Adsorbate-driven morphological changes on Cu(111) nano-pits

DOE PAGES

Mudiyanselage, K.; Xu, F.; Hoffmann, F. M.; ...

2014-12-09

Adsorbate-driven morphological changes of pitted-Cu(111) surfaces have been investigated following the adsorption and desorption of CO and H. The morphology of the pitted-Cu(111) surfaces, prepared by Ar + sputtering, exposed a few atomic layers deep nested hexagonal pits of diameters from 8 to 38 nm with steep step bundles. The roughness of pitted-Cu(111) surfaces can be healed by heating to 450-500 K in vacuum. Adsorption of CO on the pitted-Cu(111) surface leads to two infrared peaks at 2089-2090 and 2101-2105 cm -1 for CO adsorbed on under-coordinated sites in addition to the peak at 2071 cm -1 for CO adsorbedmore » on atop sites of the close-packed Cu(111) surface. CO adsorbed on under-coordinated sites is thermally more stable than that of atop Cu(111) sites. Annealing of the CO-covered surface from 100 to 300 K leads to minor changes of the surface morphology. In contrast, annealing of a H covered surface to 300 K creates a smooth Cu(111) surface as deduced from infrared data of adsorbed CO and scanning tunnelling microscopy (STM) imaging. The observation of significant adsorbate-driven morphological changes with H is attributed to its stronger modification of the Cu(111) surface by the formation of a sub-surface hydride with a hexagonal structure, which relaxes into the healed Cu(111) surface upon hydrogen desorption. These morphological changes occur ~150 K below the temperature required for healing of the pitted-Cu(111) surface by annealing in vacuum. In contrast, the adsorption of CO, which only interacts with the top-most Cu layer and desorbs by 160 K, does not significantly change the morphology of the pitted-Cu(111) surface.« less

Coverage dependent non-adiabaticity of CO on a copper surface

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

Omiya, Takuma; Surface and Interface Science Laboratory, RIKEN, Wako 351-0198; Arnolds, Heike

2014-12-07

We have studied the coverage-dependent energy transfer dynamics between hot electrons and CO on Cu(110) with femtosecond visible pump, sum frequency probe spectroscopy. We find that transients of the C–O stretch frequency display a red shift, which increases from 3 cm{sup −1} at 0.1 ML to 9 cm{sup −1} at 0.77 ML. Analysis of the transients reveals that the non-adiabatic coupling between the adsorbate vibrational motion and the electrons becomes stronger with increasing coverage. This trend requires the frustrated rotational mode to be the cause of the non-adiabatic behavior, even for relatively weak laser excitation of the adsorbate. We attributemore » the coverage dependence to both an increase in the adsorbate electronic density of states and an increasingly anharmonic potential energy surface caused by repulsive interactions between neighboring CO adsorbates. This work thus reveals adsorbate-adsorbate interactions as a new way to control adsorbate non-adiabaticity.« less

Metal-organic frameworks for adsorption and separation of noble gases

DOEpatents

Allendorf, Mark D.; Greathouse, Jeffery A.; Staiger, Chad

2017-05-30

A method including exposing a gas mixture comprising a noble gas to a metal organic framework (MOF), including an organic electron donor and an adsorbent bed operable to adsorb a noble gas from a mixture of gases, the adsorbent bed including a metal organic framework (MOF) including an organic electron donor.

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

Sedlacek, J. A.; Kim, E.; Rittenhouse, S. T.

We investigate the (0001) surface of single crystal quartz with a submonolayer of Rb adsorbates. Using Rydberg atom electromagnetically induced transparency, we investigate the electric elds resulting from Rb adsorbed on the quartz surface, and measure the activation energy of the Rb adsorbates. We show that the Rb induces a negative electron affnity (NEA) on the quartz surface. The NEA surface allows for low energy electrons to bind to the surface and cancel the electric eld from the Rb adsorbates. Our results have implications for integrating Rydberg atoms into hybrid quantum systems and the fundamental study of atom-surface interactions, asmore » well as applications for electrons bound to a 2D surface.« less

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Electron solvation and localization at interfaces

NASA Astrophysics Data System (ADS)

Harris, Charles B.; Szymanski, Paul; Garrett-Roe, Sean; Miller, Andre D.; Gaffney, Kelly J.; Liu, Simon H.; Bezel, Ilya

2003-12-01

Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 +/- 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.

