient perovskite materials. In this report, we demonstrate the fabrication of Br concentration gradient mixed halide perovskite materials using a novel and facile halide conversion method based on vaporized hydrobromic acid. Accelerated hole extraction and enhanced lifetime due to Br gradient was verified by observing photoluminescence properties. Through the combination of secondary ion mass spectroscopy and transmission electron microscopy with energy-dispersive X-ray spectroscopy analysis, the diffusion behavior of Br ions in perovskite materials was investigated. The Br-gradient was found to be eventually converted into a homogeneous mixed halide layer after undergoing an intermixing process. Br-substituted perovskite solar cells exhibited a power conversion efficiency of 18.94% due to an increase in open circuit voltage from 1.08 to 1.11 V and an advance in fill-factor from 0.71 to 0.74. Long-term stability was also dramatically enhanced after the conversion process, i.e., the power conversion efficiency of the post-treated device has remained over 97% of the initial value under high humid conditions (40-90%) without any encapsulation for 4 weeks.

Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

NASA Astrophysics Data System (ADS)

Ndolomingo, Matumuene Joe; Meijboom, Reinout

2017-03-01

Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al2O3 supported copper and gold nanoparticles. Li2O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of catalyst and oxidant amounts was investigated, with the apparent rate constant, kapp being proportional to the amount of nano catalyst and oxygen present in the system.

Conversion-electron spectroscopy and gamma-gamma angular correlation measurements in 116Sn

NASA Astrophysics Data System (ADS)

Cross, D. S.; Pore, J. L.; Andreoiu, C.; Ball, G. C.; Bender, P. C.; Chester, A. S.; Churchman, R.; Demand, G. A.; Diaz Varela, A.; Dunlop, R.; Garnsworthy, A. B.; Garrett, P. E.; Hackman, G.; Hadinia, B.; Jigmeddorj, B.; Laffoley, A. T.; Liblong, A.; Kanungo, R.; Miller, D. T.; Noakes, B.; Petrache, C. M.; Starosta, K.; Svensson, C. E.; Voss, P.; Wang, Z.-M.; Wilson, J. M.; Wood, J. L.; Yates, S. W.

2017-11-01

The 116Sn nucleus was studied via the β- decay of 116In utilizing the 8π spectrometer and its auxiliary detectors at TRIUMF-ISAC. The resulting K-shell conversion coefficients, K/L ratios, and multipole mixing ratios are presented. The 23+ → 21+ 931 keV and 22+ → 21+ 819 keV transition mixing ratios were re-measured and found to be δ = +1.8_{-0.5}^{+0.7} and -1.83(8), respectively. Newly measured mixing ratios for transitions among the low-lying I^{π} = 4+ states in 116Sn, when combined with γ-ray intensity data, suggest that the 2529 keV 42+ state possesses a neutron broken-pair admixture in addition to its dominant proton 2p-2h component.

The adhesion performance of epoxy coating on AA6063 treated in Ti/Zr/V based solution

NASA Astrophysics Data System (ADS)

Zhu, Wen; Li, Wenfang; Mu, Songlin; Yang, Yunyu; Zuo, Xi

2016-10-01

An environment-friendly titanium/zirconium/vanadium-based (Ti/Zr/V) conversion coating was prepared on aluminum alloy 6063 (AA6063). The epoxy powder coatings were applied on the AA6063 samples with/without Ti/Zr/V conversion coatings via electrostatic spraying. The morphology and composition of the conversion coating were studied by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The surface free energy components of AA6063 samples were measured by a static contact angle measuring device with Owens method. The adhesion properties of the epoxy coating on AA6063 treated with different conversion times were evaluated using a pull-off tester. The Ti/Zr/V conversion coating was mainly composed of metal oxide (TiO2, ZrO2, V2O5, Al2O3, etc.), metal fluoride (ZrF4, AlF3, etc.) and metal organic complex. The formation time of this conversion coating was reduced to 50 s. After such surface treatment, the samples' surface roughness was increased and the contact angle with water was decreased. Both the surface free energy and the work of adhesion were increased. The adhesion strength between the epoxy coating and AA6063 was enhanced significantly.

Catalytic conversion of aliphatic alcohols on carbon nanomaterials: The roles of structure and surface functional groups

NASA Astrophysics Data System (ADS)

Tveritinova, E. A.; Zhitnev, Yu. N.; Chernyak, S. A.; Arkhipova, E. A.; Savilov, S. V.; Lunin, V. V.

2017-03-01

Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of C2-C4 aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer-Emmett-Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified.

Enhanced Third-Order Optical Nonlinearity Driven by Surface-Plasmon Field Gradients.

PubMed

Kravtsov, Vasily; AlMutairi, Sultan; Ulbricht, Ronald; Kutayiah, A Ryan; Belyanin, Alexey; Raschke, Markus B

2018-05-18

Efficient nonlinear optical frequency mixing in small volumes is key for future on-chip photonic devices. However, the generally low conversion efficiency severely limits miniaturization to nanoscale dimensions. Here we demonstrate that gradient-field effects can provide for an efficient, conventionally dipole-forbidden nonlinear response. We show that a longitudinal nonlinear source current can dominate the third-order optical nonlinearity of the free electron response in gold in the technologically important near-IR frequency range where the nonlinearities due to other mechanisms are particularly small. Using adiabatic nanofocusing to spatially confine the excitation fields, from measurements of the 2ω_{1}-ω_{2} four-wave mixing response as a function of detuning ω_{1}-ω_{2}, we find up to 10^{-5} conversion efficiency with a gradient-field contribution to χ_{Au}^{(3)} of up to 10^{-19}  m^{2}/V^{2}. The results are in good agreement with the theory based on plasma hydrodynamics and underlying electron dynamics. The associated increase in the nonlinear conversion efficiency with a decreasing sample size, which can even overcompensate the volume decrease, offers a new approach for enhanced nonlinear nano-optics. This will enable more efficient nonlinear optical devices and the extension of coherent multidimensional spectroscopies to the nanoscale.

Enhanced Third-Order Optical Nonlinearity Driven by Surface-Plasmon Field Gradients

NASA Astrophysics Data System (ADS)

Kravtsov, Vasily; AlMutairi, Sultan; Ulbricht, Ronald; Kutayiah, A. Ryan; Belyanin, Alexey; Raschke, Markus B.

2018-05-01

Efficient nonlinear optical frequency mixing in small volumes is key for future on-chip photonic devices. However, the generally low conversion efficiency severely limits miniaturization to nanoscale dimensions. Here we demonstrate that gradient-field effects can provide for an efficient, conventionally dipole-forbidden nonlinear response. We show that a longitudinal nonlinear source current can dominate the third-order optical nonlinearity of the free electron response in gold in the technologically important near-IR frequency range where the nonlinearities due to other mechanisms are particularly small. Using adiabatic nanofocusing to spatially confine the excitation fields, from measurements of the 2 ω1-ω2 four-wave mixing response as a function of detuning ω1-ω2, we find up to 10-5 conversion efficiency with a gradient-field contribution to χAu(3 ) of up to 10-19 m2/V2 . The results are in good agreement with the theory based on plasma hydrodynamics and underlying electron dynamics. The associated increase in the nonlinear conversion efficiency with a decreasing sample size, which can even overcompensate the volume decrease, offers a new approach for enhanced nonlinear nano-optics. This will enable more efficient nonlinear optical devices and the extension of coherent multidimensional spectroscopies to the nanoscale.

Final Test Report: Hexavalent Chrome Free Coatings for Electronics Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

NASA Technical Reports Server (NTRS)

Kessel, Kurt R.

2016-01-01

The test results for Salt Spray Resistance, Static Heat and Humidity and Marine Environment can be found in Sections 3.1.3.3, 3.1.4.3 and 3.1.5.3 respectively. In summary, both the Metalast TCP and SurTec 650 Type 2 conversion coatings perform very similar to the incumbent Type 1 conversion coating against both 6061 and 5052 aluminum under all three test conditions. Significant prior work was performed to select the aluminum and conversion coating included within this test cycle; Reference - NASA GSDO Program Hexavalent Chrome Alternatives Final Pretreatments Test Report Task Order: NNH12AA45D September 01, 2013. As illustrated in the data, the 6061 aluminum panels SLIGHTLY out-performed the 5052 aluminum panels. Individual shielding effectiveness graphs for each panel are included within Appendix C and D. One other notable effect found during review of the data is that the Test Panels exposed to B117 Salt Fog reduced in shielding effectiveness significantly more than the Marine Environment Test Panels. The shielding effectiveness of the Marine Test Panels was approximately 20dB higher than the Test Panels that underwent B117 Salt Fog Exposure. The intent of this evaluation was not to maximize shielding effectiveness values. The same Parker Chomerics Cho-Seal 6503 gasket material was used for all panels with aluminum and conversion coating variants. A typical EMI gasket design for corrosive environments would be done quite differently. The intent was to execute a test that would provide the best possible evaluation of different aluminum materials and conversion coatings in corrosive environments. The test program achieved this intent. The fact that the two aluminums and two Type II conversion coatings performed similar to the incumbent Type 1 conversion coating is a positive outcome. It was desired to have an outcome that further differentiation the performance of two aluminum types and two conversion coating types but this could not be extracted by the test results. Further analysis of the test plates may be done by X-Ray Photoelectron Spectroscopy (XPS) or Electrochemical Impedance Spectroscopy (EIS). Feasibility of this is under review.

Green conversion of graphene oxide to graphene nanosheets and its biosafety study

PubMed Central

Dasgupta, Adhiraj; Sarkar, Joy; Ghosh, Manosij; Bhattacharya, Amartya; Mukherjee, Anita; Chattopadhyay, Dipankar

2017-01-01

Chemical reduction of graphene oxide (GO) to graphene employs the use of toxic and environmentally harmful reducing agents, hindering mass production of graphene which is of tremendous technological importance. In this study we report a green approach to the synthesis of graphene, bio-reduced by crude polysaccharide. The polysaccharide reduces exfoliated GO to graphene at room temperature in an aqueous medium. Transmission electron microscopy image provides clear evidence for the formation of few layer graphene. Characterization of the resulting polysaccharide reduced GO by Raman spectroscopy, Fourier transform infrared spectroscopy and Energy dispersive X-ray analysis confirms reduction of GO to graphene. We also investigated the degree of biosafety of the reduced GO and found it to be safe under 100 μg/ml. PMID:28158272

One-pot catalytic conversion of cellulose into polyols with Pt/CNTs catalysts.

PubMed

Yang, Li; Yan, Xiaopei; Wang, Qiwu; Wang, Qiong; Xia, Haian

2015-03-02

A series of Pt nanoparticles supported on carbon nanotubes (CNTs) were synthesized using the incipient-wetness impregnation method. These catalysts were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscope (TEM) techniques. The characterization results indicate that the Pt nanoparticles were highly dispersed on the surface of the CNTs, and the mean size was less than 5 nm. These catalysts were utilized to convert cellulose to hexitol, ethylene glycerol (EG), and 1,2-propylene glycol (1,2-PG) under low H2 pressure. The total yields were as high as 71.4% for EG and 1,2-PG using 1Pt/CNTs as the catalyst in the hydrolytic hydrogenation of cellulose under mild reaction conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Self-healing Li-Al layered double hydroxide conversion coating modified with aspartic acid for 6N01 Al alloy

NASA Astrophysics Data System (ADS)

Zhang, Caixia; Luo, Xiaohu; Pan, Xinyu; Liao, Liying; Wu, Xiaosong; Liu, Yali

2017-02-01

A self-healing Li-Al layered double hydroxide conversion coating (LCC) modified with aspartic acid (ALCC) was prepared on 6N01 Al alloy for corrosion protection. Scanning electron microscopy (SEM) showed that a compact thin film has been successfully formed on the alloy. X-ray diffraction (XRD) and FT-IR spectra proved that species of aspartic acid anions were successfully intercalated into LCC. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and neutral salt spray (NSS) testing showed that the resultant ALCC could provide effective corrosion protection for the Al alloy. During immersion of the ALCC-coated alloy in 3.5% NaCl solution, new film was formed in the area of artificially introduced scratch, indicating its self-healing capability. XPS results demonstrated that Cl- anions exchange partial Asp anions according to the change content of element on conversion coating. From the above results, the possible mechanism via exchange/self-assembly was proposed to illustrate the phenomenon of self-healing.

Efficiency Enhancement of Hybrid Perovskite Solar Cells with MEH-PPV Hole-Transporting Layers

PubMed Central

Chen, Hsin-Wei; Huang, Tzu-Yen; Chang, Ting-Hsiang; Sanehira, Yoshitaka; Kung, Chung-Wei; Chu, Chih-Wei; Ikegami, Masashi; Miyasaka, Tsutomu; Ho, Kuo-Chuan

2016-01-01

In this study, hybrid perovskite solar cells are fabricated using poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT) as dopant-free hole-transporting materials (HTMs), and two solution processes (one- and two-step methods, respectively) for preparing methylammonium lead iodide perovskite. By optimizing the concentrations and solvents of MEH-PPV solutions, a power conversion efficiency of 9.65% with hysteresis-less performance is achieved, while the device with 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′spirobifluorene (Spiro-OMeTAD) doped with lithium salts and tert-butylpyridine (TBP) exhibits an efficiency of 13.38%. This result shows that non-doped MEH-PPV is a suitable, low-cost HTM for efficient polymer-based perovskite solar cells. The effect of different morphologies of methylammonium lead iodide perovskite on conversion efficiency is also investigated by incident photon-to-electron conversion efficiency (IPCE) curves and electrochemical impedance spectroscopy (EIS). PMID:27698464

Intensification of steam explosion and structural intricacies impacting sugar recovery.

PubMed

Gaur, Ruchi; Semwal, Surbhi; Raj, Tirath; Yadav Lamba, Bhawna; Ramu, E; Gupta, Ravi P; Kumar, Ravindra; Puri, Suresh K

2017-10-01

Dilute acid (DA) pretreatment at pilot level failed for cotton stalk (CS) due to the technical issues posed by its inherent nature. Reasonable glucan conversion has been reported via two-stage pretreatment but adds on to the process cost. Proposed herewith is a single-stage steam explosion (SE) process preceded by water extraction resulting in high sugar recovery from CS. Raising the extraction temperature to 80°C increased the glucan conversion from 37.9 to 52.4%. Further improvement up to 68.4% was achieved when DA was incorporated during the room temperature extraction. LC-MS revealed the formation of xylo-oligomers limiting the glucan conversion in proportion to the length of xylo-oligomers. Varying extraction conditions induced structural alterations in biomass after SE evident by compositional analysis, Infrared Spectroscopy, X-Ray Diffraction and Scanning Electron Microscopy. Overall glucose recovery, i.e. 75.8-76.7% with and without DA extraction respectively was achieved. Copyright © 2017 Elsevier Ltd. All rights reserved.

Excitation transfer and trapping kinetics in plant photosystem I probed by two-dimensional electronic spectroscopy.

PubMed

Akhtar, Parveen; Zhang, Cheng; Liu, Zhengtang; Tan, Howe-Siang; Lambrev, Petar H

2018-03-01

Photosystem I is a robust and highly efficient biological solar engine. Its capacity to utilize virtually every absorbed photon's energy in a photochemical reaction generates great interest in the kinetics and mechanisms of excitation energy transfer and charge separation. In this work, we have employed room-temperature coherent two-dimensional electronic spectroscopy and time-resolved fluorescence spectroscopy to follow exciton equilibration and excitation trapping in intact Photosystem I complexes as well as core complexes isolated from Pisum sativum. We performed two-dimensional electronic spectroscopy measurements with low excitation pulse energies to record excited-state kinetics free from singlet-singlet annihilation. Global lifetime analysis resolved energy transfer and trapping lifetimes closely matches the time-correlated single-photon counting data. Exciton energy equilibration in the core antenna occurred on a timescale of 0.5 ps. We further observed spectral equilibration component in the core complex with a 3-4 ps lifetime between the bulk Chl states and a state absorbing at 700 nm. Trapping in the core complex occurred with a 20 ps lifetime, which in the supercomplex split into two lifetimes, 16 ps and 67-75 ps. The experimental data could be modelled with two alternative models resulting in equally good fits-a transfer-to-trap-limited model and a trap-limited model. However, the former model is only possible if the 3-4 ps component is ascribed to equilibration with a "red" core antenna pool absorbing at 700 nm. Conversely, if these low-energy states are identified with the P 700 reaction centre, the transfer-to-trap-model is ruled out in favour of a trap-limited model.

New application of Z-scheme Ag3PO4/g-C3N4 composite in converting CO2 to fuel.

PubMed

He, Yiming; Zhang, Lihong; Teng, Botao; Fan, Maohong

2015-01-06

This research was designed for the first time to investigate the activities of photocatalytic composite, Ag3PO4/g-C3N4, in converting CO2 to fuels under simulated sunlight irradiation. The composite was synthesized using a simple in situ deposition method and characterized by various techniques including Brunauer-Emmett-Teller method (BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and an electrochemical method. Thorough investigation indicated that the composite consisted of Ag3PO4, Ag, and g-C3N4. The introduction of Ag3PO4 on g-C3N4 promoted its light absorption performance. However, more significant was the formation of heterojunction structure between Ag3PO4 and g-C3N4, which efficiently promoted the separation of electron-hole pairs by a Z-scheme mechanism and ultimately enhanced the photocatalytic CO2 reduction performance of the Ag3PO4/g-C3N4. The optimal Ag3PO4/g-C3N4 photocatalyst showed a CO2 conversion rate of 57.5 μmol · h(-1) · gcat(-1), which was 6.1 and 10.4 times higher than those of g-C3N4 and P25, respectively, under simulated sunlight irradiation. The work found a new application of the photocatalyst, Ag3PO4/g-C3N4, in simultaneous environmental protection and energy production.

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

DOE PAGES

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.; ...

2018-02-02

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

A grafting from approach to graft polystyrene chains at the surface of graphene nanolayers by RAFT polymerization: Various graft densities from hydroxyl groups

NASA Astrophysics Data System (ADS)

Roghani-Mamaqani, Hossein; Khezri, Khezrollah

2016-01-01

(3-Aminopropyl) triethoxysilane was grafted at the surface of GO in low and high different graft densities to yield GOHAL and GOHAH, respectively. Subsequently, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (RA) was attached at the surface of GOHAL and GOHAH by an amidation reaction to yield GOHRL and GOHRH, respectively. Then, GOHRL and GOHRH were used in grafting from RAFT polymerization of styrene. Grafting of APTES and RA was approved by Fourier transform infrared spectroscopy, X-ray photo electron spectroscopy, and Raman spectroscopy. Expansion of graphene interlayer by oxidation and functionalization processes was evaluated by X-ray diffraction. Conversion values of styrene were calculated using gas chromatography. Molecular weight and PDI values of attached polystyrene (PS) chains were studied by size exclusion chromatography. Thermogravimetric analysis was also used to investigate the degradation temperatures, char contents, and graft contents of modifiers and PS chains. GOHRH and GOHRL reach to char content of 55.3 and 45.2% at 600 °C, which shows that weight ratio of modifier (APTES and RA moieties) is 15.3 and 5.2%, respectively. Scanning and transmission electron microscopies show that graphite layers with flat and smooth surface wrinkled after oxidation and turned to opaque layers by grafting PS.

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

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

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

Dendrimer-based Nanoparticle for Dye Sensitized Solar Cells with Improved Efficiency.

PubMed

Ghann, William; Kang, Hyeonggon; Uddin, Jamal; Gonawala, Sunalee J; Mahatabuddin, Sheikh; Ali, Meser M

2018-01-01

Dye sensitized solar cells were fabricated with DyLight680 (DL680) dye and its corresponding europium conjugated dendrimer, DL680-Eu-G5PAMAM, to study the effect of europium on the current and voltage characteristics of the DL680 dye sensitized solar cell. The dye samples were characterized by using Absorption Spectroscopy, Emission Spectroscopy, Fluorescence lifetime and Fourier Transform Infrared measurements. Transmission electron microscopy imaging was carried out on the DL680-Eu-G5PAMAM dye and DL680-Eu-G5PAMAM dye sensitized titanium dioxide nanoparticles to analyze the size of the dye molecules and examine the interaction of the dye with titanium dioxide nanoparticles. The DL680-Eu-G5PAMAM dye sensitized solar cells demonstrated an enhanced solar-to-electric energy conversion of 0.32% under full light illumination (100 mWcm -2 , AM 1.5 Global) in comparison with that of DL680 dye sensitized cells which recorded an average solar-to-electric energy conversion of only 0.19%. The improvement of the efficiency could be due to the presence of the europium that enhances the propensity of dye to absorb sunlight.

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

NASA Technical Reports Server (NTRS)

Meier, Anne J.; Shah, Malay; Petersen, Elspeth; Hintze, Paul; Muscatello, Tony

2017-01-01

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

SAPO-34/AlMCM-41, as a novel hierarchical nanocomposite: preparation, characterization and investigation of synthesis factors using response surface methodology

NASA Astrophysics Data System (ADS)

Roohollahi, Hossein; Halladj, Rouein; Askari, Sima; Yaripour, Fereydoon

2018-06-01

SAPO-34/AlMCM-41, as a new hierarchical nanocomposite was successfully synthesized via hydrothermal and dry-gel conversion. In an experimental and statistical study, effect of five input parameters including synthesis period, drying temperature, NaOH/Si, water/dried-gel and SAPO% were investigated on range-order degree of mesochannels and the relative crystallinity. X-ray diffraction (XRD) patterns were recorded to characterize the ordered AlMCM-41 and crystalline SAPO-34 structures. Nitrogen adsorption-desorption technique, scanning electron microscopy (SEM), field-emission SEM (FESEM) equipped with an energy-dispersive X-ray spectroscopy (EDS-Map) and transmission electron microscopy (TEM) were used to study the textural properties, morphology and surface elemental composition. Two reduced polynomials were fitted to the responses with good precision. Further, based on analysis of variances, SAPO% and time duration of dry-gel conversion were observed as the most effective parameters on the composite structure. The hierarchical porosity, narrow pore size distribution, high external surface area and large specific pore volume were of interesting characteristics for this novel nanocomposite.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions.

PubMed

Jiao, Yan; Zheng, Yao; Jaroniec, Mietek; Qiao, Shi Zhang

2015-04-21

A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

Probing the Ultrafast Energy Dissipation Mechanism of the Sunscreen Oxybenzone after UVA Irradiation.

PubMed

Baker, Lewis A; Horbury, Michael D; Greenough, Simon E; Coulter, Philip M; Karsili, Tolga N V; Roberts, Gareth M; Orr-Ewing, Andrew J; Ashfold, Michael N R; Stavros, Vasilios G

2015-04-16

Oxybenzone is a common constituent of many commercially available sunscreens providing photoprotection from ultraviolet light incident on the skin. Femtosecond transient electronic and vibrational absorption spectroscopies have been used to investigate the nonradiative relaxation pathways of oxybenzone in cyclohexane and methanol after excitation in the UVA region. The present data suggest that the photoprotective properties of oxybenzone can be understood in terms of an initial ultrafast excited state enol → keto tautomerization, followed by efficient internal conversion and subsequent vibrational relaxation to the ground state (enol) tautomer.

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors

PubMed Central

Mahjouri-Samani, Masoud; Lin, Ming-Wei; Wang, Kai; Lupini, Andrew R.; Lee, Jaekwang; Basile, Leonardo; Boulesbaa, Abdelaziz; Rouleau, Christopher M.; Puretzky, Alexander A.; Ivanov, Ilia N.; Xiao, Kai; Yoon, Mina; Geohegan, David B.

2015-01-01

The formation of semiconductor heterojunctions and their high-density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional crystalline semiconductors as building blocks in next-generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate an approach for the formation of lithographically patterned arrays of lateral semiconducting heterojunctions within a single two-dimensional crystal. Electron beam lithography is used to pattern MoSe2 monolayer crystals with SiO2, and the exposed locations are selectively and totally converted to MoS2 using pulsed laser vaporization of sulfur to form MoSe2/MoS2 heterojunctions in predefined patterns. The junctions and conversion process are studied by Raman and photoluminescence spectroscopy, atomically resolved scanning transmission electron microscopy and device characterization. This demonstration of lateral heterojunction arrays within a monolayer crystal is an essential step for the integration of two-dimensional semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin devices. PMID:26198727

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

NASA Astrophysics Data System (ADS)

Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

2017-08-01

Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Reduced energy offset via substitutional doping for efficient organic/inorganic hybrid solar cells.

PubMed

Jin, Xiao; Sun, Weifu; Zhang, Qin; Ruan, Kelian; Cheng, Yuanyuan; Xu, Haijiao; Xu, Zhongyuan; Li, Qinghua

2015-06-01

Charge carrier transport in bulk heterojunction that is central to the device performance of solar cells is sensitively dependent on the energy level alignment of acceptor and donor. However, the effect of energy level regulation induced by nickel ions on the primary photoexcited electron transfer and the performance of P3HT/TiO₂ hybrid solar cells remains being poorly understood and rarely studied. Here we demonstrate that the introduction of the versatile nickel ions into TiO₂ nanocrystals can significantly elevate the conduction and valence band energy levels of the acceptor, thus resulting in a remarkable reduction of energy level offset between the conduction band of acceptor and lowest unoccupied molecular orbital of donor. By applying transient photoluminescence and femtosecond transient absorption spectroscopies, we demonstrate that the electron transfer becomes more competitive after incorporating nickel ions. In particular, the electron transfer life time is shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO₂ acceptor, thus leading to a notable increase of power conversion efficiency in organic/inorganic hybrid solar cells. This work underscores the promising virtue of engineering the reduction of 'excess' energy offset to accelerate electron transport and demonstrates the potential of nickel ions in applications of solar energy conversion and photon detectors.

Effect of thermal annealing treatment with titanium chelate on buffer layer in inverted polymer solar cells

NASA Astrophysics Data System (ADS)

Liu, Zhiyong; Wang, Ning; Fu, Yan

2016-12-01

The solution processable electron extraction layer (EEL) is crucial for polymer solar cells (PSCs). Here, we investigated titanium (diisopropoxide) bis(2,4-pentanedionate) (TIPD) as an EEL and fabricated inverted PSCs with a blend of poly(3-hexylthiophene) (P3HT) and indene-C60 bisadduct (ICBA) acting as the photoactive layer, with a structure of ITO/TIPD/P3HT:ICBA/MoO3/Ag. After thermal annealing treatment at 150 °C for 15 min, the PSC performances increased from 3.85% to 6.84% and they achieve stable power conversion efficiency (PCE), with a similar PCE compared with TiO2 as an EEL by the vacuum evaporated method. Fourier transform infrared spectroscopy (FTIR) and ultraviolet photoelectron spectroscopy (UPS) confirmed that the TIPD decomposed and formed the Tidbnd O bond, and the energy level of the lowest unoccupied molecular orbital and the highest occupied molecular orbital increased. The space charge limited current (SCLC) measurements further confirmed the improvement in electron collection and the transport ability using TIPD as the EEL and thermal annealing.

X-ray emission spectroscopy of biomimetic Mn coordination complexes

DOE PAGES

Jensen, Scott C.; Davis, Katherine M.; Sullivan,

2017-05-19

Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [Mn IV(OH) 2(Me 2EBC)] 2+ and [Mn IV(O)(OH)(Me 2EBC)] +, the second of which contains a key Mn IV=O structural fragment. Despite having the same formal oxidation state (Mn IV) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield differentmore » localized spin densities for the two complexes resulting from Mn IV–OH conversion to Mn IV=O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. In conclusion, a model of the S 3 intermediate state of photosystem II containing a Mn IV=O fragment is compared to recent time-resolved X-ray diffraction data of the same state.« less

X-ray Emission Spectroscopy of Biomimetic Mn Coordination Complexes.

PubMed

Jensen, Scott C; Davis, Katherine M; Sullivan, Brendan; Hartzler, Daniel A; Seidler, Gerald T; Casa, Diego M; Kasman, Elina; Colmer, Hannah E; Massie, Allyssa A; Jackson, Timothy A; Pushkar, Yulia

2017-06-15

Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [Mn IV (OH) 2 (Me 2 EBC)] 2+ and [Mn IV (O)(OH)(Me 2 EBC)] + , the second of which contains a key Mn IV ═O structural fragment. Despite having the same formal oxidation state (Mn IV ) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield different localized spin densities for the two complexes resulting from Mn IV -OH conversion to Mn IV ═O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. A model of the S 3 intermediate state of photosystem II containing a Mn IV ═O fragment is compared to recent time-resolved X-ray diffraction data of the same state.

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell

PubMed Central

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-01-01

In this work, Cu2O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode. PMID:28335366

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell.

PubMed

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-12-09

In this work, Cu₂O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode.

A combined spectroscopic and TDDFT study of natural dyes extracted from fruit peels of Citrus reticulata and Musa acuminata for dye-sensitized solar cells.

PubMed

Prima, Eka Cahya; Hidayat, Novianto Nur; Yuliarto, Brian; Suyatman; Dipojono, Hermawan Kresno

2017-01-15

This study reports the novel spectroscopic investigations and enhanced the electron transfers of Citrus reticulata and Musa acuminata fruit peels as the photosensitizers for the dye-sensitized solar cells. The calculated TD-DFT-UB3LYP/6-31+G(d,p)-IEFPCM(UAKS), experiment spectra of ultra-violet-visible spectroscopy, and Fourier transform infrared spectroscopy studies indicate the main flavonoid (hesperidin and gallocatechin) structures of the dye extracts. The optimized flavonoid structures are calculated using Density functional theory (DFT) at 6-31+G(d,p) level. The rutinosyl group of the hesperidin pigment (Citrus reticulata) will be further investigated compared to the gallocatechin (Musa acuminata) pigment. The acidity of the dye extract is treated by adding 2% acetic acid. The energy levels of the HOMO-LUMO dyes are measured by a combined Tauc plot and cyclic voltammetry contrasted with the DFT data. The electrochemical impedance spectroscopy will be performed to model the dye electron transfer. As for the rutinosyl group presence and the acidic treatment, the acidified Citrus reticulata cell under continuous light exposure of 100mW·cm -2 yields a short-circuit current density (J sc ) of 3.23mA/cm 2 , a photovoltage (V oc ) of 0.48V, and a fill factor of 0.45 corresponding to an energy conversion efficiency (η) of 0.71% because the shifting down HOMO-LUMO edges and the broadening dye's absorbance evaluated by a combined spectroscopic and TD-DFT method. The result also leads to the longest diffusion length of 32.2μm, the fastest electron transit of 0.22ms, and the longest electron lifetime of 4.29ms. Copyright © 2016 Elsevier B.V. All rights reserved.

A combined spectroscopic and TDDFT study of natural dyes extracted from fruit peels of Citrus reticulata and Musa acuminata for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Prima, Eka Cahya; Hidayat, Novianto Nur; Yuliarto, Brian; Suyatman; Dipojono, Hermawan Kresno

2017-01-01

This study reports the novel spectroscopic investigations and enhanced the electron transfers of Citrus reticulata and Musa acuminata fruit peels as the photosensitizers for the dye-sensitized solar cells. The calculated TD-DFT-UB3LYP/6-31 + G(d,p)-IEFPCM(UAKS), experiment spectra of ultra-violet-visible spectroscopy, and Fourier transform infrared spectroscopy studies indicate the main flavonoid (hesperidin and gallocatechin) structures of the dye extracts. The optimized flavonoid structures are calculated using Density functional theory (DFT) at 6-31 + G(d,p) level. The rutinosyl group of the hesperidin pigment (Citrus reticulata) will be further investigated compared to the gallocatechin (Musa acuminata) pigment. The acidity of the dye extract is treated by adding 2% acetic acid. The energy levels of the HOMO-LUMO dyes are measured by a combined Tauc plot and cyclic voltammetry contrasted with the DFT data. The electrochemical impedance spectroscopy will be performed to model the dye electron transfer. As for the rutinosyl group presence and the acidic treatment, the acidified Citrus reticulata cell under continuous light exposure of 100 mW·cm- 2 yields a short-circuit current density (Jsc) of 3.23 mA/cm2, a photovoltage (Voc) of 0.48 V, and a fill factor of 0.45 corresponding to an energy conversion efficiency (η) of 0.71% because the shifting down HOMO-LUMO edges and the broadening dye's absorbance evaluated by a combined spectroscopic and TD-DFT method. The result also leads to the longest diffusion length of 32.2 μm, the fastest electron transit of 0.22 ms, and the longest electron lifetime of 4.29 ms.

Single-Molecule Interfacial Electron Transfer

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

Ho, Wilson

Interfacial electron transfer (ET) plays an important role in many chemical and biological processes. Specifically, interfacial ET in TiO 2-based systems is important to solar energy technology, catalysis, and environmental remediation technology. However, the microscopic mechanism of interfacial ET is not well understood with regard to atomic surface structure, molecular structure, bonding, orientation, and motion. In this project, we used two complementary methodologies; single-molecule fluorescence spectroscopy, and scanning-tunneling microscopy and spectroscopy (STM and STS) to address this scientific need. The goal of this project was to integrate these techniques and measure the molecular dependence of ET between adsorbed molecules andmore » TiO 2 semiconductor surfaces and the ET induced reactions such as the splitting of water. The scanning probe techniques, STM and STS, are capable of providing the highest spatial resolution but not easily time-resolved data. Single-molecule fluorescence spectroscopy is capable of good time resolution but requires further development to match the spatial resolution of the STM. The integrated approach involving Peter Lu at Bowling Green State University (BGSU) and Wilson Ho at the University of California, Irvine (UC Irvine) produced methods for time and spatially resolved chemical imaging of interfacial electron transfer dynamics and photocatalytic reactions. An integral aspect of the joint research was a significant exchange of graduate students to work at the two institutions. This project bridged complementary approaches to investigate a set of common problems by working with the same molecules on a variety of solid surfaces, but using appropriate techniques to probe under ambient (BGSU) and ultrahigh vacuum (UCI) conditions. The molecular level understanding of the fundamental interfacial electron transfer processes obtained in this joint project will be important for developing efficient light harvesting, solar energy conversion, and broadly applicable to problems in interface chemistry and surface physics.« less

Limitations of Cs3Bi2I9 as lead-free photovoltaic absorber materials.

PubMed

Ghosh, Biplab; Wu, Bo; Mulmudi, Hemant Kumar; Guet, Claude; Weber, Klaus; Sum, Tze Chien; Mhaisalkar, Subodh G; Mathews, Nripan

2018-01-17

Lead (Pb) halide perovskites have attracted tremendous attention in recent years due to their rich optoelectronic properties, which have resulted in more than 22% power conversion efficient photovoltaics. Nevertheless, Pb-metal toxicity remains a huge hurdle for extensive applications of these compounds. Thus, alternative compounds with similar optoelectronic properties need to be developed. Bismuth possesses similar electronic structure as that of lead with the presence of ns2 electrons that exhibit rich structural variety as well as interesting optical and electronic properties. Herein, we critically assess Cs3Bi2I9 as a candidate for thin-film solar cell absorber. Despite a reasonable optical bandgap (~2eV) and absorption coefficient, the power conversion efficiency of the Cs3Bi2I9 mesoscopic solar cells was found to be severely lacking, limited by poor photocurrent density. The efficiency of the Cs3Bi2I9 solar cell can be slightly improved by changing the stoichiometry of the precursor solutions. We have investigated the possible reasons behind the poor performance of Cs3Bi2I9 by transient absorption and luminescence spectroscopy. Comparison between thin-films and single crystals highlights the presence of intrinsic defects in thin-films which act as nonradiative recombination centers.

Influence of Hemostatic Solution on Bond Strength and Physicochemical Properties of Resin Cement.

PubMed

Araújo, Isabela Sousa de; Prado, Célio Jesus do; Raposo, Luís Henrique Araújo; Soares, Carlos José; Zanatta, Rayssa Ferreira; Torres, Carlos Rocha Gomes; Ruggiero, Reinaldo; Silva, Gisele Rodrigues da

2017-01-01

The aim of this study was to evaluate the degree of conversion, color stability, chemical composition, and bond strength of a light-cured resin cement contaminated with three different hemostatic solutions. Specimens were prepared for the control (uncontaminated resin cement) and experimental groups (resin cement contaminated with one of the hemostatic solutions) according to the tests. For degree of conversion, DC (n = 5) and color analyses (n = 10), specimens (3 mm in diameter and 2 mm thick) were evaluated by Fourier transform infrared spectroscopy (FTIR) and CIELAB spectrophotometry (L*, a*, b*), respectively. For elemental chemical analysis (n = 1), specimens (2 mm thick and 6 mm in diameter) were evaluated by x-ray energy-dispersive spectroscopy (EDS). The bond strengths of the groups were assessed by the microshear test (n = 20) in a leucite-reinforced glass ceramic substrate, followed by failure mode analysis by scanning electron microscopy (SEM). The mean values, except for the elemental chemical evaluation and failure mode, were evaluated by ANOVA and Tukey's HSD test. The color stability was influenced by storage time (p<0.001) and interaction between contamination and storage time (p<0.001). Hemostop and Viscostat Clear contamination did not affect the DC, however Viscostat increased the DC. Bond strength of the resin cement to ceramic was negatively affected by the contaminants (p<0.001). Contamination by hemostatic agents affected the bond strength, degree of conversion, and color stability of the light-cured resin cement tested.

Synthesis of NaYF4:Yb/Er/Gd up-conversion luminescent nanoparticles and luminescence resonance energy transfer-based protein detection

PubMed Central

Zhang, Jingpu; Mi, Congcong; Wu, Hongyan; Huang, Huaiqing; Mao, Chuanbin; Xu, Shukun

2012-01-01

High-quality NaYF4:Yb/Er/Gd up-conversion nanoparticles (UCNPs) were first synthesized by a solvothermal method using rare earth stearate, sodium fluoride, ethanol, water, and oleic acid as precursors. Doped Gd3+ ions can promote the transition of NaYF4 from cubic to hexagonal phase, shorten the reaction time, and reduce the reaction temperature without reducing the luminescence intensity of NaYF4:Yb/Er UCNPs. X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and luminescence spectroscopy were applied to characterize the UCNPs. The nanoparticles exhibited small size and excellent green up-conversion photoluminescence, making them suitable for biological applications. After the surfaces of NaYF4:Yb/Er/Gd UCNPs were modified with amino groups through the Stöber method, they could be brought close enough to the analytically important protein called R-phycoerythrin (R-PE) bearing multiple carboxyl groups so that energy transfer could occur. A luminescence resonance energy transfer (LRET) system was developed using NaYF4:Yb/Er/Gd UCNPs as an energy donor and R-PE as an energy acceptor. As a result, a detection limit of R-PE of 0.5 μg/ml was achieved by the LRET system with a relative standard deviation of 2.0%. Although this approach was first used successfully to detect R-PE, it can also be extended to the detection of other biological molecules. PMID:22155069

Roll-to-roll Slot-die Printed Polymer Solar Cell by Self-Assembly.

PubMed

Yang, Junyu; Lin, Yuanbao; Zheng, Wenhao; Liu, Alei; Cai, Wanzhu; Yu, Xiaomin; Zhang, Fengling; Liang, Quanbin; Wu, Hongbin; Qin, Donghuan; Hou, Lintao

2018-06-12

Extremely simplified one-step roll-to-roll slot-die printed flexible ITO-free polymer solar cells (PSCs) are demonstrated based on ternary blends of electron-donor polymer thieno [3,4-b]thiophene/benzodithiophene (PTB7), electron-acceptor fullerene [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) and electron extracting polymer poly [(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) at room temperature (RT) in ambient air. The flexible ITO-free PSC exhibits a comparable power conversion efficiency (PCE) with the device employing complicated two-step slot-die printing (5.29% vs 5.41%), which indicates that PFN molecules can migrate from the ternary nanocomposite towards Ag cathode via vertical self-assembly during the one-step slot-die printing process in air. To confirm the migration of PFN, the morphology and elemental analysis as well as charge transport of different active layers are investigated with in-situ transient film drying process, transmission electron microscopy, atomic force microscopy, contact angle and surface energy, X-ray photoelectron spectroscopy, scanning electron microscope, impedance spectroscopy, transient photovoltage and transient photocurrent as well as laser beam induced current. Moreover, the good air and mechanical stability of the flexible device with a decent PCE achieved in 1 cm2 PSCs at RT in air suggests the feasibility of energy-saving and time-saving one-step slot-die printing to large-scale roll-to-roll manufacture in the future.

Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

NASA Astrophysics Data System (ADS)

Ponseca, C. S., Jr.; Sundström, V.

2016-03-01

Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

Water adsorption on the P-rich GaP(100) surface: optical spectroscopy from first principles

NASA Astrophysics Data System (ADS)

May, Matthias M.; Sprik, Michiel

2018-03-01

The contact of water with semiconductors typically changes its surface electronic structure by oxidation or corrosion processes. A detailed knowledge—or even control of—the surface structure is highly desirable, as it impacts the performance of opto-electronic devices from gas-sensing to energy conversion applications. It is also a prerequisite for density functional theory-based modelling of the electronic structure in contact with an electrolyte. The P-rich GaP(100) surface is extraordinary with respect to its contact with gas-phase water, as it undergoes a surface reordering, but does not oxidise. We investigate the underlying changes of the surface in contact with water by means of theoretically derived reflection anisotropy spectroscopy (RAS). A comparison of our results with experiment reveals that a water-induced hydrogen-rich phase on the surface is compatible with the boundary conditions from experiment, reproducing the optical spectra. We discuss potential reaction paths that comprise a water-enhanced hydrogen mobility on the surface. Our results also show that computational RAS—required for the interpretation of experimental signatures—is feasible for GaP in contact with water double layers. Here, RAS is sensitive to surface electric fields, which are an important ingredient of the Helmholtz-layer. This paves the way for future investigations of RAS at the semiconductor–electrolyte interface.

Improved electron density through hetero-junction binary sensitized TiO2/ CdTe / D719 system as photoanode for dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Pandey, A. K.; Ahmad, Muhammad Shakeel; Alizadeh, Mahdi; Rahim, Nasrudin Abd

2018-07-01

The combined effect of dual sensitization and hetero-junction symmetry has been investigated on the performance of TiO2 based dye sensitized solar cell. CdTe nanoparticles have been introduced in TiO2 matrix to function as sensitizer as well as act as hetero-junction between D719 dye and TiO2 nanoarchitecture. Four concentrations of CdTe i.e. 0.5 wt%, 2 wt%, 5 wt% and 8 wt% have been investigated. Morphological and compositional studies have been conducted using scanning electron microscope (SEM) and X-ray diffraction (XRD) respectively. Light absorption characteristics have been investigated by employing Uv-vis spectroscopy and the overall performance has been studied using solar simulator and electrochemical impedance spectroscopy (EIS). Performance has been found to be increased with the addition of CdTe due to high electron density and reduction in recombination reactions. An increase of 41.73% in incident photo conversion efficiency (IPCE) and 75.57% in short circuit current density (Jsc) have been recorded for the specimens containing 5 wt% CdTe compared to bare TiO2 based DSSCs. Further addition of CdTe leads to reduction in overall performance of DSSCs.

Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

DOE PAGES

Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; ...

2015-09-18

Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealedmore » both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.« less

Patterned arrays of lateral heterojunctions within monolayer two-dimensional semiconductors

DOE PAGES

Mahjouri-Samani, Masoud; Lin, Ming-Wei; Wang, Kai; ...

2015-07-22

The formation of semiconductor heterojunctions and their high density integration are foundations of modern electronics and optoelectronics. To enable two-dimensional (2D) crystalline semiconductors as building blocks in next generation electronics, developing methods to deterministically form lateral heterojunctions is crucial. Here we demonstrate a process strategy for the formation of lithographically-patterned lateral semiconducting heterojunctions within a single 2D crystal. E-beam lithography is used to pattern MoSe 2 monolayer crystals with SiO 2, and the exposed locations are selectively and totally converted to MoS 2 using pulsed laser deposition (PLD) of sulfur in order to form MoSe 2/MoS 2 heterojunctions in predefinedmore » patterns. The junctions and conversion process are characterized by atomically resolved scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. This demonstration of lateral semiconductor heterojunction arrays within a single 2D crystal is an essential step for the lateral integration of 2D semiconductor building blocks with different electronic and optoelectronic properties for high-density, ultrathin circuitry.« less

Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells.

PubMed

Zhong, Yu; Trinh, M Tuan; Chen, Rongsheng; Purdum, Geoffrey E; Khlyabich, Petr P; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y; Black, Charles T; Steigerwald, Michael L; Loo, Yueh-Lin; Ng, Fay; Zhu, X-Y; Nuckolls, Colin

2015-09-18

Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells.

Chemical Reactions Triggered Using Electrons Photodetached from "Clean" Distributions of Anions Deposited in Cryogenic Matrices via Counterion Codeposition.

PubMed

Ludwig, Ryan M; Moore, David T

2014-09-04

Application of matrix isolation spectroscopy to ionic species is typically complicated by the presence of neutral contaminants during matrix deposition. Herein we demonstrate that simultaneous deposition of balanced currents of counterions with mass-selected ions of interest generates "clean" distributions of matrix-isolated metal carbonyl anions, where the only bands appearing in the CO-stretching region of the vibrational spectrum arise from ions. (Neutrals are initially absent.) Photodetachment by mild irradiation with visible light leads to complete conversion of the anions into their corresponding neutral species. The photodetached electrons, in turn, initiate covalent chemistry, inducing C-C bond formation following electron-capture by CO van der Waals dimers to produce trans-OCCO(-). The initial clean distribution of ions enables clear connections to be drawn between the spectral changes occurring at each experimental step, thus demonstrating the potential of the counterion codeposition technique to facilitate detailed studies of chemistry involving ions and electron transfer in cryogenic matrices.

Element Selectivity in Second-Harmonic Generation of GaFeO3 by a Soft-X-Ray Free-Electron Laser

NASA Astrophysics Data System (ADS)

Yamamoto, Sh.; Omi, T.; Akai, H.; Kubota, Y.; Takahashi, Y.; Suzuki, Y.; Hirata, Y.; Yamamoto, K.; Yukawa, R.; Horiba, K.; Yumoto, H.; Koyama, T.; Ohashi, H.; Owada, S.; Tono, K.; Yabashi, M.; Shigemasa, E.; Yamamoto, S.; Kotsugi, M.; Wadati, H.; Kumigashira, H.; Arima, T.; Shin, S.; Matsuda, I.

2018-06-01

Nonlinear optical frequency conversion has been challenged to move down to the extreme ultraviolet and x-ray region. However, the extremely low signals have allowed researchers to only perform transmission experiments of the gas phase or ultrathin films. Here, we report second harmonic generation (SHG) of the reflected beam of a soft x-ray free-electron laser from a solid, which is enhanced by the resonant effect. The observation revealed that the double resonance condition can be met by absorption edges for transition metal oxides in the soft x-ray range, and this suggests that the resonant SHG technique can be applicable to a wide range of materials. We discuss the possibility of element-selective SHG spectroscopy measurements in the soft x-ray range.

Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Juan; Lin, Dong-Yang; Yan, Xiao-Hui; Wang, Xiao-Xiang

2011-12-01

A homogeneous amorphous calcium phosphate (ACP) coating containing magnesium was achieved on titanium substrates by electrochemical deposition (ECD). Its amorphous structure is confirmed by transmission electron microscope (TEM) together with grazing reflection absorption infrared spectroscopy (IR) spectrometer. In the images of high-resolution transmission electron microscope (HRTEM), the ACP spheres are assembled by nano-particles with the diameter of 5-10 nm. In the alkaline environment, nucleation of hydroxyapatite (HAP) occurs on the surfaces of ACP spheres. By consuming the Ca and PO 4 ions inside the ACP spheres, the HAP nuclei grow outward. Confirmed by TEM, the ACP spheres converse to hollow HAP spheres composed of HAP nano-needles. The coating is finally constructed by the HAP nano-needles, which are themselves aggregated by numerous nano-particles.