Role of Defects and Adsorbed Water Film in Influencing the Electrical, Optical and Catalytic Properties of Transition Metal Oxides

NASA Astrophysics Data System (ADS)

Wang, Qi

Transition metal oxides (TMOs) constitute a large group of materials that exhibit a wide range of optical, electrical, electrochemical, dielectric and catalytic properties, and thus making them highly regarded as promising materials for a variety of applications in next generation electronic, optoelectronic, catalytic, photonic, energy storage and energy conversion devices. Some of the unique properties of TMOs are their strong electron-electron correlations that exists between the valence electrons of narrow d- or f-shells and their ability to exist in variety of oxidation states. This gives TMOs an enormous range of fascinating electronic and other physical properties. Many of these remarkable properties of TMOs arises from the complex surface charge transfer processes at the oxide surface/electrochemical redox species interface and non-stoichiometry due to the presence of lattice vacancies that may cause significant perturbation to the electronic structure of the material. Stoichiometry, oxidation state of the metal center and lattice vacancy defects all play important roles in affecting the physical properties, electronic structures, device behavior and other functional properties of TMOs. However, the underlying relationships between them is not clearly known. For instance, the exchange of electrons between adsorbates and defects can lead to the passivation of existing defect states or formation of new defects, both of which affect defect equilibria, and consequently, functional properties. In depth understanding of the role of lattice defects on the electrical, catalytic and optical properties of TMOs is central to further expansion of the technological applications of TMO based devices. The focus of this work is to elucidate the interactions of vacancy defects with various electrochemical adsorbates in TMOs. The ability to directly probe the interactions of vacancy defects with gas and liquid phase species under in-operando conditions is highly desirable to obtain a mechanistic understanding of the charge transfer process. We have developed a spectroscopic technique for studying vacancy defects in TMOs using near-infrared photoluminescence (NIR-PL) spectroscopy and showed that this technique is uniquely suited for studying defect-adsorbate interactions. In this work, a series of studies were carried out to elucidate the underlying structure-defect-property correlations of TMOs and their role in catalyzing electrical and electrochemical properties. In the first study, we report a new type of electrical phase transition in p-type, non-stoichiometric nickel oxide involving a semiconductor-to-insulator-to-metal transition along with the complete change of conductivity from p- to n-type at room temperature induced by electrochemical Li+ intercalation. Direct observation of vacancy-ion interactions using in-situ NIR-PL show that the transition is a result of passivation of native nickel (cationic) vacancy defects and subsequent formation of oxygen (anionic) vacancy defects driven by Li+ insertion into the lattice. X-ray photoemission spectroscopy studies performed to examine the changes in the oxidation states of nickel due to defect interactions support the above conclusions. In the second study, main effects of oxygen vacancy defects on the electronic and optical properties of V2O5 nanowires were studied using in-situ Raman, photoluminescence, absorption, and photoemission spectroscopy. We show that both thermal reduction and electrochemical reduction via Li+ insertion results in the creation of oxygen vacancy defects in the crystal that leads to band filling and an increase in the optical band gap of V2O5 from 1.95 eV to 2.45 eV, an effect known as the Burstein-Moss effect. In the third study, we report a new type of semiconductor-adsorbed water interaction in metal oxides known as "electrochemical surface transfer doping," a phenomenon that has been previously been observed on hydrogen-terminated diamond, carbon nanotube, gallium nitride and zinc oxide. Most TMOs at room temperature are known to be strongly hydrated. We show that an adsorbed water film present on the surface of TMOs facilitates the dissolution of gaseous species and promotes charge transfers at the adsorbed-water/oxide interfaces. Further, we show the role of vacancy defects in enhancing catalytic processes by directly monitoring the charge transfer process between gaseous species and vacancy defects in non-stoichiometric p-type nickel oxide and n-type tungsten oxide using in-situ NIR-PL, electrical resistance, and X-ray photoelectron spectroscopy. We find the importance of adsorbed water and vacancy defects in affecting catalytic, electronic, electrical, and optical changes such as insulator-to-metal transitions and radiative emissions during electrochemical reactions. In addition, we demonstrate that electrochemical surface transfer doping exists in another system, specifically, in gallium nitride, and the presence of this adsorbed water film present on the surface of GaN induces electron transfer from GaN that leads to the formation of an electron depletion region on the surface.