Current at Metal-Organic Interfaces

NASA Astrophysics Data System (ADS)

Kern, Klaus

2012-02-01

Charge transport through atomic and molecular constrictions greatly affects the operation and performance of organic electronic devices. Much of our understanding of the charge injection and extraction processes in these systems relays on our knowledge of the electronic structure at the metal-organic interface. Despite significant experimental and theoretical advances in studying charge transport in nanoscale junctions, a microscopic understanding at the single atom/molecule level is missing. In the present talk I will present our recent results to probe directly the nanocontact between single molecules and a metal electrode using scanning probe microscopy and spectroscopy. The experiments provide unprecedented microscopic details of single molecule and atom junctions and open new avenues to study quantum critical and many body phenomena at the atomic scale. Implications for energy conversion devices and carbon based nanoelectronics will also be discussed.

Perpendicular State of an Electronically Excited Stilbene: Observation by Femtosecond-Stimulated Raman Spectroscopy.

PubMed

Quick, Martin; Dobryakov, Alexander L; Ioffe, Ilya N; Granovsky, Alex A; Kovalenko, Sergey A; Ernsting, Nikolaus P

2016-10-20

In the photoisomerization path of stilbene, a perpendicular state P on the S 1 potential energy surface is expected just before internal conversion through a conical intersection S 1 /S 0 . For decades the observation of P was thwarted by a short lifetime τ P in combination with slow population flow over a barrier. But these limitations can be overcome by ethylenic substitution. Following optical excitation of trans-1,1'-dicyanostilbene, P is populated significantly (τ P = 27 ps in n-hexane) and monitored by an exited-state absorption band at 370 nm. Here we report stimulated Raman lines of P. The strongest, at 1558 cm -1 , is attributed to stretching vibrations of the phenyl rings. Transient electronic states, resonance conditions, and corresponding Raman signals are discussed.

Thermal Characterization of Carbon Nanotubes by Photothermal Techniques

NASA Astrophysics Data System (ADS)

Leahu, G.; Li Voti, R.; Larciprete, M. C.; Sibilia, C.; Bertolotti, M.; Nefedov, I.; Anoshkin, I. V.

2015-06-01

Carbon nanotubes (CNTs) are multifunctional materials commonly used in a large number of applications in electronics, sensors, nanocomposites, thermal management, actuators, energy storage and conversion, and drug delivery. Despite recent important advances in the development of CNT purity assessment tools and atomic resolution imaging of individual nanotubes by scanning tunnelling microscopy and high-resolution transmission electron microscopy, the macroscale assessment of the overall surface qualities of commercial CNT materials remains a great challenge. The lack of quantitative measurement technology to characterize and compare the surface qualities of bulk manufactured and engineered CNT materials has negative impacts on the reliable and consistent nanomanufacturing of CNT products. In this paper it is shown how photoacoustic spectroscopy and photothermal radiometry represent useful non-destructive tools to study the optothermal properties of carbon nanotube thin films.

Ultrafast dynamics of colloidal semiconductor nanocrystals relevant to solar fuels production

NASA Astrophysics Data System (ADS)

Cogan, Nicole M. B.; Liu, Cunming; Qiu, Fen; Burke, Rebeckah; Krauss, Todd D.

2017-05-01

Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. Ultrafast transient absorption spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts reveal extremely fast ET, and provide a fundamental explanation for the exceptional photocatalytic H2 activity. Additionally, by studying H2 production of the Ni catalyst with CdSe/CdS nanoparticles of various structures, it was determined that surface charge density plays an important role in charge transfer and ultimately H2 production activity.

Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Gang; Liu, Haiou

2018-01-01

A kind of multi-functional sites metal-organic framework (MOF) composite (MIL-101-IMBr) was successfully prepared by post-synthesis modification of MIL-101 with imidazolium-based ionic liquids. The ionic liquids not only functionalize as basic sites but also provide halide anions, which serve as a nucleophile in cycloaddition reaction. The prepared functional MOF materials were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, N2 adsorption-desorption and CO2 temperature programmed desorption. The results of fourier transform infrared spectroscopy and energy dispersive spectroscopy show that the MIL-101-IMBr composite was successfully synthesized. The N2 adsorption-desorption results clearly demonstrated that the modified composites still preserve high BET surface area and total pore volume. The composite exhibits high catalytic activity for the cycloaddition of CO2 with epoxides under mild and co-catalyst free conditions. The conversion of propylene oxide was 95.8% and the selectivity of cyclic carbonate was 97.6% under 0.8 MPa at 80 °C for 4 h. Moreover, the catalyst can be used for at least five times.

Investigation of a combined platinum and electron lifetime control treatment for silicon

NASA Astrophysics Data System (ADS)

Jia, Yunpeng; Cui, Zhihang; Yang, Fei; Zhao, Bao; Zou, Shikai; Liang, Yongsheng

2017-02-01

In silicon, the effect of Combined Lifetime Treatment (CLT) involving platinum diffusion and subsequent electron irradiation is different from the separate treatments of platinum diffusion and electron irradiation, even the treatment of electron irradiation followed by platinum diffusion. In this paper, we investigated the experimental behavior of different kinds of lifetime treated samples. We found that the reverse leakage current (Irr) increases with the increasing platinum diffusion temperature or electron irradiation dose in the separate treatments. Conversely, Irr of the CLT samples decreased with rising platinum diffusion temperature at the same dose of subsequent electron irradiation. By deep-level transient spectroscopy (DLTS), a new energy level E7 (Ec -0.376 eV) was found in our CLT samples. The new level E7 suppresses the dominance of the deeper level E8 (Ec -0.476 eV), which is caused by electron irradiation directly and results in Irr's increase. The formation of the level E7 comes from the complex defect-combined effect between platinum atoms and silicon vacancies, and it affects device's characteristics finally. These research will be helpful to the development of platinum-diffused devices used in intense electron irradiation environments.

Cu/Cu2O nanocomposite films as a p-type modified layer for efficient perovskite solar cells.

PubMed

Chen, You-Jyun; Li, Ming-Hsien; Huang, Jung-Chun-Andrew; Chen, Peter

2018-05-16

Cu/Cu 2 O films grown by ion beam sputtering were used as p-type modified layers to improve the efficiency and stability of perovskite solar cells (PSCs) with an n-i-p heterojunction structure. The ratio of Cu to Cu 2 O in the films can be tuned by the oxygen flow ratio (O 2 /(O 2  + Ar)) during the sputtering of copper. Auger electron spectroscopy was performed to determine the elemental composition and chemical state of Cu in the films. Ultraviolet photoelectron spectroscopy and photoluminescence spectroscopy revealed that the valence band maximum of the p-type Cu/Cu 2 O matches well with the perovskite. The Cu/Cu 2 O film not only acts as a p-type modified layer but also plays the role of an electron blocking buffer layer. By introducing the p-type Cu/Cu 2 O films between the low-mobility hole transport material, spiro-OMeTAD, and the Ag electrode in the PSCs, the device durability and power conversion efficiency (PCE) were effectively improved as compared to the reference devices without the Cu/Cu 2 O interlayer. The enhanced PCE is mainly attributed to the high hole mobility of the p-type Cu/Cu 2 O film. Additionally, the Cu/Cu 2 O film serves as a protective layer against the penetration of humidity and Ag into the perovskite active layer.

Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation

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

Li, Zhi-Jun; Fan, Xiang-Bing; Li, Xu-Bing

2017-01-01

Here we present a facile aqueous approach to synthesize heterostructured CdSe/CdS QDs with all-inorganic chalcogenide S2- ligands under mild conditions. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and steady-state emission spectroscopy demonstrate that the heterostructured CdSe/CdS QDs with sulfur-rich surface composition are formed by heterogeneous nucleation of Cd2+ and S2- precursors on the CdSe QDs. After adsorption of small Ni(OH)(2) clusters over the surface in situ, the CdSe/CdS-Ni(OH)(2) photocatalyst enables H-2 production efficiently with an internal quantum yield of 52% under visible light irradiation at 455 nm, up to an 8-fold increase ofmore » activity to that of spherical CdSe QDs-Ni(OH)(2) under the same conditions. Femtosecond transient absorption spectroscopy, X-ray transient absorption (XTA) spectroscopy, steady-state and time-resolved emission spectroscopy show that the quasi-type-II band alignment in the CdSe/CdS heterostructure is responsible for the efficiency enhancement of light harvesting and surface/interfacial charge separation in solar energy conversion. The unprecedented results exemplify an easily accessible pattern of aqueous synthesis of all-inorganic heterostructured QDs for advanced photosynthetic H-2 evolution.« less

Interfacial chemical reactions between MoS2 lubricants and bearing materials

NASA Technical Reports Server (NTRS)

Zabinski, J. S.; Tatarchuk, B. J.

1989-01-01

XPS and conversion-electron Moessbauer spectroscopy (CEMS) were used to examine iron that was deposited on the basal plane of MoS2 single crystals and subjected to vacuum annealing, oxidizing, and reducing environments. Iron either intercalated into the MoS2 structure or formed oriented iron sulfides, depending on the level of excess S in the MoS2 structure. CEMS data demonstrated that iron sulfide crystal structures preferentially aligned with respect to the MoS2 basal plane, and that alignment (and potentially adhesion) could be varied by appropriate high-temperature annealing procedures.

Heterojunction between the delafossite TCO n-copper indium oxide and p-Si for solar cell applications

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

Keerthi, K.; Nair, B. G.; Philip, R. R., E-mail: reenatara@rediffmail.com

2016-05-23

Junction formation of n-copper indium oxide (CIO) (extrinsically undoped) with p-Si leading to conversion of photons in the UV-Vis range is being reported for the first time. I-V and temporal photoconductivity data confirm positively the carrier generation in CIO under irradiation while optical absorbance data furnish its band gap to be ~ 3.1 eV. Ultraviolet photoelectron spectroscopy is used to study the electronic band structure of CIO on Si and to construct a schematic diagram of the hetero-junction to explain the observed photovoltaic phenomena.

Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

PubMed Central

Wickman, B.; Bastos Fanta, A.; Burrows, A.; Hellman, A.; Wagner, J. B.; Iandolo, B.

2017-01-01

Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance. PMID:28091573

Influence of irradiance on Knoop hardness, degree of conversion, and polymerization shrinkage of nanofilled and microhybrid composite resins.

PubMed

Fugolin, Ana Paula Piovezan; Correr-Sobrinho, Lourenço; Correr, Américo Bortolazzo; Sinhoreti, Mário Alexandre Coelho; Guiraldo, Ricardo Danil; Consani, Simonides

2016-01-01

The purpose of this study was to investigate the influence of the irradiance emitted by a light-curing unit on microhardness, degree of conversion (DC), and gaps resulting from shrinkage of 2 dental composite resins. Cylinders of nanofilled and microhybrid composites were fabricated and light cured. After 24 hours, the tops and bottoms of the specimens were evaluated via indentation testing and Fourier transform infrared spectroscopy to determine Knoop hardness number (KHN) and DC, respectively. Gap width (representing polymerization shrinkage) was measured under a scanning electron microscope. The nanofilled composite specimens presented significantly greater KHNs than did the microhybrid specimens (P < 0.05). The microhybrid composite resin exhibited significantly greater DC and gap width than the nanofilled material (P < 0.05). Irradiance had a mostly material-dependent influence on the hardness and DC, but not the polymerization shrinkage, of composite resins.

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

Yang, Dong; Xu, Pinghong; Browning, Nigel D.

The initial steps of rhodium cluster formation from zeolite-supported mononuclear Rh(C2H4)2 complexes in H2 at 373 K and 1 bar were investigated by infrared and extended X-ray absorption fine structure spectroscopies and scanning transmission electron microscopy (STEM). The data show that ethylene ligands on the rhodium react with H2 to give supported rhodium hydrides and trigger the formation of rhodium clusters. STEM provided the first images of the smallest rhodium clusters (Rh2) and their further conversion into larger clusters. The samples were investigated in a plug-flow reactor as catalysts for the conversion of ethylene + H2 in a molar ratiomore » of 4:1 at 1 bar and 298 K, with the results showing how the changes in catalyst structure affect the activity and selectivity; the rhodium clusters are more active for hydrogenation of ethylene than the single-site complexes, which are more selective for dimerization of ethylene to give butenes« less

Semiconductor hierarchically structured flower-like clusters for dye-sensitized solar cells with nearly 100% charge collection efficiency.

PubMed

Xin, Xukai; Liu, Hsiang-Yu; Ye, Meidan; Lin, Zhiqun

2013-11-21

By combining the ease of producing ZnO nanoflowers with the advantageous chemical stability of TiO2, hierarchically structured hollow TiO2 flower-like clusters were yielded via chemical bath deposition (CBD) of ZnO nanoflowers, followed by their conversion into TiO2 flower-like clusters in the presence of TiO2 precursors. The effects of ZnO precursor concentration, precursor amount, and reaction time on the formation of ZnO nanoflowers were systematically explored. Dye-sensitized solar cells fabricated by utilizing these hierarchically structured ZnO and TiO2 flower clusters exhibited a power conversion efficiency of 1.16% and 2.73%, respectively, under 100 mW cm(-2) illumination. The intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) studies suggested that flower-like structures had a fast electron transit time and their charge collection efficiency was nearly 100%.

Effect of Thickness on the Morphology and Corrosion Behavior of Cerium-Based Conversion Coatings on AZ31B Magnesium Alloy

NASA Astrophysics Data System (ADS)

Castano, Carlos E.; Maddela, Surender; O'Keefe, Matthew J.; Wang, Yar-Ming

Cerium-based conversion coatings (CeCCs) were deposited onto AZ31B magnesium alloy substrates using a spontaneous reaction of CeCl3, H2O2 and gelatin in a water-based solution. The coating thickness was adjusted by controlling the immersion time in the deposition solution. Prior to deposition, the AZ31B substrates were treated using an acid pickling in nitric acid and then an alkaline cleaning in sodium metasilicate pentahydrate. After deposition, the coated samples were immersed in a phosphate bath that converted cerium oxide/hydroxide into cerium phosphate. Electrochemical impedance spectroscopy, potentiodynamic polarization and neutral salt spray testing studies indicated that 100 nm thick CeCC had better corrosion performance than 400 nm coatings. Characterization of the CeCCs by transmission electron microscopy (TEM) revealed a three layer structure with different compositions.

Exploring between the extremes: conversion-dependent kinetics of phosphite-modified hydroformylation catalysis.

PubMed

Kubis, Christoph; Selent, Detlef; Sawall, Mathias; Ludwig, Ralf; Neymeyr, Klaus; Baumann, Wolfgang; Franke, Robert; Börner, Armin

2012-07-09

The kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a rhodium monophosphite catalyst has been studied in detail. Time-dependent concentration profiles covering the entire olefin conversion range were derived from in situ high-pressure FTIR spectroscopic data for both, pure organic components and catalytic intermediates. These profiles fit to Michaelis-Menten-type kinetics with competitive and uncompetitive side reactions involved. The characteristics found for the influence of the hydrogen concentration verify that the pre-equilibrium towards the catalyst substrate complex is not established. It has been proven experimentally that the hydrogenolysis of the intermediate acyl complex remains rate limiting even at high conversions when the rhodium hydride is the predominant resting state and the reaction is nearly of first order with respect to the olefin. Results from in situ FTIR and high-pressure (HP) NMR spectroscopy and from DFT calculations support the coordination of only one phosphite ligand in the dominating intermediates and a preferred axial position of the phosphite in the electronically saturated, trigonal bipyramidal (tbp)-structured acyl rhodium complex. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Device physics of Cu(In,Ga)Se2 solar cells for long-term operation

NASA Astrophysics Data System (ADS)

Nishinaga, J.; Shibata, H.

2017-02-01

The degradation mechanism of Cu(In,Ga)Se2 (CIGS) solar cells on exposure to air has been investigated. Exposure to air at room temperature slightly reduces the conversion efficiency of CIGS solar cells, and the conversion efficiency decreases significantly under damp heat testing at 85 °C and 85% relative humidity due to low shunt resistance. On the other hand, shunt resistance increases after dry nitrogen heating. Therefore, oxygen and humidity should degenerate the solar cell performance. The low shunt resistance and conversion efficiency are completely recovered after removing the side edges of the CIGS solar cells by mechanical scribing. These results suggest that low-resistive layers are formed on the sidewalls of the solar cells during damp heat testing. The low-resistive layers on the sidewalls are identified to be molybdenum oxides and sodium molybdate by Auger electron spectroscopy. After etching the oxides on the sidewalls by alkaline solution, the saturation current density and ideality factor are confirmed to be improved. These results suggest that metal oxides on the sidewalls of CIGS solar cells may act as recombination centers.

Direct conversion of h-BN into c-BN and formation of epitaxial c-BN/diamond heterostructures

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

Narayan, Jagdish, E-mail: narayan@ncsu.edu; Bhaumik, Anagh; Xu, Weizong

2016-05-14

We have created a new state of BN (named Q-BN) through rapid melting and super undercooling and quenching by using nanosecond laser pulses. Phase pure c-BN is formed either by direct quenching of super undercooled liquid or by nucleation and growth from Q-BN. Thus, a direct conversion of hexagonal boron nitride (h-BN) into phase-pure cubic boron nitride (c-BN) is achieved by nanosecond pulsed laser melting at ambient temperatures and atmospheric pressure in air. According to the P-T phase diagram, the transformation from h-BN into c-BN under equilibrium processing can occur only at high temperatures and pressures, as the hBN-cBN-Liquid triplemore » point is at 3500 K/9.5 GPa or 3700 K/7.0 GPa with a recent theoretical refinement. Using nonequilibrium nanosecond laser melting, we have created super undercooled state and shifted this triple point to as low as 2800 K and atmospheric pressure. The rapid quenching from super undercooled state leads to the formation of a new phase, named as Q-BN. We present detailed characterization of Q-BN and c-BN layers by using Raman spectroscopy, high-resolution scanning electron microscopy, electron-back-scatter diffraction, high-resolution TEM, and electron energy loss spectroscopy, and discuss the mechanism of formation of nanodots, nanoneedles, microneedles, and single-crystal c-BN on sapphire substrate. We have also deposited diamond by pulsed laser deposition of carbon on c-BN and created c-BN/diamond heterostructures, where c-BN acts as a template for epitaxial diamond growth. We discuss the mechanism of epitaxial c-BN and diamond growth on lattice matching c-BN template under pulsed laser evaporation of amorphous carbon, and the impact of this discovery on a variety of applications.« less

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

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less

Enhanced performance of dye-sensitized solar cell using Bi2Te3 nanotube/ZnO nanoparticle composite photoanode by the synergistic effect of photovoltaic and thermoelectric conversion

NASA Astrophysics Data System (ADS)

Dou, Yuanyao; Wu, Fang; Fang, Liang; Liu, Gaobin; Mao, Caiying; Wan, Kai; Zhou, Miao

2016-03-01

Ultralong and highly crystalline rhombohedral Bi2Te3 nanotubes were fabricated by a two-step solution phase reaction. A novel photoanode architecture has been fabricated by embedding 0-2.5 wt.% Bi2Te3 nanotubes into ZnO nanoparticles. The photocurrent density-voltage (J-V) characteristics reveal that the dye sensitized solar cells (DSSCs) with Bi2Te3/ZnO composite photoanode exhibit significantly enhanced photovoltaic performance. Notably, the DSSC incorporating 1.5 wt.% Bi2Te3 in the ZnO photoanode demonstrates an energy conversion efficiency (η) of 4.27%, which is 44.3% higher than that of the bare ZnO photoanode. The electrochemical impedance spectroscopy (EIS) analysis shows that the Bi2Te3 nanotubes can provide a direct pathway for electron transportation, prolong the lifetime of electrons, suppress the charge recombination and improve the electron collection efficiency. The thermoelectric effect analysis indicates that with the increase of irradiation time, Bi2Te3/ZnO composite photoanode could convert both heat and photon energies to electrical energy simultaneously and slow down the decline of η. The calculated electron density (ns) further proves that the increment of short-circuit current density (Jsc) is attributed to Seebeck effect in the composite photoanode. These results suggest that compositing 1D thermoelectric nano-materials in photoanode is a promising route to improve the performance of DSSCs.

Enhanced Photocatalytic Activity toward Organic Pollutants Degradation and Mechanism Insight of Novel CQDs/Bi₂O₂CO₃ Composite.

PubMed

Zhang, Zisheng; Lin, Shuanglong; Li, Xingang; Li, Hong; Zhang, Tong; Cui, Wenquan

2018-05-15

Novel carbon quantum dots (CQDs) modified with Bi₂O₂CO₃ (CQDs/Bi₂O₂CO₃) were prepared using a simple dynamic-adsorption precipitation method. X-ray diffractometry (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM) were used to test the material composition, structure, and band structures of the as-prepared samples. Methylene blue (MB) and colorless phenol, as target organic pollutants, were used to evaluate the photocatalytic performance of the CQDs/Bi₂O₂CO₃ hybrid materials under visible light irradiation. Experimental investigation shows that 2⁻5 nm CQDs were uniformly decorated on the surface of Bi₂O₂CO₃; CQDs/Bi₂O₂CO₃ possess an efficient photocatalytic performance, and the organic matter removal rate of methylene blue and phenol can reach up to 94.45% and 61.46% respectively, within 2 h. In addition, the degradation analysis of phenol by high performance liquid chromatography (HPLC) proved that there are no other impurities in the degradation process. Photoelectrochemical testing proved that the introduction of CQDs (electron acceptor) effectively suppresses the recombination of e - -h⁺, and promotes charge transfer. Quenching experiments and electron spin resonance (ESR) suggested that ·OH, h⁺, and ·O₂ - were involved in the photocatalytic degradation process. These results suggested that the up-conversion function of CQDs could improve the electron transfer and light absorption ability of photocatalysts and ·O₂ - formation. Furthermore, the up-conversion function of CQDs would help maintain photocatalytic stability. Finally, the photocatalytic degradation mechanism was proposed according to the above experimental result.

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

PubMed

Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

2015-11-01

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

Enhanced photovoltaic properties in dye sensitized solar cells by surface treatment of SnO2 photoanodes

PubMed Central

Basu, Kaustubh; Benetti, Daniele; Zhao, Haiguang; Jin, Lei; Vetrone, Fiorenzo; Vomiero, Alberto; Rosei, Federico

2016-01-01

We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (SnO2) particles of average size ~20 nm. Fluorine-doped tin oxide (FTO) conducting glass substrates were treated with TiOx or TiCl4 precursor solutions to create a blocking layer before tape casting the SnO2 mesoporous anode. In addition, SnO2 photoelectrodes were treated with the same precursor solutions to deposit a TiO2 passivating layer covering the SnO2 particles. We found that the modification enhances the short circuit current, open-circuit voltage and fill factor, leading to nearly 2-fold increase in power conversion efficiency, from 1.48% without any treatment, to 2.85% achieved with TiCl4 treatment. The superior photovoltaic performance of the DSSCs assembled with modified photoanode is attributed to enhanced electron lifetime and suppression of electron recombination to the electrolyte, as confirmed by electrochemical impedance spectroscopy (EIS) carried out under dark condition. These results indicate that modification of the FTO and SnO2 anode by titania can play a major role in maximizing the photo conversion efficiency. PMID:26988622

Identification and Quantification of Carbon Phases in Conversion Fuel for the Transient Reactor Test Facility

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

Steele, Robert; Mata, Angelica; Dunzik-Gougar, Mary Lou

2016-06-01

As part of an overall effort to convert US research reactors to low-enriched uranium (LEU) fuel use, a LEU conversion fuel is being designed for the Transient Reactor Test Facility (TREAT) at the Idaho National Laboratory. TREAT fuel compacts are comprised of UO2 fuel particles in a graphitic matrix material. In order to refine heat transfer modeling, as well as determine other physical and nuclear characteristics of the fuel, the amount and type of graphite and non-graphite phases within the fuel matrix must be known. In this study, we performed a series of complementary analyses, designed to allow detailed characterizationmore » of the graphite and phenolic resin based fuel matrix. Methods included Scanning Electron and Transmission Electron Microscopies, Raman spectroscopy, X-ray Diffraction, and Dual-Beam Focused Ion Beam Tomography. Our results indicate that no single characterization technique will yield all of the desired information; however, through the use of statistical and empirical data analysis, such as curve fitting, partial least squares regression, volume extrapolation and spectra peak ratios, a degree of certainty for the quantity of each phase can be obtained.« less

Characterization of hydrothermally synthesized SnS nanoparticles for solar cell application

NASA Astrophysics Data System (ADS)

Rajwar, Birendra Kumar; Sharma, Shailendra Kumar

2018-05-01

In the present study, SnS nanoparticles were synthesized by simple hydrothermal method using stannous chloride and thiourea as tin (Sn) and sulfur (S) precursor respectively. Synthesized nanoparticles were characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy and UV-Vis Spectroscopy techniques. XRD pattern reveals that as-prepared nanoparticles exhibit orthorhombic structure. Average particles size was calculated using Scherrer's formula and found to be 23 nm. FESEM image shows that the as-prepared nanoparticles are in plate like structure. Direct optical band gap (Eg) of as-synthesized nanoparticles was calculated through UV-Vis Spectroscopy measurement and found to be 1.34 eV, which is near to optimum need for photovoltaic solar energy conversion (1.5 eV). Thus this SnS, narrowband gap semiconductor material can be applied as an alternative absorber material for solar cell application.

Synthesis and high temperature stability of amorphous Si(B)CN-MWCNT composite nanowires

NASA Astrophysics Data System (ADS)

Bhandavat, Romil; Singh, Gurpreet

2012-02-01

We demonstrate synthesis of a hybrid nanowire structure consisting of an amorphous polymer-derived silicon boron-carbonitride (Si-B-C-N) shell with a multiwalled carbon nanotube core. This was achieved through a novel process involving preparation of a boron-modified liquid polymeric precursor through a reaction of trimethyl borate and polyureasilazane under atmospheric conditions; followed by conversion of polymer to glass-ceramic on carbon nanotube surfaces through controlled heating. Chemical structure of the polymer was studied by liquid-NMR while evolution of various ceramic phases was studied by Raman spectroscopy, solid-NMR, Fourier transform infrared and X-ray photoelectron spectroscopy. Electron microscopy and X-ray diffraction confirms presence of amorphous Si(B)CN coating on individual nanotubes for all specimen processed below 1400 degree C. Thermogravimetric analysis, followed by TEM revealed high temperature stability of the carbon nanotube core in flowing air up to 1300 degree C.

Gold nanoparticle decorated multi-walled carbon nanotubes as counter electrode for dye sensitized solar cells.

PubMed

Kaniyoor, Adarsh; Ramaprabhu, Sundara

2012-11-01

A novel counter electrode material for dye sensitized solar cells (DSSCs) composed of nanostructured Au particles decorated on functionalized multi-walled carbon nanotubes (f-MWNTs) is demonstrated for the first time. MWNTs synthesized by catalytic chemical vapor deposition technique are purified and functionalized by treating with concentrated acids. Au nanoparticles are decorated on f-MWNTs by a rapid and facile microwave assisted polyol reduction method. The materials are characterized by X-ray diffractometry, Fourier transform infra red spectroscopy and electron microscopy. The DSSC fabricated with Au/f-MWNTs based counter electrode shows enhanced power conversion efficiency (eta) of 4.9% under AM 1.5G simulated solar radiation. In comparison, the reference DSSCs fabricated with f-MWNTs and Pt counter electrodes show eta of 2.1% and 4.5%. This high performance of Au/f-MWNTs counter electrode is investigated using electrochemical impedance spectroscopy and cyclic voltammetry studies.

Understanding the interactions of CO 2 with doped and undoped SrTiO 3

DOE PAGES

Wu, Qiyuan; Cen, Jiajie; Goodman, Kenneth R.; ...

2016-06-17

SrTiO 3 and doped SrTiO 3 have a wide range of applications in different fields. For example, Rh-doped SrTiO 3 has been shown to have photocatalytic activity for both hydrogen production and CO 2 conversion. In this study, both undoped and Rh-doped SrTiO 3 were synthesized by hydrothermal and polymerizable complex methods. Different characterizations techniques including X-ray photoelectron spectroscopy (XPS), XRD, Raman, and UV/Vis spectroscopy were utilized to establish correlations between the preparation methods and the electronic/structural properties of Rh-doped SrTiO 3. The presence of dopants and oxygen vacancies substantially influenced the CO 2 interactions with the surface, as revealedmore » by the in situ infrared spectroscopic study. As a result, the presence of distinctly different adsorption sites was correlated to oxygen vacancies and oxidation states of Ti and Rh.« less

Near-unity quantum yields from chloride treated CdTe colloidal quantum dots

DOE PAGES

Page, Robert C.; Espinobarro-Velazquez, Daniel; Leontiadou, Marina A.; ...

2014-10-27

Colloidal quantum dots (CQDs) are promising materials for novel light sources and solar energy conversion. However, trap states associated with the CQD surface can produce non-radiative charge recombination that significantly reduces device performance. Here a facile post-synthetic treatment of CdTe CQDs is demonstrated that uses chloride ions to achieve near-complete suppression of surface trapping, resulting in an increase of photoluminescence (PL) quantum yield (QY) from ca. 5% to up to 97.2 ± 2.5%. The effect of the treatment is characterised by absorption and PL spectroscopy, PL decay, scanning transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. We find thismore » process also dramatically improves the air-stability of the CQDs: before treatment the PL is largely quenched after 1 hour of air-exposure, whilst the treated samples showed a PL QY of nearly 50% after more than 12 hours.« less

Formation and Corrosion Resistance of Mg-Al Hydrotalcite Film on Mg-Gd-Zn Alloy

NASA Astrophysics Data System (ADS)

Ba, Z. X.; Dong, Q. S.; Kong, S. X.; Zhang, X. B.; Xue, Y. J.; Chen, Y. J.

2017-06-01

An environment-friendly technique for depositing a Mg-Al hydrotalcite (HT) (Mg6Al2(OH)16-CO3ṡ4H2O) conversion film was developed to protect the Mg-Gd-Zn alloy from corrosion. The morphology and chemical compositions of the film were analyzed by scanning electronic microscope (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Raman spectroscopy (RS), respectively. The electrochemical test and hydrogen evolution test were employed to evaluate the biocorrosion behavior of Mg-Gd-Zn alloy coated with the Mg-Al HT film in the simulated body fluid (SBF). It was found that the formation of Mg-Al HT film was a transition from amorphous precursor to a crystalline HT structure. The HT film can effectively improve the corrosion resistance of magnesium alloy. It indicates that the process provides a promising approach to modify Mg-Gd-Zn alloy.

Terahertz Sum-Frequency Excitation of a Raman-Active Phonon.

PubMed

Maehrlein, Sebastian; Paarmann, Alexander; Wolf, Martin; Kampfrath, Tobias

2017-09-22

In stimulated Raman scattering, two incident optical waves induce a force oscillating at the difference of the two light frequencies. This process has enabled important applications such as the excitation and coherent control of phonons and magnons by femtosecond laser pulses. Here, we experimentally and theoretically demonstrate the so far neglected up-conversion counterpart of this process: THz sum-frequency excitation of a Raman-active phonon mode, which is tantamount to two-photon absorption by an optical transition between two adjacent vibrational levels. Coherent control of an optical lattice vibration of diamond is achieved by an intense terahertz pulse whose spectrum is centered at half the phonon frequency of 40 THz. Remarkably, the carrier-envelope phase of the THz pulse is directly transferred into the phase of the lattice vibration. New prospects in general infrared spectroscopy, action spectroscopy, and lattice trajectory control in the electronic ground state emerge.

Preparation and properties of low-cost graphene counter electrodes for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Wu, Qishuang; Shen, Yue; Wang, Qiandi; Gu, Feng; Cao, Meng; Wang, Linjun

2013-12-01

With the advantages of excellent electrical properties, high catalytic activity and low-cost preparation, Graphene is one of the most expected carbon materials to replace the expensive Pt as counter electrodes for dye-sensitized solar cells (DSSCs). In this paper, graphene counter electrodes were obtained by simple doctor-blade coating method on fluorine tin oxides (FTOs). The samples were investigated by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscope (SEM). Then the low-cost graphene electrodes were applied in typical sandwich-type DSSCs with TiO2 or ZnO as photoanodes, and their photoelectric conversion efficiency (η) were about 4.34% and 2.28%, respectively, which were a little lower than those of Pt electrodes but much higher than those of graphite electrodes. This law was consistent with the test results of electrochemical impedance spectroscopy (EIS). Low-cost graphene electrodes can be applied in DSSCs by process optimization.

Heterogeneous Electron-Transfer Dynamics through Dipole-Bridge Groups.

PubMed

Nieto-Pescador, Jesus; Abraham, Baxter; Li, Jingjing; Batarseh, Alberto; Bartynski, Robert A; Galoppini, Elena; Gundlach, Lars

2016-01-14

Heterogeneous electron transfer (HET) between photoexcited molecules and colloidal TiO 2 has been investigated for a set of Zn-porphyrin chromophores attached to the semiconductor via linkers that allow to change level alignment by 200 meV by reorientation of the dipole moment. These unique dye molecules have been studied by femtosecond transient absorption spectroscopy in solution and adsorbed on the TiO 2 colloidal film in vacuum. In solution energy transfer from the excited chromophore to the dipole group has been identified as a slow relaxation pathway competing with S 2 -S 1 internal conversion. On the film heterogeneous electron transfer occurred in 80 fs, much faster compared to all intramolecular pathways. Despite a difference of 200 meV in level alignment of the excited state with respect to the semiconductor conduction band, identical electron transfer times were measured for different linkers. The measurements are compared to a quantum-mechanical model that accounts for electronic-vibronic coupling and finite band width for the acceptor states. We conclude that HET occurs into a distribution of transition states that differs from regular surface states or bridge mediated states.

Advances in solid-state NMR of cellulose.

PubMed

Foston, Marcus

2014-06-01

Nuclear magnetic resonance (NMR) spectroscopy is a well-established analytical and enabling technology in biofuel research. Over the past few decades, lignocellulosic biomass and its conversion to supplement or displace non-renewable feedstocks has attracted increasing interest. The application of solid-state NMR spectroscopy has long been seen as an important tool in the study of cellulose and lignocellulose structure, biosynthesis, and deconstruction, especially considering the limited number of effective solvent systems and the significance of plant cell wall three-dimensional microstructure and component interaction to conversion yield and rate profiles. This article reviews common and recent applications of solid-state NMR spectroscopy methods that provide insight into the structural and dynamic processes of cellulose that control bulk properties and biofuel conversion. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improved photovoltaic performance and stability of quantum dot sensitized solar cells using Mn-ZnSe shell structure with enhanced light absorption and recombination control.

PubMed

Gopi, Chandu V V M; Venkata-Haritha, M; Kim, Soo-Kyoung; Kim, Hee-Je

2015-08-07

To make quantum-dot-sensitized solar cells (QDSSCs) competitive, photovoltaic parameters comparable to those of other emerging solar cell technologies are necessary. In the present study, ZnSe was used as an alternative to ZnS, one of the most widely used passivation materials in QDSSCs. ZnSe was deposited on a TiO2-CdS-CdSe photoanode to form a core-shell structure, which was more efficient in terms of reducing the electron recombination in QDSSCs. The development of an efficient passivation layer is a requirement for preventing recombination processes in order to attain high-performance and stable QDSSCs. A layer of inorganic Mn-ZnSe was applied to a QD-sensitized photoanode to enhance the adsorption and strongly inhibit interfacial recombination processes in QDSSCs, which greatly improved the power conversion efficiency. Impedance spectroscopy revealed that the combined Mn doping with ZnSe treatment reduces interfacial recombination and increases charge collection efficiency compared with Mn-ZnS, ZnS, and ZnSe. A solar cell based on the CdS-CdSe-Mn-ZnSe photoanode yielded excellent performance with a solar power conversion efficiency of 5.67%, Voc of 0.584 V, and Jsc of 17.59 mA cm(-2). Enhanced electron transport and reduced electron recombination are responsible for the improved Jsc and Voc of the QDSSCs. The effective electron lifetime of the device with Mn-ZnSe was higher than those with Mn-ZnS, ZnSe, and ZnS, leading to more efficient electron-hole separation and slower electron recombination.

CCD sensors in synchrotron X-ray detectors

NASA Astrophysics Data System (ADS)

Strauss, M. G.; Naday, I.; Sherman, I. S.; Kraimer, M. R.; Westbrook, E. M.; Zaluzec, N. J.

1988-04-01

The intense photon flux from advanced synchrotron light sources, such as the 7-GeV synchrotron being designed at Argonne, require integrating-type detectors. Charge-coupled devices (CCDs) are well suited as synchrotron X-ray detectors. When irradiated indirectly via a phosphor followed by reducing optics, diffraction patterns of 100 cm 2 can be imaged on a 2 cm 2 CCD. With a conversion efficiency of ˜ 1 CCD electron/X-ray photon, a peak saturation capacity of > 10 6 X-rays can be obtained. A programmable CCD controller operating at a clock frequency of 20 MHz has been developed. The readout rate is 5 × 10 6 pixels/s and the shift rate in the parallel registers is 10 6 lines/s. The test detector was evaluated in two experiments. In protein crystallography diffraction patterns have been obtained from a lysozyme crystal using a conventional rotating anode X-ray generator. Based on these results we expect to obtain at a synchrotron diffraction images at a rate of ˜ 1 frame/s or a complete 3-dimensional data set from a single crystal in ˜ 2 min. In electron energy-loss spectroscopy (EELS), the CCD was used in a parallel detection mode which is similar to the mode array detectors are used in dispersive EXAFS. With a beam current corresponding to 3 × 10 9 electron/s on the detector, a series of 64 spectra were recorded on the CCD in a continuous sequence without interruption due to readout. The frame-to-frame pixel signal fluctuations had σ = 0.4% from which DQE = 0.4 was obtained, where the detector conversion efficiency was 2.6 CCD electrons/X-ray photon. These multiple frame series also showed the time-resolved modulation of the electron microscope optics by stray magnetic fields.

Combined experimental and theoretical description of direct current magnetron sputtering of Al by Ar and Ar/N2 plasma

NASA Astrophysics Data System (ADS)

Trieschmann, Jan; Ries, Stefan; Bibinov, Nikita; Awakowicz, Peter; Mráz, Stanislav; Schneider, Jochen M.; Mussenbrock, Thomas

2018-05-01

Direct current magnetron sputtering of Al by Ar and Ar/N2 low pressure plasmas was characterized by experimental and theoretical means in a unified consideration. Experimentally, the plasmas were analyzed by optical emission spectroscopy, while the film deposition rate was determined by weight measurements and laser optical microscopy, and the film composition by energy dispersive x-ray spectroscopy. Theoretically, a global particle and power balance model was used to estimate the electron temperature T e and the electron density n e of the plasma at constant discharge power. In addition, the sputtering process and the transport of the sputtered atoms were described using Monte Carlo models—TRIDYN and dsmcFoam, respectively. Initially, the non-reactive situation is characterized based on deposition experiment results, which are in agreement with predictions from simulations. Subsequently, a similar study is presented for the reactive case. The influence of the N2 addition is found to be twofold, in terms of (i) the target and substrate surface conditions (e.g., sputtering, secondary electron emission, particle sticking) and (ii) the volumetric changes of the plasma density n e governing the ion flux to the surfaces (e.g., due to additional energy conversion channels). It is shown that a combined experimental/simulation approach reveals a physically coherent and, in particular, quantitative understanding of the properties (e.g., electron density and temperature, target surface nitrogen content, sputtered Al density, deposited mass) involved in the deposition process.

Impedance changes during setting of amorphous calcium phosphate composites.

PubMed

Par, Matej; Šantić, Ana; Gamulin, Ozren; Marovic, Danijela; Moguš-Milanković, Andrea; Tarle, Zrinka

2016-11-01

To investigate the electrical properties of experimental light-curable composite materials based on amorphous calcium phosphate (ACP) with the admixture of silanized barium glass and silica fillers. Short-term setting was investigated by impedance measurements at a frequency of 1kHz, while for the long-term setting the impedance spectra were measured consecutively over a frequency range of 0.05Hz to 1MHz for 24h. The analysis of electrical resistivity changes during curing allowed the extraction of relevant kinetic parameters. The impedance results were correlated to the degree of conversion assessed by Raman spectroscopy, water content determined by gravimetry, light transmittance measured by CCD spectrometer and microstructural features observed by scanning electron microscopy. ACP-based composites have shown higher immediate degree of conversion and less post-cure polymerization than the control composites, but lower polymerization rate. The polymerization rate assessed by impedance measurements correlated well with the light transmittance. The differences in the electrical conductivity values observed among the materials were correlated to the amount of water introduced into composites by the ACP filler. High correlation was found between the degree of conversion and electrical resistivity. Equivalent circuit modeling revealed two electrical contributions for the ACP-based composites and a single contribution for the control composites. The impedance spectroscopy has proven a valuable method for gaining insight into various features of ACP-based composites. Better understanding of the properties of ACP-based composites should further the development of these promising bioactive materials. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Observations of Ball-Lightning-Like Plasmoids Ejected from Silicon by Localized Microwaves.

PubMed

Meir, Yehuda; Jerby, Eli; Barkay, Zahava; Ashkenazi, Dana; Mitchell, James Brian; Narayanan, Theyencheri; Eliaz, Noam; LeGarrec, Jean-Luc; Sztucki, Michael; Meshcheryakov, Oleg

2013-09-11

This paper presents experimental characterization of plasmoids (fireballs) obtained by directing localized microwave power (<1 kW at 2.45 GHz) onto a silicon-based substrate in a microwave cavity. The plasmoid emerges up from the hotspot created in the solid substrate into the air within the microwave cavity. The experimental diagnostics employed for the fireball characterization in this study include measurements of microwave scattering, optical spectroscopy, small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Various characteristics of these plasmoids as dusty plasma are drawn by a theoretical analysis of the experimental observations. Aggregations of dust particles within the plasmoid are detected at nanometer and micrometer scales by both in - situ SAXS and ex-situ SEM measurements. The resemblance of these plasmoids to the natural ball-lightning (BL) phenomenon is discussed with regard to silicon nano-particle clustering and formation of slowly-oxidized silicon micro-spheres within the BL. Potential applications and practical derivatives of this study (e.g., direct conversion of solids to powders, material identification by breakdown spectroscopy (MIBS), thermite ignition, and combustion) are discussed.

Novel synthesis strategy for composite hydrogel of collagen/hydroxyapatite-microsphere originating from conversion of CaCO3 templates.

PubMed

Wei, Qingrong; Lu, Jian; Wang, Qiaoying; Fan, Hongsong; Zhang, Xingdong

2015-03-20

Inspired by coralline-derived hydroxyapatite, we designed a methodological route to synthesize carbonated-hydroxyapatite microspheres from the conversion of CaCO3 spherulite templates within a collagen matrix under mild conditions and thus constructed the composite hydrogel of collagen/hydroxyapatite-microspheres. Fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD) were employed to confirm the successful generation of the carbonated hydroxyapatite phase originating from CaCO3, and the ratios of calcium to phosphate were tracked over time. Variations in the weight portion of the components in the hybrid gels before and after the phase transformation of the CaCO3 templates were identified via thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) shows these composite hydrogels have a unique multiscale microstructure consisting of a collagen nanofibril network and hydroxyapatite microspheres. The relationship between the hydroxyapatite nanocrystals and the collagen fibrils was revealed by transmission electron microscopy (TEM) in detail, and the selected area electron diffraction (SAED) pattern further confirmed the results of the XRD analyses which show the typical low crystallinity of the generated hydroxyapatite. This smart synthesis strategy achieved the simultaneous construction of microscale hydroxyapatite particles and collagen fibrillar hydrogel, and appears to provide a novel route to explore an advanced functional hydrogel materials with promising potentials for applications in bone tissue engineering and reconstruction medicine.

Effect of Reaction Period on Stoichiometry, Phase Purity, and Morphology of Hydrothermally Synthesized Cu2NiSnS4 Nanopowder

NASA Astrophysics Data System (ADS)

Babu, G. Sahaya Dennish; Shajan, X. Sahaya; Alwin, S.; Ramasubbu, V.; Balerao, Gopal M.

2018-01-01

The effect of reaction period on the phase purity, morphology, and stoichiometry of Cu2NiSnS4 (CNTS) nanopowder prepared by hydrothermal method has been investigated. Polyvinylpyrrolidone (PVP) and thioglycolic acid were used as capping agent and sulfur source, respectively. The presence of cubic stannite crystal structure and its phase purity were confirmed by powder x-ray diffraction analysis and Raman spectroscopy. Furthermore, the morphological, crystallographic, and optical features of the prepared CNTS nanopowder were characterized by field-emission scanning electron microscopy, transmission electron microscopy, and ultraviolet-visible (UV-Vis) spectrophotometry. The elemental ratios of Cu/(Ni + Sn) and Ni/Sn showed that the stoichiometry of CNTS was maintained for the compounds synthesized at 230°C with reaction period of 24 h. The occurrence of Cu+, Ni2+, Sn4+, and S2- was evaluated by x-ray photoelectron spectroscopy. The prepared material was used as counter electrode in a dye-sensitized solar cell (DSSC) as an alternative to platinum (Pt), resulting in conversion efficiency of 0.92%. These results indicate that CNTS is a prospective material to replace conventional Pt-based counter electrodes in DSSCs.

“Roller-Wheel”-Type Pt-Containing Small Molecules and the Impact of “Rollers” on Material Crystallinity, Electronic Properties, and Solar Cell Performance

DOE PAGES

He, Wenhan; Livshits, Maksim Y.; Dickie, Diane A.; ...

2017-07-21

We report the synthesis, characterization, and detailed comparison of a series of novel Pt-bisacetylide containing conjugated small molecules possessing an unconventional “roller-wheel” shaped structure that is distinctly different from the “dumbbell” designs in traditional Pt-bisacetylide containing conjugated polymers and small molecules. The relationships between the chemical nature and length of the “rollers” and the electronic and physical properties of the materials are carefully studied by steady-state spectroscopy, cyclic voltammetry, differential scanning calorimetry, single-crystal X-ray diffraction, transient absorption spectroscopy, theoretical calculation, and device application. It was revealed that if the roller are long enough, these molecules can “slip-stack” in the solidmore » state, leading to high crystallinity and charge mobility. Organic solar cells were fabricated and showed power conversion efficiencies up to 5.9%, out-performing all existing Pt-containing materials. The device performance was also found to be sensitive to optimization conditions and blend morphologies, which are a result of the intricate interplay among materials crystallinity, phase separation, and the relative positions of the lowest singlet and triplet excited states.« less

“Roller-Wheel”-Type Pt-Containing Small Molecules and the Impact of “Rollers” on Material Crystallinity, Electronic Properties, and Solar Cell Performance

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

He, Wenhan; Livshits, Maksim Y.; Dickie, Diane A.

We report the synthesis, characterization, and detailed comparison of a series of novel Pt-bisacetylide containing conjugated small molecules possessing an unconventional “roller-wheel” shaped structure that is distinctly different from the “dumbbell” designs in traditional Pt-bisacetylide containing conjugated polymers and small molecules. The relationships between the chemical nature and length of the “rollers” and the electronic and physical properties of the materials are carefully studied by steady-state spectroscopy, cyclic voltammetry, differential scanning calorimetry, single-crystal X-ray diffraction, transient absorption spectroscopy, theoretical calculation, and device application. It was revealed that if the roller are long enough, these molecules can “slip-stack” in the solidmore » state, leading to high crystallinity and charge mobility. Organic solar cells were fabricated and showed power conversion efficiencies up to 5.9%, out-performing all existing Pt-containing materials. The device performance was also found to be sensitive to optimization conditions and blend morphologies, which are a result of the intricate interplay among materials crystallinity, phase separation, and the relative positions of the lowest singlet and triplet excited states.« less

Spinel Co3O4 nanomaterials for efficient and stable large area carbon-based printed perovskite solar cells.

PubMed

Bashir, Amna; Shukla, Sudhanshu; Lew, Jia Haur; Shukla, Shashwat; Bruno, Annalisa; Gupta, Disha; Baikie, Tom; Patidar, Rahul; Akhter, Zareen; Priyadarshi, Anish; Mathews, Nripan; Mhaisalkar, Subodh G

2018-02-01

Carbon based perovskite solar cells (PSCs) are fabricated through easily scalable screen printing techniques, using abundant and cheap carbon to replace the hole transport material (HTM) and the gold electrode further reduces costs, and carbon acts as a moisture repellent that helps in maintaining the stability of the underlying perovskite active layer. An inorganic interlayer of spinel cobaltite oxides (Co 3 O 4 ) can greatly enhance the carbon based PSC performance by suppressing charge recombination and extracting holes efficiently. The main focus of this research work is to investigate the effectiveness of Co 3 O 4 spinel oxide as the hole transporting interlayer for carbon based perovskite solar cells (PSCs). In these types of PSCs, the power conversion efficiency (PCE) is restricted by the charge carrier transport and recombination processes at the carbon-perovskite interface. The spinel Co 3 O 4 nanoparticles are synthesized using the chemical precipitation method, and characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Vis spectroscopy. A screen printed thin layer of p-type inorganic spinel Co 3 O 4 in carbon PSCs provides a better-energy level matching, superior efficiency, and stability. Compared to standard carbon PSCs (PCE of 11.25%) an improved PCE of 13.27% with long-term stability, up to 2500 hours under ambient conditions, is achieved. Finally, the fabrication of a monolithic perovskite module is demonstrated, having an active area of 70 cm 2 and showing a power conversion efficiency of >11% with virtually no hysteresis. This indicates that Co 3 O 4 is a promising interlayer for efficient and stable large area carbon PSCs.

Molecule-Doped Nickel Oxide: Verified Charge Transfer and Planar Inverted Mixed Cation Perovskite Solar Cell.

PubMed

Chen, Wei; Zhou, Yecheng; Wang, Linjing; Wu, Yinghui; Tu, Bao; Yu, Binbin; Liu, Fangzhou; Tam, Ho-Won; Wang, Gan; Djurišić, Aleksandra B; Huang, Li; He, Zhubing

2018-05-01

Both conductivity and mobility are essential to charge transfer by carrier transport layers (CTLs) in perovskite solar cells (PSCs). The defects derived from generally used ionic doping method lead to the degradation of carrier mobility and parasite recombinations. In this work, a novel molecular doping of NiO x hole transport layer (HTL) is realized successfully by 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (F6TCNNQ). Determined by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, the Fermi level (E F ) of NiO x HTLs is increased from -4.63 to -5.07 eV and valence band maximum (VBM)-E F declines from 0.58 to 0.29 eV after F6TCNNQ doping. The energy level offset between the VBMs of NiO x and perovskites declines from 0.18 to 0.04 eV. Combining with first-principle calculations, electrostatic force microscopy is applied for the first time to verify direct electron transfer from NiO x to F6TCNNQ. The average power conversion efficiency of CsFAMA mixed cation PSCs is boosted by ≈8% depending on F6TCNNQ-doped NiOx HTLs. Strikingly, the champion cell conversion efficiency of CsFAMA mixed cations and MAPbI 3 -based devices gets to 20.86% and 19.75%, respectively. Different from passivation effect, the results offer an extremely promising molecular doping method for inorganic CTLs in PSCs. This methodology definitely paves a novel way to modulate the doping in hybrid electronics more than perovskite and organic solar cells. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bragg stack-functionalized counter electrode for solid-state dye-sensitized solar cells.

PubMed

Park, Jung Tae; Prosser, Jacob H; Kim, Dong Jun; Kim, Jong Hak; Lee, Daeyeon

2013-05-01

A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO(2) (om-TiO(2)) and colloidal SiO(2) (col-SiO(2)) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO(2) layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol-gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO(2) layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pt 3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

DOE PAGES

Raciti, David; Kubal, Joseph; Ma, Cheng; ...

2015-12-25

Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt 3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well asmore » Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less

TEM analysis of irradiation-induced interaction layers in coated UMo/X/Al trilayer systems (X= Ti, Nb, Zr, and Mo)

NASA Astrophysics Data System (ADS)

Chiang, H.-Y.; Wiss, T.; Park, S.-H.; Dieste-Blanco, O.; Petry, W.

2018-02-01

Uranium-molybdenum (UMo) alloy powder embedded in an Al matrix is considered as a promising candidate for fuel conversion of research reactors. A modified system with a diffusion barrier X as coating, UMo/X/Al trilayer (X = Ti, Zr, Nb, and Mo), has been investigated to suppress interdiffusion between UMo and the Al matrix. The trilayer systems were tested by swift heavy ion irradiation, the thereby created interaction zone has been analyzed by scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDX). Detailed structural characterization are presented and compared to earlier μ-XRD analysis.

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

Pierce, Dean T.; Coughlin, D. R.; Williamson, Don L.

Here, the influence of partitioning temperature on microstructural evolution during quenching and partitioning was investigated in a 0.38C-1.54Mn-1.48Si wt.% steel using Mössbauer spectroscopy and transmission electron microscopy. η-carbide formation occurs in the martensite during the quenching, holding, and partitioning steps. More effective carbon partitioning from martensite to austenite was observed at 450 than 400°C, resulting in lower martensite carbon contents, less carbide formation, and greater retained austenite amounts for short partitioning times. Conversely, greater austenite decomposition occurs at 450°C for longer partitioning times. Lastly, cementite forms during austenite decomposition and in the martensite for longer partitioning times at 450°C.

Conversion of nuclear waste to molten glass: Formation of porous amorphous alumina in a high-Al melter feed

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

Xu, Kai; Hrma, Pavel; Washton, Nancy

The transition of Al phases in a simulated high-Al high-level nuclear waste melter feed heated at 5 K min-1 to 700°C was investigated with transmission electron microscopy, 27Al nuclear magnetic resonance spectroscopy, the Brunauer-Emmett-Teller method, and X-ray diffraction. At temperatures between 300 and 500°C, porous amorphous alumina formed from the dehydration of gibbsite, resulting in increased specific surface area of the feed (~8 m2 g-1). The high-surface-area amorphous alumina formed in this manner could potentially stop salt migration in the cold cap during nuclear waste vitrification.

Efficient semiconductor multicycle terahertz pulse source

NASA Astrophysics Data System (ADS)

Nugraha, P. S.; Krizsán, G.; Polónyi, Gy; Mechler, M. I.; Hebling, J.; Tóth, Gy; Fülöp, J. A.

2018-05-01

Multicycle THz pulse generation by optical rectification in GaP semiconductor nonlinear material is investigated by numerical simulations. It is shown that GaP can be an efficient and versatile source with up to about 8% conversion efficiency and a tuning range from 0.1 THz to about 7 THz. Contact-grating technology for pulse-front tilt can ensure an excellent focusability and scaling the THz pulse energy beyond 1 mJ. Shapeable infrared pump pulses with a constant intensity-modulation period can be delivered for example by a flexible and efficient dual-chirped optical parametric amplifier. Potential applications include linear and nonlinear THz spectroscopy and THz-driven acceleration of electrons.

The effect of zirconium-based surface treatment on the cathodic disbonding resistance of epoxy coated mild steel

NASA Astrophysics Data System (ADS)

Ghanbari, A.; Attar, M. M.

2014-10-01

The effect of zirconium-based surface treatment on the cathodic disbonding resistance and adhesion performance of an epoxy coated mild steel substrate was investigated. The obtained data from pull-off, cathodic disbonding test and electrochemical impedance spectroscopy (EIS) indicated that the zirconium conversion layer significantly improved the adhesion strength and cathodic disbonding resistance of the epoxy coating. This may be attributed to formation of some polar zirconium compounds on the surface and increment of surface roughness, that were evident in the results of field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM), respectively.

Unravelling the Electronic State of NO2 Product in Ultrafast Photodissociation of Nitromethane.

PubMed

Adachi, Shunsuke; Kohguchi, Hiroshi; Suzuki, Toshinori

2018-01-18

The primary photochemical reaction of nitromethane (NM) after ππ* excitation is known to be C-N bond cleavage (CH 3 NO 2 + hν → CH 3 + NO 2 ). On the other hand, NO 2 can be formed in both the ground and excited states, and identification of the electronic state of the NO 2 product has been a central subject in the experimental and theoretical studies. Here we present time-resolved photoelectron spectroscopy using vacuum-ultraviolet probe pulses to observe all transient electronic states of NM and the reaction products. The result indicates that ultrafast internal conversion occurs down to S 1 and S 0 within 24 fs, and the dissociation proceeds on the S 1 surface (τ diss ≲ 50 fs), leading to comparable product yields of NO 2 (A) and NO 2 (X). The overall dissociation quantum yield within our observation time window (<2 ps) is estimated to be 0.29.

Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing.

PubMed

Abraham, Baxter; Fan, Hao; Galoppini, Elena; Gundlach, Lars

2018-03-01

Molecular sensitization of semiconductor films is an important technology for energy and environmental applications including solar energy conversion, photocatalytic hydrogen production, and water purification. Dye-sensitized films are also scientifically complex and interesting systems with a long history of research. In most applications, photoinduced heterogeneous electron transfer (HET) at the molecule/semiconductor interface is of critical importance, and while great progress has been made in understanding HET, many open questions remain. Of particular interest is the role of combined electronic and vibrational effects and coherence of the dye during HET. The ultrafast nature of the process, the rapid intramolecular vibrational energy redistribution, and vibrational cooling present complications in the study of vibronic coupling in HET. We present the application of a time domain vibrational spectroscopy-pump-degenerate four-wave mixing (pump-DFWM)-to dye-sensitized solid-state semiconductor films. Pump-DFWM can measure Raman-active vibrational modes that are triggered by excitation of the sample with an actinic pump pulse. Modifications to the instrument for solid-state samples and its application to an anatase TiO 2 film sensitized by a Zn-porphyrin dye are discussed. We show an effective combination of experimental techniques to overcome typical challenges in measuring solid-state samples with laser spectroscopy and observe molecular vibrations following HET in a picosecond time window. The cation spectrum of the dye shows modes that can be assigned to the linker group and a mode that is localized on the Zn-phorphyrin chromophore and that is connected to photoexcitation.

Surface modified MXene Ti3C2 multilayers by aryl diazonium salts leading to large-scale delamination

NASA Astrophysics Data System (ADS)

Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

2016-10-01

Herein we report a simple and facile method to delaminate MXene Ti3C2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti3AlC2 and the exfoliation of Ti3AlC2 into Ti3C2 multilayers, followed by Na+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti3C2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti3C2 sheets disperse well in water and the solutions obey Lambert-Beer's law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti3C2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti3C2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2O 3–FeF 3 Conversion Compounds by Direct Fluorination

DOE PAGES

Zhou, Hui; Ruther, Rose E.; Adcock, Jamie; ...

2015-02-22

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe 2O 3) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe 2O 3-xF 2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELSmore » results showed porous interconnected nanodomains of FeF 3 and Fe 2O 3 coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF 3 + Fe 2O 3 composition, and correlate the results to their electrochemical performance. Finally and further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF 3) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.« less

Contorted Organic Semiconductors for Molecular Electronics

NASA Astrophysics Data System (ADS)

Zhong, Yu

This thesis focuses on the synthesis, properties and applications of two types of contorted organic molecules: contorted molecular ribbons and conjugated corrals. We utilized the power of reaction chemistry to writing information into conjugated molecules with contorted structures and studied "structure-property" relationships. The unique properties of the molecules were expressed in electronic and optoelectronic devices such as field-effect transistors, solar cells, photodetectors, etc. In Chapter 2, I describe the design and synthesis of a new graphene ribbon architecture that consists of perylenediimide (PDI) subunits fused together by ethylene bridges. We created a prototype series of oligomers consisting of the dimer, trimer, and tetramer. The steric congestion at the fusion point between the PDI units creates helical junctions, and longer oligomers form helical ribbons. Thin films of these oligomers form the active layer in n-type field effect transistors. UV-vis spectroscopy reveals the emergence of an intense long-wavelength transition in the tetramer. From DFT calculations, we find that the HOMO-2 to LUMO transition is isoenergetic with the HOMO to LUMO transition in the tetramer. We probe these transitions directly using femtosecond transient absorption spectroscopy. The HOMO-2 to LUMO transition electronically connects the PDI subunits with the ethylene bridges, and its energy depends on the length of the oligomer. In Chapter 3, I describe an efficiency of 6.1% for a solution processed non-fullerene solar cell using a helical PDI dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current?voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions. In Chapter 4, I discuss helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometers in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. In Chapter 5, I compare analogous cyclic and acyclic pi-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. We designed two conjugated cycles for this study. Each comprises four subunits; one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more than doubling of the power conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. In Chapter 6, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We directly compare the macrocyclic acceptor devices to an acyclic control device; we find that the superior performance of the macrocycle originates from its rigid, conjugated, and cyclic structure. The macrocycle's rigid structure reduces the number of charged defects originating from deformed sp 2 carbons and covalent defects from photo/thermo-activation. With this molecular design we are able to suppress dark current density while retaining high responsivity in an ultra-sensitive non-fullerene organic photodetector. Importantly, we achieve a detectivity of 1014 Jones at near zero bias voltage. This is without the need for extra carrier blocking layers commonly employed in fullerene-based devices. Our devices are comparable to the best fullerene-based photodetectors, and the sensitivity at low working voltages (< 0.1 V) is a record for non-fullerene OPDs.

All-polymer solar cells with bulk heterojunction nanolayers of chemically doped electron-donating and electron-accepting polymers.

PubMed

Nam, Sungho; Shin, Minjung; Park, Soohyeong; Lee, Sooyong; Kim, Hwajeong; Kim, Youngkyoo

2012-11-21

We report the improved performance of all-polymer solar cells with bulk heterojunction nanolayers of an electron-donating polymer (poly(3-hexylthiophene) (P3HT)) and an electron-accepting polymer (poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT)), which were both doped with 4-ethylbenzenesulfonic acid (EBSA). To choose the doping ratio of P3HT for all-polymer solar cells, various EBSA doping ratios (0, 1, 3, 5, 10, 20 wt%) were tested by employing optical absorption spectroscopy, photoluminescence spectroscopy, photoelectron yield spectroscopy, and space-charge-limited current (SCLC) mobility measurement. The doping reaction of P3HT with EBSA was followed by observing the colour change in solutions. The final doping ratio for P3HT was chosen as 1 wt% from the best hole mobility measured in the thickness direction, while that for F8BT was fixed as 10 wt% (F8BT-EBSA). The polymer:polymer solar cells with bulk heterojunction nanolayers of P3HT-EBSA (EBSA-doped P3HT) and F8BT-EBSA (EBSA-doped F8BT) showed greatly improved short circuit current density (J(SC)) and open circuit voltage (V(OC)), compared to the undoped solar cells. As a result, the power conversion efficiency (PCE) was enhanced by ca. 300% for the 6 : 4 (P3HT-EBSA : F8BT-EBSA) composition and ca. 400% for the 8 : 2 composition. The synchrotron-radiation grazing incidence angle X-ray diffraction (GIXD) measurement revealed that the crystallinity of the doped nanolayers significantly increased by EBSA doping owing to the formation of advanced phase segregation morphology, as supported by the surface morphology change measured by atomic force microscopy. Thus the improved PCE can be attributed to the enhanced charge transport by the formation of permanent charges and better charge percolation paths by EBSA doping.

Evolution of synchrotron-radiation-based Mössbauer absorption spectroscopy for various isotopes

NASA Astrophysics Data System (ADS)

Seto, Makoto; Masuda, Ryo; Kobayashi, Yasuhiro; Kitao, Shinji; Kurokuzu, Masayuki; Saito, Makina; Hosokawa, Shuuich; Ishibashi, Hiroki; Mitsui, Takaya; Yoda, Yoshitaka; Mibu, Ko

2017-11-01

Synchrotron-radiation-based Mössbauer spectroscopy that yields absorption type Mössbauer spectra has been applied to various isotopes. This method enables the advanced measurement by using the excellent features of synchrotron radiation, such as Mössbauer spectroscopic measurement under high-pressures. Furthermore, energy selectivity of synchrotron radiation allows us to measure 40K Mössbauer spectra, of which observation is impossible by using ordinary radioactive sources because the first excited state of 40K is not populated by any radioactive parent nuclides. Moreover, this method has flexibility of the experimental setup that the measured sample can be used as a transmitter or a scatterer, depending on the sample conditions. To enhance the measurement efficiency of the spectroscopy, we developed a detection system in which a windowless avalanche photodiode (APD) detector is combined with a vacuum cryostat to detect internal conversion electrons adding to X-rays accompanied by nuclear de-excitation. In particular, by selecting the emission from the scatterer sample, depth selective synchrotron-radiation-based Mössbauer spectroscopy is possible. Furthermore, limitation of the time window in the delayed components enables us to obtain narrow linewidth in Mössbauer spectra. Measurement system that records velocity dependent time spectra and energy information simultaneously realizes the depth selective and narrow linewidth measurement.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE PAGES

Lin, Ye; Fang, Shumin; Su, Dong; ...

2015-04-10

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Enhanced efficiency and air-stability of NiOX-based perovskite solar cells via PCBM electron transport layer modification with Triton X-100.

PubMed

Lee, Kisu; Ryu, Jaehoon; Yu, Haejun; Yun, Juyoung; Lee, Jungsup; Jang, Jyongsik

2017-11-02

We modified phenyl-C61-butyric acid methyl ester (PCBM) for use as a stable, efficient electron transport layer (ETL) in inverted perovskite solar cells (PSCs). PCBM containing a surfactant Triton X-100 acts as the ETL and NiO X nanocrystals act as a hole transport layer (HTL). Atomic force microscopy and scanning electron microscopy images showed that surfactant-modified PCBM (s-PCBM) forms a high-quality, uniform, and dense ETL on the rough perovskite layer. This layer effectively blocks holes and reduces interfacial recombination. Steady-state photoluminescence and electrochemical impedance spectroscopy analyses confirmed that Triton X-100 improved the electron extraction performance of PCBM. When the s-PCBM ETL was used, the average power conversion efficiency increased from 10.76% to 15.68%. This improvement was primarily caused by the increases in the open-circuit voltage and fill factor. s-PCBM-based PSCs also showed good air-stability, retaining 83.8% of their initial performance after 800 h under ambient conditions.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

PubMed Central

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-01-01

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2−δ–CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2−δ–Ce0.8Gd0.2O2−δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution. PMID:25857355

Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors.

PubMed

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-04-10

Mixed ionic-electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2-δ-CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2-δ-Ce0.8Gd0.2O2-δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic-electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

Evolution of the secondary electron emission during the graphitization of thin C films

NASA Astrophysics Data System (ADS)

Larciprete, Rosanna; Grosso, Davide Remo; Di Trolio, Antonio; Cimino, Roberto

2015-02-01

The relation between the atomic hybridization and the secondary electron emission yield (SEY) in carbon materials has been investigated during the thermal graphitization of thin amorphous carbon layers deposited by magnetron sputtering on Cu substrates. C1s core level, valence band and Raman spectroscopy were used to follow the sp3→sp2 structural reorganization while the SEY curves as a function of the kinetic energy of the incident electron beam were measured in parallel. We found that an amorphous C layer with a thickness of a few tens of nanometers is capable to modify the secondary emission properties of the clean copper surface, reducing the maximum yield from 1.4 to 1.2. A further SEY decrease observed with the progressive conversion of sp3 hybrids into six-fold aromatic domains was related to the electronic structure close to the Fermi level of the C-films. We found that a moderate structural quality of the C layer is sufficient to notably decrease the SEY as aromatic clusters of limited size approach the secondary emission properties of graphite.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

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

Lin, Ye; Fang, Shumin; Su, Dong

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

PubMed

Jakowetz, Andreas C; Böhm, Marcus L; Zhang, Jiangbin; Sadhanala, Aditya; Huettner, Sven; Bakulin, Artem A; Rao, Akshay; Friend, Richard H

2016-09-14

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

Local protein solvation drives direct down-conversion in phycobiliprotein PC645 via incoherent vibronic transport

PubMed Central

Blau, Samuel M.; Bennett, Doran I. G.; Kreisbeck, Christoph; Scholes, Gregory D.; Aspuru-Guzik, Alán

2018-01-01

The mechanisms controlling excitation energy transport (EET) in light-harvesting complexes remain controversial. Following the observation of long-lived beats in 2D electronic spectroscopy of PC645, vibronic coherence, the delocalization of excited states between pigments supported by a resonant vibration, has been proposed to enable direct excitation transport from the highest-energy to the lowest-energy pigments, bypassing a collection of intermediate states. Here, we instead show that for phycobiliprotein PC645 an incoherent vibronic transport mechanism is at play. We quantify the solvation dynamics of individual pigments using ab initio quantum mechanics/molecular mechanics (QM/MM) nuclear dynamics. Our atomistic spectral densities reproduce experimental observations ranging from absorption and fluorescence spectra to the timescales and selectivity of down-conversion observed in transient absorption measurements. We construct a general model for vibronic dimers and establish the parameter regimes of coherent and incoherent vibronic transport. We demonstrate that direct down-conversion in PC645 proceeds incoherently, enhanced by large reorganization energies and a broad collection of high-frequency vibrations. We suggest that a similar incoherent mechanism is appropriate across phycobiliproteins and represents a potential design principle for nanoscale control of EET. PMID:29588417

Stabilization of Wide Band-Gap p-Type Wurtzite MnTe Thin Films on Amorphous Substrates

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

Zakutayev, Andriy A; Siol, Sebastian; Han, Yanbing

An important challenge in the development of optoelectronic devices for energy conversion applications is the search for suitable p-type contact materials. For example, p-type MnTe would be a promising alternative back contact to due to their chemical compatibility, but at normal conditions it has too narrow band gap due to octahedrally coordinated nickeline (NC) structure. The tetrahedrally coordinated wurtzite (WZ) polymorph of MnTe has not been reported, but it is especially interesting due to its predicted wider band gap, and because of better structural compatibility with CdTe and related II-VI semiconductor materials. Here, we report on the stabilization of WZ-MnTemore » thin films on amorphous indium zinc oxide (a-IZO) substrates relevant to photovoltaic applications. Optical spectroscopy of the WZ-MnTe films shows a wide direct band gap of Eg = 2.7 eV, while PES measurements reveal weak p-type doping with the Fermi level 0.6 eV above the valence band maximum. The results of electron microscopy and photoelectron spectroscopy (PES) measurements indicate that the WZ-MnTe is stabilized due to interdiffusion at the interface with IZO. The results of this work introduce a substrate stabilized WZ-MnTe polymorph as a potential p-type contact material candidate for future applications in CdTe devices for solar energy conversion and other optoelectronic technologies.« less

Shaking Alone Induces De Novo Conversion of Recombinant Prion Proteins to β-Sheet Rich Oligomers and Fibrils

PubMed Central

Ladner-Keay, Carol L.; Griffith, Bethany J.; Wishart, David S.

2014-01-01

The formation of β-sheet rich prion oligomers and fibrils from native prion protein (PrP) is thought to be a key step in the development of prion diseases. Many methods are available to convert recombinant prion protein into β-sheet rich fibrils using various chemical denaturants (urea, SDS, GdnHCl), high temperature, phospholipids, or mildly acidic conditions (pH 4). Many of these methods also require shaking or another form of agitation to complete the conversion process. We have identified that shaking alone causes the conversion of recombinant PrP to β-sheet rich oligomers and fibrils at near physiological pH (pH 5.5 to pH 6.2) and temperature. This conversion does not require any denaturant, detergent, or any other chemical cofactor. Interestingly, this conversion does not occur when the water-air interface is eliminated in the shaken sample. We have analyzed shaking-induced conversion using circular dichroism, resolution enhanced native acidic gel electrophoresis (RENAGE), electron microscopy, Fourier transform infrared spectroscopy, thioflavin T fluorescence and proteinase K resistance. Our results show that shaking causes the formation of β-sheet rich oligomers with a population distribution ranging from octamers to dodecamers and that further shaking causes a transition to β-sheet fibrils. In addition, we show that shaking-induced conversion occurs for a wide range of full-length and truncated constructs of mouse, hamster and cervid prion proteins. We propose that this method of conversion provides a robust, reproducible and easily accessible model for scrapie-like amyloid formation, allowing the generation of milligram quantities of physiologically stable β-sheet rich oligomers and fibrils. These results may also have interesting implications regarding our understanding of prion conversion and propagation both within the brain and via techniques such as protein misfolding cyclic amplification (PMCA) and quaking induced conversion (QuIC). PMID:24892647

Light, Molecules, Action: Broadband UV-visible transient absorption studies of excited state dynamics in photoactive molecules

NASA Astrophysics Data System (ADS)

Sension, Roseanne

2015-03-01

Broadband UV-visible transient absorption spectroscopy provides a powerful tool for the investigation of the dynamics of electronically excited molecules in the condensed phase. It is now possible to obtain transient spectra on a routine basis spanning the range from <300 nm to >800 nm with femtosecond time resolution. We have used this method to study the excited state dynamics and internal conversion of a range of molecular systems with potential application as optically powered molecular devices. The cyclohexadiene ring-opening reaction is the basis of a class of important optical switches and of the biological synthesis of previtamin D3. The ring-opening reaction is ultrafast, occurring on a picosecond to subpicosecond times scale depending on the substituents around the ring. These have a significant influence on the dynamics and electronic structure of the electronically excited molecule. The results of a series of transient absorption studies as a function of chromophore substitution and environment will be presented. The cis-trans isomerization of polyene molecules, especially substituted stilbenes, provides another important class of functional molecular transformations. Again the excited state dynamics can be ultrafast with photochemistry controlled by details of the curve crossings and conical intersections. Finally the photochemistry of the even more complex set of cobalamin chromophores with a photoalabile C-Co bond has been proposed as a tool for spatio-temporal control of molecule delivery including drug delivery. Broadband transient absorption spectroscopy has been used to investigate the ultrafast electronic dynamics of a range of cobalamin compounds with comparison to detailed theoretical calculations. The results of these studies will be presented.

Effect of pyrophosphate ions on the conversion of calcium-lithium-borate glass to hydroxyapatite in aqueous phosphate solution.

PubMed

Fu, Hailuo; Rahaman, Mohamed N; Day, Delbert E; Huang, Wenhai

2010-10-01

The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium-lithium-borate glass to HA was investigated. Particles of the glass (150-355 μm) were immersed for up to 28 days in 0.25 M K(2)HPO(4) solution containing 0-0.1 M K(4)P(2)O(7). The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K(4)P(2)O(7) concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K(4)P(2)O(7)) to 10 days (0.01 M K(4)P(2)O(7)). When the K(4)P(2)O(7) concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K(2)CaP(2)O(7) and Ca(2)P(2)O(7)). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed.

Effect of pyrophosphate ions on the conversion of calcium–lithium–borate glass to hydroxyapatite in aqueous phosphate solution

PubMed Central

Fu, Hailuo; Day, Delbert E.; Huang, Wenhai

2010-01-01

The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium–lithium–borate glass to HA was investigated. Particles of the glass (150–355 µm) were immersed for up to 28 days in 0.25 M K2HPO4 solution containing 0–0.1 M K4P2O7. The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K4P2O7 concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K4P2O7) to 10 days (0.01 M K4P2O7). When the K4P2O7 concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K2CaP2O7 and Ca2P2O7). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed. PMID:20680413

Structural, Morphological, and Electron Transport Studies of Annealing Dependent In2O3 Dye-Sensitized Solar Cell

PubMed Central

Mahalingam, S.; Abdullah, H.; Shaari, S.; Muchtar, A.; Asshari, I.

2015-01-01

Indium oxide (In2O3) thin films annealed at various annealing temperatures were prepared by using spin-coating method for dye-sensitized solar cells (DSSCs). The objective of this research is to enhance the photovoltaic conversion efficiency in In2O3 thin films by finding the optimum annealing temperature and also to study the reason for high and low performance in the annealed In2O3 thin films. The structural and morphological characteristics of In2O3 thin films were studied via XRD patterns, atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), EDX sampling, and transmission electron microscopy (TEM). The annealing treatment modified the nanostructures of the In2O3 thin films viewed through FESEM images. The In2O3-450°C-based DSSC exhibited better photovoltaic performance than the other annealed thin films of 1.54%. The electron properties were studied by electrochemical impedance spectroscopy (EIS) unit. The In2O3-450°C thin films provide larger diffusion rate, low recombination effect, and longer electron lifetime, thus enhancing the performance of DSSC. PMID:26146652

Photon-enhanced thermionic emission from p-GaAs with nonequilibrium Cs overlayers

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

Zhuravlev, A. G.; Romanov, A. S.; Alperovich, V. L., E-mail: alper@isp.nsc.ru

2014-12-22

Photon-enhanced thermionic emission (PETE), which is promising for increasing the efficiency of solar energy conversion, is studied during cesium deposition on the As- and Ga-rich p-GaAs(001) surfaces and subsequent relaxation in the nonequilibrium Cs overlayer by means of photoemission quantum yield spectroscopy adapted for systems with time-variable parameters. Along with direct photoemission of “hot” electrons excited by light above the vacuum level, the spectra contain PETE contribution of “thermalized” electrons, which are excited below the vacuum level and emit in vacuum due to thermalization up in energy by phonon absorption. Comparing the measured and calculated spectra, the effective electron affinitymore » and escape probabilities of hot and thermalized electrons are obtained as functions of submonolayer Cs coverage. The minima in the affinity and pronounced peaks in the escape probabilities are observed for Cs deposition on both the As- and Ga-rich surfaces. Possible reasons for the low mean values of the electron escape probabilities and for the observed enhancement of the probabilities at certain Cs coverages are discussed, along with the implications for the PETE device realization.« less

Chemical aspects of lifetime extension at Paks Nuclear Power Plant

NASA Astrophysics Data System (ADS)

Schunk, J.; Patek, G.; Pintér, T.; Tilky, P.; Ősz, J.; Salamon, T.; Varga, K.

2009-02-01

The review of the water regime used for the Units of Paks Nuclear Power Plant (NPP) was carried out in 2005, after 18-23 years of operation. In order to determine the phase composition of the surface oxide layers primary equipment, samples were measured by Conversion Electron Mössbauer Spectroscopy (CEMS). Due to the absorption of the conversion electrons, information can be obtained from the outermost ˜300 nm thick layer of the surface. It was clearly concluded after processing the huge data base of the water regime and CEMS data, that there is nothing to hamper the life time extension of the Units. In 2006, a new water regime was developed that will be applied during the preparation for the life time extension and the extended service life as well. In connection with this work, recommendations were made for some modifications of the previously used water regime. Currently there is no uniform start-up and shutdown water regime for WWER-440 Units. Therefore, special attention was paid to developing of a start-up water regime, which will be applied for the outages as early as 2008. The summarised recommendations for water regime modification will be subject to international expert review in 2008, and the modifications judged to be implemented will be finalised after the review.

Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

PubMed

Yao, Hiroshi; Iwatsu, Mana

2016-04-05

Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes

PubMed Central

Shon, Jeong Kuk; Lee, Hyo Sug; Park, Gwi Ok; Yoon, Jeongbae; Park, Eunjun; Park, Gyeong Su; Kong, Soo Sung; Jin, Mingshi; Choi, Jae-Man; Chang, Hyuk; Doo, Seokgwang; Kim, Ji Man; Yoon, Won-Sub; Pak, Chanho; Kim, Hansu; Stucky, Galen D.

2016-01-01

Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g−1 for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems. PMID:27001935

Tracking the coherent generation of polaron pairs in conjugated polymers

NASA Astrophysics Data System (ADS)

de Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita; Réhault, Julien; Sommer, Ephraim; Lim, James; Huelga, Susana F.; Plenio, Martin B.; Rozzi, Carlo Andrea; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

2016-12-01

The optical excitation of organic semiconductors not only generates charge-neutral electron-hole pairs (excitons), but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period peak oscillations persisting for up to about 1 ps as distinct signatures of vibronic quantum coherence at room temperature. The measured two-dimensional spectra show pronounced peak splittings revealing that the elementary optical excitations of this polymer are hybridized exciton-polaron-pairs, strongly coupled to a dominant underdamped vibrational mode. Coherent vibronic coupling induces ultrafast polaron pair formation, accelerates the charge separation dynamics and makes it insensitive to disorder. These findings open up new perspectives for tailoring light-to-current conversion in organic materials.

Efficient transformation of corn stover to furfural using p-hydroxybenzenesulfonic acid-formaldehyde resin solid acid.

PubMed

Zhang, Tingwei; Li, Wenzhi; An, Shengxin; Huang, Feng; Li, Xinzhe; Liu, Jingrong; Pei, Gang; Liu, Qiying

2018-05-24

In this work, p-hydroxybenzenesulfonic acid-formaldehyde resin acid catalyst (MSPFR), was synthesized by a hydrothermal method, and employed for the furfural production from raw corn stover. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), N 2 adsorption-desorption, elemental analysis (EA), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the MSPFR. The effects of reaction time, temperature, solvents and corn stover loading were investigated. The MSPFR presented high catalytic activity for the formation of furfural from corn stover. When the MSPFR/corn stover mass loading ratio was 0.5, a higher furfural yield of 43.4% could be achieved at 190 °C in 100 min with 30.7% 5-hydroxymethylfurfural (HMF) yield. Additionally, quite importantly, the recyclability of the MSPFR for xylose dehydration is good, and for the conversion of corn stover was reasonable. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

PubMed

Huang, Jier; Huang, Zhuangqun; Yang, Ye; Zhu, Haiming; Lian, Tianquan

2010-04-07

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

Pretreatment of Cellulose By Electron Beam Irradiation Method

NASA Astrophysics Data System (ADS)

Jusri, N. A. A.; Azizan, A.; Ibrahim, N.; Salleh, R. Mohd; Rahman, M. F. Abd

2018-05-01

Pretreatment process of lignocellulosic biomass (LCB) to produce biofuel has been conducted by using various methods including physical, chemical, physicochemical as well as biological. The conversion of bioethanol process typically involves several steps which consist of pretreatment, hydrolysis, fermentation and separation. In this project, microcrystalline cellulose (MCC) was used in replacement of LCB since cellulose has the highest content of LCB for the purpose of investigating the effectiveness of new pretreatment method using radiation technology. Irradiation with different doses (100 kGy to 1000 kGy) was conducted by using electron beam accelerator equipment at Agensi Nuklear Malaysia. Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction (XRD) analyses were studied to further understand the effect of the suggested pretreatment step to the content of MCC. Through this method namely IRR-LCB, an ideal and optimal condition for pretreatment prior to the production of biofuel by using LCB may be introduced.

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

PubMed Central

Schröder, Tim; Trusheim, Matthew E.; Walsh, Michael; Li, Luozhou; Zheng, Jiabao; Schukraft, Marco; Sipahigil, Alp; Evans, Ruffin E.; Sukachev, Denis D.; Nguyen, Christian T.; Pacheco, Jose L.; Camacho, Ryan M.; Bielejec, Edward S.; Lukin, Mikhail D.; Englund, Dirk

2017-01-01

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ∼32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ∼2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ∼51 GHz and close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ∼1.4 times the natural linewidth. This method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors. PMID:28548097

Tracking the photodissociation dynamics of liquid nitromethane at 266 nm by femtosecond time-resolved broadband transient grating spectroscopy

NASA Astrophysics Data System (ADS)

Wu, Honglin; Song, Yunfei; Yu, Guoyang; Wang, Yang; Wang, Chang; Yang, Yanqiang

2016-05-01

Femtosecond time-resolved transient grating (TG) technique was employed to get insight into the photodissociation mechanism of liquid nitromethane (NM). Broadband white-light continuum was introduced as the probe to observe the evolution of electronic excited states of NM molecules and the formation of photodissociation products simultaneously. The reaction channel of liquid NM under 266 nm excitation was obtained that NM molecules in excited state S2 relax through two channels: about 73% relax to low lying S1 state through S2/S1 internal conversion with a time constant of 0.24 ps and then go back to the ground state through S1/S0 internal conversion; the other 27% will dissociate with a time constant of 2.56 ps. NO2 was found to be one of the products from the experimental TG spectra, which confirmed that C-N bond rupture was the primary dissociation channel of liquid NM.

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

DOE PAGES

Schroder, Tim; Trusheim, Matthew E.; Walsh, Michael; ...

2017-05-26

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ~32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ~2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ~51 GHz andmore » close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ~1.4 times the natural linewidth. Furthermore, this method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors.« less

Scalable focused ion beam creation of nearly lifetime-limited single quantum emitters in diamond nanostructures

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

Schroder, Tim; Trusheim, Matthew E.; Walsh, Michael

The controlled creation of defect centre—nanocavity systems is one of the outstanding challenges for efficiently interfacing spin quantum memories with photons for photon-based entanglement operations in a quantum network. Here we demonstrate direct, maskless creation of atom-like single silicon vacancy (SiV) centres in diamond nanostructures via focused ion beam implantation with ~32 nm lateral precision and <50 nm positioning accuracy relative to a nanocavity. We determine the Si+ ion to SiV centre conversion yield to be ~2.5% and observe a 10-fold conversion yield increase by additional electron irradiation. Low-temperature spectroscopy reveals inhomogeneously broadened ensemble emission linewidths of ~51 GHz andmore » close to lifetime-limited single-emitter transition linewidths down to 126±13 MHz corresponding to ~1.4 times the natural linewidth. Furthermore, this method for the targeted generation of nearly transform-limited quantum emitters should facilitate the development of scalable solid-state quantum information processors.« less

Electrochemical Hydroxylation of C3-C12 n-Alkanes by Recombinant Alkane Hydroxylase (AlkB) and Rubredoxin-2 (AlkG) from Pseudomonas putida GPo1.

PubMed

Tsai, Yi-Fang; Luo, Wen-I; Chang, Jen-Lin; Chang, Chun-Wei; Chuang, Huai-Chun; Ramu, Ravirala; Wei, Guor-Tzo; Zen, Jyh-Myng; Yu, Steve S-F

2017-08-21

An unprecedented method for the efficient conversion of C 3 -C 12 linear alkanes to their corresponding primary alcohols mediated by the membrane-bound alkane hydroxylase (AlkB) from Pseudomonas putida GPo1 is demonstrated. The X-ray absorption spectroscopy (XAS) studies support that electrons can be transferred from the reduced AlkG (rubredoxin-2, the redox partner of AlkB) to AlkB in a two-phase manner. Based on this observation, an approach for the electrocatalytic conversion from alkanes to alcohols mediated by AlkB using an AlkG immobilized screen-printed carbon electrode (SPCE) is developed. The framework distortion of AlkB-AlkG adduct on SPCE surface might create promiscuity toward gaseous substrates. Hence, small alkanes including propane and n-butane can be accommodated in the hydrophobic pocket of AlkB for C-H bond activation. The proof of concept herein advances the development of artificial C-H bond activation catalysts.

Microbial conversion of choline to trimethylamine requires a glycyl radical enzyme

PubMed Central

Craciun, Smaranda; Balskus, Emily P.

2012-01-01

Choline and trimethylamine (TMA) are small molecules that play central roles in biological processes throughout all kingdoms of life. These ubiquitous metabolites are linked through a single biochemical transformation, the conversion of choline to TMA by anaerobic microorganisms. This metabolic activity, which contributes to methanogenesis and human disease, has been known for over a century but has eluded genetic and biochemical characterization. We have identified a gene cluster responsible for anaerobic choline degradation within the genome of a sulfate-reducing bacterium and verified its function using both a genetic knockout strategy and heterologous expression in Escherichia coli. Bioinformatics and electron paramagnetic resonance (EPR) spectroscopy revealed the involvement of a C–N bond cleaving glycyl radical enzyme in TMA production, which is unprecedented chemistry for this enzyme family. Our discovery provides the predictive capabilities needed to identify choline utilization clusters in numerous bacterial genomes, underscoring the importance and prevalence of this metabolic activity within the human microbiota and the environment. PMID:23151509

Synthesis and Characterization of Poly (styrene-co-butyl acrylate)/Silica Aerogel Nanocomposites by in situ AGET ATRP: Investigating Thermal Properties

NASA Astrophysics Data System (ADS)

Khezri, Khezrollah; Fazli, Yousef

2017-10-01

Hydrophilic silica aerogel nanoparticles surface was modified with hexamethyldisilazane. Then, the resultant modified nanoparticles were used in random copolymerization of styrene and butyl acrylate via activators generated by electron transfer for atom transfer radical polymerization. Conversion and molecular weight determinations were performed using gas and size exclusion chromatography respectively. Addition of modified nanoparticles by 3 wt% results in a decrease of conversion from 68 to 46 %. Molecular weight of copolymer chains decreases from 12,500 to 7,500 g.mol-1 by addition of 3 wt% modified nanoparticles; however, PDI values increase from 1.1 to 1.4. Proton nuclear magnetic resonance spectroscopy results indicate that the molar ratio of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of them. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

Structural studies with the use of XRD and Mössbauer spectroscopy of new high Manganese steels

NASA Astrophysics Data System (ADS)

Jablonska, Magdalena Barbara

2014-04-01

New high-strength austenitic and austenitic-ferritic manganese steels represent a significant potential in applications for structural components in the automotive and railway industry due to the excellent combination of high mechanical properties and good plasticity. They belong to the group of steels called AHSS (Advanced High Strength Steels) and UHSS (Ultra High Strength Steels). Application of this combination of properties allows a reduction in the weight of vehicles by the use of reduced cross-section components, and thus to reduce fuel consumption. The development and implementation of industrial production of such interesting and promising steel and its use as construction material requires an improvement of their casting properties and susceptibility to deformation in plastic working conditions. In this work, XRD, Transmission Mössbauer Spectroscopy and Conversion Electron Mössbauer Spectroscopy were employed in a study of the new high-manganese steels with a austenite and austenite-ferrite structure. The influence of the plastic deformation parameters on the changes in the structure, distribution of ferrite and disclosure of the presence of carbides was determined. The analysis of phase transformations in various times using CEMS method made possible to reveal their fine details.

Rapid biological synthesis of platinum nanoparticles using Ocimum sanctum for water electrolysis applications.

PubMed

Soundarrajan, C; Sankari, A; Dhandapani, P; Maruthamuthu, S; Ravichandran, S; Sozhan, G; Palaniswamy, N

2012-06-01

The leaf extract of Ocimum sanctum was used as a reducing agent for the synthesis of platinum nanoparticles from an aqueous chloroplatinic acid (H(2)PtCl(6)·6H(2)O). A greater conversion of platinum ions to nanoparticles was achieved by employing a tulsi leaf broth with a reaction temperature of 100 °C. Energy-dispersive absorption X-ray spectroscopy confirmed the platinum particles as major constituent in the reduction process. It is evident from scanning electron microscopy that the reduced platinum particles were found as aggregates with irregular shape. Fourier-transform infrared spectroscopy revealed that the compounds such as ascorbic acid, gallic acid, terpenoids, certain proteins and amino acids act as reducing agents for platinum ions reduction. X-ray diffraction spectroscopy suggested the associated forms of platinum with other molecules and the average particle size of platinum nanoparticle was 23 nm, calculated using Scherer equation. The reduced platinum showed similar hydrogen evolution potential and catalytic activity like pure platinum using linear scan voltammetry. This environmentally friendly method of biological platinum nanoparticles production increases the rates of synthesis faster which can potentially be used in water electrolysis applications.

Observations of Ball-Lightning-Like Plasmoids Ejected from Silicon by Localized Microwaves

PubMed Central

Meir, Yehuda; Jerby, Eli; Barkay, Zahava; Ashkenazi, Dana; Mitchell, James Brian; Narayanan, Theyencheri; Eliaz, Noam; LeGarrec, Jean-Luc; Sztucki, Michael; Meshcheryakov, Oleg

2013-01-01

This paper presents experimental characterization of plasmoids (fireballs) obtained by directing localized microwave power (<1 kW at 2.45 GHz) onto a silicon-based substrate in a microwave cavity. The plasmoid emerges up from the hotspot created in the solid substrate into the air within the microwave cavity. The experimental diagnostics employed for the fireball characterization in this study include measurements of microwave scattering, optical spectroscopy, small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Various characteristics of these plasmoids as dusty plasma are drawn by a theoretical analysis of the experimental observations. Aggregations of dust particles within the plasmoid are detected at nanometer and micrometer scales by both in-situ SAXS and ex-situ SEM measurements. The resemblance of these plasmoids to the natural ball-lightning (BL) phenomenon is discussed with regard to silicon nano-particle clustering and formation of slowly-oxidized silicon micro-spheres within the BL. Potential applications and practical derivatives of this study (e.g., direct conversion of solids to powders, material identification by breakdown spectroscopy (MIBS), thermite ignition, and combustion) are discussed. PMID:28788315

Safe disposal of toxic chrome buffing dust generated from leather industries.

PubMed

Swarnalatha, S; Srinivasulu, T; Srimurali, M; Sekaran, G

2008-01-31

The high concentration of trivalent chromium along with organic/inorganic compounds in chrome buffing dust (CBD), the solid waste discharged from leather industries, causes severe groundwater contamination on land co-disposal and chronic air pollution during thermal incineration. In the present investigation, CBD was subjected to starved air incineration (SAI) at 800 degrees C in a thermal incinerator under different flow rates of oxygen to optimize the oxygen required to incinerate the organic compounds and simultaneously preventing the conversion of Cr(3+) to Cr(6+). The energy audit of SAI of buffing dust under the external supply of oxygen was carried out under different incineration conditions. The bottom ash from SAI was effectively solidified/stabilized using Portland cement and fine aggregate. The solidified blocks were tested for unconfined compressive strength and heavy metal leaching. Unconfined compressive strength of the blocks was in the range of 120-180 kg/cm(2). The stabilization of chromium(III) in the cement gel matrix was confirmed using Scanning Electron Microscopy SEM, Electron Paramagnetic Resonance spectroscopy (EPR) and X-ray diffraction spectroscopy (XRD). Leachability studies through TCLP on solidified blocks were carried out to determine the degree of leaching of chromium and organic compounds (expressed as COD) under standard conditions.