In situ FTIR studies on the oxidation of isopropyl alcohol over SnO2 as a function of temperature up to 600 °C and a comparison to the analogous plasma-driven process.

PubMed

Christensen, P A; Mashhadani, Z T A W; Md Ali, Abd Halim Bin

2018-04-04

This paper reports the application of in situ reflectance Fourier Transform InfraRed spectroscopy to the study of the thermal and plasma driven reaction of IsoPropyl Alcohol (IPA) at SnO2-coated Macor, the latter a ceramic material comprised of the oxides of Al, Mg and Si. The data so obtained were compared to those obtained using uncoated Macor. When uncoated Macor was employed, no reaction of the IPA was observed up to 600 °C in the thermal experiments, whereas a number of products were observed in the plasma-driven experiments. The results obtained using coated Macor were somewhat different, with no reaction taking place in the plasma-driven experiments, whilst significant reaction took place in the thermally-driven process. In the latter experiments, the chemistry was observed to show four distinct temperature regions, with electron injection into the conduction band of the SnO2 playing a significant role, culminating in the production of CO2. The data were interpreted in terms of a model in which physisorbed IPA was converted to two forms of isopropoxide: this was converted to acetone and acetaldehyde via adsorbed enolate. The data clearly support the catalytic activity of Macor in the plasma-driven conversion of IPA.

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

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

Preparation and characterization of novel carbon dioxide adsorbents based on polyethylenimine-modified Halloysite nanotubes.

PubMed

Cai, Haohao; Bao, Feng; Gao, Jie; Chen, Tao; Wang, Si; Ma, Rui

2015-01-01

New nano-sized carbon dioxide (CO2) adsorbents based on Halloysite nanotubes impregnated with polyethylenimine (PEI) were designed and synthesized, which were excellent adsorbents for the capture of CO2 at room temperature and had relatively high CO2 adsorption capacity. The prepared adsorbents were characterized by various techniques such as Fourier transform infrared spectrometry, gel permeation chromatography, dynamic light scattering, thermogravimetry, thermogravimetry-Fourier transform-infrared spectrometry, scanning electron microscopy and transmission electron microscopy. The adsorption characteristics and capacity were studied at room temperature, the highest CO2 adsorption capacity of 156.6 mg/g-PEI was obtained and the optimal adsorption capacity can reach a maximum value of 54.8 mg/g-adsorbent. The experiment indicated that this kind of adsorbent has a high stability at 80°C and PEI-impregnated adsorbents showed good reversibility and stability during cyclic adsorption-regeneration tests.

Adsorption of Xyloglucan onto Cellulose Surfaces of Different Morphologies: An Entropy-Driven Process.

PubMed

Benselfelt, Tobias; Cranston, Emily D; Ondaral, Sedat; Johansson, Erik; Brumer, Harry; Rutland, Mark W; Wågberg, Lars

2016-09-12

The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.

Electrochemically driven catalysis of Rhizobium sp. NT-26 arsenite oxidase with its native electron acceptor cytochrome c552.

PubMed

Kalimuthu, Palraj; Heath, Matthew D; Santini, Joanne M; Kappler, Ulrike; Bernhardt, Paul V

2014-01-01

We describe the catalytic voltammograms of the periplasmic arsenite oxidase (Aio) from the chemolithoautotrophic bacterium Rhizobium sp. str. NT-26 that oxidizes arsenite to arsenate. Electrochemistry of the enzyme was accomplished using its native electron transfer partner, cytochrome c552 (cyt c552), as a mediator. The protein cyt c552 adsorbed on a mercaptoundecanoic acid (MUA) modified Au electrode exhibited a stable, reversible one-electron voltammetric response at +275mV vs NHE (pH6). In the presence of arsenite and Aio the voltammetry of cyt c552 is transformed from a transient response to an amplified sigmoidal (steady state) wave consistent with an electro-catalytic system. Digital simulation was performed using a single set of parameters for all catalytic voltammetries obtained at different sweep rates and various substrate concentrations. The obtained kinetic constants from digital simulation provide new insight into the kinetics of the NT-26 Aio catalytic mechanism. © 2013.