Quantitative evaluation of the accuracy and variance of individual pixels in a scientific CMOS (sCMOS) camera for computational imaging

NASA Astrophysics Data System (ADS)

Watanabe, Shigeo; Takahashi, Teruo; Bennett, Keith

2017-02-01

The"scientific" CMOS (sCMOS) camera architecture fundamentally differs from CCD and EMCCD cameras. In digital CCD and EMCCD cameras, conversion from charge to the digital output is generally through a single electronic chain, and the read noise and the conversion factor from photoelectrons to digital outputs are highly uniform for all pixels, although quantum efficiency may spatially vary. In CMOS cameras, the charge to voltage conversion is separate for each pixel and each column has independent amplifiers and analog-to-digital converters, in addition to possible pixel-to-pixel variation in quantum efficiency. The "raw" output from the CMOS image sensor includes pixel-to-pixel variability in the read noise, electronic gain, offset and dark current. Scientific camera manufacturers digitally compensate the raw signal from the CMOS image sensors to provide usable images. Statistical noise in images, unless properly modeled, can introduce errors in methods such as fluctuation correlation spectroscopy or computational imaging, for example, localization microscopy using maximum likelihood estimation. We measured the distributions and spatial maps of individual pixel offset, dark current, read noise, linearity, photoresponse non-uniformity and variance distributions of individual pixels for standard, off-the-shelf Hamamatsu ORCA-Flash4.0 V3 sCMOS cameras using highly uniform and controlled illumination conditions, from dark conditions to multiple low light levels between 20 to 1,000 photons / pixel per frame to higher light conditions. We further show that using pixel variance for flat field correction leads to errors in cameras with good factory calibration.

Enhancing Efficiency of Perovskite Solar Cells via Surface Passivation with Graphene Oxide Interlayer.

PubMed

Li, Hao; Tao, Leiming; Huang, Feihong; Sun, Qiang; Zhao, Xiaojuan; Han, Junbo; Shen, Yan; Wang, Mingkui

2017-11-08

Perovskite solar cells have been demonstrated as promising low-cost and highly efficient next-generation solar cells. Enhancing V OC by minimization the interfacial recombination kinetics can further improve device performance. In this work, we for the first time reported on surface passivation of perovskite layers with chemical modified graphene oxides, which act as efficient interlayer to reduce interfacial recombination and enhance hole extraction as well. Our modeling points out that the passivation effect mainly comes from the interaction between functional group (4-fluorophenyl) and under-coordinated Pb ions. The resulting perovskite solar cells achieved high efficient power conversion efficiency of 18.75% with enhanced high open circuit V OC of 1.11 V. Ultrafast spectroscopy, photovoltage/photocurrent transient decay, and electronic impedance spectroscopy characterizations reveal the effective passivation effect and the energy loss mechanism. This work sheds light on the importance of interfacial engineering on the surface of perovskite layers and provides possible ways to improve device efficiency.

Photo-excited charge carriers suppress sub-terahertz phonon mode in silicon at room temperature

DOE PAGES

Liao, Bolin; Maznev, A. A.; Nelson, Keith A.; ...

2016-10-12

There is a growing interest in the mode-by-mode understanding of electron and phonon transport for improving energy conversion technologies, such as thermoelectrics and photovoltaics. Whereas remarkable progress has been made in probing phonon–phonon interactions, it has been a challenge to directly measure electron–phonon interactions at the single-mode level, especially their effect on phonon transport above cryogenic temperatures. Here in this paper, we use three-pulse photoacoustic spectroscopy to investigate the damping of a single sub-terahertz coherent phonon mode by free charge carriers in silicon at room temperature. Building on conventional pump–probe photoacoustic spectroscopy, we introduce an additional laser pulse to opticallymore » generate charge carriers, and carefully design temporal sequence of the three pulses to unambiguously quantify the scattering rate of a single-phonon mode due to the electron–phonon interaction. Our results confirm predictions from first-principles simulations and indicate the importance of the often-neglected effect of electron–phonon interaction on phonon transport in doped semiconductors.« less

Dewar Lesion Formation in Single- and Double-Stranded DNA is Quenched by Neighboring Bases.

PubMed

Bucher, Dominik B; Pilles, Bert M; Carell, Thomas; Zinth, Wolfgang

2015-07-16

UV-induced Dewar lesion formation is investigated in single- and double-stranded oligonucleotides with ultrafast vibrational spectroscopy. The quantum yield for the conversion of the (6-4) lesion to the Dewar isomer in DNA strands is reduced by a factor of 4 in comparison to model dinucleotides. Time resolved spectroscopy reveals a fast process in the excited state with spectral characteristics of bases which are adjacent to the excited (6-4) lesion. These kinetic components have large amplitudes and indicate that an additional quenching channel acts in the stranded DNA systems and reduces the Dewar formation yield. Presumably relaxation evolves via a charge transfer to the neighboring guanine and the paired cytosine participates in a double-stranded oligomer. Changes in the decay of the relaxed excited electronic state of the (6-4) chromophore point to modifications in the excited state energy landscape which may lead to an additional reduction of the Dewar formation yield.

Origin of Capacity Fading in Nano-Sized Co3O4 Electrodes: Electrochemical Impedance Spectroscopy Study

NASA Astrophysics Data System (ADS)

Kang, Jin-Gu; Ko, Young-Dae; Park, Jae-Gwan; Kim, Dong-Wan

2008-10-01

Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4 with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4 anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

Layer-by-Layer Assembly of a Self-Healing Anticorrosion Coating on Magnesium Alloys.

PubMed

Fan, Fan; Zhou, Chunyu; Wang, Xu; Szpunar, Jerzy

2015-12-16

Fabrication of self-healing anticorrosion coatings has attracted attention as it has the ability to extend the service life and prevent the substrate from corrosive attack. However, a coating system with a rapid self-healing ability and an improved corrosion resistance is rarely reported. In this work, we developed a self-healing anticorrosion coating on a magnesium alloy (AZ31). The coating comprises a cerium-based conversion layer, a graphene oxide layer, and a branched poly(ethylene imine) (PEI)/poly(acrylic acid) (PAA) multilayer. We incorporated the graphene oxide as corrosion inhibitors and used the PEI/PAA multilayers to provide the self-healing ability to the coating systems. X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the composition of the multilayers, and scanning electron microscopy (SEM) was used to analyze the surface morphology. The electrochemical impedance spectroscopy (EIS) results illustrate the improved corrosion resistance of the coating. The proposed coating also has a rapid self-healing ability in the presence of water.

Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

2017-09-01

Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant 13C nuclei coupled to the observer spins.

Magnetic and Mössbauer characterization of the magnetic properties of single-crystalline sub-micron sized Bi₂Fe₄O₉ cubes

DOE PAGES

Papaefthymiou, Georgia C.; Wong, Stanislaus S.; Viescas, Arthur J.; ...

2014-11-25

Magnetic and Mössbauer characterization of single crystalline, sub-micron sized Bi₂Fe₄O₉ cubes has been performed using SQUID magnetometry and transmission Mössbauer spectroscopy in the temperature range of 4.2 K ≤ T ≤ 300 K. A broad magnetic phase transition from the paramagnetic to the anti-ferromagnetic state is observed below 250 K, with the Mössbauer spectra exhibiting a superposition of magnetic, collapsed and quadrupolar spectra in the transition region of 200 K < T < 245 K. Room temperature Mössbauer spectra obtained in transmission geometry are identical to those recorded in back-scattering geometry via conversion electron Mössbauer spectroscopy, indicating the absence ofmore » strain at the surface. A small hysteresis loop is observed in SQUID measurements at 5 K, attributable to the presence of weak-ferromagnetism arising from the canting of Fe³⁺ ion sublattices in the antiferromagnetic matrix.« less

Quaternary Cu2ZnSnS4 quantum dot-sensitized solar cells: Synthesis, passivation and ligand exchange

NASA Astrophysics Data System (ADS)

Bai, Bing; Kou, Dongxing; Zhou, Wenhui; Zhou, Zhengji; Tian, Qingwen; Meng, Yuena; Wu, Sixin

2016-06-01

The quaternary Cu2ZnSnS4 (CZTS) QDs had been successfully introduced into quantum dot-sensitized solar cells (QDSC) via hydrolysis approach in our previous work [Green Chem. 2015, vol. 17, p. 4377], but the obtained cell efficiency was still limited by low open-circuit voltage and fill factor. Herein, we use 1-dodecanethiol (DDT) as capping ligand for fairly small-sized CZTS QDs synthesis to improve their intrinsic properties. Since this strong bonded capping ligand can not be replaced by 3-mercaptopropionic acid (MPA) directly, the nature cation (Cu, Zn or Sn)-DDT units of QDs are first exchanged by the preconjugated Cd-oleate via successive ionic layer adsorption and reaction (SILAR) procedure accompanied with the formation of a core/shell structure. The weak bonded oleic acid (OA) can be finally replaced by MPA and the constructed water soluble CZTS/CdSe QDSC achieves an impressive conversion efficiency of 4.70%. The electron transport and recombination dynamic processes are confirmed by intensity-modulated photocurrent spectroscopy (IMPS)/intensity-modulated photovoltage spectroscopy (IMVS) measurements. It is found that the removal of long alkyl chain is conducive to improve the electron transport process and the type-II core/shell structure is beneficial to accelerate electron transport and retard charge recombination. This effective ligand removal strategy is proved to be more convenient for the applying of quaternary QDs in QDSC and would boost a more powerful efficiency in the future work.

Visible-light-responsive photocatalysts toward water oxidation based on NiTi-layered double hydroxide/reduced graphene oxide composite materials.

PubMed

Li, Bei; Zhao, Yufei; Zhang, Shitong; Gao, Wa; Wei, Min

2013-10-23

A visible-light responsive photocatalyst was fabricated by anchoring NiTi-layered double hydroxide (NiTi-LDH) nanosheets to the surface of reduced graphene oxide sheets (RGO) via an in situ growth method; the resulting NiTi-LDH/RGO composite displays excellent photocatalytic activity toward water splitting into oxygen with a rate of 1.968 mmol g(-1) h(-1) and a quantum efficiency as high as 61.2% at 500 nm, which is among the most effective visible-light photocatalysts. XRD patterns and SEM images indicate that the NiTi-LDH nanosheets (diameter: 100-200 nm) are highly dispersed on the surface of RGO. UV-vis absorption spectroscopy exhibits that the introduction of RGO enhances the visible-light absorption range of photocatalysts, which is further verified by the largely decreased band gap (∼1.78 eV) studied by cyclic voltammetry measurements. Moreover, photoluminescence (PL) measurements indicate a more efficient separation of electron-hole pairs; electron spin resonance (ESR) and Raman scattering spectroscopy confirm the electrons transfer from NiTi-LDH nanosheets to RGO, accounting for the largely enhanced carrier mobility and the resulting photocatalytic activity in comparison with pristine NiTi-LDH material. Therefore, this work demonstrates a facile approach for the fabrication of visible-light responsive NiTi-LDH/RGO composite photocatalysts, which can be used as a promising candidate in solar energy conversion and environmental science.

Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

PubMed

Ji, Gengwu; Zheng, Guanhaojie; Zhao, Bin; Song, Fei; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Xiong, Yimin; Gao, Xingyu; Cao, Liang; Qi, Dong-Chen

2017-03-01

The electronic structures of rubrene films deposited on CH 3 NH 3 PbI 3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH 3 NH 3 PbI 3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH 3 NH 3 PbI 3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

Direct Observation of Electron Capture and Reemission by the Divacancy via Charge Transient Positron Spectroscopy

NASA Astrophysics Data System (ADS)

Edwardson, C. J.; Coleman, P. G.; Paez, D. J.; Doylend, J. K.; Knights, A. P.

2013-03-01

Electron capture during forward bias and reemission at zero bias by divacancies in the depletion region of a silicon diode structure at room temperature have been studied for the first time using monoenergetic positrons. The positron response increases essentially linearly with electron current, as a result of increased positron trapping by negatively charged divacancies. The measurements indicate that ≤1% of the divacancies become negatively charged in the steady state at a forward bias of 1 V. Changes in the mean positron response when applying a square wave bias to the sample (1 V forward bias and 0 V, duty cycle 1∶4, times at 0 V in the range 0.1-100μs), were consistent with a rapid conversion of doubly to singly charged divacancies (in ˜101ns), followed by slower defilling of the singly charged divacancies with a time constant of ˜101μs. These ac measurements allow determination of the relative populations of singly and doubly charged divacancies. The results provide confirmation of consistency between the positron’s response to the silicon divacancy and previously extracted capture and emission kinetics determined through charge transient measurements and assigned to the same defect. The possibility of combining these two, orthogonal techniques suggest a promising new and powerful approach to defect spectroscopy in which the structure and electrical properties of a defect may be determined in a single measurement.

Energy efficient microwave synthesis of mesoporous Ce 0.5M 0.5O 2 (Ti, Zr, Hf) nanoparticles for low temperature CO oxidation in an ionic liquid – a comparative study

DOE PAGES

Alammar, Tarek; Chow, Ying -Kit; Mudring, Anja -Verena

2014-11-19

Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles have been successfully synthesized by microwave irradiation in the ionic liquid [C 4mim][Tf 2N] (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide). The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N 2–adsorption measurements. XRD and Raman spectroscopy analyses confirmed the formation of solid solutions with cubic fluorite structure. The catalytic activities of the Ce 0.5M 0.5O 2 (M = Ti, Zr, Hf) nanoparticles were investigated in the low-temperature oxidation of CO. Ce 0.5Zr 0.5O 2 nanospheresmore » exhibit the best performance (100% conversion at 350 °C), followed by Ce 0.5Hf 0.5O 2 (55% conversion at 360 °C) and Ce 0.5Ti 0.5O 2 (11% conversion at 350 °C). Heating the as-prepared Ce 0.5Zr 0.5O 2 to 600 °C for extended time leads to a decrease in surface area and, as expected decreased catalytic activity. Depending on the ionic liquid the obtained Ce 0.5Zr 0.5O 2 exhibits different morphologies, varying from nano-spheres in [C 4mim][Tf 2N] and [P 66614][Tf 2N] (P 66614 = trishexyltetradecylphosphonium) to sheet-like assemblies in [C 3mimOH][Tf 2N] (C 3mimOH = 1-(3-hydroxypropyl)-3-methylimidazolium). As a result, the microwave synthesis superiority to other heating methods like sonochemical synthesis and conventional heating was proven by comparative experiments where the catalytic activity of Ce 0.5Zr 0.5O 2 obtained by alternate methods such as conventional heating was found to be poorer than that of the microwave-synthesised material.« less

Highly Efficient Performance and Conversion Pathway of Photocatalytic CH3SH Oxidation on Self-Stabilized Indirect Z-Scheme g-C3N4/I3--BiOI.

PubMed

Hu, Lingling; He, Huanjunwa; Xia, Dehua; Huang, Yajing; Xu, Jiarong; Li, Haoyue; He, Chun; Yang, Wenjing; Shu, Dong; Wong, Po Keung

2018-06-06

A self-stabilized Z-scheme porous g-C 3 N 4 /I 3- -containing BiOI ultrathin nanosheets (g-C 3 N 4 /I 3- -BiOI) heterojunction photocatalyst with I 3 - /I - redox mediator was successfully synthesized by a facile solvothermal method coupling with light illumination. The structure and optical properties of g-C 3 N 4 /I 3- -BiOI composites were systematically characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, N 2 adsorption/desorption, UV-vis diffuse reflectance spectrum, and photoluminescence. The g-C 3 N 4 /I 3- -BiOI composites, with a heterojunction between porous g-C 3 N 4 and BiOI ultrathin nanosheets, were first applied for the photocatalytic elimination of ppm-leveled CH 3 SH under light-emitting diode visible light illumination. The g-C 3 N 4 /I 3- -BiOI heterojunction with 10% g-C 3 N 4 showed a dramatically enhanced photocatalytic activity in the removal of CH 3 SH compared with pure BiOI and g-C 3 N 4 due to its effective interfacial charge transfer and separation. The adsorption and photocatalytic oxidation of CH 3 SH over g-C 3 N 4 /I 3- -BiOI were deeply explored by in situ diffuse reflectance infrared Fourier transform spectroscopy, and the intermediates and conversion pathways were elucidated and compared. Furthermore, on the basis of reactive species trapping, electron spin resonance and Mott-Schottky experiments, it was revealed that the responsible reactive species for catalytic CH 3 SH composition were h + , • O 2 - , and 1 O 2 ; thus, the g-C 3 N 4 /I 3- -BiOI heterojunction followed an indirect all-solid state Z-scheme charge-transfer mode with self-stabilized I 3 - /I - pairs as redox mediator, which could accelerate the separation of photogenerated charge and enhance the redox reaction power of charged carriers simultaneously.

Electron Spectroscopic Methods in Teaching.

ERIC Educational Resources Information Center

Allan, Michael

1987-01-01

Discusses electron-loss spectroscopy and the experimentally observed excitation energies in terms of qualitative MO theory. Reviews information on photoelectron spectroscopy and electron transmission spectroscopy and their relation to the occupied and unoccupied orbital levels. Focuses on teaching applications. (ML)

Synthesis and formation mechanism of pinnoite by the phase transition process

NASA Astrophysics Data System (ADS)

Lin, Feng; Dong, Yaping; Peng, Jiaoyu; Wang, Liping; Li, Wu

2016-06-01

Pinnoite (MgB2O(OH)6) for the first time was synthesized using the solid-liquid-solid conversion method. The effects of reaction time, pH value and concentrations of magnesium and borate were investigated. Pinnoite was synthesized under the optimum condition of 8 mmol hungtsaoite and 1% boric acid solution at 80 °C. The products were determined using X-ray diffraction, Fourier-transform infrared spectroscopy, TG-DSC and a UV-vis spectrometer. The change processes of the surface morphology of pinnoite were investigated using scanning electron microscopy. In addition, the formation mechanism of pinnoite was discussed according to the changes in the content of precipitation and pH value.

Photo protection of RNA building blocks: Adenosine 5‧-monophosphate, cytidine 5‧-monophosphate and cytosine

NASA Astrophysics Data System (ADS)

Nielsen, Jakob Brun; Thøgersen, Jan; Jensen, Svend Knak; Keiding, Søren Rud

2013-04-01

Photoprotection of the RNA nucleotides adenosine 5'-monophosphate and cytidine 5'-monophosphate, and the nucleobase cytosine was studied using UV pump, IR probe femtosecond transient absorption spectroscopy. The excitation energy is contained in the aromatic ring system, protecting the RNA backbone. All three molecules dissipate the excitation energy by internal conversion and subsequent vibrational relaxation to the electronic ground state in less than 10 ps. In addition, a second deactivation channel is found in cytidine 5'-monophosphate, illustrated by a signal at 1563 cm-1 with a lifetime of 33 ps assigned to an nπ∗ state in agreement with observations in the UV region.

Fabrication and electrochemical properties of insoluble fullerene-diamine adduct thin-films as buffer layer by alternate immersion process

NASA Astrophysics Data System (ADS)

Saito, Jo; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

2017-01-01

Insoluble fullerene-diamine adduct thin-films consisting of C60 and 1,2-diaminoethane were easily fabricated on an electrode by an alternate immersion process. Formation of the C60-diamine adduct films were confirmed using transmission absorption spectroscopy and atomic force microscopy. An inverted-type organic solar cells were fabricated by using the C60-diamine adduct film as the electron transport layer. The resultant photoelectric conversation performance of the solar cells suggested that photocurrent is generated via the photoexcitation of polythiophene. The result suggests that the present insoluble fullerene-diamine adduct films worked as buffer layer for organic thin-film solar cells.

CEMS study of strain induced phase transformation in manganese Hadfield steel

NASA Astrophysics Data System (ADS)

Cabanillas, E. D.; Alvarez, E. P.; Hey, A.; Mercader, R. C.

1991-11-01

A Conversion Electron Mössbauer Spectroscopy, (CEMS), study of phase transformations in a Hadfield steel induced by high rate strains is reported. Hadfield steel samples were impact deformed and the ensuing changes in the magnetic properties at the deformed zone and its surroundings have been studied by CEMS. The CEMS results are compared with wear tests and optical microscopy and show a formation of martensite by impact deformation only at the surface. Martensite is not produced by compression or tensile stresses but appears after wear tests in proportions that depend on the load and velocity conditions of test. The understanding of martensite phase formation and its evolution during deformation processes is also addressed.

Application of Fourier transform infrared (FT-IR) spectroscopy to the study of the modification of epoxidized sunflower oil by acrylation.

PubMed

Irinislimane, Ratiba; Belhaneche-Bensemra, Naima

2012-12-01

Commercial sunflower oil was epoxidized at the laboratory-scale. The epoxidized sunflower oil (ESFO) was modified following the acrylation reaction. Modification was carried out simultaneously using acrylic acid (AA) and triethylamine (TEA). To optimize the reaction conditions, the effects of four temperatures (40, 60, 80, and 100 °C), the ESFO:AA (100:100) ratio, and 0.2% TEA were investigated. The rate of conversion was analyzed with both FT-IR and titration of the oxirane ring. After that, the temperature with the highest conversion was selected and used throughout for all modification reactions. Then, four ratios (100:100, 100:90, 100:80, and 100:75) of ESFO:AA were analyzed at four different concentrations of TEA (0.2, 0.3, 0.4, and 0.5%) to determine the best estimate for both the ESFO:AA ratio and the catalyst concentration. Conversion rate was analyzed using FT-IR spectroscopy by measuring the concentrations of ester, carbonyl, and alcohol groups. Moreover, oxirane-ring concentration was estimated using the titration method (with gentian violet as indicator) and FT-IR spectroscopy (epoxy ring absorptions at 1270 cm(-1) and 877 cm(-1)). Based on conversion yield, the optimum ESFO:AA ratio corresponds to 100:80; the best temperature reaction was at 60 °C, and the best TEA concentration was 0.2%. The critical amounts of reactants needed to reach maximum conversion were established. The final acid value of the acrylated ESFO after washing (pH = 7) was 2.1 mg potassium hydroxide (KOH)·g(-1). All results show that FT-IR spectroscopy is a simple, low-cost, rapid method for investigating the kinetics of a reaction.

Catalytic potential of bio-synthesized silver nanoparticles using Convolvulus arvensis extract for the degradation of environmental pollutants.

PubMed

Rasheed, Tahir; Bilal, Muhammad; Li, Chuanlong; Nabeel, Faran; Khalid, Muhammad; Iqbal, Hafiz M N

2018-04-01

Herein, we reported a facile, green and environmental friendlier biosynthesis of silver nanoparticles using the Convolvulus arvensis extract. The influences of various physicochemical factors such as the concentration of the plant extract, reaction time, and different pH levels were investigated by UV-Vis spectroscopy. The UV-Visible absorption spectrum of biogenic silver nanoparticles at λ max around ~400 nm suggested the biosynthesis of silver nanoparticles. Fourier transform infrared spectroscopy was employed to confirm the chemical transformation and role of various phyto-reductants in the conversion of Ag + to Ag 0 . The surface morphology, topography, and elemental composition were analyzed by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy, respectively. X-ray diffraction corroborated the face-centered cubic crystalline structure. The dynamic light scattering and zeta potential demonstrate the size distribution (90.9 nm) and surface charge (-18.5). Finally, the newly developed C. arvensis based silver nanoparticles were exploited as a catalyst for the catalytic reduction of azo dyes in the presence of NaBH 4 as a reducing agent, and reducing the activity of C. arvensis based silver nanoparticles was evaluated by a decrease in optical density using UV-Vis spectrophotometer. The nanoparticles developed herein displayed potential efficiency for the degradation of all the tested dye pollutants. Conclusively, plant-based synthesis of nanoparticles provides an environmentally-responsive option for the reduction of highly environmental-polluted organic compounds including toxic azo dyes as compared to chemical and physical methods. Copyright © 2018 Elsevier B.V. All rights reserved.

Mulberry leaf extract mediated synthesis of gold nanoparticles and its anti-bacterial activity against human pathogens

NASA Astrophysics Data System (ADS)

Adavallan, K.; Krishnakumar, N.

2014-06-01

Gold nanoparticles (Au-NPs) were synthesized at room temperature using Morus alba (mulberry) leaf extract as reducing and stabilizing agent. The development of plant mediated synthesis of nanoparticles is gaining importance due to its simplicity, low cost, non-toxicity, eco-friendliness, long term stability and reproducible aqueous synthesis method to obtain a self-assembly of nearly monodispersed Au-NPs. The formation and morphology of biosynthesized nanoparticles are investigated with the help of UV-Vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), x-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) techniques. Au-NPs formation was screened by UV-Vis spectroscopy through color conversion due to surface plasmon resonance band at 538 nm for Au-NPs. DLS studies revealed that the average size of Au-NPs was 50 nm. TEM studies showed the particles to be nearly spherical with few irregular shapes and particle size ranges 15-53 nm. The AFM image clearly shows the surface morphology of the well-dispersed Au-NPs with less than 50 nm. The high crystallinity of nanoparticles is evident from bright circular spots in the selected area electron diffraction (SAED) pattern. X-ray diffraction pattern showed high purity and face-centered cubic structure of Au-NPs. The FT-IR results indicate the presence of different functional groups present in the biomolecule capping the nanoparticles. Further, biosynthesized Au-NPs show strong zone of inhibition against Vibrio cholera (gram-negative) and Staphylococcus aureus (gram-positive) whereas, chemically synthesized Au-NPs and mulberry leaf extract exhibit a fair zone of inhibition.

Anthracene-Based Organic Small-Molecule Electron-Injecting Material for Inverted Organic Light-Emitting Diodes.

PubMed

Matsuo, Yutaka; Okada, Hiroshi; Kondo, Yasuhiro; Jeon, Il; Wang, Huan; Yu, Yun; Matsushita, Takeshi; Yanai, Motoki; Ikuta, Toshiaki

2018-04-11

A diphenylanthracene dimethylamine derivative (9-{3,5-di( N, N-dimethylaminoethoxy)phenyl}-10-phenyl-anthracene, DPAMA) was synthesized by the Suzuki-Miyaura cross-coupling reaction. Its ammonium salt, 9-{3,5-di(trimethylammonium ethoxy)phenyl}-10-phenyl-anthracene dichloride (DPAMA-Cl), was also synthesized as a reference material. DPAMA was characterized by UV-vis and fluorescence spectroscopy, cyclic voltammetry, photoelectron yield spectroscopy, and X-ray photoelectron spectroscopy to evaluate the work function-modifying ability of DPAMA on indium tin oxide (ITO) and ZnO. The work functions of ITO and ZnO changed from 4.4 and 4.0 eV (pristine) to 3.8 and 3.9 eV, respectively. Using this surface modification effect of DPAMA, inverted organic light-emitting diodes were fabricated with device structures of ITO/DPAMA/Alq 3 /NPD/MoO 3 /Al (Alq 3 = tris(8-hydroxyquinolinato)aluminum; NPD = N, N'-di-[(1-naphthyl)- N, N'-diphenyl]-1,1'-(biphenyl)-4,4'-diamine) and ITO/ZnO/DPAMA/Alq 3 /NPD/MoO 3 /Al. Both devices showed good performance at the range of current density, 1-300 mA/cm 2 . The best inverted organic light-emitting diodes device showed luminance of 7720 cd/m 2 , current efficiency of 4.51 cd/A, and external quantum efficiency of 1.45%. Also, poly(3-hexylthiophene):mixed phenyl-C 61 and C 71 butyric acid methyl ester-based organic solar cells using DPAMA and DPAMA-Cl as electron-transporting materials showed power conversion efficiencies of 3.3 and 3.4%, respectively.

AXSIS: Exploring the frontiers in attosecond X-ray science, imaging and spectroscopy.

PubMed

Kärtner, F X; Ahr, F; Calendron, A-L; Çankaya, H; Carbajo, S; Chang, G; Cirmi, G; Dörner, K; Dorda, U; Fallahi, A; Hartin, A; Hemmer, M; Hobbs, R; Hua, Y; Huang, W R; Letrun, R; Matlis, N; Mazalova, V; Mücke, O D; Nanni, E; Putnam, W; Ravi, K; Reichert, F; Sarrou, I; Wu, X; Yahaghi, A; Ye, H; Zapata, L; Zhang, D; Zhou, C; Miller, R J D; Berggren, K K; Graafsma, H; Meents, A; Assmann, R W; Chapman, H N; Fromme, P

2016-09-01

X-ray crystallography is one of the main methods to determine atomic-resolution 3D images of the whole spectrum of molecules ranging from small inorganic clusters to large protein complexes consisting of hundred-thousands of atoms that constitute the macromolecular machinery of life. Life is not static, and unravelling the structure and dynamics of the most important reactions in chemistry and biology is essential to uncover their mechanism. Many of these reactions, including photosynthesis which drives our biosphere, are light induced and occur on ultrafast timescales. These have been studied with high time resolution primarily by optical spectroscopy, enabled by ultrafast laser technology, but they reduce the vast complexity of the process to a few reaction coordinates. In the AXSIS project at CFEL in Hamburg, funded by the European Research Council, we develop the new method of attosecond serial X-ray crystallography and spectroscopy, to give a full description of ultrafast processes atomically resolved in real space and on the electronic energy landscape, from co-measurement of X-ray and optical spectra, and X-ray diffraction. This technique will revolutionize our understanding of structure and function at the atomic and molecular level and thereby unravel fundamental processes in chemistry and biology like energy conversion processes. For that purpose, we develop a compact, fully coherent, THz-driven atto-second X-ray source based on coherent inverse Compton scattering off a free-electron crystal, to outrun radiation damage effects due to the necessary high X-ray irradiance required to acquire diffraction signals. This highly synergistic project starts from a completely clean slate rather than conforming to the specifications of a large free-electron laser (FEL) user facility, to optimize the entire instrumentation towards fundamental measurements of the mechanism of light absorption and excitation energy transfer. A multidisciplinary team formed by laser-, accelerator,- X-ray scientists as well as spectroscopists and biochemists optimizes X-ray pulse parameters, in tandem with sample delivery, crystal size, and advanced X-ray detectors. Ultimately, the new capability, attosecond serial X-ray crystallography and spectroscopy, will be applied to one of the most important problems in structural biology, which is to elucidate the dynamics of light reactions, electron transfer and protein structure in photosynthesis.

Ultrafast photoelectron spectroscopy of small molecule organic films

NASA Astrophysics Data System (ADS)

Read, Kendall Laine

As research in the field of ultrafast optics has produced shorter and shorter pulses, at an ever-widening range of frequencies, ultrafast spectroscopy has grown correspondingly. In particular, ultrafast photoelectron spectroscopy allows direct observation of electrons in transient or excited states, regardless of the eventual relaxation mechanisms. High-harmonic conversion of 800nm, femtosecond, Ti:sapphire laser pulses allows excite/probe spectroscopy down into atomic core level states. To this end, an ultrafast, X-UV photoelectron spectroscopic system is described, including design considerations for the high-harmonic generation line, the time of flight detector, and the subsequent data collection electronics. Using a similar experimental setup, I have performed several ultrafast, photoelectron excited state decay studies at the IBM, T. J. Watson Research Center. All of the observed materials were electroluminescent thin film organics, which have applications as the emitter layer in organic light emitting devices. The specific materials discussed are: Alq, BAlq, DPVBi, and Alq doped with DCM or DMQA. Alq:DCM is also known to lase at low photoexcitation thresholds. A detailed understanding of the involved relaxation mechanisms is beneficial to both applications. Using 3.14 eV excite, and 26.7 eV probe, 90 fs laser pulses, we have observed the lowest unoccupied molecular orbital (LUMO) decay rate over the first 200 picoseconds. During this time, diffusion is insignificant, and all dynamics occur in the absence of electron transport. With excitation intensities in the range of 100μJ/cm2, we have modeled the Alq, BAlq, and DPVBi decays via bimolecular singlet-singlet annihilation. At similar excitations, we have modeled the Alq:DCM decay via Förster transfer, stimulated emission, and excimeric formation. Furthermore, the Alq:DCM occupied to unoccupied molecular orbital energy gap was seen to shrink as a function of excite-to-probe delay, in accordance with the expected relaxation within the excited states. Stable, shorter pulses allow finer temporal resolution and more efficient high-harmonic generation. This work therefore concludes by discussing a method for further shortening 25 femtosecond pulses via self-phase modulation, using filamentation in air and subsequent fiber channeling.

Vibrational spectroscopy in the electron microscope.

PubMed

Krivanek, Ondrej L; Lovejoy, Tracy C; Dellby, Niklas; Aoki, Toshihiro; Carpenter, R W; Rez, Peter; Soignard, Emmanuel; Zhu, Jiangtao; Batson, Philip E; Lagos, Maureen J; Egerton, Ray F; Crozier, Peter A

2014-10-09

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample--that is, for 'aloof' spectroscopy that largely avoids radiation damage.

Graphene/cobalt nanocarrier for hyperthermia therapy and MRI diagnosis.

PubMed

Hatamie, Shadie; Ahadian, Mohammad Mahdi; Ghiass, Mohammad Adel; Iraji Zad, Azam; Saber, Reza; Parseh, Benyamin; Oghabian, Mohammad Ali; Shanehsazzadeh, Saeed

2016-10-01

Graphene/cobalt nanocomposites are promising materials for theranostic nanomedicine applications, which are defined as the ability to diagnose, provide targeted therapy and monitor the response to the therapy. In this study, the composites were synthesized via chemical method, using graphene oxide as the source material and assembling cobalt nanoparticles of 15nm over the surface of graphene sheets. Various characterization techniques were then employed to reveal the morphology, size and structure of the nanocomposites, such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, high resolution transmission electron microscopy and ultraviolet visible spectroscopy. Using ion-coupled plasma optical emission spectroscopy, cobalt concentration in the nanocomposites was found to be 80%. In addition, cytotoxicity of graphene/cobalt nanocomposites were evaluated using 3-[4,5-dimethylthiazol-2yl]-2,5-diphenyltetrazolium bromide or MTT assay. MTT viability assay exhibited biocompatibility to L929 mouse fibroblasts cells, under a high dose of 100μg/mL over 24h. Hyperthermia results showed the superior conversion of electromagnetic energy into heat at 350kHz frequency for 0.01 and 0.005g/L of the nanocomposites solution. The measured heat generation and energy transfer results were anticipated by the finite element analysis, conducted for the 3D structure. Magnetic resonance imaging characteristics also showed that negatively charge graphene/cobalt nanocomposites are suitable for T1-weighted imaging. Copyright © 2016 Elsevier B.V. All rights reserved.

A systematic approach to baseline assessment of nursing documentation and enterprise-wide prioritization for electronic conversion.

PubMed

Dykes, Patricia C; Spurr, Cindy; Gallagher, Joan; Li, Qi; Ives Erickson, Jeanette

2006-01-01

An important challenge associated with making the transition from paper to electronic documentation systems is achieving consensus regarding priorities for electronic conversion across diverse groups. In our work we focus on applying a systematic approach to evaluating the baseline state of nursing documentation across a large healthcare system and establishing a unified vision for electronic conversion. A review of the current state of nursing documentation across PHS was conducted using structured tools. Data from this assessment was employed to facilitate an evidence-based approach to decision-making regarding conversion to electronic documentation at local and PHS levels. In this paper we present highlights of the assessment process and the outcomes of this multi-site collaboration.

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution.

PubMed

Wernet, Ph; Kunnus, K; Josefsson, I; Rajkovic, I; Quevedo, W; Beye, M; Schreck, S; Grübel, S; Scholz, M; Nordlund, D; Zhang, W; Hartsock, R W; Schlotter, W F; Turner, J J; Kennedy, B; Hennies, F; de Groot, F M F; Gaffney, K J; Techert, S; Odelius, M; Föhlisch, A

2015-04-02

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16 - 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution

NASA Astrophysics Data System (ADS)

Wernet, Ph.; Kunnus, K.; Josefsson, I.; Rajkovic, I.; Quevedo, W.; Beye, M.; Schreck, S.; Grübel, S.; Scholz, M.; Nordlund, D.; Zhang, W.; Hartsock, R. W.; Schlotter, W. F.; Turner, J. J.; Kennedy, B.; Hennies, F.; de Groot, F. M. F.; Gaffney, K. J.; Techert, S.; Odelius, M.; Föhlisch, A.

2015-04-01

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

Enhanced photo-stability and photocatalytic activity of Ag3PO4 via modification with BiPO4 and polypyrrole

NASA Astrophysics Data System (ADS)

Cai, Li; Jiang, Hui; Wang, Luxi

2017-10-01

Ag3PO4 photocatalysts modified with BiPO4 and polypyrrole (PPy) were successfully synthesized via a combination of co-precipitation hydrothermal technique and oxidative polymerization method. Their morphologies, structures and optical and electronic properties were characterized by means of scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM), Brunauer-Emmett-Teller (BET) surface areas, X-ray diffraction (XRD), fourier transform infrared spectra (FT-IR), X-ray photo-electron spectroscopy (XPS), UV-vis diffuse reflection spectra (UV-vis DRS), photocurrent technique and electrochemical impedance spectra (EIS). The typical triphenylmethane dye (malachite green) was chosen as a target organic contaminants to estimate the photocatalytic activities and photo-stabilities of Ag3PO4-BiPO4-PPy heterostructures under visible light irradiation. The results indicated that the existence of BiPO4 and PPy not only showed great influences on the photocatalytic activity, but also significantly enhanced photo-stability of Ag3PO4 in repeated and long-term applications. The degradation conversion of Ag3PO4-BiPO4-PPy heterostructures (ABP-3) was 1.58 times of that of pure Ag3PO4. The photo-corrosion phenomenon of Ag3PO4 was effectively avoided. The photocatalytic activity of up to 87% in the Ag3PO4-BiPO4-PPy heterostructures (ABP-3) can be remained after five repeated cycles, while only about 33% of the degradation efficiency can be reserved in pure Ag3PO4. The possible mechanism of enhanced photo-stability and photocatalytic activity of Ag3PO4-BiPO4-PPy heterostructures was also discussed in this work.

Reaction mechanisms for enhancing carbon dioxide mineral sequestration

NASA Astrophysics Data System (ADS)

Jarvis, Karalee Ann

Increasing global temperature resulting from the increased release of carbon dioxide into the atmosphere is one of the greatest problems facing society. Nevertheless, coal plants remain the largest source of electrical energy and carbon dioxide gas. For this reason, researchers are searching for methods to reduce carbon dioxide emissions into the atmosphere from the combustion of coal. Mineral sequestration of carbon dioxide reacted in electrolyte solutions at 185°C and 2200 psi with olivine (magnesium silicate) has been shown to produce environmentally benign carbonates. However, to make this method feasible for industrial applications, the reaction rate needs to be increased. Two methods were employed to increase the rate of mineral sequestration: reactant composition and concentration were altered independently in various runs. The products were analyzed with complete combustion for total carbon content. Crystalline phases in the product were analyzed with Debye-Scherrer X-ray powder diffraction. To understand the reaction mechanism, single crystals of San Carlos Olivine were reacted in two solutions: (0.64 M NaHCO3/1 M NaCl) and (5.5 M KHCO3) and analyzed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and fluctuation electron microscopy (FEM) to study the surface morphology, atomic crystalline structure, composition and amorphous structure. From solution chemistry studies, it was found that increasing the activity of the bicarbonate ion increased the conversion rate of carbon dioxide to magnesite. The fastest conversion, 60% conversion in one hour, occurred in a solution of 5.5 M KHCO3. The reaction product particles, magnesium carbonate, significantly increased in both number density and size on the coupon when the bicarbonate ion activity was increased. During some experiments reaction vessel corrosion also altered the mineral sequestration mechanism. Nickel ions from vessel corrosion led to nickel precipitation in the carbonate particles and the lack of an amorphous silica reaction layer on the olivine. It was concluded that nickel ions destabilized the silica passivation layer and led to faster growth of carbonate precipitates. Overall, nickel ions increased the reaction rate of mineral sequestration of carbon dioxide.

Passive Optical Locking Techniques for Diode Lasers

NASA Astrophysics Data System (ADS)

Zhang, Quan

1995-01-01

Most current diode-based nonlinear frequency converters utilize electronic frequency locking techniques. However, this type of locking technique typically involves very complex electronics, and suffers the 'power-drop' problem. This dissertation is devoted to the development of an all-optical passive locking technique that locks the diode laser frequency to the external cavity resonance stably without using any kind of electronic servo. The amplitude noise problem associated with the strong optical locking has been studied. Single-mode operation of a passively locked single-stripe diode with an amplitude stability better than 1% has been achieved. This passive optical locking technique applies to broad-area diodes as well as single-stripe diodes, and can be easily used to generate blue light. A schematic of a milliwatt level blue laser based on the single-stripe diode locking technique has been proposed. A 120 mW 467 nm blue laser has been built using the tapered amplifier locking technique. In addition to diode-based blue lasers, this passive locking technique has applications in nonlinear frequency conversions, resonant spectroscopy, particle counter devices, telecommunications, and medical devices.

Heuristic method of fabricating counter electrodes in dye-sensitized solar cells based on a PEDOT:PSS layer as a catalytic material

NASA Astrophysics Data System (ADS)

Edalati, Sh; Houshangi far, A.; Torabi, N.; Baneshi, Z.; Behjat, A.

2017-02-01

Poly(3,4-ethylendioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) was deposited on a fluoride-doped tin oxide glass substrate using a heuristic method to fabricate platinum-free counter electrodes for dye-sensitized solar cells (DSSCs). In this heuristic method a thin layer of PEDOT:PPS is obtained by spin coating the PEDOT:PSS on a Cu substrate and then removing the substrate with FeCl3. The characteristics of the deposited PEDOT:PSS were studied by energy dispersive x-ray analysis and scanning electron microscopy, which revealed the micro-electronic specifications of the cathode. The aforementioned DSSCs exhibited a solar conversion efficiency of 3.90%, which is far higher than that of DSSCs with pure PEDOT:PSS (1.89%). This enhancement is attributed not only to the micro-electronic specifications but also to the HNO3 treatment through our heuristic method. The results of cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and Tafel polarization plots show the modified cathode has a dual function, including excellent conductivity and electrocatalytic activity for iodine reduction.

Mesoporous CdS via Network of Self-Assembled Nanocrystals: Synthesis, Characterization and Enhanced Photoconducting Property.

PubMed

Patra, Astam K; Banerjee, Biplab; Bhaumik, Asim

2018-01-01

Semiconduction nanoparticles are intensively studied due to their huge potential in optoelctronic applications. Here we report an efficient chemical route for hydrothermal synthesis of aggregated mesoporous cadmium sulfide (CdS) nanoparticles using supramolecular-assembly of ionic and water soluble sodium salicylate as the capping agent. The nanostructure, mesophase, optical property and photoconductivity of these mesoporous CdS materials have been characterized by using small and wide angle powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2-sorption, Raman analysis, Fourier transformed infrared (FT-IR), UV-Visible DSR spectroscopy, and photoconductivity measurement. Wide angle XRD pattern and high resolution TEM image analysis suggested that the particle size of the materials is within 10 nm and the nanoparticles are in well-crystallized cubic phase. Mesoporous CdS nanoparticles showed drastically enhanced photoelectrochemical response under visible light irradiation on entrapping a photosensitizer (dye) molecule in the interparticle spaces. Efficient synthesis strategy and the enhanced photo response in the mesoporous CdS material could facilitate the designing of other porous semiconductor oxide/sulfide and their applications in photon-to-electron conversion processes.

Ultrafast hydrogen bond dynamics and partial electron transfer after photoexcitation of diethyl ester of 7-(diethylamino)-coumarin-3-phosphonic acid and its benzoxaphosphorin analog.

PubMed

Wagner, M S; Ilieva, E D; Petkov, P St; Nikolova, R D; Kienberger, R; Iglev, H

2015-04-21

The solvation dynamics after optical excitation of two phosphono-substituted coumarin derivatives dissolved in various solutions are studied by fluorescence up-conversion spectroscopy and quantum chemical simulations. The Kamlet-Taft analysis of the conventional absorption and emission spectra suggests weakening of the solvent-solute H-bonds upon optical excitation, which is in contrast to the results gained by the quantum simulations and earlier studies reported for coumarin derivatives without phosphono groups. The simulations give evidence that the solvent reorganisation around the excited fluorophore leads to partial electron transfer to the first solvation shell. The process occurs on a timescale between 1 and 10 ps depending on the solvent polarity and leads to a fast decay of the time-resolved emission signal. Using the ultrafast spectral shift of the time-dependent fluorescence we estimated the relaxation time of the H-bonds in the electronically excited state to be about 0.6 ps in water, 1.5 ps in ethanol and 2.8 ps in formamide.

Capacitive coupling in hybrid graphene/GaAs nanostructures

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

Simonet, Pauline, E-mail: psimonet@phys.ethz.ch; Rössler, Clemens; Krähenmann, Tobias

2015-07-13

Coupled hybrid nanostructures are demonstrated using the combination of lithographically patterned graphene on top of a two-dimensional electron gas (2DEG) buried in a GaAs/AlGaAs heterostructure. The graphene forms Schottky barriers at the surface of the heterostructure and therefore allows tuning the electronic density of the 2DEG. Conversely, the 2DEG potential can tune the graphene Fermi energy. Graphene-defined quantum point contacts in the 2DEG show half-plateaus of quantized conductance in finite bias spectroscopy and display the 0.7 anomaly for a large range of densities in the constriction, testifying to their good electronic properties. Finally, we demonstrate that the GaAs nanostructure canmore » detect charges in the vicinity of the heterostructure's surface. This confirms the strong coupling of the hybrid device: localized states in the graphene ribbon could, in principle, be probed by the underlying confined channel. The present hybrid graphene/GaAs nanostructures are promising for the investigation of strong interactions and coherent coupling between the two fundamentally different materials.« less

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations.

PubMed

Ferreira da Silva, F; Lange, E; Limão-Vieira, P; Jones, N C; Hoffmann, S V; Hubin-Franskin, M-J; Delwiche, J; Brunger, M J; Neves, R F C; Lopes, M C A; de Oliveira, E M; da Costa, R F; Varella, M T do N; Bettega, M H F; Blanco, F; García, G; Lima, M A P; Jones, D B

2015-10-14

The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations

NASA Astrophysics Data System (ADS)

Ferreira da Silva, F.; Lange, E.; Limão-Vieira, P.; Jones, N. C.; Hoffmann, S. V.; Hubin-Franskin, M.-J.; Delwiche, J.; Brunger, M. J.; Neves, R. F. C.; Lopes, M. C. A.; de Oliveira, E. M.; da Costa, R. F.; Varella, M. T. do N.; Bettega, M. H. F.; Blanco, F.; García, G.; Lima, M. A. P.; Jones, D. B.

2015-10-01

The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

Unraveling surface and bulk trap states in lead halide perovskite solar cells using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Han, Changfeng; Wang, Kai; Zhu, Xixiang; Yu, Haomiao; Sun, Xiaojuan; Yang, Qin; Hu, Bin

2018-03-01

Organic-inorganic hybrid perovskites (OIHPs) have been widely recognized as an excellent candidate for next-generation photovoltaic materials because of their highly efficient power conversion. Acquiring a complete understanding of trap states and dielectric properties in OIHP-based solar cells at the steady state is highly desirable in order to further explore and improve their optoelectronic functionalities and properties. We report CH3NH3PbI3-x Cl x -based planar solar cells with a power conversion efficiency (PCE) of 15.8%. The illumination intensity dependence of the current density-voltage (J-V) revealed the presence of trap-assisted recombination at low fluences. Non-destructive ac impedance spectroscopy (ac-IS) was applied to characterize the device at the steady state. The capacitance-voltage (C-V) spectra exhibited some distinct variations at a wide range of ac modulation frequencies with and without photo-excitations. Since the frequency-dependent chemical capacitance ({{C}μ }) is concerned with the surface and bulk related density of states (DOS) in CH3NH3PbI3-x Cl x , we verified this by fitting the corresponding DOS by a Gaussian distribution function. We ascertained that the electronic sub-gap trap states present in the solution processed CH3NH3PbI3-x Cl x and their distribution differs from the surface to the bulk. In fact, we demonstrated that both surfaces that were adjacent to the electron and hole transport layers featured analogous DOS. Despite this, photo- and bias-induced giant dielectric responses (i.e. both real and imaginary parts) were detected. A remarkable reduction of {{C}μ } at higher frequencies (i.e. more than 100 kHz) was ascribed to the effect of dielectric loss in CH3NH3PbI3-x Cl x .

Molecular symmetry determines the mechanism of a very efficient ultrafast excitation-to-heat conversion in Ni-substituted chlorophylls.

PubMed

Pilch, Mariusz; Dudkowiak, Alina; Jurzyk, Barbara; Lukasiewicz, Jędrzej; Susz, Anna; Stochel, Grażyna; Fiedor, Leszek

2013-01-01

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes. Copyright © 2012. Published by Elsevier B.V.

Characterization of III-V Semiconductors.

DTIC Science & Technology

1981-04-01

Conversion Photoluminescence InP Hall Effect Mass Spectroscopy Ion Implantation Photoconductivity Donor-Acceptor 20. ABSTRACT (Continue on reverse side If...Characteristiss .. 72 10.0 FAR INFRARED STUDIES IN GaAs. ....................... 76I11.0 SPARK-SOURCE MASS SPECTROSCOPY IN GaAs...concen- tration, as measured by spark-source mass spectroscopy (SSMS), and the Hall 7 mobility. However, we found that, unfortunately, commercially

Achieving copper sulfide leaf like nanostructure electrode for high performance supercapacitor and quantum-dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Durga, Ikkurthi Kanaka; Rao, S. Srinivasa; Reddy, Araveeti Eswar; Gopi, Chandu V. V. M.; Kim, Hee-Je

2018-03-01

Copper sulfide is an important multifunctional semiconductor that has attracted considerable attention owing to its outstanding properties and multiple applications, such as energy storage and electrochemical energy conversion. This paper describes a cost-effective and simple low-temperature solution approach to the preparation of copper sulfide for supercapacitors (SCs) and quantum-dot sensitized solar cells (QDSSCs). X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy confirmed that the nickel foam with a coriander leaf like nanostructure had been coated successfully with copper sulfide. As an electrode material for SCs, the CC-3 h showed excellent specific capacitance (5029.28 at 4 A g-1), energy density (169.73 W h kg-1), and superior cycling durability with 107% retention after 2000 cycles. Interestingly, the QDSSCs equipped with CC-2 h and CC-3 h counter electrodes (CEs) exhibited a maximum power conversion efficiency of 2.52% and 3.48%, respectively. The improved performance of the CC-3 h electrode was attributed mainly to the large surface area (which could contribute sufficient electroactive species), good conductivity, and high electrocatalytic activity. Overall, this work delivers novel insights into the use of copper sulfide and offers an important guidelines for the fabrication of next level energy storage and conversion devices.

Properties of 83mKr conversion electrons and their use in the KATRIN experiment

NASA Astrophysics Data System (ADS)

Vénos, D.; Sentkerestiová, J.; Dragoun, O.; Slezák, M.; Ryšavý, M.; Špalek, A.

2018-02-01

The gaseous 83mKr will be used as a source of monoenergetic conversion electrons for systematic studies and calibration of the energy scale in the KArlsruhe TRItium Neutrino experiment (KATRIN). Using all existing experimental data the adopted values of the electron binding energies for free krypton were established and the basic conversion electron properties in 83mKr decay were compiled. Modes of the measurements with gaseous 83mKr were suggested for KATRIN.

Formation of Semimetallic Cobalt Telluride Nanotube Film via Anion Exchange Tellurization Strategy in Aqueous Solution for Electrocatalytic Applications.

PubMed

Patil, Supriya A; Kim, Eun-Kyung; Shrestha, Nabeen K; Chang, Jinho; Lee, Joong Kee; Han, Sung-Hwan

2015-11-25

Metal telluride nanostructures have demonstrated several potential applications particularly in harvesting and storing green energy. Metal tellurides are synthesized by tellurization process performed basically at high temperature in reducing gas atmosphere, which makes the process expensive and complicated. The development of a facile and economical process for desirable metal telluride nanostructures without complicated manipulation is still a challenge. In an effort to develop an alternative strategy of tellurization, herein we report a thin film formation of self-standing cobalt telluride nanotubes on various conducting and nonconducting substrates using a simple binder-free synthetic strategy based on anion exchange transformation from a thin film of cobalt hydroxycarbonate nanostructures in aqueous solution at room temperature. The nanostructured films before and after ion exchange transformation reaction are characterized using field emission scanning electron microscope, energy dispersive X-ray analyzer, X-ray photoelectron spectroscopy, thin film X-ray diffraction technique, high resolution transmission electron microscope, and selected area electron diffraction analysis technique. After the ion exchange transformation of nanostructures, the film shows conversion from insulator to highly electrical conductive semimetallic characteristic. When used as a counter electrode in I3(-)/I(-) redox electrolyte based dye-sensitized solar cells, the telluride film exhibits an electrocatalytic reduction activity for I3(-) with a demonstration of solar-light to electrical power conversion efficiency of 8.10%, which is highly competitive to the efficiency of 8.20% exhibited by a benchmarked Pt-film counter electrode. On the other hand, the telluride film electrode also demonstrates electrocatalytic activity for oxygen evolution reaction from oxidation of water.

Early bacteriopheophytin reduction in charge separation in reaction centers of Rhodobacter sphaeroides.

PubMed

Zhu, Jingyi; van Stokkum, Ivo H M; Paparelli, Laura; Jones, Michael R; Groot, Marie Louise

2013-06-04

A question at the forefront of biophysical sciences is, to what extent do quantum effects and protein conformational changes play a role in processes such as biological sensing and energy conversion? At the heart of photosynthetic energy transduction lie processes involving ultrafast energy and electron transfers among a small number of tetrapyrrole pigments embedded in the interior of a protein. In the purple bacterial reaction center (RC), a highly efficient ultrafast charge separation takes place between a pair of bacteriochlorophylls: an accessory bacteriochlorophyll (B) and bacteriopheophytin (H). In this work, we applied ultrafast spectroscopy in the visible and near-infrared spectral region to Rhodobacter sphaeroides RCs to accurately track the timing of the electron on BA and HA via the appearance of the BA and HA anion bands. We observed an unexpectedly early rise of the HA⁻ band that challenges the accepted simple picture of stepwise electron transfer with 3 ps and 1 ps time constants. The implications for the mechanism of initial charge separation in bacterial RCs are discussed in terms of a possible adiabatic electron transfer step between BA and HA, and the effect of protein conformation on the electron transfer rate. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Fast Holes, Slow Electrons, and Medium Control of Polaron Size and Mobility in the DA Polymer F8BT

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

Bird, Matthew J.; Bakalis, Jin; Asaoka, Sadayuki

For this research, the nature of electron and hole polarons on poly(9,9-di-n-hexylfluorenyl-2,7-diyl) (pF) and a copolymer poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) has been studied by chemical doping, pulse radiolysis, charge modulation spectroscopy, quantum chemical calculations, and microwave conductivity. While pF exhibits very similar behavior in all respects for the electron and the hole, this paper explores the hypothesis that the donor acceptor (push–pull) nature of F8BT will tend to localize charges. Optical spectra and quantum chemical calculations point to an electron localized on the thiadiazole unit in polar liquids but becoming more delocalized as the solvent polarity decreases. Indeed, in the nonpolar solventmore » benzene, the electron mobility is only 2.7 times lower than that of the hole, which conversely is shown to be delocalized in all environments and has a similar mobility to polarons on the homopolymer polyfluorene. Lastly, advantageous modifications to the optoelectronic properties of conjugated polymers that come about by using alternating donor acceptor repeat units have thus been shown to not significantly hinder charge transport despite the corrugated energy landscape along the backbone.« less

Fast Holes, Slow Electrons, and Medium Control of Polaron Size and Mobility in the DA Polymer F8BT

DOE PAGES

Bird, Matthew J.; Bakalis, Jin; Asaoka, Sadayuki; ...

2017-06-28

For this research, the nature of electron and hole polarons on poly(9,9-di-n-hexylfluorenyl-2,7-diyl) (pF) and a copolymer poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT) has been studied by chemical doping, pulse radiolysis, charge modulation spectroscopy, quantum chemical calculations, and microwave conductivity. While pF exhibits very similar behavior in all respects for the electron and the hole, this paper explores the hypothesis that the donor acceptor (push–pull) nature of F8BT will tend to localize charges. Optical spectra and quantum chemical calculations point to an electron localized on the thiadiazole unit in polar liquids but becoming more delocalized as the solvent polarity decreases. Indeed, in the nonpolar solventmore » benzene, the electron mobility is only 2.7 times lower than that of the hole, which conversely is shown to be delocalized in all environments and has a similar mobility to polarons on the homopolymer polyfluorene. Lastly, advantageous modifications to the optoelectronic properties of conjugated polymers that come about by using alternating donor acceptor repeat units have thus been shown to not significantly hinder charge transport despite the corrugated energy landscape along the backbone.« less

Contribution of Jahn-Teller and charge transfer excitations to the photovoltaic effect of manganite/titanite heterojunctions

NASA Astrophysics Data System (ADS)

Ifland, Benedikt; Hoffmann, Joerg; Kressdorf, Birte; Roddatis, Vladimir; Seibt, Michael; Jooss, Christian

2017-06-01

The effect of correlation effects on photovoltaic energy conversion at manganite/titanite heterojunctions is investigated. As a model system we choose a heterostructure consisting of the small polaron absorber Pr0.66Ca0.34MnO3 (PCMO) epitaxially grown on single-crystalline Nb-doped SrTi0.998Nb0.002O3 (STNO) substrates. The high structural and chemical quality of the interfaces is proved by detailed characterization using high-resolution transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) studies. Spectrally resolved and temperature-dependent photovoltaic measurements show pronounced contributions of both the Jahn-Teller (JT) excitations and the charge transfer (CT) transitions to the photovoltaic effect at different photon energies. A linear temperature dependence of the open-circuit voltage for an excitation in the PCMO manganite is only observed below the charge-ordering temperature, indicating that the diffusion length of the photocarrier exceeds the size of the space charge region. The photovoltaic response is compared to that of a heterojunction of lightly doped Pr0.05Ca0.95MnO3 (CMO)/STNO, where the JT transition is absent. Here, significant contributions of the CT transition to the photovoltaic effect set in below the Neel temperature. We conclude that polaronic correlations and ordering effects are essentials for photovoltaic energy conversion in manganites.

Aqueous-Phase Hydrogenolysis of Glycerol over Re Promoted Ru Catalysts Encapuslated in Porous Silica Nanoparticles

PubMed Central

Li, Kuo-Tseng; Yen, Ruey-Hsiang

2018-01-01

Activity improvement of Ru-based catalysts is needed for efficient production of valuable chemicals from glycerol hydrogenolysis. In this work, a series of Re promoted Ru catalysts encapuslated in porous silica nanoparticles (denoted as Re-Ru@SiO2) were prepared by coating silica onto the surface of chemically reduced Ru-polyvinylpyrrolidone colloids, and were used to catalyze the conversion of glycerol to diols and alcohols in water. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) were used to characterize these nanoparticles. Effects of Ru/Si atomic ratio, Re addition, glycerol and catalyst concentrations, reaction time, temperature, and hydrogen pressure were investigated. Re addition retarded the reduction of ruthenium oxide, but increased the catalyst reactivity for glycerol hydrogenolysis. Due to its greater Ru content, Re-Ru@ SiO2 showed much better activity (reacted at much lower temperature) and more yields of 1,2-propanediol and overall liquid-phase products than Re-Ru/SiO2 (prepared by conventional impregnation method) reported before. The rate of glycerol disappearance exhibited first-order dependence on glycerol concentration and hydrogen pressure, with an activation energy of 107.8 kJ/mol. The rate constant increased linearly with increasing Ru/Si atomic ratio and catalyst amount. The yield of overall liquid-phase products correlated well with glycerol conversion. PMID:29522432

Nickel-based xerogel catalysts: Synthesis via fast sol-gel method and application in catalytic hydrogenation of p-nitrophenol to p-aminophenol

NASA Astrophysics Data System (ADS)

Feng, Jin; Wang, Qiang; Fan, Dongliang; Ma, Lirong; Jiang, Deli; Xie, Jimin; Zhu, Jianjun

2016-09-01

In order to investigate the roles of three-dimensional network structure and calcium on Ni catalysts, the Ni, Ni-Al2O3, Ni-Ca-Al2O3 xerogel catalysts were successfully synthesized via the fast sol-gel process and chemical reduction method. The crystal structure of three different catalysts was observed with X-ray powder diffraction (XRD). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption-desorption were employed to investigate the role of network structure of xerogel catalysts and the size distribution of Ni nanoparticles. The catalyst composition was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) measurement and energy-dispersive X-ray spectroscopy (EDS). Temperature-programmed reduction (TPR) experiments were carried out to investigate the reducibility of nickel species and the interaction between nickel species and alumina. The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over the prepared nickel-based xerogel catalysts. The conversion of p-nitrophenol was monitored by UV spectrophotometry and high performance liquid chromatography (HPLC). The results show that the catalysts are highly selective for the conversion of p-nitrophenol to p-aminophenol and the order of catalytic activities of the catalysts is Ni < Ni-Al2O3 < Ni-Ca-Al2O3. The catalysts were recycled and were used to evaluate the reutilization.

Plasmolysis for efficient CO2 -to-fuel conversion

NASA Astrophysics Data System (ADS)

van Rooij, Gerard

2015-09-01

The strong non-equilibrium conditions provided by the plasma phase offer the opportunity to beat traditional thermal process energy efficiencies via preferential excitation of molecular vibrational modes. It is therefore a promising option for creating artificial solar fuels from CO2as raw material using (intermittently available) sustainable energy surpluses, which can easily be deployed within the present infrastructure for conventional fossil fuels. In this presentation, a common microwave reactor approach is evaluated experimentally with Rayleigh scattering and Fourier transform infrared spectroscopy to assess gas temperatures and conversion degrees, respectively. The results are interpreted on basis of estimates of the plasma dynamics obtained with electron energy distribution functions calculated with a Boltzmann solver. It indicates that the intrinsic electron energies are higher than is favourable for preferential vibrational excitation due to dissociative excitation, which causes thermodynamic equilibrium chemistry still to dominate the initial experiments. Novel reactor approaches are proposed to tailor the plasma dynamics to achieve the non-equilibrium in which vibrational excitation is dominant. In collaboration with Dirk van den Bekerom, Niek den Harder, Teofil Minea, Dutch Institute For Fundamental Energy Research, Eindhoven, Netherlands; Gield Berden, Institute for Molecules and Materials, FELIX facility, Radboud University, Nijmegen, Netherlands; Richard Engeln, Applied Physics, Plasma en Materials Processing, Eindhoven University of Technology; and Waldo Bongers, Martijn Graswinckel, Erwin Zoethout, Richard van de Sanden, Dutch Institute For Fundamental Energy Research, Eindhoven, Netherlands.

Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis

DTIC Science & Technology

2016-07-08

AFRL-AFOSR-VA-TR-2016-0244 Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis Jahan Dawlaty UNIVERSITY OF SOUTHERN...TITLE AND SUBTITLE Ultrafast Spectroscopy of Proton-Coupled Electron Transfer (PCET) in Photocatalysis 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550...298 Back (Rev. 8/98) DISTRIBUTION A: Distribution approved for public release. Final Report: AFOSR YIP Grant FA9550-13-1-0128: Ultrafast Spectroscopy

Study of clusters using negative ion photodetachment spectroscopy

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

Zhao, Yuexing

1995-12-01

The weak van der Waals interaction between an open-shell halogen atom and a closed-shell atom or molecule has been investigated using zero electron kinetic energy (ZEKE) spectroscopy. This technique is also applied to study the low-lying electronic states in GaAs and GaAs -. In addition, the spectroscopy and electron detachment dynamics of several small carbon cluster anions are studied using resonant multiphoton detachment spectroscopy.

Subcritical hydrothermal liquefaction of cattle manure to bio-oil: Effects of conversion parameters on bio-oil yield and characterization of bio-oil.

PubMed

Yin, Sudong; Dolan, Ryan; Harris, Matt; Tan, Zhongchao

2010-05-01

In this study, cattle manure was converted to bio-oil by subcritical hydrothermal liquefaction in the presence of NaOH. The effects of conversion temperature, process gas, initial conversion pressure, residence time and mass ratio of cattle manure to water on the bio-oil yield were studied. The bio-oil was characterized in terms of elemental composition, higher heating value, ultraviolet-visible (UV/Vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR), gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Results showed that the bio-oil yield depended on the conversion temperature and the process gas. Higher initial conversion pressure, longer residence time and larger mass ratio of cattle manure to water, however, had negative impacts on the bio-oil yield. The higher heating value of bio-oil was 35.53MJ/kg on average. The major non-polar components of bio-oil were toluene, ethyl benzene and xylene, which are components of crude oil, gasoline and diesel. Copyright 2010 Elsevier Ltd. All rights reserved.

A study on the anisole-water complex by molecular beam-electronic spectroscopy and molecular mechanics calculations.

PubMed

Becucci, M; Pietraperzia, G; Pasquini, M; Piani, G; Zoppi, A; Chelli, R; Castellucci, E; Demtroeder, W

2004-03-22

An experimental and theoretical study is made on the anisole-water complex. It is the first van der Waals complex studied by high resolution electronic spectroscopy in which the water is seen acting as an acid. Vibronically and rotationally resolved electronic spectroscopy experiments and molecular mechanics calculations are used to elucidate the structure of the complex in the ground and first electronic excited state. Some internal dynamics in the system is revealed by high resolution spectroscopy. (c) 2004 American Institute of Physics

Handling Density Conversion in TPS.

PubMed

Isobe, Tomonori; Mori, Yutaro; Takei, Hideyuki; Sato, Eisuke; Tadano, Kiichi; Kobayashi, Daisuke; Tomita, Tetsuya; Sakae, Takeji

2016-01-01

Conversion from CT value to density is essential to a radiation treatment planning system. Generally CT value is converted to the electron density in photon therapy. In the energy range of therapeutic photon, interactions between photons and materials are dominated with Compton scattering which the cross-section depends on the electron density. The dose distribution is obtained by calculating TERMA and kernel using electron density where TERMA is the energy transferred from primary photons and kernel is a volume considering spread electrons. Recently, a new method was introduced which uses the physical density. This method is expected to be faster and more accurate than that using the electron density. As for particle therapy, dose can be calculated with CT-to-stopping power conversion since the stopping power depends on the electron density. CT-to-stopping power conversion table is also called as CT-to-water-equivalent range and is an essential concept for the particle therapy.

Compact x-ray source and panel

DOEpatents

Sampayon, Stephen E [Manteca, CA

2008-02-12

A compact, self-contained x-ray source, and a compact x-ray source panel having a plurality of such x-ray sources arranged in a preferably broad-area pixelized array. Each x-ray source includes an electron source for producing an electron beam, an x-ray conversion target, and a multilayer insulator separating the electron source and the x-ray conversion target from each other. The multi-layer insulator preferably has a cylindrical configuration with a plurality of alternating insulator and conductor layers surrounding an acceleration channel leading from the electron source to the x-ray conversion target. A power source is connected to each x-ray source of the array to produce an accelerating gradient between the electron source and x-ray conversion target in any one or more of the x-ray sources independent of other x-ray sources in the array, so as to accelerate an electron beam towards the x-ray conversion target. The multilayer insulator enables relatively short separation distances between the electron source and the x-ray conversion target so that a thin panel is possible for compactness. This is due to the ability of the plurality of alternating insulator and conductor layers of the multilayer insulators to resist surface flashover when sufficiently high acceleration energies necessary for x-ray generation are supplied by the power source to the x-ray sources.

Single-molecule interfacial electron transfer dynamics in solar energy conversion

NASA Astrophysics Data System (ADS)

Dhital, Bharat

This dissertation work investigated the parameters affecting the interfacial electron transfer (ET) dynamics in dye-semiconductor nanoparticles (NPs) system by using single-molecule fluorescence spectroscopy and imaging combined with electrochemistry. The influence of the molecule-substrate electronic coupling, the molecular structure, binding geometry on the surface and the molecule-attachment surface chemistry on interfacial charge transfer processes was studied on zinc porphyrin-TiO2 NP systems. The fluorescence blinking measurement on TiO2 NP demonstrated that electronic coupling regulates dynamics of charge transfer processes at the interface depending on the conformation of molecule on the surface. Moreover, semiconductor surface charge induced electronic coupling of molecule which is electrostatically adsorbed on the semiconductor surface also predominantly alters the ET dynamics. Furthermore, interfacial electric field and electron accepting state density dependent ET dynamics has been dissected in zinc porphyrin-TiO2 NP system by observing the single-molecule fluorescence blinking dynamics and fluorescence lifetime with and without applied bias. The significant difference in fluorescence fluctuation and lifetime suggested the modulation of charge transfer dynamics at the interface with external electric field perturbation. Quasi-continuous distribution of fluorescence intensity with applied negative potential was attributed to the faster charge recombination due to reduced density of electron accepting states. The driving force and electron accepting state density ET dependent dynamics has also been probed in zinc porphyrin-TiO2 NP and zinc porphyrin-indium tin oxide (ITO) systems. Study of a molecule adsorbed on two different semiconductors (ITO and TiO2), with large difference in electron densities and distinct driving forces, allows us to observe the changes in rates of back electron transfer process reflected by the suppressed fluorescence blinking of molecule on ITO surface. Finally, the electric field effect on the interface properties has been probed by using surface-enhanced Raman spectroscopy and supported by density functional theory calculations in alizarin-TiO2 system. The perturbation, created by the external potential, has been observed to cause a shift and/or splitting interfacial bond vibrational mode, typical indicator of the coupling energy changes between alizarin and TiO2. Such splitting provides evidence for electric field-dependent electronic coupling changes that have a significant impact on the interfacial electron transfer dynamics.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

NASA Astrophysics Data System (ADS)

Ilisca, Ernest; Ghiglieno, Filippo

2016-09-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main `symmetry-breaking' interactions are brought together. In a typical channel, the electron spin-orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule-solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted `electronic' conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted `nuclear', the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and `continui' of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule-solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures.

Evaluation of biochars by temperature programmed oxidation/mass spectroscopy

USDA-ARS?s Scientific Manuscript database

Biochar from the thermochemical conversion of biomass was evaluated by Temperature Programmed Oxidation (TPO) coupled with mass spectroscopy. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. ...

Polyurethane acrylate networks including cellulose nanocrystals: a comparison between UV and EB- curing

NASA Astrophysics Data System (ADS)

Furtak-Wrona, K.; Kozik-Ostrówka, P.; Jadwiszczak, K.; Maigret, J. E.; Aguié-Béghin, V.; Coqueret, X.

2018-01-01

A water-based polyurethane (PUR) acrylate water emulsion was selected as a radiation curable matrix for preparing nanocomposites including cellulose nanocrystals (CNC) prepared by controlled hydrolysis of Ramie fibers. Cross-linking polymerization of samples prepared in the form of films or of 1 mm-thick bars was either initiated by exposure to the 395 nm light of a high intensity LED lamp or by treatment with low energy electron beam (EB). The conversion level of acrylate functions in samples submitted to increasing radiation doses was monitored by Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) were used to characterize changes in the glass transition temperature of the PUR-CNC nanocomposites as a function of acrylate conversion and of CNC content. Micromechanical testing indicates the positive effect of 1 wt% CNC on Young's modulus and on the tensile strength at break (σ) of cured nanocomposites. The presence of CNC in the PUR acrylate matrix was shown to double the σ value of the nanocomposite cured to an acrylate conversion level of 85% by treatment with a 25 kGy dose under EB, whereas no increase of σ was observed in UV-cured samples exhibiting the same acrylate conversion level. The occurrence of grafting reactions inducing covalent linkages between the polysaccharide nanofiller and the PUR acrylate matrix during the EB treatment is advanced as an explanation to account for the improvement observed in samples cured under ionizing radiation.

Physicochemical and bioactive properties of innovative resin-based materials containing functional halloysite-nanotubes fillers.

PubMed

Degrazia, Felipe Weidenbach; Leitune, Vicente Castelo Branco; Takimi, Antonio Shigueaki; Collares, Fabrício Mezzomo; Sauro, Salvatore

2016-09-01

This study aimed to assess the degree of conversion, microhardness, solvent degradation, contact angle, surface free energy and bioactivity (e.g., mineral precipitation) of experimental resin-based materials containing, pure or triclosan-encapsulated, aluminosilicate-(halloysite) nanotubes. An experimental resin blend was prepared using bis-GMA/TEGDMA, 75/25wt% (control). Halloysite nanotubes (HNT) doped with or without triclosan (TCN) were first analyzed using transmission electron microscopy (TEM). HNT or HNT/TCN fillers were incorporated into the resin blend at different concentrations (5, 10, and 20wt%). Seven experimental resins were created and the degree of conversion, microhardness, solvent degradation and contact angle were assessed. Bioactive mineral precipitation induced by the experimental resins was evaluated through Raman spectroscopy and SEM-EDX. TEM showed a clear presence of TCN particles inside the tubular lumen and along the outer surfaces of the halloysite nanotubes. The degree of conversion, surface free energy, microhardness, and mineral deposition of polymers increased with higher amount of HNTs. Conversely, the higher the amount (20wt%) of TCN-loaded HNTs the lower the microhardness of the experimental resins. The incorporation of pure or TCN-loaded aluminosilicate-(halloysite) nanotubes into resin-based materials increase the bioactivity of such experimental restorative materials and promotes mineral deposition. Therefore, innovative resin-based materials containing functional halloysite-nanotube fillers may represent a valuable alternative for therapeutic minimally invasive treatments. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

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

Wu, Guorong; State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023; Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026

The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths hasmore » previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.« less

"Spider"-shaped porphyrins with conjugated pyridyl anchoring groups as efficient sensitizers for dye-sensitized solar cells.

PubMed

Stangel, Christina; Bagaki, Anthi; Angaridis, Panagiotis A; Charalambidis, Georgios; Sharma, Ganesh D; Coutsolelos, Athanasios G

2014-11-17

Two novel "spider-shaped" porphyrins, meso-tetraaryl-substituted 1PV-Por and zinc-metalated 1PV-Zn-Por, bearing four oligo(p-phenylenevinylene) (oPPV) pyridyl groups with long dodecyloxy chains on the phenyl groups, have been synthesized. The presence of four pyridyl groups in both porphyrins, which allow them to act as anchoring groups upon coordination to various Lewis acid sites, the conjugated oPPV bridges, which offer the possibility of electronic communication between the porphyrin core and the pyridyl groups, and the dodecyloxy groups, which offer the advantage of high solubility in a variety of organic solvents of different polarities and could prevent porphyrin aggregation, renders porphyrins 1PV-Por and 1PV-Zn-Por very promising sensitizers for dye-sensitized solar cells (DSSCs). Photophysical measurements, together with electrochemistry experiments and density functional theory calculations, suggest that both porphyrins have frontier molecular orbital energy levels that favor electron injection and dye regeneration in DSSCs. Solar cells sensitized by 1PV-Por and 1PV-Zn-Por were fabricated, and it was found that they show power conversion efficiencies (PCEs) of 3.28 and 5.12%, respectively. Photovoltaic measurements (J-V curves) together with incident photon-to-electron conversion efficiency spectra of the two cells reveal that the higher PCE value of the DSSC based on 1PV-Zn-Por is ascribed to higher short-circuit current (Jsc), open-circuit voltage (Voc), and dye loading values. Emission spectra and electrochemistry experiments suggest a greater driving force for injection of the photogenerated electrons into the TiO2 conduction band for 1PV-Zn-Por rather than its free-base analogue. Furthermore, electrochemical impedance spectroscopy measurements prove that the utilization of 1PV-Zn-Por as a sensitizer offers a high charge recombination resistance and, therefore, leads to a longer electron lifetime.

Study by AES, EELS Spectroscopy of electron Irradiation on InP and InPO4/InP in comparison with Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Lounis, Z.; Bouslama, M.; Hamaida, K.; Jardin, C.; Abdellaoui, A.; Ouerdane, A.; Ghaffour, M.; Berrouachedi, N.

2012-02-01

We give the great interest to characterise the InP and InPO4/InP submitted to electron beam irradiation owing to the Auger Electron Spectroscopy (AES) associated to both methods Electron Energy Loss Spectroscopy (EELS). The incident electron produces breaking of (In-P) chemical bonds. The electron beam even acts to stimulate oxidation of InP surface involving on the top layers. Other, the oxide InPO4 developed on InP does appear very sensitive to the irradiation due to electron beam shown by the monitoring of EELS spectra recorded versus the irradiated times of the surface. There appears a new oxide thought to be In2O3. We give the simulation methods Casino (Carlo simulation of electron trajectory in solids) for determination with accuracy the loss energy of backscattered electrons and compared with reports results have been obtained with EELS Spectroscopy. These techniques of spectroscopy alone do not be able to verify the affected depth during interaction process. So, using this simulation method, we determine the interaction of electrons in the matter.

Time-resolved vibrational spectroscopy

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

Tokmakoff, Andrei; Champion, Paul; Heilweil, Edwin J.

2009-05-14

This document contains the Proceedings from the 14th International Conference on Time-Resolved Vibrational Spectroscopy, which was held in Meredith, NH from May 9-14, 2009. The study of molecular dynamics in chemical reaction and biological processes using time-resolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE's Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation ofmore » reactive intermediates in radiation chemistry. In addition, time-resolved spectroscopy is central to all fiveof DOE's grand challenges for fundamental energy science. The Time-Resolved Vibrational Spectroscopy conference is organized biennially to bring the leaders in this field from around the globe together with young scientists to discuss the most recent scientific and technological advances. The latest technology in ultrafast infrared, Raman, and terahertz spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.« less

Physico-Chemical Condition Optimization during Biosynthesis lead to development of Improved and Catalytically Efficient Gold Nano Particles

PubMed Central

Kumari, Madhuree; Mishra, Aradhana; Pandey, Shipra; Singh, Satyendra Pratap; Chaudhry, Vasvi; Mudiam, Mohana Krishna Reddy; Shukla, Shatrunajay; Kakkar, Poonam; Nautiyal, Chandra Shekhar

2016-01-01

Biosynthesis of nanoparticles has gained great attention in making the process cost-effective and eco-friendly, but there are limited reports which describe the interdependency of physical parameters for tailoring the dimension and geometry of nanoparticles during biological synthesis. In the present study, gold nanoparticles (GNPs) of various shapes and sizes were obtained by modulating different physical parameters using Trichoderma viride filtrate. The particles were characterized on the basis of visual observation, dynamic light scattering, UV-visible spectroscopy, transmission electron microscopy, fourier transform infrared spectroscopy, and X ray diffraction. While the size varied from 2–500 nm, the shapes obtained were nanospheres, nanotriangles, nanopentagons, nanohexagons, and nanosheets. Changing the parameters such as pH, temperature, time, substrate, and culture filtrate concentration influenced the size and geometry of nanoparticles. Catalytic activity of the biosynthesized GNP was evaluated by UV-visible spectroscopy and confirmed by gas chromatography-mass spectrometric analysis for the conversion of 4-nitrophenol into 4-aminophenol which was strongly influenced by their structure and dimension. Common practices for biodegradation are traditional, expensive, require large amount of raw material, and time taking. Controlling shapes and sizes of nanoparticles could revolutionize the process of biodegradation that can remove all the hurdles in current scenario. PMID:27273371

Developing the photovoltaic performance of dye-sensitized solar cells (DSSCs) using a SnO2-doped graphene oxide hybrid nanocomposite as a photo-anode

NASA Astrophysics Data System (ADS)

Sasikumar, Ragu; Chen, Tse-Wei; Chen, Shen-Ming; Rwei, Syang-Peng; Ramaraj, Sayee Kannan

2018-05-01

Tin(IV) oxide nanoparticles (SnO2 NPs) doped on the surface of graphene oxide (GO) sheets for application in Dye-Sensitized Solar Cells (DSSCs). The effective incorporation of SnO2 on the surface of GO sheets were confirmed by powder X-ray diffraction (PXRD), Fourier transform infra-red spectroscopy (FT-IR), thermogravimetric analysis (TGA), electrochemical impedance spectroscopy (EIS), and Raman spectroscopy. The morphology of the GO/SnO2 hybrid nanocomposite was confirmed by field emission scanning electron microscopy (FE-SEM) analysis. This current study involvement with the effect of different photo-anodes such as GO, SnO2, and GO/SnO2 hybrid nanocomposite on the power conversion efficiency (PCE) of the triiodide electrolyte based DSSCs. Remarkably, GO/SnO2 hybrid nanocomposite based photo-anode for DSSC observed PCE of 8.3% and it is about 12% higher than that of un-doped TiO2 photo-anode. The equivalent short-circuit photocurrent density (Jsc) of 16.67 mA cm-2, open circuit voltage (Voc) of 0.77 V, and fill factor (FF) of 0.65 respectively. The achieved results propose that the hybrid nanocomposite is an appropriate photo-anodic material for DSSCs applications.

Symmetrical N-acylsubstituted dihydrazones containing bithiophene core - Photophysical, electrochemical and thermal characterization

NASA Astrophysics Data System (ADS)

Jarczyk-Jedryka, Anna; Filapek, Michal; Malecki, Grzegorz; Kula, Slawomir; Janeczek, Henryk; Boharewicz, Bartosz; Iwan, Agnieszka; Schab-Balcerzak, Ewa

2016-04-01

Four symmetrical N-acylsubstituted dihydrazones containing bithiophene core were synthesized from condensation of 2,2‧-bithiophene-5,5‧-dicarboxyaldehyde with benzoic, isonicotinoyl, 2-thiophenic and 2-furoic hydrazide. The obtained compounds were characterized through the data from 1H nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), elemental analysis, UV-vis absorption spectroscopy, photoluminescence (PL), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements. Additionally, the electronic properties including orbital energies and resulting energy gaps were calculated by density functional theory (DFT). Their thermal behavior was investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). They were thermal sable up to 320 °C. The prepared N-acylsubstituted dihydrazones emitted light with λem in the range of 499-530 nm in solution, whereas, in solid state as blend with PMMA blue emission was observed. They undergo quasi-reversible and irreversible electrochemical reduction and oxidation processes, respectively. Additionally, the selected compounds were tested preliminary as component of active layer in organic photovoltaic cells. The highest value of power conversion efficiency, equal to 1.68% under simulated 100 mW/cm2 AM 1.5G irradiation was found for device with the architecture ITO/PEDOT:PSS/P3HT:PCBM:FBTH (1:2:2)/Al.

Investigation of electronic and local structural changes during lithium uptake and release of nano-crystalline NiFe2O4 by X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Zhou, Dong; Permien, Stefan; Rana, Jatinkumar; Krengel, Markus; Sun, Fu; Schumacher, Gerhard; Bensch, Wolfgang; Banhart, John

2017-02-01

Nano-crystalline NiFe2O4 particles were synthesized and used as active electrode material for a lithium ion battery that showed a high discharge capacity of 1534 mAh g-1 and charge capacity of 1170 mAh g-1 during the 1st cycle. X-ray absorption spectroscopy including XANES and EXAFS were used to investigate electronic and local structural changes of NiFe2O4 during the 1st lithiation and de-lithiation process. As lithium is inserted into the structure, tetrahedral site Fe3+ ions are reduced to Fe2+ and moved from tetrahedral sites to empty octahedral sites, while Ni2+ ions are unaffected. As a consequence, the matrix spinel structure collapses and transforms to an intermediate rock-salt monoxide phase. Meanwhile, the inserted Li is partially consumed by the formation of SEI and other side reactions during the conversion reaction. With further lithiation, the monoxide phase is reduced to highly disordered metallic Fe/Ni nanoparticles with a number of nearest neighbors of 6.0(8) and 8.1(4) for Fe and Ni, respectively. During subsequent de-lithiation, the metal particles are individually re-oxidized to Fe2O3 and NiO phases instead to the original NiFe2O4 spinel phase.

A novel fast-neutron detector concept for energy-selective imaging and imaging spectroscopy.

PubMed

Cortesi, M; Dangendorf, V; Zboray, R; Prasser, H-M

2014-07-01

We present and discuss the operational principle of a new fast-neutron detector concept suitable for either energy-selective imaging or for imaging spectroscopy. The detector is comprised of a series of energy-selective stacks of converter foils immersed in a noble-gas based mixture, coupled to a position-sensitive charge readout. Each foil in the various stacks is made of two layers of different thicknesses, fastened together: a hydrogen-rich (plastic) layer for neutron-to-proton conversion, and a hydrogen-free coating to selectively stop/absorb the recoil protons below a certain energy cut-off. The neutron-induced recoil protons, that escape the converter foils, release ionization electrons in the gas gaps between consecutive foils. The electrons are then drifted towards and localized by a position-sensitive charge amplification and readout stage. Comparison of the images detected by stacks with different energy cut-offs allows energy-selective imaging. Neutron energy spectrometry is realized by analyzing the responses of a sufficient large number of stacks of different energy response and unfolding techniques. In this paper, we present the results of computer simulation studies and discuss the expected performance of the new detector concept. Potential applications in various fields are also briefly discussed, in particularly, the application of energy-selective fast-neutron imaging for nuclear safeguards application, with the aim of determining the plutonium content in Mixed Oxide (MOX) fuels.

Iron-containing pigment from an archaeological rupestrian painting of the Planalto Tradition in Minas Gerais, Brazil

NASA Astrophysics Data System (ADS)

Floresta, D. L.; Fagundes, M.; Fabris, J. D.; Ardisson, J. D.

2015-06-01

Archaeological rupestrian arts of the Planalto Tradition are of relatively widespread occurrence all over the land area of the state of Minas Gerais (MG), Brazil. They are typically composed by monochromic zoomorphic figures, especially of cervids, mainly in red or orange color. A fragment of a rock wall containing an archaeological painting was collected at the Itanguá site, in the municipality of Senador Modestino Gonçalves (geographical coordinates, 17° 56' 51″ S 43° 13' 22″ W), MG. The rock piece was covered with an archaeological painting with pigments of two different hues of red. The X-ray fluorescence (XRF) analysis revealed only a slight difference in Fe and P content for the two different color zones. The pigment materials on this small fragment of rock were analyzed by X-ray diffraction on the conventional incidence mode (XRD) and on grazing incidence X-ray mode (GIXRD), scanning electron microscopy with energy dispersive x-ray detector (SEM/EDS) and conversion electron Mössbauer spectroscopy (CEMS) at room temperature. Results indicated the occurrence of mainly hematite but also of diopside in the pigment. CEMS at RT reveal the presence of hematite and (super)paramagnetic ferric components. In order to confirm these results a small amount of powder from the painting pigments was also analyzed by transmission Mössbauer spectroscopy at 20 K.

Oxidation characteristics of gasoline direct-injection (GDI) engine soot: Catalytic effects of ash and modified kinetic correlation

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

Choi, Seungmok; Seong, Heeje

In this paper, experimental analyses are conducted into the GDI soot oxidation characteristics as dependent on engine operating conditions. Soot is sampled at various engine operating conditions of a commercial 2.4 L GDI engine with a naturally aspirated, homogeneous, and stoichiometric operation strategy. The oxidation reactivity, ash composition, and carbon nanostructure of the GDI soot samples are analyzed using thermogravimetric analysis (TGA), scanning electron microscope–energy-dispersive spectroscopy (SEM-EDS), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. Based on the analyses, a global GDI soot oxidation mechanism is proposed which includes the effects of soluble organic fractions (SOF)/weakly bonded carbon (WBC), andmore » three types of ash on GDI soot oxidation. The results show that GDI soot contains an order of magnitude higher ash fraction than does conventional diesel soot, and oxidation reactivity is significantly enhanced by the catalytic effects of ash, as a function of ash content in soot. A modified empirical kinetic correlation for GDI soot oxidation is suggested on the basis of the results, and the modified kinetic correlation predicts the GDI soot oxidation rate accurately for various engine operation points at wide ranges of soot conversion and temperature without modifying kinetic parameters. The kinetic parameters are determined from isothermal and non-isothermal thremogravimetric analysis (TGA) soot oxidation tests; the methods are elucidated in detail.« less

Oxidation characteristics of gasoline direct-injection (GDI) engine soot: Catalytic effects of ash and modified kinetic correlation

DOE PAGES

Choi, Seungmok; Seong, Heeje

2015-03-02

In this paper, experimental analyses are conducted into the GDI soot oxidation characteristics as dependent on engine operating conditions. Soot is sampled at various engine operating conditions of a commercial 2.4 L GDI engine with a naturally aspirated, homogeneous, and stoichiometric operation strategy. The oxidation reactivity, ash composition, and carbon nanostructure of the GDI soot samples are analyzed using thermogravimetric analysis (TGA), scanning electron microscope–energy-dispersive spectroscopy (SEM-EDS), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. Based on the analyses, a global GDI soot oxidation mechanism is proposed which includes the effects of soluble organic fractions (SOF)/weakly bonded carbon (WBC), andmore » three types of ash on GDI soot oxidation. The results show that GDI soot contains an order of magnitude higher ash fraction than does conventional diesel soot, and oxidation reactivity is significantly enhanced by the catalytic effects of ash, as a function of ash content in soot. A modified empirical kinetic correlation for GDI soot oxidation is suggested on the basis of the results, and the modified kinetic correlation predicts the GDI soot oxidation rate accurately for various engine operation points at wide ranges of soot conversion and temperature without modifying kinetic parameters. The kinetic parameters are determined from isothermal and non-isothermal thremogravimetric analysis (TGA) soot oxidation tests; the methods are elucidated in detail.« less

Carrier transport dynamics in Mn-doped CdSe quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Poudyal, Uma; Maloney, Francis S.; Sapkota, Keshab; Wang, Wenyong

2017-10-01

In this work quantum dot sensitized solar cells (QDSSCs) were fabricated with CdSe and Mn-doped CdSe quantum dots (QDs) using the SILAR method. QDSSCs based on Mn-doped CdSe QDs exhibited improved incident photon-to-electron conversion efficiency. Carrier transport dynamics in the QDSSCs were studied using the intensity modulated photocurrent/photovoltage spectroscopy technique, from which transport and recombination time constants could be derived. Compared to CdSe QDSSCs, Mn-CdSe QDSSCs exhibited shorter transport time constant, longer recombination time constant, longer diffusion length, and higher charge collection efficiency. These observations suggested that Mn doping in CdSe QDs could benefit the performance of solar cells based on such nanostructures.

Controlled defects in semiconducting carbon nanotubes promote efficient generation and luminescence of trions.

PubMed

Brozena, Alexandra H; Leeds, Jarrett D; Zhang, Yin; Fourkas, John T; Wang, YuHuang

2014-05-27

We demonstrate efficient creation of defect-bound trions through chemical doping of controlled sp(3) defect sites in semiconducting, single-walled carbon nanotubes. These tricarrier quasi-particles luminesce almost as brightly as their parent excitons, indicating a remarkably efficient conversion of excitons into trions. Substantial populations of trions can be generated at low excitation intensities, even months after a sample has been prepared. Photoluminescence spectroscopy reveals a trion binding energy as high as 262 meV, which is substantially larger than any previously reported values. This discovery may have important ramifications not only for studying the basic physics of trions but also for the application of these species in fields such as photonics, electronics, and bioimaging.

Quantitative investigation into the influence of temperature on carbide and austenite evolution during partitioning of a quenched and partitioned steel

DOE PAGES

Pierce, Dean T.; Coughlin, D. R.; Williamson, Don L.; ...

2016-05-03

Here, the influence of partitioning temperature on microstructural evolution during quenching and partitioning was investigated in a 0.38C-1.54Mn-1.48Si wt.% steel using Mössbauer spectroscopy and transmission electron microscopy. η-carbide formation occurs in the martensite during the quenching, holding, and partitioning steps. More effective carbon partitioning from martensite to austenite was observed at 450 than 400°C, resulting in lower martensite carbon contents, less carbide formation, and greater retained austenite amounts for short partitioning times. Conversely, greater austenite decomposition occurs at 450°C for longer partitioning times. Lastly, cementite forms during austenite decomposition and in the martensite for longer partitioning times at 450°C.

Nanoparticle conversion to biofilms: in vitro demonstration using serum-derived mineralo-organic nanoparticles.

PubMed

Wong, Tsui-Yin; Peng, Hsin-Hsin; Wu, Cheng-Yeu; Martel, Jan; Ojcius, David M; Hsu, Fu-Yung; Young, John D

2015-01-01

Mineralo-organic nanoparticles (NPs) detected in biological fluids have been described as precursors of physiological and pathological calcifications in the body. Our main objective was to examine the early stages of mineral NP formation in body fluids. A nanomaterial approach based on atomic force microscopy, dynamic light scattering, electron microscopy and spectroscopy was used. The mineral particles, which contain the serum proteins albumin and fetuin-A, initially precipitate in the form of round amorphous NPs that gradually grow in size, aggregate and coalesce to form crystalline mineral films similar to the structures observed in calcified human arteries. Our study reveals the early stages of particle formation and provides a platform to analyze the role(s) of mineralo-organic NPs in human tissues.

[Effect of calcium cations on acid-base properties and free radical oxidation of dopamine and pyrocatechol].

PubMed

Lebedev, A V; Ivanova, M V; Timoshin, A A; Ruuge, E K

2008-01-01

Ca2+-induced increase in the rate of pyrocatechol and dopamine oxidation by dioxygen and Ca2+-dependent acid-base properties of the catechols were studied by potentiometric titration, UV/Vis-spectrophotometry, EPR-spectroscopy, and by measurement of oxygen consumption. The effect of Ca2+ on the chain reactions of oxidation can be explained by additional deprotonation (decrease in pKai) of the catechols that accelerates one electron transport to dioxygen and formation of calcium semiquinonate, undergoing further oxidation. The described Ca2+-dependent redox-conversion of ortho-phenols proposes that an additional function of calcium in the cell can be its involvement in free radical oxidoreductive reactions at pH > pKai.

Copper interstitial recombination centers in Cu3N

NASA Astrophysics Data System (ADS)

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; Hanifi, David; Salleo, Alberto; Magyari-Köpe, Blanka; Nishi, Yoshio; Bent, Stacey F.; Clemens, Bruce M.

2018-06-01

We present a comprehensive study of the earth-abundant semiconductor Cu3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies VCu have shallow defect levels while copper interstitials Cui behave as deep potential wells in the conduction band, which mediate Shockley-Read-Hall recombination. The existence of Cui defects has been experimentally verified using photothermal deflection spectroscopy. A Cu3N /ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. The absence of photocurrent can be explained by a large concentration of Cui recombination centers capturing electrons in p -type Cu3N .

In situ monitoring of cocrystals in formulation development using low-frequency Raman spectroscopy.