Electronic and magnetic properties of nonmetal atoms adsorbed ReS{sub 2} monolayers

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

Zhang, Xiaoou; Li, Qingfang, E-mail: qingfangli@nuist.edu.cn; Department of Physics, Nanjing University of Information Science and Technology, Nanjing 210044

2015-08-14

The stable configurations and electronic and magnetic properties of nonmetal atoms (H, N, P, O, S, F, and Cl) adsorbed ReS{sub 2} monolayers have been investigated by first-principles calculations. It is found that H, O, S, F, and Cl prefer to occupy the peak sites of S atoms, while both N and P atoms favor the valley sites of S atoms. The ReS{sub 2} sheet exhibits a good adsorption capability to nonmetal atoms. The reconstruction of the surface is pronounced in N- and P-adsorbed ReS{sub 2} monolayers. In H-adsorbed case, the Fermi level is pulled into the conduction band, whichmore » results in the semiconductor-metal transition. The same magnetic moment of 1μ{sub B} is found in the N-, P-, F-, and Cl-adsorbed ReS{sub 2} monolayers, while the mechanisms of forming magnetic moment for N (P)- and F (Cl)-adsorbed cases are different. In addition, the spatial extensions of spin density in P-, F-, and Cl-adsorbed cases are larger than that in N-adsorbed case, which is more suitable to achieve long-range magnetic coupling interaction at low defect concentrations. Our results provide insight for achieving metal-free magnetism and a tunable band gap for various electronic and spintronic devices based on ReS{sub 2}.« less

Low-energy electron point projection microscopy/diffraction study of suspended graphene

NASA Astrophysics Data System (ADS)

Hsu, Wei-Hao; Chang, Wei-Tse; Lin, Chun-Yueh; Chang, Mu-Tung; Hsieh, Chia-Tso; Wang, Chang-Ran; Lee, Wei-Li; Hwang, Ing-Shouh

2017-11-01

In this work, we present our study of suspended graphene with low-energy electrons based on a point projection microscopic/diffractive imaging technique. Both exfoliated and chemical vapor deposition (CVD) graphene samples were studied in an ultra-high vacuum chamber. This method allows imaging of individual adsorbates at the nanometer scale and characterizing graphene layers, graphene lattice orientations, ripples on graphene membranes, etc. We found that long-duration exposure to low-energy electron beams induced aggregation of adsorbates on graphene when the electron dose rate was above a certain level. We also discuss the potential of this technique to conduct coherent diffractive imaging for determining the atomic structures of biological molecules adsorbed on suspended graphene.

Electronic properties of NH{sub 4}-adsorbed graphene nanoribbon as a promising candidate for a gas sensor

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

Harada, Naoki, E-mail: harada.naoki@jp.fujitsu.com; Sato, Shintaro

2016-05-15

The electronic properties of NH{sub 4}-adsorbed N = 7 armchair graphene nanoribbons (AGNRs) were theoretically investigated using self-consistent atomistic simulations to explore the feasibility of AGNRs as a gas sensing material. Whereas a pristine AGNR has a finite band gap and is an intrinsic semiconductor, an NH{sub 4}-adsorbed AGNR exhibits heavily doped n-type properties similar to a graphene sheet with the molecules adsorbed. The electric characteristics of a back-gated AGNR gas sensor were also simulated and the drain current changed exponentially with increasing number of adsorbed molecules. We may conclude that an AGNR is promising as a highly sensitive gas-sensingmore » material with large outputs.« less

Angle-resolved investigation of Auger electrons from Cu and Au adsorbed on W(110)

NASA Astrophysics Data System (ADS)

Koshikawa, T.; Von Dem Hagen, T.; Bauer, E.

1981-08-01

The angular distribution of Cu M 2,3VV and Au N 6,7VV Auger electrons from Cu and Au mono- and double layers on W(110) is measured with the goal of obtaining information on the contribution of the backscattered wave on the angular distribution of Auger electrons from adsorbed atoms.

Surface Confined Metallosupramolecular Architectures: Formation and STM Characterization

PubMed Central

Li, Shan-Shan; Northrop, Brian H.; Yuan, Qun-Hui; Wan, Li-Jun; Stang, Peter J.