PubMed

Otaki, Takashi; Tanabe, Yuta; Kojima, Takashi; Miura, Masaru; Ikeda, Yukihiro; Koide, Tatsuo; Fukami, Toshiro

2018-05-05

In recent years, to guarantee a quality-by-design approach to the development of pharmaceutical products, it is important to identify properties of raw materials and excipients in order to determine critical process parameters and critical quality attributes. Feedback obtained from real-time analyses using various process analytical technology (PAT) tools has been actively investigated. In this study, in situ monitoring using low-frequency (LF) Raman spectroscopy (10-200 cm -1 ), which may have higher discriminative ability among polymorphs than near-infrared spectroscopy and conventional Raman spectroscopy (200-1800 cm -1 ), was investigated as a possible application to PAT. This is because LF-Raman spectroscopy obtains information about intermolecular and/or lattice vibrations in the solid state. The monitoring results obtained from Furosemide/Nicotinamide cocrystal indicate that LF-Raman spectroscopy is applicable to in situ monitoring of suspension and fluidized bed granulation processes, and is an effective technique as a PAT tool to detect the conversion risk of cocrystals. LF-Raman spectroscopy is also used as a PAT tool to monitor reactions, crystallizations, and manufacturing processes of drug substances and products. In addition, a sequence of conversion behaviors of Furosemide/Nicotinamide cocrystals was determined by performing in situ monitoring for the first time. Copyright © 2018 Elsevier B.V. All rights reserved.

Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs).

PubMed

Yuan, Jia; Hapis, Stefania; Breitzke, Hergen; Xu, Yeping; Fasel, Claudia; Kleebe, Hans-Joachim; Buntkowsky, Gerd; Riedel, Ralf; Ionescu, Emanuel

2014-10-06

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

Comparison of chitosan and chitosan nanoparticles on the performance and charge recombination of water-based gel electrolyte in dye sensitized solar cells.

PubMed

Khalili, Malihe; Abedi, Mohammad; Amoli, Hossein Salar; Mozaffari, Seyed Ahmad

2017-11-01

In commercialization of liquid dye-sensitized solar cells (DSSCs), whose leakage, evaporation and toxicity of organic solvents are limiting factors, replacement of organic solvents with water-based gel electrolyte is recommended. This work reports on utilizing and comparison of chitosan and chitosan nanoparticle as different gelling agents in preparation of water-based gel electrolyte in fabrication of dye sensitized solar cells. All photovoltaic parameters such as open circuit voltage (V oc ), fill factor (FF), short circuit current density (J sc ) and conversion efficiency (η) were measured. For further characterization, electrochemical impedance spectroscopy (EIS) was used to study the charge transfer at Pt/electrolyte interface and charge recombination and electron transport at TiO 2 /dye/electrolyte interface. Significant improvements in conversion efficiency and short circuit current density of DSSCs fabricated by chitosan nanoparticle were observed that can be attributed to the higher mobility of I 3 - due to the lower viscosity and smaller size of chitosan nanoparticles. Copyright © 2017 Elsevier Ltd. All rights reserved.

nanostructures for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Rashad, M. M.; Shalan, A. E.

2014-08-01

Hierarchical architectures consisting of one-dimensional (1D) nanostructures are of great interest for potential use in energy and environmental applications in recent years. In this work, hierarchical tungsten oxide (WO3) has been synthesized via a facile hydrothermal route from ammonium metatungstate hydrate and implemented as photoelectrode for dye-sensitized solar cells. The urchin-like WO3 micro-patterns are constructed by self-organized nanoscale length 1D building blocks, which are single crystalline in nature, grown along (001) direction and confirm an orthorhombic crystal phase. The obtained powders were investigated by XRD, SEM, TEM and UV-Vis Spectroscopy. The photovoltaic performance of dye-sensitized solar cells based on WO3 photoanodes was investigated. With increasing the calcination temperature of the prepared nanopowders, the light-electricity conversion efficiency ( η) was increased. The results were attributed to increase the crystallinity of the particles and ease of electron movement. The DSSC based on hierarchical WO3 showed a short-circuit current, an open-circuit voltage, a fill factor, and a conversion efficiency of 4.241 mA/cm2, 0.656 V, 66.74, and 1.85 %, respectively.

Probing interfacial energetics and charge transfer kinetics in semiconductor nanocomposites: New insights into heterostructured TiO 2/BiVO 4 photoanodes

DOE PAGES

Hess, Lucas H.; Cooper, Jason K.; Loiudice, Anna; ...

2017-02-28

Heterostructured nanocomposites offer promise for creating systems exhibiting functional properties that exceed those of the isolated components. For solar energy conversion, such combinations of semiconducting nanomaterials can be used to direct charge transfer along pathways that reduce recombination and promote efficient charge extraction. However, interfacial energetics and associated kinetic pathways often differ significantly from predictions derived from the characteristics of pure component materials, particularly at the nanoscale. Here, the emergent properties of TiO 2/BiVO 4 nanocomposite photoanodes are explored using a combination of X-ray and optical spectroscopies, together with photoelectrochemical (PEC) characterization. Application of these methods to both the puremore » components and the fully assembled nanocomposites reveals unpredicted interfacial energetic alignment, which promotes ultrafast injection of electrons from BiVO 4 into TiO 2. Physical charge separation yields extremely long-lived photoexcited states and correspondingly enhanced photoelectrochemical functionality. This work highlights the importance of probing emergent interfacial energetic alignment and kinetic processes for understanding mechanisms of solar energy conversion in complex nanocomposites.« less

Production of 5-hydroxymethylfurfural from starch-rich food waste catalyzed by sulfonated biochar.

PubMed

Cao, Leichang; Yu, Iris K M; Chen, Season S; Tsang, Daniel C W; Wang, Lei; Xiong, Xinni; Zhang, Shicheng; Ok, Yong Sik; Kwon, Eilhann E; Song, Hocheol; Poon, Chi Sun

2018-03-01

Sulfonated biochar derived from forestry wood waste was employed for the catalytic conversion of starch-rich food waste (e.g., bread) into 5-hydroxymethylfurfural (HMF). Chemical and physical properties of catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and elemental analysis. The conversion of HMF was investigated via controlling the reaction parameters such as catalyst loading, temperature, and reaction time. Under the optimum reaction conditions the HMF yield of 30.4 Cmol% (i.e., 22 wt% of bread waste) was achieved in the mixture of dimethylsulfoxide (DMSO)/deionized-water (DIW) at 180 °C in 20 min. The effectiveness of sulfonated biochar catalyst was positively correlated to the density of strong/weak Brønsted acidity (SO 3 H, COOH, and OH groups) and inversely correlated to humins content on the surface. With regeneration process, sulfonated biochar catalyst displayed excellent recyclability for comparable HMF yield from bread waste over five cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

One step conversion of wheat straw to sugars by simultaneous ball milling, mild acid, and fungus Penicillium simplicissimum treatment.

PubMed

Yuan, Li; Chen, Zhenhua; Zhu, Yonghua; Liu, Xuanming; Liao, Hongdong; Chen, Ding

2012-05-01

Wheat straw is one of the major lignocellulosic plant residues in many countries including China. An attractive alternative is the utilization of wheat straw for bioethanol production. This article mainly studies a simple one-step wet milling with Penicillium simplicissimum and weak acid to hydrolysis of wheat straw. The optimal condition for hydrolysis was ball milling 48 h in citrate solvent (pH = 4) with P. simplicissimum H5 at the speed of 500 rpm and the yield of sugar increased with increased milling time. Corresponding structure transformations before and after milling analyzed by X-ray diffraction, transmission Fourier transform infrared spectroscopy, and environmental scanning electron microscopy clearly indicated that this combined treatment could be attributed to the crystalline and chemical structure changes of cellulose in wheat straw during ball milling. This combined treatment of ball milling, mild acid, and fungus hydrolysis enabled the conversion of the wheat straw. Compared with traditional method of ball milling, this work showed a more simple, novel, and environmentally friendly way in mechanochemical treatment of wheat straw.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete.

PubMed

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 . After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

NASA Astrophysics Data System (ADS)

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

UV-driven microvalve based on a micro-nano TiO₂/SiO₂ composite surface for microscale flow control.

PubMed

Guo, Ting; Meng, Tao; Li, Wei; Qin, Jilong; Tong, Zhiping; Zhang, Qing; Li, Xueru

2014-03-28

This paper presents a novel ultraviolet (UV)-driven microvalve based on the concept of inserting a trimethyl chlorosilane (CTMS) modified TiO₂/SiO₂ composite patch of switchable wettability in a microfluidic system. A unique micro-nano hierarchical structure was designed and used to enhance the overall wetting contrast with the aim of improving the wetting-based valve performances. Field-emission scanning electron microscopy (FE-SEM) and x-ray photoelectron spectroscopy (XPS) were used to characterize the morphology and chemical composition of the surface. UV-driven wettability conversion on the patched microchannel was investigated using water column relative height tests, and the results confirmed the significant improvement of the hierarchical structure with the surface hydrophobic/hydrophilic conversion, which produced enhancements of 276% and 95% of the water-repellent and water-sucking pressures, respectively, compared with those of the single-scale TiO₂ nanopatterned structure. Accordingly, a good reversible and repeated on-off performance was identified by the valve tests, highlighting the potential application of the novel microvalve in the efficient control of microscale flow.

UV-driven microvalve based on a micro-nano TiO2/SiO2 composite surface for microscale flow control

NASA Astrophysics Data System (ADS)

Guo, Ting; Meng, Tao; Li, Wei; Qin, Jilong; Tong, Zhiping; Zhang, Qing; Li, Xueru

2014-03-01

This paper presents a novel ultraviolet (UV)-driven microvalve based on the concept of inserting a trimethyl chlorosilane (CTMS) modified TiO2/SiO2 composite patch of switchable wettability in a microfluidic system. A unique micro-nano hierarchical structure was designed and used to enhance the overall wetting contrast with the aim of improving the wetting-based valve performances. Field-emission scanning electron microscopy (FE-SEM) and x-ray photoelectron spectroscopy (XPS) were used to characterize the morphology and chemical composition of the surface. UV-driven wettability conversion on the patched microchannel was investigated using water column relative height tests, and the results confirmed the significant improvement of the hierarchical structure with the surface hydrophobic/hydrophilic conversion, which produced enhancements of 276% and 95% of the water-repellent and water-sucking pressures, respectively, compared with those of the single-scale TiO2 nanopatterned structure. Accordingly, a good reversible and repeated on-off performance was identified by the valve tests, highlighting the potential application of the novel microvalve in the efficient control of microscale flow.

Study of Proton Transfer in E. Coli Photolyase

NASA Astrophysics Data System (ADS)

Zhang, Meng; Liu, Zheyun; Li, Jiang; Wang, Lijuan; Zhong, Dongping

2013-06-01

Photolyase is a flavoprotein which utilizes blue-light energy to repair UV-light damaged DNA. The catalytic cofactor of photolyase, flavin adenine dinucleotide (FAD), has five redox states. Conversions between these redox states involve intraprotein electron transfer and proton transfer, which play important role in protein function. Here we systematically studied proton transfer in E. coli photolyase in vitro by site-directed mutagenesis and steady-state UV-vis spectroscopy, and proposed the proton channel in photolyase. We found that in the mutant N378C/E363L, proton channel was completely eliminated when DNA substrate was bound to the protein. Proton is suggested to be transported from protein surface to FAD by two pathways: the proton relay pathway through E363 and surface water to N378 and then to FAD; and the proton diffusion pathway through the substrate binding pocket. In addition, reaction kinetics of conversions between the redox states was then solved and redox potentials of the redox states were determined. These results described a complete picture of FAD redox changes, which are fundamental to the functions of all flavoenzymes.

g-C3N4 modified TiO2 nanosheets with enhanced photoelectric conversion efficiency in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Xu, Jian; Wang, Guanxi; Fan, Jiajie; Liu, Baoshun; Cao, Shaowen; Yu, Jiaguo

2015-01-01

Dye-sensitized solar cells (DSSCs) were fabricated by using g-C3N4 modified TiO2 nanosheets (CTS) as photoanode materials in this research. A thin layer of g-C3N4 was coated on the surface of TiO2 nanosheets by simply heating the mixture of TiO2 nanosheets and urea, which led to the formation of TiO2@g-C3N4 nanosheet heterostructure. The experimental results showed that the photoelectric conversion efficiency of DSSCs was obviously improved after modified by g-C3N4. The measurements of I-V characteristic indicated that the introduction of g-C3N4 could increase both the open circuit voltage and short-circuit photocurrent density. Along with the analysis of electrochemical impedance spectroscopy, it is considered that the thin layer of g-C3N4 can act as the blocking layer for electron backward recombination with electrolyte, which can be used as the functional material to increase the DSSC performance.

Lipase-inorganic hybrid nanoflower constructed through biomimetic mineralization: A new support for biodiesel synthesis.

PubMed

Jiang, Wei; Wang, Xinghuo; Yang, Jiebing; Han, Haobo; Li, Quanshun; Tang, Jun

2018-03-15

We reported a facile, economic and green method based on biomimetic mineralization to acquire lipase-inorganic hybrid nanoflower, which was then employed as a biocatalyst for biodiesel production. In the hybrid nanoflower, enzyme molecules and Cu 2+ ions were utilized as the organic and inorganic components, respectively. The morphology of nanoflower and the distribution and loading of proteins were systematically characterized by scanning electron microscopy, confocal laser scanning microscopy and ultraviolet-visible spectroscopy, which indicated the successful encapsulation of lipase in the hybrid nanoflower. Using the hydrolysis of p-nitrophenyl caprylate as a model, lipase-inorganic hybrid nanoflower was observed to possess favorable catalytic activity and stability in the ester hydrolysis. Further, the hybrid nanoflower was used as a catalyst for biodiesel production, in which it could convert sunflower oil to biodiesel with 96.5% conversion and remain 72.5% conversion after being used for 5 cycles. Thus, the lipase-inorganic hybrid nanoflower is potential to be used as an economically viable biocatalyst for the production of biofuel as the future petrol-fuel replacement. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

PubMed Central

Simescu, Florica; Idrissi, Hassane

2008-01-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating. PMID:27878037

Single-electron detection and spectroscopy via relativistic cyclotron radiation

DOE PAGES

Asner, D. M.; Bradley, R. F.; de Viveiros, L.; ...

2015-04-20

Since 1897, we've understood that accelerating charges must emit electromagnetic radiation. Cyclotron radiation, the particular form of radiation emitted by an electron orbiting in a magnetic field, was first derived in 1904. Despite the simplicity of this concept, and the enormous utility of electron spectroscopy in nuclear and particle physics, single-electron cyclotron radiation has never been observed directly. We demonstrate single-electron detection in a novel radiofrequency spec- trometer. Here, we observe the cyclotron radiation emitted by individual magnetically-trapped electrons that are produced with mildly-relativistic energies by a gaseous radioactive source. The relativistic shift in the cyclotron frequency permits a precisemore » electron energy measurement. Precise beta electron spectroscopy from gaseous radiation sources is a key technique in modern efforts to measure the neutrino mass via the tritium decay endpoint, and this work demonstrates a fundamentally new approach to precision beta spectroscopy for future neutrino mass experiments.« less

Improving tribological and anti-bacterial properties of titanium external fixation pins through surface ceramic conversion.

PubMed

Dong, Huan; Mukinay, Tatiana; Li, Maojun; Hood, Richard; Soo, Sein Leung; Cockshott, Simon; Sammons, Rachel; Li, Xiaoying

2017-01-01

In this study, an advanced ceramic conversion surface engineering technology has been applied for the first time to self-drilling Ti6Al4V external fixation pins to improve their performance in terms of biomechanical, bio-tribological and antibacterial properties. Systematic characterisation of the ceramic conversion treated Ti pins was carried out using Scanning electron microscope, X-ray diffraction, Glow-discharge optical emission spectroscopy, nano- and micro-indentation and scratching; the biomechanical and bio-tribological properties of the surface engineered Ti pins were evaluated by insertion into high density bone simulation material; and the antibacterial behaviour was assessed with Staphylococcus aureus NCTC 6571. The experimental results have demonstrated that the surfaces of Ti6Al4V external fixation pins were successfully converted into a TiO 2 rutile layer (~2 μm in thickness) supported by an oxygen hardened case (~15 μm in thickness) with very good bonding due to the in-situ conversion nature. The maximum insertion force and temperature were reduced from 192N and 31.2 °C when using the untreated pins to 182N and 26.1 °C when the ceramic conversion treated pins were tested. This is mainly due to the significantly increased hardness (more than three times) and the effectively enhanced wear resistance of the cutting edge of the self-drilling Ti pins following the ceramic conversion treatment. The antibacterial tests also revealed that there was a significantly reduced number of bacteria isolated from the ceramic conversion treated pins compared to the untreated pins of around 50 % after 20 h incubation, P < 0.01 (0.0024). The results reported are encouraging and could pave the way towards high-performance anti-bacterial titanium external fixation pins with reduced pin-track infection and pin loosing.

Photochemical Energy Storage and Electrochemically Triggered Energy Release in the Norbornadiene-Quadricyclane System: UV Photochemistry and IR Spectroelectrochemistry in a Combined Experiment.

PubMed

Brummel, Olaf; Waidhas, Fabian; Bauer, Udo; Wu, Yanlin; Bochmann, Sebastian; Steinrück, Hans-Peter; Papp, Christian; Bachmann, Julien; Libuda, Jörg

2017-07-06

The two valence isomers norbornadiene (NBD) and quadricyclane (QC) enable solar energy storage in a single molecule system. We present a new photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) experiment, which allows monitoring of the complete energy storage and release cycle by in situ vibrational spectroscopy. Both processes were investigated, the photochemical conversion from NBD to QC using the photosensitizer 4,4'-bis(dimethylamino)benzophenone (Michler's ketone, MK) and the electrochemically triggered cycloreversion from QC to NBD. Photochemical conversion was obtained with characteristic conversion times on the order of 500 ms. All experiments were performed under full potential control in a thin-layer configuration with a Pt(111) working electrode. The vibrational spectra of NBD, QC, and MK were analyzed in the fingerprint region, permitting quantitative analysis of the spectroscopic data. We determined selectivities for both the photochemical conversion and the electrochemical cycloreversion and identified the critical steps that limit the reversibility of the storage cycle.

Morphological and Compositional (S)TEM Analysis of Multiple Exciton Generation Solar Cells

NASA Astrophysics Data System (ADS)

Wisnivesky-Rocca-Rivarola, F.; Davis, N. J. L. K.; Bohm, M.; Ducati, C.

2015-10-01

Quantum confinement of charge carriers in semiconductor nanocrystals produces optical and electronic properties that have the potential to enhance the power conversion efficiency of solar cells. One of these properties is the efficient formation of more than one electron-hole pair from a single absorbed photon, in a process called multiple exciton generation (MEG). In this work we studied the morphology of nanocrystal multilayers of PbSe treated with CdCl2 using complementary imaging and spectroscopy techniques to characterise the chemical composition and morphology of full MEG devices made with PbSe nanorods (NRs). IN the scanning TEM (STEM), plan view images and chemical maps were obtained of the nanocrystal layers, which allowed for the analysis of crystal structure and orientation, as well as size distribution and aspect ratio. These results were complemented by cross-sectional images of full devices, which allowed accessing the structure of each layer that composes the device, including the nanorod packing in the active nanocrystal layer.

How exciton-vibrational coherences control charge separation in the photosystem II reaction center.

PubMed

Novoderezhkin, Vladimir I; Romero, Elisabet; van Grondelle, Rienk

2015-12-14

In photosynthesis absorbed sun light produces collective excitations (excitons) that form a coherent superposition of electronic and vibrational states of the individual pigments. Two-dimensional (2D) electronic spectroscopy allows a visualization of how these coherences are involved in the primary processes of energy and charge transfer. Based on quantitative modeling we identify the exciton-vibrational coherences observed in 2D photon echo of the photosystem II reaction center (PSII-RC). We find that the vibrations resonant with the exciton splittings can modify the delocalization of the exciton states and produce additional states, thus promoting directed energy transfer and allowing a switch between the two charge separation pathways. We conclude that the coincidence of the frequencies of the most intense vibrations with the splittings within the manifold of exciton and charge-transfer states in the PSII-RC is not occurring by chance, but reflects a fundamental principle of how energy conversion in photosynthesis was optimized.

Atomically-thick two-dimensional crystals: electronic structure regulation and energy device construction.

PubMed

Sun, Yongfu; Gao, Shan; Xie, Yi

2014-01-21

Atomically-thick two-dimensional crystals can provide promising opportunities to satisfy people's requirement of next-generation flexible and transparent nanodevices. However, the characterization of these low-dimensional structures and the understanding of their clear structure-property relationship encounter many great difficulties, owing to the lack of long-range order in the third dimensionality. In this review, we survey the recent progress in fine structure characterization by X-ray absorption fine structure spectroscopy and also overview electronic structure modulation by density-functional calculations in the ultrathin two-dimensional crystals. In addition, we highlight their structure-property relationship, transparent and flexible device construction as well as wide applications in photoelectrochemical water splitting, photodetectors, thermoelectric conversion, touchless moisture sensing, supercapacitors and lithium ion batteries. Finally, we outline the major challenges and opportunities that face the atomically-thick two-dimensional crystals. It is anticipated that the present review will deepen people's understanding of this field and hence contribute to guide the future design of high-efficiency energy-related devices.

Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol

DOE PAGES

Xu, Ping; Kang, Leilei; Mack, Nathan H.; ...

2013-10-21

We investigate surface plasmon assisted catalysis (SPAC) reactions of 4-aminothiophenol (4ATP) to and back from 4,4'-dimercaptoazobenzene (DMAB) by single particle surface enhanced Raman spectroscopy, using a self-designed gas flow cell to control the reductive/oxidative environment over the reactions. Conversion of 4ATP into DMAB is induced by energy transfer (plasmonic heating) from surface plasmon resonance to 4ATP, where O 2 (as an electron acceptor) is essential and H 2O (as a base) can accelerate the reaction. In contrast, hot electron (from surface plasmon decay) induction drives the reverse reaction of DMAB to 4ATP, where H 2O (or H 2) acts asmore » the hydrogen source. More interestingly, the cyclic redox between 4ATP and DMAB by SPAC approach has been demonstrated. Finally, this SPAC methodology presents a unique platform for studying chemical reactions that are not possible under standard synthetic conditions.« less

The influence of annealing temperature on the interface and photovoltaic properties of CdS/CdSe quantum dots sensitized ZnO nanorods solar cells.

PubMed

Qiu, Xiaofeng; Chen, Ling; Gong, Haibo; Zhu, Min; Han, Jun; Zi, Min; Yang, Xiaopeng; Ji, Changjian; Cao, Bingqiang

2014-09-15

Arrays of ZnO/CdS/CdSe core/shell nanocables with different annealing temperatures have been investigated for CdS/CdSe quantum dots sensitized solar cells (QDSSCs). CdS/CdSe quantum dots were synthesized on the surface of ZnO nanorods that serve as the scaffold via a simple ion-exchange approach. The uniform microstructure was verified by scanning electron microscope and transmission electron microscope. UV-Visible absorption spectrum and Raman spectroscopy analysis indicated noticeable influence of annealing temperature on the interface structural and optical properties of the CdS/CdSe layers. Particularly, the relationship between annealing temperatures and photovoltaic performance of the corresponding QDSSCs was investigated employing photovoltaic conversion, quantum efficiency and electrochemical impedance spectra. It is demonstrated that higher cell efficiency can be obtained by optimizing the annealing temperature through extending the photoresponse range and improving QD layer crystal quality. Copyright © 2014 Elsevier Inc. All rights reserved.

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers

DOE PAGES

Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B.; ...

2016-05-05

Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley–Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ~2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). But, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur viamore » a direct coupling mechanism that is independent of CT states. Moreover, we show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, despite weak direct coupling.« less

Room-Temperature Processing of TiOx Electron Transporting Layer for Perovskite Solar Cells.

PubMed

Deng, Xiaoyu; Wilkes, George C; Chen, Alexander Z; Prasad, Narasimha S; Gupta, Mool C; Choi, Joshua J

2017-07-20

In order to realize high-throughput roll-to-roll manufacturing of flexible perovskite solar cells, low-temperature processing of all device components must be realized. However, the most commonly used electron transporting layer in high-performance perovskite solar cells is based on TiO 2 thin films processed at high temperature (>450 °C). Here, we demonstrate room temperature solution processing of the TiO x layer that performs as well as the high temperature TiO 2 layer in perovskite solar cells, as evidenced by a champion solar cell efficiency of 16.3%. Using optical spectroscopy, electrical measurements, and X-ray diffraction, we show that the room-temperature processed TiO x is amorphous with organic residues, and yet its optical and electrical properties are on par with the high-temperature TiO 2 . Flexible perovskite solar cells that employ a room-temperature TiO x layer with a power conversion efficiency of 14.3% are demonstrated.

Structural, mechanical, and magnetic properties of ferrite-austenite mixture in evaporated 304 stainless steel thin films

NASA Astrophysics Data System (ADS)

Merakeb, Noureddine; Messai, Amel; Djelloul, Abdelkader; Ayesh, Ahmad I.

2015-11-01

In this paper, we investigate the structure, composition, magnetic, and mechanical properties of stainless steel thin films formed by thermal evaporation technique. These thin films reveal novel structural and physical properties where they were found to consist of nanocrystals that are ~90 % body-centred cubic crystal structure which holds ferromagnetic properties (α-phase), and ~10 % face-centred cubic crystal structure which is paramagnetic at room temperature (γ-phase). The presence of the above phases was quantified by X-ray diffraction, transmission electron microscopy, and conversion electron Mössbauer spectroscopy. The magnetic properties were evaluated by a superconducting quantum interference device magnetometer, and they confirmed the dual-phase crystal structure of the stainless thin films, where the presence of γ-phase reduced the magnetization of the produced thin films. In addition, the fabricated stainless steel thin films did not contain micro-cracks, and they exhibit a tensile stress of about 1.7 GPa, hardness of 7.5 GPa, and elastic modulus of 104 GPa.

Non-radiative relaxation of photoexcited chlorophylls: Theoretical and experimental study

DOE PAGES

Bricker, William P.; Shenai, Prathamesh M.; Ghosh, Avishek; ...

2015-09-08

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. With modeling this process, non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are ablemore » to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.« less

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert

2018-04-01

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.

Perylene-Diimide Based Donor-Acceptor-Donor Type Small-Molecule Acceptors for Solution-Processable Organic Solar Cells

NASA Astrophysics Data System (ADS)

Ganesamoorthy, Ramasamy; Vijayaraghavan, Rajagopalan; Sakthivel, Pachagounder

2017-12-01

Development of nonfullerene acceptors plays an important role in the commercial availability of plastic solar cells. We report herein synthesis of bay-substituted donor-acceptor-donor (D-A-D)-type perylene diimide (PDI)-based small molecules (SM-1 to SM-4) by Suzuki coupling method and their use as acceptors in bulk heterojunction organic solar cells (BHJ-OSCs) with poly(3-hexylthiophene) (P3HT) polymer donor. We varied the number of electron-rich thiophene units and the solubilizing side chains and also evaluated the optical and electrochemical properties of the small molecules. The synthesized small molecules were confirmed by Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and high-resolution mass spectroscopy (HR-MS). The small molecules showed extensive and strong absorption in the ultraviolet-visible (UV-Vis) region up to 750 nm, with bandgap (E_{{g}}^{{opt}} ) reduced below <2 eV. The energy levels of small molecules SM-1 to SM-4 were suitable for use as electron-accepting materials. The small molecules showed good thermal stability up to 300°C. BHJ-OSCs with SM-1 and P3HT polymer donor showed maximum power conversion efficiency (PCE) of 0.19% with V oc of 0.30 V, J sc of 1.72 mA cm-2, and fill factor (FF) of 37%. The PCE decreased with the number of thiophene units. The PCE of SM-2 was lower than that of SM-1. This difference in PCE can be explained by the higher aggregation tendency of the bithiophene compared with the thiophene unit. Introduction of the solubilizing group in the bay position increased the aggregation property, leading to much lower PCE than for the small molecules without solubilizing group.

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

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

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1B u (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans’ correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us tomore » report the direct observation of the famously elusive S 1(2 1A g) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 1 1B u and 2 1A g states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S 2(1 1B u) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1B u surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. Lastly, in Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.« less

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

DOE PAGES

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; ...

2018-04-27

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1B u (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans’ correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us tomore » report the direct observation of the famously elusive S 1(2 1A g) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 1 1B u and 2 1A g states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S 2(1 1B u) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1B u surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. Lastly, in Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.« less

Photocatalytic reduction of CO2 with H2O to CH4 on Cu(I) supported TiO2 nanosheets with defective {001} facets.

PubMed

Zhu, Shuying; Liang, Shijing; Tong, Yuecong; An, Xiaohan; Long, Jinlin; Fu, Xianzhi; Wang, Xuxu

2015-04-21

Highly dispersed Cu2O clusters loaded on TiO2 nanosheets with dominant exposed {001} facets are prepared by a hydrothermal treatment followed by photodeposition. The physicochemical properties of the as-prepared samples are characterized carefully. The deposition position and chemical state of the Cu2O clusters are characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, EPR spectroscopy, and in situ CO-adsorbed FTIR spectroscopy, respectively. The results show that in situ Cu deposition leads to in situ formation of abundant oxygen vacancies (Vo) on the surface of the TiO2 nanosheets. Interestingly, the co-existence of Vo and Cu2O clusters could promote the photoactivity of CO2 reduction efficiently. The surface Vo play a significant role in the reduction of CO2. Meanwhile, the deposited Cu(I) species serve also as active sites for the formation of CH4, and then protect CH4 from degradation by generated oxidation species. For the photoreduction of CO2 to CH4, it is found that the content level of Cu2O has a significant influence on the activity. Cu-TiO2-1.0 shows the highest photocatalytic activity, which is over 30 times higher than that of the parent TiO2. This great enhancement of photocatalytic activity may be contributed by high CO2 adsorption capacity, high electron mobility, and high concentration of Vo. However, the effect of the surface area of the samples on the activity is negligible. All of this evidence is obtained by CO2-sorption, electrochemistry, in situ FTIR spectroscopy, in situ ERP techniques, etc. The reaction intermediates are detected by in situ FTIR spectroscopy. Finally, a probable mechanism is proposed based on the experimental results. It is hoped that our work could render one of the most effective strategies to achieve advanced properties over photofunctional materials for solar energy conversion of CO2.

Feasibility of the Simultaneous Determination of Monomer Concentrations and Particle Size in Emulsion Polymerization Using in Situ Raman Spectroscopy

PubMed Central

2015-01-01

An immersion Raman probe was used in emulsion copolymerization reactions to measure monomer concentrations and particle sizes. Quantitative determination of monomer concentrations is feasible in two-monomer copolymerizations, but only the overall conversion could be measured by Raman spectroscopy in a four-monomer copolymerization. The feasibility of measuring monomer conversion and particle size was established using partial least-squares (PLS) calibration models. A simplified theoretical framework for the measurement of particle sizes based on photon scattering is presented, based on the elastic-sphere-vibration and surface-tension models. PMID:26900256

Opto-electronic conversion logic behaviour through dynamic modulation of electron/energy transfer states at the TiO2-carbon quantum dot interface.

PubMed

Wang, Fang; Zhang, Yonglai; Liu, Yang; Wang, Xuefeng; Shen, Mingrong; Lee, Shuit-Tong; Kang, Zhenhui

2013-03-07

Here we show a bias-mediated electron/energy transfer process at the CQDs-TiO(2) interface for the dynamic modulation of opto-electronic properties. Different energy and electron transfer states have been observed in the CQDs-TNTs system due to the up-conversion photoluminescence and the electron donation/acceptance properties of the CQDs decorated on TNTs.

Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

PubMed

Rury, Aaron S; Wiley, Theodore E; Sension, Roseanne J

2015-03-17

Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron tetraphenyl porphyrin chloride (Fe((III))TPPCl) exhibits picosecond decay to a metal centered d → d* (4)T state. This state decays on a ca. 16 ps time scale in room temperature solution but persists for much longer in a cryogenic glass. The photoreactivity of the (4)T state may lead to novel future applications for these compounds. In contrast, the nonplanar cob(III)alamins contain two axial ligands to the central cobalt atom. The upper axial ligand can be an alkyl group as in the two biologically active coenzymes or a nonalkyl ligand such as -CN in cyanocobalamin (vitamin B12) or -OH in hydroxocobalamin. The electronic structure, energy cascade, and bond cleavage of these compounds is sensitive to the details of the axial ligand. Nonalkylcobalamins exhibit ultrafast internal conversion to a low-lying state of metal to ligand or ligand to metal charge transfer character. The compounds are generally photostable with ground state recovery complete on a time scale of 2-7 ps in room temperature aqueous solution. Alkylcobalamins exhibit ultrafast internal conversion to an S1 state of d/π → π* character. Most compounds undergo bond cleavage from this state with near unit quantum yield within ∼100 ps. Recent theoretical calculations provide a potential energy surface accounting for these observations. Conformation dependent mixing of the corrin π and cobalt d orbitals plays a significant role in the observed photochemistry and photophysics.

Application of nitrogen-doped TiO2 nano-tubes in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Tran, Vy Anh; Truong, Trieu Thinh; Phan, Thu Anh Pham; Nguyen, Trang Ngoc; Huynh, Tuan Van; Agresti, Antonio; Pescetelli, Sara; Le, Tien Khoa; Di Carlo, Aldo; Lund, Torben; Le, So-Nhu; Nguyen, Phuong Tuyet

2017-03-01

Our research aimed to improve the overall energy conversion efficiency of DSCs by applying nitrogen-doped TiO2 nano-tubes (N-TNT) for the preparation of DSCs photo-anodes. The none-doped TiO2 nano-tubes (TNTs) were synthesized by alkaline hydrothermal treatment of Degussa P25 TiO2 particles in 10 M NaOH. The nano-tubes were N-doped by reflux in various concentrations of NH4NO3. The effects of nitrogen doping on the structure, morphology, and crystallography of N-TNT were analyzed by transmission electron microscopy (TEM), infrared spectroscopy (IR), Raman spectroscopy, and X-ray photoelectron spectra (XPS). DSCs fabricated with doped N-TNT and TNT was characterized by J-V measurements. Results showed that nitrogen doping significantly enhanced the efficiency of N-TNT cells, reaching the optimum value (η = 7.36%) with 2 M nitrogen dopant, compared to η = 4.75% of TNT cells. The high efficiency of the N-TNT cells was attributed to increased current density due to the reduction of dark current in the DSCs.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei; Xiong, Yan; Tsai, Fang-Chang

2018-03-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm-2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ doping into CdSe QDs is an innovative and simple method-chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density-voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs.

Changes of the surface structure of corn stalk in the cooking process with active oxygen and MgO-based solid alkali as a pretreatment of its biomass conversion.

PubMed

Pang, Chunsheng; Xie, Tujun; Lin, Lu; Zhuang, Junping; Liu, Ying; Shi, Jianbin; Yang, Qiulin

2012-01-01

This study presents a novel, efficient and environmentally friendly process for the cooking of corn stalk that uses active oxygen (O2 and H2O2) and a recoverable solid alkali (MgO). The structural changes on the surface of corn stalk before and after cooking were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The results showed that lignin and extractives were effectively removed, especially those on the surface of corn stalk. Additionally, the changes included becoming fibrillar, the exposure of cellulose and hemi-cellulose and the pitting corrosion on the surface, etc. The results also showed that the removal reaction is from outside to inside, but the main reaction is possibly on the surface. Furthermore, the results of active oxygen cooking with a solid alkali are compared with those of alkaline cooking in the paper. Copyright © 2011 Elsevier Ltd. All rights reserved.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells.

PubMed

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei; Xiong, Yan; Tsai, Fang-Chang

2018-03-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm -2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO 2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn 2+ doping into CdSe QDs is an innovative and simple method-chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn 2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn 2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density-voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs.

Spectral and ion emission features of laser-produced Sn and SnO2 plasmas

NASA Astrophysics Data System (ADS)

Hui, Lan; Xin-Bing, Wang; Du-Luo, Zuo

2016-03-01

We have made a detailed comparison of the atomic and ionic debris, as well as the emission features of Sn and SnO2 plasmas under identical experimental conditions. Planar slabs of pure metal Sn and ceramic SnO2 are irradiated with 1.06 μm, 8 ns Nd:YAG laser pulses. Fast photography employing an intensified charge coupled device (ICCD), optical emission spectroscopy (OES), and optical time of flight emission spectroscopy are used as diagnostic tools. Our results show that the Sn plasma provides a higher extreme ultraviolet (EUV) conversion efficiency (CE) than the SnO2 plasma. However, the kinetic energies of Sn ions are relatively low compared with those of SnO2. OES studies show that the Sn plasma parameters (electron temperature and density) are lower compared to those of the SnO2 plasma. Furthermore, we also give the effects of the vacuum degree and the laser pulse energy on the plasma parameters. Project supported by the National Natural Science Foundation of China (Grant No. 11304235) and the Director Fund of WNLO, China.

Selection of an anti-solvent for efficient and stable cesium-containing triple cation planar perovskite solar cells.

PubMed

Xiao, Meng; Zhao, Li; Geng, Min; Li, Yanyan; Dong, Binghai; Xu, Zuxun; Wan, Li; Li, Wenlu; Wang, Shimin

2018-06-19

The perovskite layer is a crucial component influencing high-performance perovskite solar cells (PSCs). In the one-step solution method, anti-solvents are important for obtaining smooth and uniform perovskite active layers. This work explored the effect of various anti-solvents on the preparation of triple cation perovskite active layers. In general, anti-solvents with low dielectric constants, low polarity, and low boiling point are suitable for the preparation of perovskite films. Microstructural and elemental analyses of the perovskite films were systematically conducted by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The photoelectric properties, carrier transfer, and recombination process in the PSCs were investigated using photocurrent-voltage characteristic curves and electrochemical impedance spectroscopy. Optimum performance was obtained when the anti-solvent was diethyl ether (DEE) and the ratio of the optimum amount of DEE to the volume of the precursor was 1 : 10. Meanwhile, we found that the partial replacement of formamidinium/methylammonium by cesium could increase the stability of the PSCs and enhance the power conversion efficiency from 15.49% to over 17.38%.

Strongly bound excitons in anatase TiO 2 single crystals and nanoparticles

DOE PAGES

Baldini, E.; Chiodo, L.; Dominguez, A.; ...

2017-04-13

Anatase TiO 2 is among the most studied materials for light-energy conversion applications, but the nature of its fundamental charge excitations is still unknown. Yet it is crucial to establish whether light absorption creates uncorrelated electron-hole pairs or bound excitons and, in the latter case, to determine their character. Here, by combining steady-state angle-resolved photoemission spectroscopy and spectroscopic ellipsometry with state-of-the-art ab initio calculations, we demonstrate that the direct optical gap of single crystals is dominated by a strongly bound exciton rising over the continuum of indirect interband transitions. This exciton possesses an intermediate character between the Wannier-Mott and Frenkelmore » regimes and displays a peculiar two-dimensional wavefunction in the three-dimensional lattice. The nature of the higher-energy excitations is also identified. Furthermore, the universal validity of our results is confirmed up to room temperature by observing the same elementary excitations in defect-rich samples (doped single crystals and nanoparticles) via ultrafast two-dimensional deep-ultraviolet spectroscopy.« less

Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Ru-based catalysts

NASA Astrophysics Data System (ADS)

Li, Hongwei; Ji, Dong; Li, Yu; Liang, Yalan; Li, Gui Xian

2015-12-01

A series of Ru-based catalysts modified by alkaline earth metals were prepared by the impregnation-precipitation method and characterized using transmission electron microscopy, X-ray diffraction, ICP optical emission spectroscopy, Infrared Spectroscopy of adsorbed pyridine analysis and surface area analysis. The performance of the catalysts was measured via liquid-phase hydroquinone hydrogenation reaction. Results show that the Ru-Sr/NaY catalyst has the best activity and selectivity among those Ru-based catalysts. The conversion of hydroquinone and the selectivity to 1,4-cyclohexanediol reached up to 99.6% and 89.6% at optimum reaction condition (700 r/min, 423 K and 5 MPa pressure of H2 in 3 h). This may be attributed to the fact that the right amount of Strontium is beneficial to the good dispersion of the ruthenium nanoclusters on the surface of NaY and modify the acidic properties of the catalyst. Moreover, IR of adsorbed pyridine analysis suggested the proper ratio of L/B acid of the catalysts played an important role in the performance of the hydroquinone hydrogenation reaction.

Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells

PubMed Central

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei

2018-01-01

A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm−2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ doping into CdSe QDs is an innovative and simple method—chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density–voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs. PMID:29657776

Construction of an improved amperometric acrylamide biosensor based on hemoglobin immobilized onto carboxylated multi-walled carbon nanotubes/iron oxide nanoparticles/chitosan composite film.

PubMed

Batra, Bhawna; Lata, Suman; Pundir, C S

2013-11-01

A method is described for construction of an improved amperometric acrylamide biosensor based on covalent immobilization of hemoglobin (Hb) onto nanocomposite of carboxylated multi-walled carbon nanotubes (cMWCNT) and iron oxide nanoparticles (Fe3O4NPs) electrodeposited onto Au electrode through chitosan (CHIT) film. The Hb/cMWCNT-Fe3O4NP/CHIT/Au electrode was characterized by scanning electron microscopy, Fourier transform infra-red spectroscopy, electrochemical impedance spectroscopy, and differential pulse voltammetry at different stages of its construction. The biosensor was based on interaction between acrylamide and Hb, which led to decrease in the electroactivity of Hb, i.e., current generated during its reversible conversion [Fe(II)/Fe(III)]. The biosensor showed optimum response within 8 s at pH 5.0 and 30 °C. The linear working range for acrylamide was 3-90 nM, with a detection limit of 0.02 nM and sensitivity of 36.9 μA/nM/cm(2). The biosensor was evaluated and employed for determination of acrylamide in potato crisps.

Electrochemical synthesis and photoelectrochemical properties of grass-like nanostructured α-Fe2O3 photoanodes for use in solar water oxidation

NASA Astrophysics Data System (ADS)

Hanedar, Yesim; Demir, Umit; Oznuluer, Tuba

2016-10-01

Grass-like nanostructured α-Fe2O3 photoelectrodes were prepared for the first time through a simple cathodic electrodeposition method from an oxygenated aqueous solution of Fe3+ at room temperature without using surfactant, capping agents or any other additives. The α-Fe2O3 electrodeposits were characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis absorption and photoelectrochemical (PEC) techniques. The SEM and XRD results indicated that the as-deposited α-Fe2O3 are composed of single crystalline nanoleaves. The formation mechanisms of α-Fe2O3 have also been proposed based on a series of cyclic voltammetric and XPS studies. This new electrochemical method is expected to be a useful technique for the fabrication of single crystalline and photoactive α-Fe2O3 nanostructures directly onto the electrode surface, which is required in most applications, such as energy conversion and storage and sensors.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

PubMed Central

Ghiglieno, Filippo

2016-01-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main ‘symmetry-breaking’ interactions are brought together. In a typical channel, the electron spin–orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule–solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted ‘electronic’ conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted ‘nuclear’, the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and ‘continui’ of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule–solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures. PMID:27703681

Thin films as a platform for understanding the conversion mechanism of FeF2 cathodes in lithium-ion microbatteries

NASA Astrophysics Data System (ADS)

Santos-Ortiz, Reinaldo

Conversion material electrodes such as FeF2 possess the potential to deliver transformative improvements in lithium ion battery performance because they permit a reversible change of more than one Li-ion per 3d metal cation. They outperform current state of the art intercalation cathodes such as LiCoO2, which have volumetric and gravimetric energy densities that are intrinsically limited by single electron transfer. Current studies focus on composite electrodes that are formed by mixing with carbon (FeF 2-C), wherein the carbon is expected to act as a binder to support the matrix and facilitate electronic conduction. These binders complicate the understanding of the electrode-electrolyte interface (SEI) passivation layer growth, of Li agglomeration, of ion and electron transport, and of the basic phase transformation processes under electrochemical cycling. This research uses thin-films as a model platform for obtaining basic understanding to the structural and chemical foundations of the phase conversion processes. Thin film cathodes are free of the binders used in nanocomposite structures and may potentially provide direct basic insight to the evolution of the SEI passivation layer, electron and ion transport, and the electrochemical behavior of true complex phases. The present work consisted of three main tasks (1) Development of optimized processes to deposit FeF2 and LiPON thin-films with the required phase purity and microstructure; (2) Understanding their electron and ion transport properties and; (3) Obtaining insight to the correlation between structure and capacity in thin-film microbatteries with FeF2 thin-film cathode and LiPON thin-film solid electrolyte. Optimized pulsed laser deposition (PLD) growth produced polycrystalline FeF2 films with excellent phase purity and P42/mnm crystallographic symmetry. A schematic band diagram was deduced using a combination of UPS, XPS and UV-Vis spectroscopies. Room temperature Hall measurements reveal that as-deposited FeF2 is n-type with an electron mobility of 0.33 cm 2/V.s and a resistivity was 0.255 O.cm. The LiPON films were deposited by reactive sputtering in nitrogen, and the results indicate that the ionic conductivity is dependent on the amount of nitrogen incorporated into the film during processing. The highest ionic conductivity obtained was 1.431.9E-6 Scm-1 and corresponded to a chemical composition of Li1.9PO3.3N.21.

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.

Study of an efficient conversion of 1,3-dimethyl-5-(Arylazo)-6-Amino-Uracils to 1,3-dimethyl-8-(Aryl)-Azapurin-2,6-Diones

NASA Astrophysics Data System (ADS)

Debnath, Diptanu; Purkayastha, Atanu; Kirillov, Alexander; Ganguly, Rakesh; Misra, Tarun Kumar

2017-12-01

6-Aminouracils have extensively been used as precursors for synthesizing numerous uracil derivatives of biological and pharmaceutical significance. This study describes an application of 1,3-dimethyl-5-(arylazo)-6-aminouracils (Uazo: Uazo1-Uazo4, precursors) for an efficient synthesis of a series of 8-substituted-azapurins (AP), namely 1,3-dimethyl-8-(aryl)-azapurin-2,6-diones (aryl = p-HC6H4 (AP1), -MeC6H4 (AP2), sbnd ClC6H4 (AP3), and sbnd SO2NH2C6H4 (AP4)) following an oxidation method in the presence of copper (II) nitrate and in alkaline medium. The obtained compounds were isolated in good yields as crystalline air-stable products and have been fully characterized in the solution by UV-vis and NMR spectroscopy, as well as in the solid state by FT-IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction (for AP2 and AP4). UV-vis study evidences that the conversion of the 6-aminouracil precursors occurs via an intermediate, Cu(II)-complex and a plausible mechanism for the formation of AP1-AP4 has been proposed. Unlike AP2 the crystal structure of AP4 reveals the formation of interdigitated 1D H-bonded chains that has been topologically classified within the 2C1 type. The 1H NMR spectra of the products have proton signals that completely devoid of hydrazone (sbnd NHsbnd) and imine (=NH) signals of their parent Uazo derivatives, thus confirming their full conversion and a stability of the AP1-AP4 in solution. The excitation and emission spectra of AP1-AP4 were also recorded in solution, revealing electronic transitions between similar vibrational energy levels of S0 (singlet ground state) and S1 (singlet first excited state).

Electronic-To-Optical-To-Electronic Packet-Data Conversion

NASA Technical Reports Server (NTRS)

Monacos, Steve

1996-01-01

Space-time multiplexer (STM) cell-based communication system designed to take advantage of both high throughput attainable in optical transmission links and flexibility and functionality of electronic processing, storage, and switching. Long packets segmented and transmitted optically by wavelength-division multiplexing. Performs optoelectronic and protocol conversion between electronic "store-and-forward" protocols and optical "hot-potato" protocols.

Development of an Electron-Positron Source for Positron Annihilation Lifetime Spectroscopy

DTIC Science & Technology

2007-01-01

positron source for positron annihilation lifetime spectroscopy Final Report Report Title...Development of an Electron- Positron Source for Position Annihilation Lifetime Spectroscopy DAAD19-03-1-0287 Final Report 2/17/2007... annihilation lifetime spectroscopy REPORT DOCUMENTATION PAGE 18. SECURITY CLASSIFICATION ON THIS PAGE UNCLASSIFIED 2. REPORT DATE: 12b. DISTRIBUTION

Photoemission of Energetic Hot Electrons Produced via Up-Conversion in Doped Quantum Dots.

PubMed

Dong, Yitong; Parobek, David; Rossi, Daniel; Son, Dong Hee

2016-11-09

The benefits of the hot electrons from semiconductor nanostructures in photocatalysis or photovoltaics result from their higher energy compared to that of the band-edge electrons facilitating the electron-transfer process. The production of high-energy hot electrons usually requires short-wavelength UV or intense multiphoton visible excitation. Here, we show that highly energetic hot electrons capable of above-threshold ionization are produced via exciton-to-hot-carrier up-conversion in Mn-doped quantum dots under weak band gap excitation (∼10 W/cm 2 ) achievable with the concentrated solar radiation. The energy of hot electrons is as high as ∼0.4 eV above the vacuum level, much greater than those observed in other semiconductor or plasmonic metal nanostructures, which are capable of performing energetically and kinetically more-challenging electron transfer. Furthermore, the prospect of generating solvated electron is unique for the energetic hot electrons from up-conversion, which can open a new door for long-range electron transfer beyond short-range interfacial electron transfer.

Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

PubMed

Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Weinstein, Julia A

2015-04-21

The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and vibrational movement are coupled in a donor-bridge-acceptor complex based on a Pt(II) trans-acetylide design motif. Time-resolved IR (TRIR) spectroscopy reveals that the rate of electron transfer (ET) is highly dependent on the amount of excess energy localized on the bridge following electronic excitation. Using an adaptation of T-2DIR, we are able to selectively perturb bridge-localized vibrational modes during charge separation, resulting in the donor-acceptor charge separation pathway being completely switched off, with all excess energy redirected toward the formation of a long-lived intraligand triplet state. A series of control experiments reveal that this effect is mode specific: it is only when the high-frequency bridging C≡C stretching mode is pumped that radical changes in photoproduct yields are observed. These experiments therefore suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light. These studies add to a growing body of evidence suggesting that controlling the pathways and efficiency of charge transfer may be achieved through synthetic and perturbative approaches aiming to modulate vibronic coupling. Achieving such control would represent a breakthrough for charge transfer-based applications such as solar energy conversion and molecular electronics.

Laser x-ray Conversion and Electron Thermal Conductivity

NASA Astrophysics Data System (ADS)

Wang, Guang-yu; Chang, Tie-qiang

2001-02-01

The influence of electron thermal conductivity on the laser x-ray conversion in the coupling of 3ωo laser with Au plane target has been investigated by using a non-LTE radiation hydrodynamic code. The non-local electron thermal conductivity is introduced and compared with the other two kinds of the flux-limited Spitzer-Härm description. The results show that the non-local thermal conductivity causes the increase of the laser x-ray conversion efficiency and important changes of the plasma state and coupling feature.

Institute for Advanced Materials at University of Louisville

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

Sunkara, Mahendra; Sumaneskara, Gamini; Starr, Thomas L

2009-10-29

In this project, a university-wide, academic center has been established entitled Institute for Advanced Materials and Renewable Energy. In this institute, a comprehensive materials characterization facility has been established by co-locating several existing characterization equipment and acquiring several state of the art instrumentation such as field emission transmission electron microscope, scanning electron microscope, high resolution X-ray diffractometer, Particle Size Distribution/Zeta Potential measurement system, and Ultra-microtome for TEM specimen. In addition, a renewable energy conversion and storage research facility was also established by acquiring instrumentation such as UV-Vis absorption spectroscopy, Atomic Layer Deposition reactor, Solar light simulator, oxygen-free glove box, potentiostat/galvanostatsmore » and other miscellaneous items. The institute is staffed with three full-time staff members (one senior research technologist, a senior PhD level research scientist and a junior research scientist) to enable proper use of the techniques. About thirty faculty, fifty graduate students and several researchers access the facilities on a routine basis. Several industry R&D organizations (SudChemie, Optical Dynamics and Hexion) utilize the facility. The established Institute for Advanced Materials at UofL has three main objectives: (a) enable a focused research effort leading to the rapid discovery of new materials and processes for advancing alternate energy conversion and storage technologies; (b) enable offering of several laboratory courses on advanced materials science and engineering; and (c) develop university-industry partnerships based on the advanced materials research. The Institute's efforts were guided by an advisory board comprising eminent researchers from outside KY. Initial research efforts were focused on the discovery of new materials and processes for solar cells and Li ion battery electrodes. Initial sets of results helped PIs to secure a successful EPSCoR cluster implementation grant by teaming with additional researchers from UK. In addition to research efforts, the project enabled several other outcomes: (a) helped recruit a junior faculty member (Dr. Moises Carreon) and establish a lab focused on meso-porous materials toward separation and catalysis; (b) enabled offering of three new, graduate level courses (Materials characterization using spectroscopy and microscopy; Electron and x-ray diffraction; and renewable energy systems); and (c) mentoring of a junior faculty members (Dr. Gerold Willing).« less

Synthesis and study of photovoltaic performance on various photoelectrode materials for DSSCs: Optimization of compact layer on nanometer thickness

NASA Astrophysics Data System (ADS)

Surya, Subramanian; Thangamuthu, Rangasamy; Senthil Kumar, Sakkarapalayam Murugesan; Murugadoss, Govindhasamy

2017-02-01

Dye-sensitized solar cells (DSSCs) have gained widespread attention in recent years because of their low production costs, ease of fabrication process and tuneable optical properties, such as colour and transparency. In this work, we explored a strategy wherein nanoparticles of pure TiO2, TiO2sbnd SnO2 nanocomposite, Sn (10%) doped TiO2 and SnO2 synthesized by the simple chemical precipitation method were employed as photoelectrodes to enhance the photovoltaic conversion efficiency of solar cells. The nanoparticles were characterized by different characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM with EDX), transmission electron microscopy (TEM), high resolution electron microscopy (HR-TEM), UV-Visible absorbance (UV-vis), photoluminescence (PL), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) measurements. Moreover, we also demonstrated the effect of thin compact layer in DSSCs by architecture with various precursor materials of different concentrations. We found that the optimized compact layer material TDIP (titanium diisopropoxide) with a concentration of 0.3 M % is produced the highest efficiency of 2.25% for Sn (10%) doped TiO2 electron transport material (ETM) and 4.38% was achieved for pure TiO2 ETM using SnCl2 compact layer with 0.1 M concentrations.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Reaction landscape of a pentadentate N5-ligated Mn(II) complex with O2˙- and H2O2 includes conversion of a peroxomanganese(III) adduct to a bis(μ-oxo)dimanganese(III,IV) species.

PubMed

Leto, Domenick F; Chattopadhyay, Swarup; Day, Victor W; Jackson, Timothy A

2013-09-28

Herein we describe the chemical reactivity of the mononuclear [Mn(II)(N4py)(OTf)](OTf) (1) complex with hydrogen peroxide and superoxide. Treatment of 1 with one equivalent superoxide at -40 °C in MeCN formed the peroxomanganese(III) adduct, [Mn(III)(O2)(N4py)](+) (2) in ~30% yield. Complex 2 decayed over time and the formation of the bis(μ-oxo)dimanganese(III,IV) complex, [Mn(III)Mn(IV)(μ-O)2(N4py)2](3+) (3) was observed. When 2 was formed in higher yields (~60%) using excess superoxide, the [Mn(III)(O2)(N4py)](+) species thermally decayed to Mn(II) species and 3 was formed in no greater than 10% yield. Treatment of [Mn(III)(O2)(N4py)](+) with 1 resulted in the formation of 3 in ~90% yield, relative to the concentration of [Mn(III)(O2)(N4py)](+). This reaction mimics the observed chemistry of Mn-ribonucleotide reductase, as it features the conversion of two Mn(II) species to an oxo-bridged Mn(III)Mn(IV) compound using O2(-) as oxidant. Complex 3 was independently prepared through treatment of 1 with H2O2 and base at -40 °C. The geometric and electronic structures of 3 were probed using electronic absorption, electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and X-ray absorption (XAS) spectroscopies. Complex 3 was structurally characterized by X-ray diffraction (XRD), which revealed the N4py ligand bound in an unusual tetradentate fashion.

Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

A simple aloe vera plant-extracted microwave and conventional combustion synthesis: Morphological, optical, magnetic and catalytic properties of CoFe2O4 nanostructures

NASA Astrophysics Data System (ADS)

Manikandan, A.; Sridhar, R.; Arul Antony, S.; Ramakrishna, Seeram

2014-11-01

Nanocrystalline magnetic spinel CoFe2O4 was synthesized by a simple microwave combustion method (MCM) using ferric nitrate, cobalt nitrate and Aloe vera plant extracted solution. For the comparative study, it was also prepared by a conventional combustion method (CCM). Powder X-ray diffraction, energy dispersive X-ray and selected-area electron diffraction results indicate that the as-synthesized samples have only single-phase spinel structure with high crystallinity and without the presence of other phase impurities. The crystal structure and morphology of the powders were revealed by high resolution scanning electron microscopy and transmission electron microscopy, show that the MCM products of CoFe2O4 samples contain sphere-like nanoparticles (SNPs), whereas the CCM method of samples consist of flake-like nanoplatelets (FNPs). The band gap of the samples was determined by UV-Visible diffuse reflectance and photoluminescence spectroscopy. The magnetization (Ms) results showed a ferromagnetic behavior of the CoFe2O4 nanostructures. The Ms value of CoFe2O4-SNPs is higher i.e. 77.62 emu/g than CoFe2O4-FNPs (25.46 emu/g). The higher Ms value of the sample suggest that the MCM technique is suitable for preparing high quality nanostructures for magnetic applications. Both the samples were successfully tested as catalysts for the conversion of benzyl alcohol. The resulting spinel ferrites were highly selective for the oxidation of benzyl alcohol and exhibit important difference among their activities. It was found that CoFe2O4-SNPs catalyst show the best performance, whereby 99.5% selectivity of benzaldehyde was achieved at close to 93.2% conversion.

Conversion electron spectrometry of Pu isotopes with a silicon drift detector.

PubMed

Pommé, S; Paepen, J; Peräjärvi, K; Turunen, J; Pöllänen, R

2016-03-01

An electron spectrometry set-up was built at IRMM consisting of a vacuum chamber with a moveable source holder and windowless Peltier-cooled silicon drift detector (SDD). The SDD is well suited for measuring low-energy x rays and electrons emitted from thin radioactive sources with low self-absorption. The attainable energy resolution is better than 0.5keV for electrons of 30keV. It has been used to measure the conversion electron spectra of three plutonium isotopes, i.e. (238)Pu, (239)Pu, (240)Pu, as well as (241)Am (being a decay product of (241)Pu). The obtained mixed x-ray and electron spectra are compared with spectra obtained with a close-geometry set-up using another SDD in STUK and spectra measured with a Si(Li) detector at IRMM. The potential of conversion electron spectrometry for isotopic analysis of mixed plutonium samples is investigated. With respect to the (240)Pu/(239)Pu isotopic ratio, the conversion electron peaks of both isotopes are more clearly separated than their largely overlapping peaks in alpha spectra. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Development of Inorganic Nanomaterials as Photocatalysts for the Water Splitting Reaction

NASA Astrophysics Data System (ADS)

Frame, Fredrick Andrew

The photochemical water splitting reaction is of great interest for converting solar energy into usable fuels. This dissertation focuses on the development of inorganic nanoparticle catalysts for solar energy driven conversion of water into hydrogen and oxygen. The results from these selected studies have allowed greater insight into nanoparticle chemistry and the role of nanoparticles in photochemical conversion of water in to hydrogen and oxygen. Chapter 2 shows that CdSe nanoribbons have photocatalytic activity for hydrogen production from water in the presence of Na2S/Na2SO 3 as sacrificial electron donors in both UV and visible light. Quantum confinement of this material leads to an extended bandgap of 2.7 eV and enables the photocatalytic activity of this material. We report on the photocatalytic H2 evolution, and its dependence on platinum co-catalysts, the concentration of the electron donor, and the wavelength of incident radiation. Transient absorption measurements reveal decay of the excited state on multiple timescales, and an increase of lifetimes of trapped electrons due to the sacrificial electron donors. In chapter 3, we explore the catalytic activity of citrate-capped CdSe quantum dots. We show that the process is indeed catalytic for these dots in aqueous 0.1 M Na2S:Na2SO3, but not in pure water. Furthermore, optical spectroscopy was used to report electronic transitions in the dots and electron microscopy was used to obtain morphology of the catalyst. Interestingly, an increasing catalytic rate is noted for undialyzed catalyst. Dynamic light scattering experiments show an increased hydrodynamic radius in the case of undialyzed CdSe dots in donor solution. In chapter 4 we show that CdSe:MoS2 nanoparticle composites with improved catalytic activity can be assembled from CdSe and MoS2 nanoparticle building units. We report on the photocatalytic H 2 evolution, quantum efficiency using LED irriadiation, and its dependence on the co-catalyst loading. Furthermore, optical spectroscopy, cyclic voltammetry, and electron microscopy were used to obtain morphology, optical properties, and electronic structure of the catalysts. In chapter 5, illumination with visible light (lambda > 400 nm) photoconverts a red V2O5 gel in aqueous methanol solution into a green VO2 gel. The presence of V(4+) in the green VO2 gel is supported by Electron Energy Loss Spectra. High-resolution electron micrographs, powder X-ray diffraction, and selective area electron diffraction (SAED) data show that the crystalline structure of the V2O5 gel is retained upon reduction. After attachment of colloidal Pt nanoparticles, H2 evolution proceeds catalytically on the VO2 gel. The Pt nanoparticles reduce the H2 evolution overpotential. However, the activity of the new photocatalyst remains limited by the VO2 conduction band edge just below the proton reduction potential. Chapter 6 studies the ability of IrO2 to evolve oxygen from aqueous solutions under UV irradiation. We show that visible illumination (lambda > 400 nm) of iridium dioxide (IrO2) nanocrystals capped in succinic acid in aqueous sodium persulfate solution leads to catalytic oxygen evolution. While the majority of catalytic hydrogen evolution comes from UV light, the process can still be driven with visible light. Morphology, optical properties, surface photovoltage measurements, and oxygen evolution rates are discussed.

Analytical Chemistry of Surfaces: Part II. Electron Spectroscopy.

ERIC Educational Resources Information Center

Hercules, David M.; Hercules, Shirley H.

1984-01-01

Discusses two surface techniques: X-ray photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES). Focuses on fundamental aspects of each technique, important features of instrumentation, and some examples of how ESCA and AES have been applied to analytical surface problems. (JN)

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors

NASA Astrophysics Data System (ADS)

Muralee Gopi, Chandu V. V.; Ravi, Seenu; Rao, S. Srinivasa; Eswar Reddy, Araveeti; Kim, Hee-Je

2017-04-01

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg-1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices.

Carbon nanotube/metal-sulfide composite flexible electrodes for high-performance quantum dot-sensitized solar cells and supercapacitors.

PubMed

Muralee Gopi, Chandu V V; Ravi, Seenu; Rao, S Srinivasa; Eswar Reddy, Araveeti; Kim, Hee-Je

2017-04-19

Carbon nanotubes (CNT) and metal sulfides have attracted considerable attention owing to their outstanding properties and multiple application areas, such as electrochemical energy conversion and energy storage. Here we describes a cost-effective and facile solution approach to the preparation of metal sulfides (PbS, CuS, CoS, and NiS) grown directly on CNTs, such as CNT/PbS, CNT/CuS, CNT/CoS, and CNT/NiS flexible electrodes for quantum dot-sensitized solar cells (QDSSCs) and supercapacitors (SCs). X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscopy confirmed that the CNT network was covered with high-purity metal sulfide compounds. QDSSCs equipped with the CNT/NiS counter electrode (CE) showed an impressive energy conversion efficiency (η) of 6.41% and remarkable stability. Interestingly, the assembled symmetric CNT/NiS-based polysulfide SC device exhibited a maximal energy density of 35.39 W h kg -1 and superior cycling durability with 98.39% retention after 1,000 cycles compared to the other CNT/metal-sulfides. The elevated performance of the composites was attributed mainly to the good conductivity, high surface area with mesoporous structures and stability of the CNTs and the high electrocatalytic activity of the metal sulfides. Overall, the designed composite CNT/metal-sulfide electrodes offer an important guideline for the development of next level energy conversion and energy storage devices.

Surface Termination Conversion during SrTiO3 Thin Film Growth Revealed by X-ray Photoelectron Spectroscopy

PubMed Central

Baeumer, Christoph; Xu, Chencheng; Gunkel, Felix; Raab, Nicolas; Heinen, Ronja Anika; Koehl, Annemarie; Dittmann, Regina

2015-01-01

Emerging electrical and magnetic properties of oxide interfaces are often dominated by the termination and stoichiometry of substrates and thin films, which depend critically on the growth conditions. Currently, these quantities have to be measured separately with different sophisticated techniques. This report will demonstrate that the analysis of angle dependent X-ray photoelectron intensity ratios provides a unique tool to determine both termination and stoichiometry simultaneously in a straightforward experiment. Fitting the experimental angle dependence with a simple analytical model directly yields both values. The model is calibrated through the determination of the termination of SrTiO3 single crystals after systematic pulsed laser deposition of sub-monolayer thin films of SrO. We then use the model to demonstrate that during homoepitaxial SrTiO3 growth, excess Sr cations are consumed in a self-organized surface termination conversion before cation defects are incorporated into the film. We show that this termination conversion results in insulating properties of interfaces between polar perovskites and SrTiO3 thin films. These insights about oxide thin film growth can be utilized for interface engineering of oxide heterostructures. In particular, they suggest a recipe for obtaining two-dimensional electron gases at thin film interfaces: SrTiO3 should be deposited slightly Ti-rich to conserve the TiO2-termination. PMID:26189436

Template-free hydrothermal synthesis of beaded nanochain bundles of ZnO and their application as photoanode in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Ballal, Reshma; Shinde, Manish; Waghadkar, Yogesh; Arbuj, Sudhir; Rane, Sunit; Chauhan, Ratna

2018-02-01

ZnO shows promising candidature as photoanode material for dye-sensitized solar cells (DSSCs) due to its high bulk electron mobility and easily tailorable geometrical structures. The objective of this study is to facilitate the development of highly porous hierarchical ZnO for enhanced power conversion efficiency in dye-sensitized solar cells (DSSC) due to its greater dye adsorption. This study investigated the influence of reaction temperatures of 120 °C (sample Z-1) and 180 °C (sample Z-2) in hydrothermal synthesis on structural, morphological and optical properties of resultant ZnO nanostructures and their performance as photoanode material in DSSCs. The synthesized beaded nanochain bundles of ZnO, with multilayered and highly ordered texture, have diameters of several micrometers. Structural and morphological analysis shows that the ZnO beaded nanochain-like architectures possess wurtzite crystalline nature. These morphological improvements (beaded nanochains) of ZnO were found to exhibit higher dye loading and conversion efficiency due to increase in the surface area while reducing charge recombination. The maximum conversion efficiency was obtained with Z-1 and Z-2 is 2.95 and 3.56% with photocurrent of 7.73 and 9.24 mA/cm2, respectively. The obtained results pertaining to the DSSC performance studies were corroborated by the impedance spectroscopy data.

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Solution-Processible Crystalline NiO Nanoparticles for High-Performance Planar Perovskite Photovoltaic Cells.

PubMed

Kwon, Uisik; Kim, Bong-Gi; Nguyen, Duc Cuong; Park, Jong-Hyeon; Ha, Na Young; Kim, Seung-Joo; Ko, Seung Hwan; Lee, Soonil; Lee, Daeho; Park, Hui Joon

2016-07-28

In this work, we report on solution-based p-i-n-type planar-structured CH3NH3PbI3 perovskite photovoltaic (PV) cells, in which precrystallized NiO nanoparticles (NPs) without post-treatment are used to form a hole transport layer (HTL). X-ray diffraction and high-resolution transmission electron microscopy showed the crystallinity of the NPs, and atomic force microscopy and scanning electron microscopy confirmed the uniform surfaces of the resultant NiO thin film and the subsequent perovskite photoactive layer. Compared to the conventional poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PSS) HTL, the NiO HTL had excellent energy-level alignment with that of CH3NH3PbI3 and improved electron-blocking capability, as analyzed by photoelectron spectroscopy and diode modeling, resulting in Voc ~0.13 V higher than conventional PSS-based devices. Consequently, a power conversion efficiency (PCE) of 15.4% with a high fill factor (FF, 0.74), short-circuit current density (Jsc, 20.2 mA·cm(-2)), and open circuit voltage (Voc, 1.04 V) having negligible hysteresis and superior air stability has been achieved.

Solution-Processible Crystalline NiO Nanoparticles for High-Performance Planar Perovskite Photovoltaic Cells

PubMed Central

Kwon, Uisik; Kim, Bong-Gi; Nguyen, Duc Cuong; Park, Jong-Hyeon; Ha, Na Young; Kim, Seung-Joo; Ko, Seung Hwan; Lee, Soonil; Lee, Daeho; Park, Hui Joon

2016-01-01

In this work, we report on solution-based p-i-n-type planar-structured CH3NH3PbI3 perovskite photovoltaic (PV) cells, in which precrystallized NiO nanoparticles (NPs) without post-treatment are used to form a hole transport layer (HTL). X-ray diffraction and high-resolution transmission electron microscopy showed the crystallinity of the NPs, and atomic force microscopy and scanning electron microscopy confirmed the uniform surfaces of the resultant NiO thin film and the subsequent perovskite photoactive layer. Compared to the conventional poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL, the NiO HTL had excellent energy-level alignment with that of CH3NH3PbI3 and improved electron-blocking capability, as analyzed by photoelectron spectroscopy and diode modeling, resulting in Voc ~0.13 V higher than conventional PEDOT:PSS-based devices. Consequently, a power conversion efficiency (PCE) of 15.4% with a high fill factor (FF, 0.74), short-circuit current density (Jsc, 20.2 mA·cm−2), and open circuit voltage (Voc, 1.04 V) having negligible hysteresis and superior air stability has been achieved. PMID:27465263

Bio-inspired sustainable and green synthesis of plasmonic Ag/AgCl nanoparticles for enhanced degradation of organic compound from aqueous phase.

PubMed

Devi, Th Babita; Ahmaruzzaman, M

2016-09-01

In the current study, we report the utilization of the biogenic potential of Benincasa hispida (ash gourd) peel extract for the synthesis of Ag embedded AgCl nanoparticles nanoparticles (Ag/AgCl NPs) without the use of any external organic solvents. The appearance of dark brown color from the pale yellow color confirmed the formation of Ag/AgCl nanoparticles which was further validated by absorbance peak using UV-visible spectroscopy. The phytochemicals (flavones) present in the B. hispida peel extract acts as a reducing/stabilizing agents. The morphology and size of the synthesized NPs were characterized by transmission electron microscope (TEM), selected area electron microscope (SAED) and high resolution transmission electron microscope (HR-TEM). FT-IR spectra of the B. hispida peel extract and after the development of nanoparticles are determined to identify the functional groups responsible for the conversion of metal ions to metal nanoparticles. The synthesized nanoparticles showed an excellent photocatalytic property in the degradation of toxic dye like malachite green oxalate under sunlight irradiation. For the first time, malachite green oxalate dye was degraded by Ag/AgCl nanoparticles under sunlight irradiation.

Conditions for a carrier multiplication in amorphous-selenium based photodetector

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

Masuzawa, Tomoaki; Kuniyoshi, Shingo; Onishi, Masanori

2013-02-18

Amorphous selenium is a promising candidate for high sensitivity photodetector due to its unique carrier multiplication phenomenon. More than 10 carriers can be generated per incident photon, which leads to high photo-conversion efficiency of 1000% that allows real-time imaging in dark ambient. However, application of this effect has been limited to specific devices due to the lack in material characterization. In this article, mechanism of carrier multiplication has been clarified using time-of-flight secondary ion mass spectroscopy and Raman spectroscopy. A prototype photodetector achieved photo conversion efficiency of 4000%, which explains the signal enhancement mechanism in a-Se based photodetector.

Synchronized energy and electron transfer processes in covalently linked CdSe-squaraine dye-TiO2 light harvesting assembly.

PubMed

Choi, Hyunbong; Santra, Pralay K; Kamat, Prashant V

2012-06-26

Manipulation of energy and electron transfer processes in a light harvesting assembly is an important criterion to mimic natural photosynthesis. We have now succeeded in sequentially assembling CdSe quantum dot (QD) and squaraine dye (SQSH) on TiO(2) film and couple energy and electron transfer processes to generate photocurrent in a hybrid solar cell. When attached separately, both CdSe QDs and SQSH inject electrons into TiO(2) under visible-near-IR irradiation. However, CdSe QD if linked to TiO(2) with SQSH linker participates in an energy transfer process. The hybrid solar cells prepared with squaraine dye as a linker between CdSe QD and TiO(2) exhibited power conversion efficiency of 3.65% and good stability during illumination with global AM 1.5 solar condition. Transient absorption spectroscopy measurements provided further insight into the energy transfer between excited CdSe QD and SQSH (rate constant of 6.7 × 10(10) s(-1)) and interfacial electron transfer between excited SQSH and TiO(2) (rate constant of 1.2 × 10(11) s(-1)). The synergy of covalently linked semiconductor quantum dots and near-IR absorbing squaraine dye provides new opportunities to harvest photons from selective regions of the solar spectrum in an efficient manner.

Single-Electron Detection and Spectroscopy via Relativistic Cyclotron Radiation.

PubMed

Asner, D M; Bradley, R F; de Viveiros, L; Doe, P J; Fernandes, J L; Fertl, M; Finn, E C; Formaggio, J A; Furse, D; Jones, A M; Kofron, J N; LaRoque, B H; Leber, M; McBride, E L; Miller, M L; Mohanmurthy, P; Monreal, B; Oblath, N S; Robertson, R G H; Rosenberg, L J; Rybka, G; Rysewyk, D; Sternberg, M G; Tedeschi, J R; Thümmler, T; VanDevender, B A; Woods, N L

2015-04-24

It has been understood since 1897 that accelerating charges must emit electromagnetic radiation. Although first derived in 1904, cyclotron radiation from a single electron orbiting in a magnetic field has never been observed directly. We demonstrate single-electron detection in a novel radio-frequency spectrometer. The relativistic shift in the cyclotron frequency permits a precise electron energy measurement. Precise beta electron spectroscopy from gaseous radiation sources is a key technique in modern efforts to measure the neutrino mass via the tritium decay end point, and this work demonstrates a fundamentally new approach to precision beta spectroscopy for future neutrino mass experiments.

Influence of Conditioning Time of Universal Adhesives on Adhesive Properties and Enamel-Etching Pattern.

PubMed

Cardenas, A M; Siqueira, F; Rocha, J; Szesz, A L; Anwar, M; El-Askary, F; Reis, A; Loguercio, A

2016-01-01

To evaluate the effect of application protocol in resin-enamel microshear bond strength (μSBS), in situ degree of conversion, and etching pattern of three universal adhesive systems. Sixty-three extracted third molars were sectioned in four parts (buccal, lingual, and proximals) and divided into nine groups, according to the combination of the main factors-Adhesive (Clearfil Universal, Kuraray Noritake Dental Inc, Tokyo, Japan; Futurabond U, VOCO, Cuxhaven, Germany; and Scotchbond Universal Adhesive, 3M ESPE, St Paul, MN, USA)-and enamel treatment/application time (etch-and-rinse mode [ER], self-etch [SE] application for 20 seconds [SE20], and SE application for 40 seconds [SE40]). Specimens were stored in water (37°C/24 h) and tested at 1.0 mm/min (μSBS). The degree of conversion of the adhesives at the resin-enamel interfaces was evaluated using micro-Raman spectroscopy. The enamel-etching pattern was evaluated under a scanning electron microscope. Data were analyzed with two-way analysis of variance and Tukey test (α=0.05). In general, the application of the universal adhesives in the SE40 produced μSBS and degree of conversion that were higher than in the SE20 (p<0.01) and similar to the ER mode. The deepest enamel-etching pattern was obtained in the ER mode, followed by the SE40. The active and prolonged application of universal adhesives in the SE mode may be a viable alternative to increase the degree of conversion, etching pattern, and resin-enamel bond strength.

Photon up-conversion production in Tb{sup 3+}–Yb{sup 3+} co-doped CaF{sub 2} phosphors prepared by combustion synthesis

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

Rakov, Nikifor, E-mail: nikifor.gomez@univasf.edu.br; Guimarães, Renato B.; Maciel, Glauco S., E-mail: glauco@if.uff.br

2016-02-15

Graphical abstract: Up-conversion luminescence from Tb{sup 3+} obtained by energy transfer from Yb{sup 3+} pairs in CaF{sub 2} powder prepared by combustion synthesis. - Highlights: • Calcium fluoride (CaF{sub 2}) powders were prepared by combustion synthesis. • Rare-earth ions doped in this material were found in interstitial sites. • Cooperative up-conversion was observed in Tb{sup 3+}:Yb{sup 3+}:CaF{sub 2} powder. • Energy transfer between Tb{sup 3+} and pairs of Yb{sup 3+} was analyzed using rate equations. - Abstract: Calcium fluoride (CaF{sub 2}) crystalline powders were successfully prepared by the combustion synthesis method. The powder material containing luminescent rare-earth ions, more specificallymore » terbium (Tb{sup 3+}) and ytterbium (Yb{sup 3+}), was studied by X-ray diffraction, scanning electronic microscopy and optical spectroscopy. These ions are allocated in charge compensated interstitial positions of tetragonal (C{sub 4v}) and trigonal (C{sub 3v}) symmetry sites of the cubic (O{sub h}) CaF{sub 2} lattice. Up-conversion (UC) luminescence in Tb{sup 3+} was achieved using a low power diode laser operating at 975 nm. Tb{sup 3+} is insensitive to near-infrared radiation but UC can be achieved via energy transfer from pairs of Yb{sup 3+} ions to Tb{sup 3+} ions. The UC luminescence dynamics of Tb{sup 3+} was used to study the energy transfer mechanism.« less

Ion-beam mixing at Fe:metallic-glass (Fe67Co18B14Si1) interface: A conversion-electron Mössbauer spectroscopic study

NASA Astrophysics Data System (ADS)

Bhandarkar, Y. V.; Ghaisas, S. V.; Ogale, S. B.

1988-07-01

Ion-beam mixing at an Fe:metallic glass (Fe67Co18B14Si1) interface is studied by employing the technique of conversion electron Mössbauer spectroscopy (CEMS). A 230-Å-thick overlayer of iron (enriched to 33% in the concentration of 57Fe Mössbauer isotope) was deposited on the shiny surface of metallic glass and such composites were bombarded with 100-keV Kr+ ions at dose values in the range between 1×1015 and 2×1016 ions/cm2. The transformations in the local atomic arrangements across the interface were investigated by monitoring the changes in the hyperfine-interaction parameters. It is shown that mixing leads to significant changes in the composition, in the vicinity of the interface as a function of the ion dose. At low dose (1×1015 ions/cm2) the local atomic coordination is found to be rich in the transition-metal concentration, while at a higher dose (2×1016 ions/cm2) it is observed to be rich in the boron concentration. Interestingly, at an intermediate dose 1×1016 ions/cm2 the composite near the interface region partially crystallizes and this structural state is found to revert back to the amorphous state upon thermal annealing at 300 °C. The observations made on the basis of CEMS are well supported by x-ray diffraction measurements.

Luminescent and transparent nanopaper based on rare-earth up-converting nanoparticle grafted nanofibrillated cellulose derived from garlic skin.

PubMed

Zhao, Jingpeng; Wei, Zuwu; Feng, Xin; Miao, Miao; Sun, Lining; Cao, Shaomei; Shi, Liyi; Fang, Jianhui

2014-09-10

Highly flexible, transparent, and luminescent nanofibrillated cellulose (NFC) nanopaper with heterogeneous network, functionalized by rare-earth up-converting luminescent nanoparticles (UCNPs), was rapidly synthesized by using a moderate pressure extrusion paper-making process. NFC was successfully prepared from garlic skin using an efficient extraction approach combined with high frequency ultrasonication and high pressure homogenization after removing the noncellulosic components. An efficient epoxidation treatment was carried out to enhance the activity of the UCNPs (NaYF4:Yb,Er) with oleic acid ligand capped on the surface. The UCNPs after epoxidation then reacted with NFC in aqueous medium to form UCNP-grafted NFC nanocomposite (NFC-UCNP) suspensions at ambient temperature. Through the paper-making process, the assembled fluorescent NFC-UCNP hybrid nanopaper exhibits excellent properties, including high transparency, strong up-conversion luminescence, and good flexibility. The obtained hybrid nanopaper was characterized by transmission electron microscopy (TEM), atomic force microscope (AFM), Fourier transform infrared spectroscopy (FTIR), field emission-scanning electron microscope (FE-SEM), up-conversion luminescence (UCL) spectrum, and ultraviolet and visible (UV-vis) spectrophotometer. The experimental results demonstrate that the UCNPs have been successfully grafted to the NFC matrix with heterogeneous network. And the superiorly optical transparent and luminescent properties of the nanopaper mainly depend on the ratio of UCNPs to NFC. Of importance here is that, NFC and UCNPs afford the nanopaper a prospective candidate for multimodal anti-counterfeiting, sensors, and ion probes applications.

In Situ STEM-EELS observation of nanoscale interfacial phenomena in all-solid-state batteries

DOE PAGES

Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei; ...

2016-05-03

Behaviors of functional interfaces are crucial factors in the performance and safety of energy storage and conversion devices. Indeed, solid electrode–solid electrolyte interfacial impedance is now considered the main limiting factor in all-solid-state batteries rather than low ionic conductivity of the solid electrolyte. In this paper, we present a new approach to conducting in situ scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) in order to uncover the unique interfacial phenomena related to lithium ion transport and its corresponding charge transfer. Our approach allowed quantitative spectroscopic characterization of a galvanostatically biased electrochemical system under in situmore » conditions. Using a LiCoO 2/LiPON/Si thin film battery, an unexpected structurally disordered interfacial layer between LiCoO 2 cathode and LiPON electrolyte was discovered to be inherent to this interface without cycling. During in situ charging, spectroscopic characterization revealed that this interfacial layer evolved to form highly oxidized Co ions species along with lithium oxide and lithium peroxide species. These findings suggest that the mechanism of interfacial impedance at the LiCoO 2/LiPON interface is caused by chemical changes rather than space charge effects. Finally, insights gained from this technique will shed light on important challenges of interfaces in all-solid-state energy storage and conversion systems and facilitate improved engineering of devices operated far from equilibrium.« less

Plasmon enhanced power conversion efficiency in inverted bulk heterojunction organic solar cell

NASA Astrophysics Data System (ADS)

Mohan, Minu; Ramkumar, S.; Namboothiry, Manoj A. G.

2017-08-01

P3HT:PCBM is one of the most studied polymer-fullerene system. However the reported power conversion efficiency (PCE) values falls within the range of 4% to 5%. The thin film architecture in OPVs exhibits low PCE compared to inorganic photovoltaic cells. This is mainly due to the low exciton diffusion length that limits the active layer thickness which in turn reduces the absorption of incident light. Several strategies are adapted in order to increase the absorption in the active layer without increasing the film thickness. Inclusion of metal nanoparticles into the polymer layer of bulk heterojunction (BHJ) solar cells is one of the promising methods. Incorporation of metal nanostructures increases the absorption of organic materials due to the high electromagnetic field strength in the vicinity of the excited surface plasmons. In this work, we used 60 nm Au plasmonic structures to improve the efficiency of organic solar cell. The prepared metal nano structures were characterized through scanning electron microscopy (SEM), and UV-Visible spectroscopy techniques. These prepared metallic nanoparticles can be incorporated either into the electron transport layer (ETL) or into the active P3HT:PC71BM layer. The effect of incorporation of plasmonic gold (Au) nanoparticle in the inverted bulk heterojunction organic photovoltaic cells (OPVs) of P3HT:PC71BM fabricated in ambient air condition is in progress. Initial studies shows an 8.5% enhancement in the PCE with the incorporation of Au nanoparticles under AM1.5G light of intensity 1 Sun.

Copper interstitial recombination centers in Cu 3 N

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

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

Preparation of Copper (II) Containing Phosphomolybdic Acid Salt as Catalyst for the Synthesis of Biodiesel by Esterification.

PubMed

Cai, Jie; Zhang, Qiu-Yun; Wei, Fang-Fang; Huang, Jin-Shu; Feng, Yun-Mei; Ma, Hai-Tao; Zhang, Yutao-

2018-04-01

Copper (II) containing phosphomolybdic acid (PMA) catalysts were synthesized by ion exchange method and characterization using various physico-chemical techniques such as X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TG) and scanning electron microscopy (SEM). The characterization results showed that the Keggin ions were retained in the catalysts and possessed well thermal stability. The catalytic esterification of lauric acid with methanol could be easily achieved about 78.7% conversion under optimum condition, the catalyst also contributed to the stability of the catalyst in which it can be reused for a certain time. This study demonstrated an alternative approach to biodiesel production with high efficiency by Cu (II) ion exchanged phosphomolybdic acid catalyst in the esterification catalytic.

Integrated Mg/TiO2-ionic liquid system for deep desulfurization

NASA Astrophysics Data System (ADS)

Yin, Yee Cia; Kait, Chong Fai; Fatimah, Hayyiratul; Wilfred, Cecilia

2014-10-01

A series of Mg/TiO2 photocatalysts were prepared using wet impregnation method followed by calcination at 300, 400 and 500°C for 1 h. The photocatalysts were characterized using Thermal Gravimetric Analysis, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, and Field Emission Scanning Electron Microscopy. The performance for deep desulfurization was investigated using model oil with 100 ppm sulfur (in the form of dibenzothiophene). The integrated system involves photocatalytic oxidation followed by ionic liquid-extraction processes. The best performing photocatalyst was 0.25wt% Mg loaded on titania calcined at 400°C (0.25Mg400), giving 98.5% conversion of dibenzothiophene to dibenzothiophene sulfone. The highest extraction efficiency of 97.8% was displayed by 1,2-diethylimidazolium diethylphosphate. The overall total sulfur removal was 96.3%.

Copper interstitial recombination centers in Cu 3 N

DOE PAGES

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; ...

2018-06-04

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

ZnO/ZnSxSe1-x core/shell nanowire arrays as photoelectrodes with efficient visible light absorption

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Zhan, Xueying; Wang, Yajun; Safdar, Muhammad; Niu, Mutong; Zhang, Jinping; Huang, Ying; He, Jun

2012-08-01

ZnO/ZnSxSe1-x core/shell nanowires have been synthesized on n+-type silicon substrate via a two-step chemical vapor deposition method. Transmission electron microscopy reveals that ZnSxSe1-x can be deposited on the entire surface of ZnO nanowire, forming coaxial heterojunction along ZnO nanowire with very smooth shell surface and high shell thickness uniformity. The photoelectrode after deposition of the ternary alloy shell significantly improves visible light absorption efficiency. Electrochemical impedance spectroscopy results explicitly indicate that the introduction of ZnSxSe1-x shell to ZnO nanowires effectively improves the photogenerated charge separation process. Our finding opens up an efficient means for achieving high efficient energy conversion devices.

Application of epithermal neutron activation in multielement analysis of silicate rocks employing both coaxial Ge(Li) and low energy photon detector systems

USGS Publications Warehouse

Baedecker, P.A.; Rowe, J.J.; Steinnes, E.

1977-01-01

The instrumental activation analysis of silicate rocks using epithermal neutrons has been studied using both high resolution coaxial Ge(Li) detectors and low energy photon detectors, and applied to the determination of 23 elements in eight new U.S.G.S. standard rocks. The analytical use X-ray peaks associated with electron capture or internal conversion processes has been evaluated. Of 28 elements which can be considered to be determinable by instrumental means, the epithermal activation approach is capable of giving improved sensitivity and precision in 16 cases, over the normal INAA procedure. In eleven cases the use of the low energy photon detector is thought to show advantages over convertional coaxial Ge(Li) spectroscopy. ?? 1977 Akade??miai Kiado??.

Martensitic phase transformations in the nanostructured surface layers induced by mechanical attrition treatment

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

Ni Zhichun; Wang Xiaowei; Wu Erdong

2005-12-01

Conversion electron Moessbauer spectroscopy (CEMS) and x-ray diffraction (XRD) analysis have been used to investigate the relationship between characteristics of phase transformation and the treatment time in surface nanocrystallized 316L stainless steel induced by surface mechanical attrition treatment (SMAT). A similar trend of development of the martensitic phase upon the treatment time has been observed from both CEMS and XRD measurements. However, in the CEMS measurement, two types of martensite phase with different magnetic hyperfine fields are revealed. Based on a random distribution of the non-iron coordinating atoms, a three-element theoretical model is developed to illustrate the difference of twomore » types of martensite phase. The calculated results indicate the segregation of the non-iron atoms associated with SMAT treatment.« less

Degradation of the Giant Magnetoresistance in Fe/Cr Multilayers Due to Ar-Ion Beam Mixing

NASA Astrophysics Data System (ADS)

Kopcewicz, M.; Stobiecki, F.; Jagielski, J.; Szymański, B.; Schmidt, M.; Kalinowska, J.

2002-12-01

The influence of 200 keV Ar-ion irradiation on the interlayer coupling in the Fe/Cr multilayer system exhibiting the giant magnetoresistance effect (GMR) is studied by conversion electron Mössbauer spectroscopy (CEMS), VSM hysteresis loops, magnetoresistivity and electric resistivity measurements and supplemented by the small-angle X-ray diffraction (SAXRD). The increase of Ar ion dose causes an increase of interface roughness, as evidenced by the increase of the Fe step-sites detected by CEMS as a result of which the GMR gradually decreases and vanishes at doses exceeding 1×1014 Ar/cm2. A degradation of GMR with increasing Ar-ion dose is related to the formation of pinholes between Fe layers and the decrease of the antiferromagnetically coupled fraction.

Redox-active thionine-graphene oxide hybrid nanosheet: one-pot, rapid synthesis, and application as a sensing platform for uric acid.

PubMed

Sun, Zhoumin; Fu, Haiying; Deng, Liu; Wang, Jianxiu

2013-01-25

In this paper, we fabricate a sensitive and stable amperometric UA amperometric biosensor using nanobiocomposite derived from thionine modified graphene oxide in this study. A simple wet-chemical strategy for synthesis of thionine-graphene oxide hybrid nanosheets (T-GOs) through π-π stacking has been demonstrated. Various techniques, such as UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscopy (AFM) and electrochemistry have been utilized to characterize the formation of the T-GOs. Due to the synergistic effect between thionine and graphene oxide, the nanosheets exhibited excellent performance toward H(2)O(2) reduction. The incorporation of thionine onto graphene oxide surface resulted in more than a twice increase in the amperometric response to H(2)O(2) of the thionine modified electrode. The as-formed T-GOs also served as a biocompatible matrix for enzyme assembly and a mediator to facilitate the electron transfer between the enzyme and the electrode. Using UOx as a model system, we have developed a simple and effective sensing platform for assay of uric acid at physiological levels. UA has been successfully detected at -0.1 V without any interference due to other electroactive compounds at physiological levels of glucose (5 mM), ascorbic acid (0.1 mM), noradrenalin (0.1 mM), and dopamine (0.1 mM). The response displays a good linear range from 0.02 to 4.5 mM with detection limit 7 μM. The application of this modified electrode in blood and urine UA exhibited a good performance. The robust and advanced hybrid materials might hold great promise in biosensing, energy conversion, and biomedical and electronic systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical Biosensors - Sensor Principles and Architectures

PubMed Central

Grieshaber, Dorothee; MacKenzie, Robert; Vörös, Janos; Reimhult, Erik

2008-01-01

Quantification of biological or biochemical processes are of utmost importance for medical, biological and biotechnological applications. However, converting the biological information to an easily processed electronic signal is challenging due to the complexity of connecting an electronic device directly to a biological environment. Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal. Over the past decades several sensing concepts and related devices have been developed. In this review, the most common traditional techniques, such as cyclic voltammetry, chronoamperometry, chronopotentiometry, impedance spectroscopy, and various field-effect transistor based methods are presented along with selected promising novel approaches, such as nanowire or magnetic nanoparticle-based biosensing. Additional measurement techniques, which have been shown useful in combination with electrochemical detection, are also summarized, such as the electrochemical versions of surface plasmon resonance, optical waveguide lightmode spectroscopy, ellipsometry, quartz crystal microbalance, and scanning probe microscopy. The signal transduction and the general performance of electrochemical sensors are often determined by the surface architectures that connect the sensing element to the biological sample at the nanometer scale. The most common surface modification techniques, the various electrochemical transduction mechanisms, and the choice of the recognition receptor molecules all influence the ultimate sensitivity of the sensor. New nanotechnology-based approaches, such as the use of engineered ion-channels in lipid bilayers, the encapsulation of enzymes into vesicles, polymersomes, or polyelectrolyte capsules provide additional possibilities for signal amplification. In particular, this review highlights the importance of the precise control over the delicate interplay between surface nano-architectures, surface functionalization and the chosen sensor transducer principle, as well as the usefulness of complementary characterization tools to interpret and to optimize the sensor response. PMID:27879772

Vibrational cooling dynamics of a [FeFe]-hydrogenase mimic probed by time-resolved infrared spectroscopy.

PubMed

Caplins, Benjamin W; Lomont, Justin P; Nguyen, Son C; Harris, Charles B

2014-12-11

Picosecond time-resolved infrared spectroscopy (TRIR) was performed for the first time on a dithiolate bridged binuclear iron(I) hexacarbonyl complex ([Fe₂(μ-bdt)(CO)₆], bdt = benzene-1,2-dithiolate) which is a structural mimic of the active site of the [FeFe]-hydrogenase enzyme. As these model active sites are increasingly being studied for their potential in photocatalytic systems for hydrogen production, understanding their excited and ground state dynamics is critical. In n-heptane, absorption of 400 nm light causes carbonyl loss with low quantum yield (<10%), while the majority (ca. 90%) of the parent complex is regenerated with biexponential kinetics (τ₁ = 21 ps and τ₂ = 134 ps). In order to understand the mechanism of picosecond bleach recovery, a series of UV-pump TRIR experiments were performed in different solvents. The long time decay (τ₂) of the transient spectra is seen to change substantially as a function of solvent, from 95 ps in THF to 262 ps in CCl₄. Broadband IR-pump TRIR experiments were performed for comparison. The measured vibrational lifetimes (T₁(avg)) of the carbonyl stretches were found to be in excellent correspondence to the observed τ₂ decays in the UV-pump experiments, signifying that vibrationally excited carbonyl stretches are responsible for the observed longtime decays. The fast spectral evolution (τ₁) was determined to be due to vibrational cooling of low frequency modes anharmonically coupled to the carbonyl stretches that were excited after electronic internal conversion. The results show that cooling of both low and high frequency vibrational modes on the electronic ground state give rise to the observed picosecond TRIR transient spectra of this compound, without the need to invoke electronically excited states.

The SPEDE spectrometer

NASA Astrophysics Data System (ADS)

Papadakis, P.; Cox, D. M.; O'Neill, G. G.; Borge, M. J. G.; Butler, P. A.; Gaffney, L. P.; Greenlees, P. T.; Herzberg, R.-D.; Illana, A.; Joss, D. T.; Konki, J.; Kröll, T.; Ojala, J.; Page, R. D.; Rahkila, P.; Ranttila, K.; Thornhill, J.; Tuunanen, J.; Van Duppen, P.; Warr, N.; Pakarinen, J.

2018-03-01

The electron spectrometer, SPEDE, has been developed and will be employed in conjunction with the Miniball spectrometer at the HIE-ISOLDE facility, CERN. SPEDE allows for direct measurement of internal conversion electrons emitted in-flight, without employing magnetic fields to transport or momentum filter the electrons. Together with the Miniball spectrometer, it enables simultaneous observation of γ rays and conversion electrons in Coulomb excitation experiments using radioactive ion beams.

Low-loss electron energy loss spectroscopy: An atomic-resolution complement to optical spectroscopies and application to graphene

DOE PAGES

Kapetanakis, Myron; Zhou, Wu; Oxley, Mark P.; ...

2015-09-25

Photon-based spectroscopies have played a central role in exploring the electronic properties of crystalline solids and thin films. They are a powerful tool for probing the electronic properties of nanostructures, but they are limited by lack of spatial resolution. On the other hand, electron-based spectroscopies, e.g., electron energy loss spectroscopy (EELS), are now capable of subangstrom spatial resolution. Core-loss EELS, a spatially resolved analog of x-ray absorption, has been used extensively in the study of inhomogeneous complex systems. In this paper, we demonstrate that low-loss EELS in an aberration-corrected scanning transmission electron microscope, which probes low-energy excitations, combined with amore » theoretical framework for simulating and analyzing the spectra, is a powerful tool to probe low-energy electron excitations with atomic-scale resolution. The theoretical component of the method combines density functional theory–based calculations of the excitations with dynamical scattering theory for the electron beam. We apply the method to monolayer graphene in order to demonstrate that atomic-scale contrast is inherent in low-loss EELS even in a perfectly periodic structure. The method is a complement to optical spectroscopy as it probes transitions entailing momentum transfer. The theoretical analysis identifies the spatial and orbital origins of excitations, holding the promise of ultimately becoming a powerful probe of the structure and electronic properties of individual point and extended defects in both crystals and inhomogeneous complex nanostructures. The method can be extended to probe magnetic and vibrational properties with atomic resolution.« less

Remanufacture of Zirconium-Based Conversion Coatings on the Surface of Magnesium Alloy

NASA Astrophysics Data System (ADS)

Liu, Zhe; Jin, Guo; Song, Jiahui; Cui, Xiufang; Cai, Zhaobing

2017-04-01

Brush plating provides an effective method for creating a coating on substrates of various shapes. A corroded zirconium-based conversion coating was removed from the surface of a magnesium alloy and then replaced with new coatings prepared via brush plating. The structure and composition of the remanufactured coating were determined via x-ray photoelectron spectroscopy, x-ray diffraction, and Fourier transform infrared spectroscopy. The results revealed that the coatings consist of oxide, fluoride, and tannin-related organics. The composition of the coatings varied with the voltage. Furthermore, as revealed via potentiodynamic polarization spectroscopy, these coatings yielded a significant increase in the corrosion resistance of the magnesium alloy. The friction coefficient remained constant for almost 300s during wear resistance measurements performed under a 1-N load and dry sliding conditions, indicating that the remanufactured coatings provide effective inhibition to corrosion.

Nano Catalysts for Diesel Engine Emission Remediation

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

Narula, Chaitanya Kumar; Yang, Xiaofan; Debusk, Melanie Moses

2012-06-01

The objective of this project was to develop durable zeolite nanocatalysts with broader operating temperature windows to treat diesel engine emissions to enable diesel engine based equipment and vehicles to meet future regulatory requirements. A second objective was to improve hydrothermal durability of zeolite catalysts to at least 675 C. The results presented in this report show that we have successfully achieved both objectives. Since it is accepted that the first step in NO{sub x} conversion under SCR (selective catalytic reduction) conditions involves NO oxidation to NO{sub 2}, we reasoned that catalyst modification that can enhance NO oxidation at low-temperaturesmore » should facilitate NO{sub x} reduction at low temperatures. Considering that Cu-ZSM-5 is a more efficient catalyst than Fe-ZSM-5 at low-temperature, we chose to modify Cu-ZSM-5. It is important to point out that the poor low-temperature efficiency of Fe-ZSM-5 has been shown to be due to selective absorption of NH{sub 3} at low-temperatures rather than poor NO oxidation activity. In view of this, we also reasoned that an increased electron density on copper in Cu-ZSM-5 would inhibit any bonding with NH{sub 3} at low-temperatures. In addition to modified Cu-ZSM-5, we synthesized a series of new heterobimetallic zeolites, by incorporating a secondary metal cation M (Sc{sup 3+}, Fe{sup 3+}, In{sup 3+}, and La{sup 3+}) in Cu exchanged ZSM-5, zeolite-beta, and SSZ-13 zeolites under carefully controlled experimental conditions. Characterization by diffuse-reflectance ultra-violet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS) and electron paramagnetic resonance spectroscopy (EPR) does not permit conclusive structural determination but supports the proposal that M{sup 3+} has been incorporated in the vicinity of Cu(II). The protocols for degreening catalysts, testing under various operating conditions, and accelerated aging conditions were provided by our collaborators at John Deere Power Systems. Among various zeolites reported here, CuFe-SSZ-13 offers the best NO{sub x} conversion activity in 150-650 C range and is hydrothermally stable when tested under accelerated aging conditions. It is important to note that Cu-SSZ-13 is now a commercial catalyst for NO{sub x} treatment on diesel passenger vehicles. Thus, our catalyst performs better than the commercial catalyst under fast SCR conditions. We initially focused on fast SCR tests to enable us to screen catalysts rapidly. Only the catalysts that exhibit high NO{sub x} conversion at low temperatures are selected for screening under varying NO{sub 2}:NO{sub x} ratio. The detailed tests of CuFe-SSZ-13 show that CuFe-SSZ-13 is more effective than commercial Cu-SSZ-13 even at NO{sub 2}:NO{sub x} ratio of 0.1. The mechanistic studies, employing stop-flow diffuse reflectance FTIR spectroscopy (DRIFTS), suggest that high concentration of NO{sup +}, generated by heterobimetallic zeolites, is probably responsible for their superior low temperature NO{sub x} activity. The results described in this report clearly show that we have successfully completed the first step in a new emission treatment catalyst which is synthesis and laboratory testing employing simulated exhaust. The next step in the catalyst development is engine testing. Efforts are in progress to obtain follow-on funding to carry out scale-up and engine testing to facilitate commercialization of this technology.« less

Influence of nanosecond pulsed plasma on the non-enzymatic pathway for the generation of nitric oxide from L-arginine and the modification of graphite oxide to increase the solar cell efficiency.

PubMed

Attri, Pankaj; Park, Ji Hoon; Gaur, Jitender; Kumar, Naresh; Park, Dae Hoon; Jeon, Su Nam; Park, Bong Sang; Chand, Suresh; Uhm, Han Sup; Choi, Eun Ha

2014-09-14

In this work, we demonstrated the action of nanosecond pulsed plasma (NPP) on the generation of nitric oxide (NO) from the non-enzymatic pathway and on the modification of graphite oxide (GO) sheets to increase polymer solar cells (PSCs) efficiency. NO is an important signal and an effector molecule in animals, which is generated from the enzyme-catalyzed oxidation of L-arginine to NO and L-citrulline. Hence, L-arginine is an important biological precursor for NO formation. Therefore, we developed a new non-enzymatic pathway for the formation of NO and L-citrulline using NPP and characterized the pathway using NO detection kit, NMR, liquid chromatography/capillary electrophoresis-mass spectrometry (LC/CE-MS) for both quantitative and qualitative bioanalysis. We then synthesized and modified the functional groups of GO using NPP, and it was characterised by X-ray photoelectron spectroscopy (XPS), confocal Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) imaging, cathodoluminescence (CL) and work function using γ-FIB. Further, we also tested the power conversion efficiency of the PSCs devices with modified GO that is similar to the one obtained with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) as HTL. This work is perceived to have great implications for inexpensive and efficient methodology for NO generation and modification of GO, which are applicable in materials from nanomaterials to biomolecules.

High-Performance Platinum-Free Dye-Sensitized Solar Cells with Molybdenum Disulfide Films as Counter Electrodes.

PubMed

Hussain, Sajjad; Shaikh, Shoyebmohamad F; Vikraman, Dhanasekaran; Mane, Rajaram S; Joo, Oh-Shim; Naushad, Mu; Jung, Jongwan

2015-12-21

By using a radio-frequency sputtering method, we synthesized large-area, uniform, and transparent molybdenum disulfide film electrodes (1, 3, 5, and 7 min) on transparent and conducting fluorine-doped tin oxide (FTO), as ecofriendly, cost-effective counter electrodes (CE) for dye-sensitized solar cells (DSSCs). These CEs were used in place of the routinely used expensive platinum CEs for the catalytic reduction of a triiodide electrolyte. The structure and morphology of the MoS2 was analyzed by using Raman spectroscopy, X-ray diffraction, and X-ray photoemission spectroscopy measurements and the DSSC characteristics were investigated. An unbroken film of MoS2 was identified on the FTO crystallites from field-emission scanning electron microscopy. Cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel curve measurements reveal the promise of MoS2 as a CE with a low charge-transfer resistance, high electrocatalytic activity, and fast reaction kinetics for the reduction of triiodide to iodide. Finally, an optimized transparent MoS2 CE, obtained after 5 min synthesis time, showed a high power-conversion efficiency of 6.0 %, which comparable to the performance obtained with a Pt CE (6.6 %) when used in TiO2 -based DSCCs, thus signifying the importance of sputtering time on DSSC performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

From Allergens to Battery Anodes: Nature-Inspired, Pollen Derived Carbon Architectures for Room- and Elevated- Temperature Li-ion Storage

PubMed Central

Tang, Jialiang; Pol, Vilas G.

2016-01-01

The conversion of allergic pollen grains into carbon microstructures was carried out through a facile, one-step, solid-state pyrolysis process in an inert atmosphere. The as-prepared carbonaceous particles were further air activated at 300 °C and then evaluated as lithium ion battery anodes at room (25 °C) and elevated (50 °C) temperatures. The distinct morphologies of bee pollens and cattail pollens are resembled on the final architecture of produced carbons. Scanning Electron Microscopy images shows that activated bee pollen carbon (ABP) is comprised of spiky, brain-like, and tiny spheres; while activated cattail pollen carbon (ACP) resembles deflated spheres. Structural analysis through X-ray diffraction and Raman spectroscopy confirmed their amorphous nature. X-ray photoelectron spectroscopy analysis of ABP and ACP confirmed that both samples contain high levels of oxygen and small amount of nitrogen contents. At C/10 rate, ACP electrode delivered high specific lithium storage reversible capacities (590 mAh/g at 50 °C and 382 mAh/g at 25 °C) and also exhibited excellent high rate capabilities. Through electrochemical impedance spectroscopy studies, improved performance of ACP is attributed to its lower charge transfer resistance than ABP. Current studies demonstrate that morphologically distinct renewable pollens could produce carbon architectures for anode applications in energy storage devices. PMID:26846311

From Allergens to Battery Anodes: Nature-Inspired, Pollen Derived Carbon Architectures for Room- and Elevated- Temperature Li-ion Storage

NASA Astrophysics Data System (ADS)

Tang, Jialiang; Pol, Vilas G.

2016-02-01

The conversion of allergic pollen grains into carbon microstructures was carried out through a facile, one-step, solid-state pyrolysis process in an inert atmosphere. The as-prepared carbonaceous particles were further air activated at 300 °C and then evaluated as lithium ion battery anodes at room (25 °C) and elevated (50 °C) temperatures. The distinct morphologies of bee pollens and cattail pollens are resembled on the final architecture of produced carbons. Scanning Electron Microscopy images shows that activated bee pollen carbon (ABP) is comprised of spiky, brain-like, and tiny spheres; while activated cattail pollen carbon (ACP) resembles deflated spheres. Structural analysis through X-ray diffraction and Raman spectroscopy confirmed their amorphous nature. X-ray photoelectron spectroscopy analysis of ABP and ACP confirmed that both samples contain high levels of oxygen and small amount of nitrogen contents. At C/10 rate, ACP electrode delivered high specific lithium storage reversible capacities (590 mAh/g at 50 °C and 382 mAh/g at 25 °C) and also exhibited excellent high rate capabilities. Through electrochemical impedance spectroscopy studies, improved performance of ACP is attributed to its lower charge transfer resistance than ABP. Current studies demonstrate that morphologically distinct renewable pollens could produce carbon architectures for anode applications in energy storage devices.

From Allergens to Battery Anodes: Nature-Inspired, Pollen Derived Carbon Architectures for Room- and Elevated-Temperature Li-ion Storage.

PubMed

Tang, Jialiang; Etacheri, Vinodkumar; Pol, Vilas G

2016-02-05

The conversion of allergic pollen grains into carbon microstructures was carried out through a facile, one-step, solid-state pyrolysis process in an inert atmosphere. The as-prepared carbonaceous particles were further air activated at 300 °C and then evaluated as lithium ion battery anodes at room (25 °C) and elevated (50 °C) temperatures. The distinct morphologies of bee pollens and cattail pollens are resembled on the final architecture of produced carbons. Scanning Electron Microscopy images shows that activated bee pollen carbon (ABP) is comprised of spiky, brain-like, and tiny spheres; while activated cattail pollen carbon (ACP) resembles deflated spheres. Structural analysis through X-ray diffraction and Raman spectroscopy confirmed their amorphous nature. X-ray photoelectron spectroscopy analysis of ABP and ACP confirmed that both samples contain high levels of oxygen and small amount of nitrogen contents. At C/10 rate, ACP electrode delivered high specific lithium storage reversible capacities (590 mAh/g at 50 °C and 382 mAh/g at 25 °C) and also exhibited excellent high rate capabilities. Through electrochemical impedance spectroscopy studies, improved performance of ACP is attributed to its lower charge transfer resistance than ABP. Current studies demonstrate that morphologically distinct renewable pollens could produce carbon architectures for anode applications in energy storage devices.

Core-shell nanophosphor architecture: toward efficient energy transport in inorganic/organic hybrid solar cells.

PubMed

Li, Qinghua; Yuan, Yongbiao; Chen, Zihan; Jin, Xiao; Wei, Tai-huei; Li, Yue; Qin, Yuancheng; Sun, Weifu

2014-08-13

In this work, a core-shell nanostructure of samarium phosphates encapsulated into a Eu(3+)-doped silica shell has been successfully fabricated, which has been confirmed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution TEM. Moreover, we report the energy transfer process from the Sm(3+) to emitters Eu(3+) that widens the light absorption range of the hybrid solar cells (HSCs) and the strong enhancement of the electron-transport of TiO2/poly(3-hexylthiophene) (P3HT) bulk heterojunction (BHJ) HSCs by introducing the unique core-shell nanoarchitecture. Furthermore, by applying femtosecond transient absorption spectroscopy, we successfully obtain the electron transport lifetimes of BHJ systems with or without incorporating the core-shell nanophosphors (NPs). Concrete evidence has been provided that the doping of core-shell NPs improves the efficiency of electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO2 acceptor. Consequently, a notable power conversion efficiency of 3.30% for SmPO4@Eu(3+):SiO2 blended TiO2/P3HT HSCs is achieved at 5 wt % as compared to 1.98% of pure TiO2/P3HT HSCs. This work indicates that the core-shell NPs can efficiently broaden the absorption region, facilitate electron-transport of BHJ, and enhance photovoltaic performance of inorganic/organic HSCs.

Linguistic Input, Electronic Media, and Communication Outcomes of Toddlers with Hearing Loss

PubMed Central

Ambrose, Sophie E.; VanDam, Mark; Moeller, Mary Pat

2013-01-01

Objectives The objectives of this study were to examine the quantity of adult words, adult-child conversational turns, and electronic media in the auditory environments of toddlers who are hard of hearing (HH) and to examine whether these variables contributed to variability in children’s communication outcomes. Design Participants were 28 children with mild to severe hearing loss. Full-day recordings of children’s auditory environments were collected within 6 months of their 2nd birthdays by utilizing LENA (Language ENvironment Analysis) technology. The system analyzes full-day acoustic recordings, yielding estimates of the quantity of adult words, conversational turns, and electronic media exposure in the recordings. Children’s communication outcomes were assessed via the receptive and expressive scales of the Mullen Scales of Early Learning at 2 years of age and the Comprehensive Assessment of Spoken Language at 3 years of age. Results On average, the HH toddlers were exposed to approximately 1400 adult words per hour and participated in approximately 60 conversational turns per hour. An average of 8% of each recording was classified as electronic media. However, there was considerable within-group variability on all three measures. Frequency of conversational turns, but not adult words, was positively associated with children’s communication outcomes at 2 and 3 years of age. Amount of electronic media exposure was negatively associated with 2-year-old receptive language abilities; however, regression results indicate that the relationship was fully mediated by the quantity of conversational turns. Conclusions HH toddlers who were engaged in more conversational turns demonstrated stronger linguistic outcomes than HH toddlers who were engaged in fewer conversational turns. The frequency of these interactions was found to be decreased in households with high rates of electronic media exposure. Optimal language-learning environments for HH toddlers include frequent linguistic interactions between parents and children. To support this goal, parents should be encouraged to reduce their children’s exposure to electronic media. PMID:24441740

Linguistic input, electronic media, and communication outcomes of toddlers with hearing loss.

PubMed

Ambrose, Sophie E; VanDam, Mark; Moeller, Mary Pat

2014-01-01

The objectives of this study were to examine the quantity of adult words, adult-child conversational turns, and electronic media in the auditory environments of toddlers who are hard of hearing (HH) and to examine whether these factors contributed to variability in children's communication outcomes. Participants were 28 children with mild to severe hearing loss. Full-day recordings of children's auditory environments were collected within 6 months of their second birthdays by using Language ENvironment Analysis technology. The system analyzes full-day acoustic recordings, yielding estimates of the quantity of adult words, conversational turns, and electronic media exposure in the recordings. Children's communication outcomes were assessed via the receptive and expressive scales of the Mullen Scales of Early Learning at 2 years of age and the Comprehensive Assessment of Spoken Language at 3 years of age. On average, the HH toddlers were exposed to approximately 1400 adult words per hour and participated in approximately 60 conversational turns per hour. An average of 8% of each recording was classified as electronic media. However, there was considerable within-group variability on all three measures. Frequency of conversational turns, but not adult words, was positively associated with children's communication outcomes at 2 and 3 years of age. Amount of electronic media exposure was negatively associated with 2-year-old receptive language abilities; however, regression results indicate that the relationship was fully mediated by the quantity of conversational turns. HH toddlers who were engaged in more conversational turns demonstrated stronger linguistic outcomes than HH toddlers who were engaged in fewer conversational turns. The frequency of these interactions was found to be decreased in households with high rates of electronic media exposure. Optimal language-learning environments for HH toddlers include frequent linguistic interactions between parents and children. To support this goal, parents should be encouraged to reduce their children's exposure to electronic media.

The Lewis Electron-Pair Model, Spectroscopy, and the Role of the Orbital Picture in Describing the Electronic Sructure of Molecules.

ERIC Educational Resources Information Center

Gallup, G. A.

1988-01-01

Describes why specific forms of orbitals used to interpret spectroscopy involving electronic transitions may not say much about the electronic structure of molecules. Discusses several theoretical approaches to explain the anomoly. Determines that the Lewis electron-pair model for molecules is a good predictor of spectroscopic results. (ML)

Low-dose electron energy-loss spectroscopy using electron counting direct detectors.

PubMed

Maigné, Alan; Wolf, Matthias

2018-03-01

Since the development of parallel electron energy loss spectroscopy (EELS), charge-coupled devices (CCDs) have been the default detectors for EELS. With the recent development of electron-counting direct-detection cameras, micrographs can be acquired under very low electron doses at significantly improved signal-to-noise ratio. In spectroscopy, in particular in combination with a monochromator, the signal can be extremely weak and the detection limit is principally defined by noise introduced by the detector. Here we report the use of an electron-counting direct-detection camera for EEL spectroscopy. We studied the oxygen K edge of amorphous ice and obtained a signal noise ratio up to 10 times higher than with a conventional CCD.We report the application of electron counting to record time-resolved EEL spectra of a biological protein embedded in amorphous ice, revealing chemical changes observed in situ while exposed by the electron beam. A change in the fine structure of nitrogen K and the carbon K edges were recorded during irradiation. A concentration of 3 at% nitrogen was detected with a total electron dose of only 1.7 e-/Å2, extending the boundaries of EELS signal detection at low electron doses.

A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

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

Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A.

2015-09-28

Two dimensional electronic spectroscopy has proven to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derivemore » response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.« less

A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

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

Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A.

2015-09-28

Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derivemore » response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.« less

A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy.

PubMed

Lewis, Nicholas H C; Dong, Hui; Oliver, Thomas A A; Fleming, Graham R

2015-09-28

Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

Nucleophilic Substitution Reactions Using Phosphine Nucleophiles: An Introduction to Phosphorus-31 NMR

ERIC Educational Resources Information Center

Sibbald, Paul A.

2015-01-01

Nuclear magnetic resonance (NMR) spectroscopy is commonly used in modern synthetic chemistry to monitor the conversion of reactants to products. Since instruction in the use of NMR spectroscopy typically does not occur until after the introduction of nucleophilic substitution reactions, organic chemistry students are not able to take advantage of…

Construction of a 1 MeV Electron Accelerator for High Precision Beta Decay Studies

NASA Astrophysics Data System (ADS)

Longfellow, Brenden

2014-09-01

Beta decay energy calibration for detectors is typically established using conversion sources. However, the calibration points from conversion sources are not evenly distributed over the beta energy spectrum and the foil backing of the conversion sources produces perturbations in the calibration spectrum. To improve this, an external, tunable electron beam coupled by a magnetic field can be used to calibrate the detector. The 1 MeV electron accelerator in development at Triangle Universities Nuclear Laboratory (TUNL) utilizes a pelletron charging system. The electron gun shoots 104 electrons per second with an energy range of 50 keV to 1 MeV and is pulsed at a 10 kHz rate with a few ns width. The magnetic field in the spectrometer is 1 T and guiding fields of 0.01 to 0.05 T for the electron gun are used to produce a range of pitch angles. This accelerator can be used to calibrate detectors evenly over its energy range and determine the detector response over a range of pitch angles. Beta decay energy calibration for detectors is typically established using conversion sources. However, the calibration points from conversion sources are not evenly distributed over the beta energy spectrum and the foil backing of the conversion sources produces perturbations in the calibration spectrum. To improve this, an external, tunable electron beam coupled by a magnetic field can be used to calibrate the detector. The 1 MeV electron accelerator in development at Triangle Universities Nuclear Laboratory (TUNL) utilizes a pelletron charging system. The electron gun shoots 104 electrons per second with an energy range of 50 keV to 1 MeV and is pulsed at a 10 kHz rate with a few ns width. The magnetic field in the spectrometer is 1 T and guiding fields of 0.01 to 0.05 T for the electron gun are used to produce a range of pitch angles. This accelerator can be used to calibrate detectors evenly over its energy range and determine the detector response over a range of pitch angles. TUNL REU Program.

Bimodal porous TiO2 structures templated by graft copolymer/homopolymer blend for dye-sensitized solar cells with polymer electrolyte

NASA Astrophysics Data System (ADS)

Kim, Jin Kyu; Lee, Chang Soo; Lee, Sang-Yup; Cho, Hyung Hee; Kim, Jong Hak

2016-12-01

Bimodal porous TiO2 (BP-TiO2) with large surface area, high porosity, good interconnectivity, and excellent light-scattering ability are synthesized via a facile one-step method using a self-assembled blend template consisting of an amphiphilic poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) graft copolymer and a hydrophobic poly(vinyl chloride) (PVC) homopolymer. The hydrophilically surface-modified TiO2 nanoparticles selectively interact with the hydrophilic POEM chains, while the addition of the PVC homopolymer increases the hydrophobic domain size, resulting in the formation of dual pores (i.e., macropores and mesopores). The sizes and numbers of macropores can easily be controlled by changing the molecular weight and amount of the PVC homopolymer. The polymer electrolyte dye-sensitized solar cells (DSSCs) fabricated with BP-TiO2 photoanodes exhibited energy conversion efficiencies of up to 7.6% at 100 mW cm-2, which is much higher than those of mesoporous TiO2 (5.8%) with PVC-g-POEM only and conventional nanocrystalline TiO2 (4.9%) with commercial Dyesol paste. The enhanced energy conversion efficiencies mostly resulted from the light-scattering effects of the macropores, which increased the light-harvesting efficiencies. The improved light-harvesting and photovoltaic performances of the DSSCs were characterized by UV-vis spectroscopy, incident photon-to-current conversion efficiency analysis, electrochemical impedance spectroscopy, intensity-modulated photocurrent spectroscopy, and intensity-modulated photovoltage spectroscopy.

Investigation of the surface sensitivity of positron-annihilation-induced Auger-electron spectroscopy

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

Mehl, D.R.

1990-01-01

The first surface sensitivity studies of positron-annihilation-induced Auger-electron spectroscopy (PAES) are presented. Preliminary measurements on polycrystalline Al with adsorbates indicate that PAES is more selective of the surface than conventional electron-induced Auger electron spectroscopy (EAES). PAES and EAES studies of well-defined overlayer-metal systems of Cu(110)+S and Cu(110)+Cs verify that PAES is selective of the top atomic layer. This surface selectivity is accounted for by theoretical calculations which indicate that the positron surface state is displaced away from the substrate by the over-layer, decreasing the annihilation rate of positrons with substrate core electrons.

Cofactors involved in light-driven charge separation in photosystem I identified by subpicosecond infrared spectroscopy.

PubMed

Di Donato, Mariangela; Stahl, Andreas D; van Stokkum, Ivo H M; van Grondelle, Rienk; Groot, Marie-Louise

2011-02-01

Photosystem I is one of the key players in the conversion of solar energy into chemical energy. While the chlorophyll dimer P(700) has long been identified as the primary electron donor, the components involved in the primary charge separation process in PSI remain undetermined. Here, we have studied the charge separation dynamics in Photosystem I trimers from Synechococcus elongatus by femtosecond vis-pump/mid-infrared-probe spectroscopy upon excitation at 700, 710, and 715 nm. Because of the high specificity of the infrared region for the redox state and small differences in the molecular structure of pigments, we were able to clearly identify specific marker bands indicating chlorophyll (Chl) oxidation. Magnitudes of chlorophyll cation signals are observed to increase faster than the time resolution of the experiment (~0.2 ps) upon both excitation conditions: 700 nm and selective red excitation. Two models, involving either ultrafast charge separation or charge transfer character of the red pigments in PSI, are discussed to explain this observation. A further increase in the magnitudes of cation signals on a subpicosecond time scale (0.8-1 ps) indicates the formation of the primary radical pair. Evolution in the cation region with time constants of 7 and 40 ps reveals the formation of the secondary radical pair, involving a secondary electron donor. Modeling of the data allows us to extract the spectra of the two radical pairs, which have IR signatures consistent with A+A₀- and P₇₀₀+A₁-. We conclude that the cofactor chlorophyll A acts as the primary donor in PSI. The existence of an equilibrium between the two radical pairs we interpret as concerted hole/electron transfer between the pairs of electron donors and acceptors, until after 40 ps, relaxation leads to a full population of the P₇₀₀+A₁. radical pair.

Analysis of Heme Iron Coordination in DGCR8: The Heme-Binding Component of the Microprocessor Complex.

PubMed

Girvan, Hazel M; Bradley, Justin M; Cheesman, Myles R; Kincaid, James R; Liu, Yilin; Czarnecki, Kazimierz; Fisher, Karl; Leys, David; Rigby, Stephen E J; Munro, Andrew W

2016-09-13

DGCR8 is the RNA-binding partner of the nuclease Drosha. Their complex (the "Microprocessor") is essential for processing of long, primary microRNAs (pri-miRNAs) in the nucleus. Binding of heme to DGCR8 is essential for pri-miRNA processing. On the basis of the split Soret ultraviolet-visible (UV-vis) spectrum of ferric DGCR8, bis-thiolate sulfur (cysteinate, Cys(-)) heme iron coordination of DGCR8 heme iron was proposed. We have characterized DGCR8 heme ligation using the Δ276 DGCR8 variant and combined electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), electron nuclear double resonance, resonance Raman, and electronic absorption spectroscopy. These studies indicate DGCR8 bis-Cys heme iron ligation, with conversion from bis-thiolate (Cys(-)/Cys(-)) axial coordination in ferric DGCR8 to bis-thiol (CysH/CysH) coordination in ferrous DGCR8. Pri-miRNA binding does not perturb ferric DGCR8's optical spectrum, consistent with the axial ligand environment being separated from the substrate-binding site. UV-vis absorption spectra of the Fe(II) and Fe(II)-CO forms indicate discrete species exhibiting peaks with absorption coefficients substantially larger than those for ferric DGCR8 and that previously reported for a ferrous form of DGCR8. Electron-nuclear double resonance spectroscopy data exclude histidine or water as axial ligands for ferric DGCR8 and favor bis-thiolate coordination in this form. UV-vis MCD and near-infrared MCD provide data consistent with this conclusion. UV-vis MCD data for ferrous DGCR8 reveal features consistent with bis-thiol heme iron coordination, and resonance Raman data for the ferrous-CO form are consistent with a thiol ligand trans to the CO. These studies support retention of DGCR8 cysteine coordination upon reduction, a conclusion distinct from those of previous studies of a different ferrous DGCR8 isoform.

Ultrashort fluorescence lifetimes of hydrogen-bonded base pairs of guanosine and cytidine in solution.

PubMed

Schwalb, Nina K; Michalak, Thomas; Temps, Friedrich

2009-12-24

The optically excited electronic states of hydrogen-bonded homo- and heterodimers of guanosine (G) and deoxycytidine (C) were investigated by femtosecond fluorescence up-conversion spectroscopy. The base pairs were prepared in CHCl(3) solution by employing tert-butyldimethylsilyl (TBDMS) groups at the OH positions of the ribose (G) or deoxyribose (C) moieties to enhance the solubilities of the nucleosides in organic solvents. The H-bonded complexes that were obtained were characterized by FTIR spectroscopy. Fluorescence lifetime measurements were performed following electronic excitation at a series of UV wavelengths from lambda(pump) = 294 nm, close to the electronic origins of the bases, to lambda(pump) = 262 nm, where significant excess vibronic energy is deposited in the molecules, at nucleoside concentrations of c(0) = 0.1 and 1.0 mM. The experimental results revealed the existence of an ultrafast deactivation pathway for the optically prepared electronically excited state(s) of the G.C Watson-Crick base pair, which was found to have a lifetime of tau(GC) = 0.30(3) ps (with 2sigma error limits) irrespective of the pump wavelength. A similar short decay time, tau(GG) = 0.32(2) ps, was observed for the respective excited G.G homodimer. In contrast, the excited G monomer displayed a significantly longer-lived and wavelength-dependent deactivation, requiring three time constants, between 0.43(6) ps < or = tau(G,1) < or = 1.2(1) ps, 4.2(8) ps < or = tau(G,2) < or = 8(1) ps, and tau(G,3) = 195(32) ps. Self-complexation of C, on the other hand, led to a longer-lived excited state with a lifetime estimated between 1 ps < or = tau(CC) < or = 10 ps, compared to the dominant initial subpicosecond decay time of the C monomer of tau(C,1) = 0.80(4) ps.

Nanostructured N-doped orthorhombic Nb2O5 as an efficient stable photocatalyst for hydrogen generation under visible light.

PubMed

Kulkarni, Aniruddha K; Praveen, C S; Sethi, Yogesh A; Panmand, Rajendra P; Arbuj, Sudhir S; Naik, Sonali D; Ghule, Anil V; Kale, Bharat B

2017-11-07

The synthesis of orthorhombic nitrogen-doped niobium oxide (Nb 2 O 5-x N x ) nanostructures was performed and a photocatalytic study carried out in their use in the conversion of toxic H 2 S and water into hydrogen under UV-Visible light. Nanostructured orthorhombic Nb 2 O 5-x N x was synthesized by a simple solid-state combustion reaction (SSCR). The nanostructural features of Nb 2 O 5-x N x were examined by FESEM and HRTEM, which showed they had a porous chain-like structure, with chains interlocked with each other and with nanoparticles sized less than 10 nm. Diffuse reflectance spectra depicted their extended absorbance in the visible region with a band gap of 2.4 eV. The substitution of nitrogen in place of oxygen atoms as well as Nb-N bond formation were confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. A computational study (DFT) of Nb 2 O 5-x N x was also performed for investigation and conformation of the crystal and electronic structure. N-Substitution clearly showed a narrowing of the band gap due to N 2p bands cascading above the O 2p band. Considering the band gap in the visible region, Nb 2 O 5-x N x exhibited enhanced photocatalytic activity toward hydrogen evolution (3010 μmol h -1 g -1 ) for water splitting and (9358 μmol h -1 g -1 ) for H 2 S splitting under visible light. The enhanced photocatalytic activity of Nb 2 O 5-x N x was attributed to its extended absorbance in the visible region due to its electronic structure being modified upon doping, which in turn generates more electron-hole pairs, which are responsible for higher H 2 generation. More significantly, the mesoporous nanostructure accelerated the supression of electron and hole recombination, which also contributed to the enhancement of its activity.

Calibration-free quantitative analysis of elemental ratios in intermetallic nanoalloys and nanocomposites using Laser Induced Breakdown Spectroscopy (LIBS).

PubMed

Davari, Seyyed Ali; Hu, Sheng; Mukherjee, Dibyendu

2017-03-01

Intermetallic nanoalloys (NAs) and nanocomposites (NCs) have increasingly gained prominence as efficient catalytic materials in electrochemical energy conversion and storage systems. But their morphology and chemical compositions play critical role in tuning their catalytic activities, and precious metal contents. While advanced microscopy techniques facilitate morphological characterizations, traditional chemical characterizations are either qualitative or extremely involved. In this study, we apply Laser Induced Breakdown Spectroscopy (LIBS) for quantitative compositional analysis of NAs and NCs synthesized with varied elemental ratios by our in-house built pulsed laser ablation technique. Specifically, elemental ratios of binary PtNi, PdCo (NAs) and PtCo (NCs) of different compositions are determined from LIBS measurements employing an internal calibration scheme using the bulk matrix species as internal standards. Morphology and qualitative elemental compositions of the aforesaid NAs and NCs are confirmed from Transmission Electron Microscopy (TEM) images and Energy Dispersive X-ray Spectroscopy (EDX) measurements. LIBS experiments are carried out in ambient conditions with the NA and NC samples drop cast on silicon wafers after centrifugation to increase their concentrations. The technique does not call for cumbersome sample preparations including acid digestions and external calibration standards commonly required in Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) techniques. Yet the quantitative LIBS results are in good agreement with the results from ICP-OES measurements. Our results indicate the feasibility of using LIBS in future for rapid and in-situ quantitative chemical characterizations of wide classes of synthesized NAs and NCs. Copyright © 2016 Elsevier B.V. All rights reserved.

Modification of local order in FePd films by low energy He{sup +} irradiation

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

Merkel, D. G.; Tancziko, F.; Sajti, Sz.

2008-07-01

Owing to their strong perpendicular magnetic anisotropy, FePd, CoPd, and their Co(Fe)Pt counterparts are candidate materials for ultrahigh density magnetic recording. The stability and magnetic properties of such films are largely dependent on the orientation and local distribution of the L1{sub 0} FePd phase fraction. Therefore, the formation and transformation of the L1{sub 0} phase in such thin films have been the subject of continued interest. Highly ordered epitaxial FePd(001) thin films (with an L1{sub 0} phase fraction of 0.81) were prepared by molecular-beam epitaxy on a MgO(001) substrate. The effect of postgrown room temperature, 130 keV He{sup +} irradiationmore » was investigated at fluences up to 14.9x10{sup 15} ions/cm{sup 2}. X-ray diffraction and conversion electron Moessbauer spectroscopy revealed that with increasing fluence, the L1{sub 0} FePd phase decomposes into the face centered cubic phase with random Fe and Pd occupation of the sites. A partially ordered local environment exhibiting a large hyperfine magnetic field also develops. Upon He{sup +} irradiation, the lattice parameter c of the FePd L1{sub 0} structure increases and the long range order parameter S steeply decreases. The Fe-Fe nearest-neighbor coordination in the Fe-containing environments increases on average from Fe{sub 47}Pd{sub 53} to Fe{sub 54}Pd{sub 46}, indicating a tendency of formation iron-rich clusters. The equilibrium parameters corresponding to the equiatomic L1{sub 0} phase were found at different fluences by conversion electron Moessbauer spectroscopy and by x-ray diffraction a difference, from which a plane-perpendicular compressive stress and a corresponding in-plane tensile stress are conjectured. The steep increase in the interface roughness above 7.4x10{sup 15} ions/cm{sup 2} is interpreted as a percolation-type behavior related to the high diffusion anisotropy in the L1{sub 0} phase.« less

Direct characterization of the energy level alignments and molecular components in an organic hetero-junction by integrated photoemission spectroscopy and reflection electron energy loss spectroscopy analysis.

PubMed

Yun, Dong-Jin; Shin, Weon-Ho; Bulliard, Xavier; Park, Jong Hwan; Kim, Seyun; Chung, Jae Gwan; Kim, Yongsu; Heo, Sung; Kim, Seong Heon

2016-08-26

A novel, direct method for the characterization of the energy level alignments at bulk-heterojunction (BHJ)/electrode interfaces on the basis of electronic spectroscopy measurements is proposed. The home-made in situ photoemission system is used to perform x-ray/ultraviolet photoemission spectroscopy (XPS/UPS), reflection electron energy loss spectroscopy (REELS) and inverse photoemission spectroscopy of organic-semiconductors (OSCs) deposited onto a Au substrate. Through this analysis system, we are able to obtain the electronic structures of a boron subphthalocyanine chloride:fullerene (SubPC:C60) BHJ and those of the separate OSC/electrode structures (SubPC/Au and C60/Au). Morphology and chemical composition analyses confirm that the original SubPC and C60 electronic structures remain unchanged in the electrodes prepared. Using this technique, we ascertain that the position and area of the nearest peak to the Fermi energy (EF = 0 eV) in the UPS (REELS) spectra of SubPC:C60 BHJ provide information on the highest occupied molecular orbital level (optical band gap) and combination ratio of the materials, respectively. Thus, extracting the adjusted spectrum from the corresponding SubPC:C60 BHJ UPS (REELS) spectrum reveals its electronic structure, equivalent to that of the C60 materials. This novel analytical approach allows complete energy-level determination for each combination ratio by separating its electronic structure information from the BHJ spectrum.

Methane to methanol conversion induced by thorium oxide through the CH3Th(O)H intermediate in solid argon.

PubMed

Gong, Yu; Andrews, Lester; Jackson, Virgil E; Dixon, David A

2012-10-15

Reactions of ThO molecules and CH(4) have been investigated in solid argon near 4 K. The CH(3)Th(O)H molecule is produced when the sample is exposed to UV irradiation. Identification of this new intermediate is substantiated by observation of the Th═O and Th-H stretching vibrational modes with isotopic substitution via matrix infrared spectroscopy, and the assignments are supported by electronic structure frequency calculations. Methanol absorptions increase together with formation of the CH(3)Th(O)H molecule, suggesting a methane to methanol conversion induced by thorium oxide proceeding through the CH(3)Th(O)H intermediate. The formation of CH(3)Th(O)H from ThO + CH(4) is exothermic (ΔH(rxn) = -11 kcal/mol) with an energy barrier of 30 kcal/mol at the CCSD(T)//B3LYP level. Decomposition of this intermediate to form methanol involves spin crossing, and the overall reaction from the intermediate is endothermic by 127 kcal/mol. There is no activation energy for the reaction of thorium atoms with methanol to give CH(3)Th(O)H, as observed in separate experiments with Th and CH(3)OH.

Photoluminescence and applications of Ni:ZnS in photovoltaic cells

NASA Astrophysics Data System (ADS)

Kalya Tulasidas, Vadiraj; Belagali, Shiddappa L.; Palakkandy, Arun; Kumar, Kuldeep

2018-05-01

An enormous amount of development has been made in the field of photovoltaics in the last 50 odd years. In recent years, the uses of semiconductor nanoparticles have given a new impetus and direction to research in the field of solar cells. This is due to the excellent photoemission properties shown by semiconductors in the quantum dot (QD) state. ZnS QDs show a further interesting feature where their photoemission properties show perceivable changes on adding dopants such as nickel. In the present work, we describe the characterization studies made on Ni:ZnS thin films using photoluminescence (PL), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), and further reports their performance as an absorbing layer in a hybrid solar cell along with poly(3-hexylthiophene) (P3HT). Fabricated Ni:ZnS cell showed a conversion efficiency of 0.25 ± 0.05% with V OC and J SC of 560 mV and 0.11 mA/cm2, respectively. Although the absolute conversion efficiency appears low (only 0.25%), the addition of nickel was found to have improved the efficiency by a hundredfold compared with undoped ZnS.

Electronic Structure of Small Lanthanide Containing Molecules

NASA Astrophysics Data System (ADS)

Kafader, Jared O.; Ray, Manisha; Topolski, Josey E.; Chick Jarrold, Caroline

2016-06-01

Lanthanide-based materials have unusual electronic properties because of the high number of electronic degrees of freedom arising from partial occupation of 4f orbitals, which make these materials optimal for their utilization in many applications including electronics and catalysis. Electronic spectroscopy of small lanthanide molecules helps us understand the role of these 4f electrons, which are generally considered core-like because of orbital contraction, but are energetically similar to valence electrons. The spectroscopy of small lanthanide-containing molecules is relatively unexplored and to broaden this understanding we have completed the characterization of small cerium, praseodymium, and europium molecules using photoelectron spectroscopy coupled with DFT calculations. The characterization of PrO, EuH, EuO/EuOH, and CexOy molecules have allowed for the determination of their electron affinity, the assignment of numerous anion to neutral state transitions, modeling of anion/neutral structures and electron orbital occupation.

HREELS to identify electronic structures of organic thin films.

PubMed

Oeter, D; Ziegler, C; Göpel, W

1995-10-01

The electronic structure of alpha-oligothiophene (alphanT) thin films has been investigated for increasing chain lengths of n= 4-8 thiophene units with high resolution electron energy loss spectroscopy (HREELS) in the specular reflection geometry at a primary energy of 15 eV. The great advantage of this technique in contrast to UV/VIS absorption spectroscopy results from the fact, that the impact scattering mechanism of HREELS makes it possible to also detect optically forbidden electronic transitions. On the other hand, the electrons used as probes in HREELS have a wavelength which is two orders of magnitudes smaller if compared to those of photons used in UV/VIS absorption spectroscopy. Therefore individual molecules are excited by HREELS independent from each other and hence the excitation of collective excitons is not possible. As a result, information about the orientation of the molecules cannot be achieved with HREELS, which, however, is possible in polarization-dependent UV/VIS spectroscopy.

Ultrafast electron transfer processes studied by pump-repump-probe spectroscopy.

PubMed

Fischer, Martin K; Gliserin, Alexander; Laubereau, Alfred; Iglev, Hristo

2011-03-01

The photodetachment of Br(-), I(-) and OH(-) in aqueous solution is studied by 2- and 3-pulse femtosecond spectroscopy. The UV excitation leads to fast electron separation followed by formation of a donor-electron pairs. An additional repump pulse is used for secondary excitation of the intermediates. The 3-pulse technique allows distinguishing the pair-intermediate from the fully separated electron. Using this method we observe a novel geminate recombination channel of .OH with adjacent hydrated electrons. The process leads to an ultrafast quenching (0.7 ps) of almost half the initial number of radicals. The phenomenon is not observed in Br(-) and I(-). Our results demonstrate the potential of the 3-pulse spectroscopy to elucidate the mechanism of ultrafast ET reactions. Photodetachment of aqueous anions studied by two- and three pulse spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron impact action spectroscopy of mass/charge selected macromolecular ions: Inner-shell excitation of ubiquitin protein

NASA Astrophysics Data System (ADS)

Ranković, Miloš Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

2016-02-01

We have performed inner-shell electron impact action spectroscopy of mass and charge selected macromolecular ions. For this purpose, we have coupled a focusing electron gun with a linear quadrupole ion trap mass spectrometer. This experiment represents a proof of principle that an energy-tunable electron beam can be used in combination with radio frequency traps as an activation method in tandem mass spectrometry (MS2) and allows performing action spectroscopy. Electron impact MS2 spectra of multiply protonated ubiquitin protein ion have been recorded at incident electron energies around the carbon 1 s excitation. Both MS2 and single ionization energy dependence spectra are compared with literature data obtained using the soft X-ray activation conditions.

Plasma chemical conversion of sulphur hexafluoride initiated by a pulsed electron beam

NASA Astrophysics Data System (ADS)

Kholodnaya, Galina; Sazonov, Roman; Ponomarev, Denis; Guzeeva, Tatiana

2017-01-01

This paper presents the results of the experimental investigation of plasma chemical conversion of sulphur hexafluoride initiated by a pulsed electron beam (TEA-500 pulsed electron accelerator) with the following characteristics: 400-450 keV electron energy, 60 ns pulse duration, up to 200 J pulse energy, and 5 cm beam diameter. Experiments were conducted on the effect of the pulsed electron beam on SF6 and on mixtures of SF6 with O2, Ar, or N2. For the mixture of SF6 and oxygen, the results indicated chemical reactions involving the formation of a number of products of which one is sulphur, confirming the Wray - Fluorescence Analysis. The plasma chemical conversion of SF6 initiated by the pulsed electron beam was not detected when SF6 was mixed with Ar or N2, suggesting a possible mechanism for the reaction of SF6 in the presence of O2.

Applied nonlinear optics in the journal 'Quantum Electronics'

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

Grechin, Sergei G; Dmitriev, Valentin G; Chirkin, Anatolii S

2011-12-31

A brief historical review of the experimental and theoretical works on nonlinear optical frequency conversion (generation of harmonics, up- and down-conversion, parametric oscillation), which have been published in the journal 'Quantum Electronics' for the last 40 years, is presented.

A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

Theoretical studies of electronically excited states

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

Besley, Nicholas A.

2014-10-06

Time-dependent density functional theory is the most widely used quantum chemical method for studying molecules in electronically excited states. However, excited states can also be computed within Kohn-Sham density functional theory by exploiting methods that converge the self-consistent field equations to give excited state solutions. The usefulness of single reference self-consistent field based approaches for studying excited states is demonstrated by considering the calculation of several types of spectroscopy including the infrared spectroscopy of molecules in an electronically excited state, the rovibrational spectrum of the NO-Ar complex, core electron binding energies and the emission spectroscopy of BODIPY in water.