2009-01-01

CONSPECTUS Metallosupramolecular compounds have attracted a great deal of attention over the past two decades largely because of their unique, highly-complex structural characteristics, the fact that they can be prepared with relative ease using coordination-driven self-assembly techniques, and their potential electronic, magnetic, optical, and catalytic properties. In particular, the use of electron-poor square planar Pt(II) transition metals in conjunction with rigid, electron-rich pyridyl donors had enabled the spontaneous self-assembly of a rich library of 2D metallacyclic and 3D metallacage assemblies via the directional-bonding approach. With the tremendous progress that has been made in the preparation and characterization of metallosupramolecules, much attention is now being turned toward fully exploring and developing their materials properties. Assembling metallosupramolecular compounds on solid supports represents a vitally important step toward developing their materials properties. Surfaces provide a means of uniformly aligning and orienting these highly symmetric metallacycles and metallacages, which increases the level of coherence between molecules above that which can be achieved in the solution phase and affords a means of integrating adlayers into a solid-state materials setting. The dynamic nature of kinetically labile Pt(II)-N coordination bonds, however, requires that deposition and imaging conditions be appropriate to retain the assemblies' stability. Toward these aims it is imperative to understand the factors that govern surface self-assembly and the interactions that influence the structure and stability of the resulting adlayer. Such insight can be obtained from Scanning Tunneling Microscopy (STM), which has emerged as a powerful technique for the imaging and characterization of self-assembled adlayers. This account describes the means by which 2D rectangular and square metallacycles and 3D trigonal bipyrimidal and chiral trigonal prism metallacages can be deposited on Highly Oriented Pyrolytic Graphite (HOPG) and Au(111) substrates such that the assemblies remain intact and result in ordered adlayers. The effects of varying the size, symmetry, and dimensionality of supramolecular adsorbates, the choice of substrate, the use of a molecular template, and the effects of chirality have been investigated. These systematic investigations provide much insight into the various adsorbate-adsorbate and substrate-adsorbate interactions that largely determine the architecture of each assembly and affect their performance in a materials setting. Exhibiting the ability to rationally control adlayer formation and structure will greatly enhance the potential of these supramolecules to be used in a variety of applications such as in host-guest sensing/diagnostic systems, molecular electronic devices, and in heterogeneous stereoselective synthesis and catalysis. PMID:19072706

Real-Time Measurement of Nanotube Resonator Fluctuations in an Electron Microscope

PubMed Central

2017-01-01

Mechanical resonators based on low-dimensional materials provide a unique platform for exploring a broad range of physical phenomena. The mechanical vibrational states are indeed extremely sensitive to charges, spins, photons, and adsorbed masses. However, the roadblock is often the readout of the resonator, because the detection of the vibrational states becomes increasingly difficult for smaller resonators. Here, we report an unprecedentedly sensitive method to detect nanotube resonators with effective masses in the 10–20 kg range. We use the beam of an electron microscope to resolve the mechanical fluctuations of a nanotube in real-time for the first time. We obtain full access to the thermally driven Brownian motion of the resonator, both in space and time domains. Our results establish the viability of carbon nanotube resonator technology at room temperature and pave the way toward the observation of novel thermodynamics regimes and quantum effects in nanomechanics. PMID:28186773

Alkali (Li, K and Na) and alkali-earth (Be, Ca and Mg) adatoms on SiC single layer

NASA Astrophysics Data System (ADS)

Baierle, Rogério J.; Rupp, Caroline J.; Anversa, Jonas

2018-03-01

First-principles calculations within the density functional theory (DFT) have been addressed to study the energetic stability, and electronic properties of alkali and alkali-earth atoms adsorbed on a silicon carbide (SiC) single layer. We observe that all atoms are most stable (higher binding energy) on the top of a Si atom, which moves out of the plane (in the opposite direction to the adsorbed atom). Alkali atoms adsorbed give raise to two spin unpaired electronic levels inside the band gap leading the SiC single layer to exhibit n-type semiconductor properties. For alkaline atoms adsorbed there is a deep occupied spin paired electronic level inside the band gap. These finding suggest that the adsorption of alkaline and alkali-earth atoms on SiC layer is a powerful feature to functionalize two dimensional SiC structures, which can be used to produce new electronic, magnetic and optical devices as well for hydrogen and oxygen evolution reaction (HER and OER, respectively). Furthermore, we observe that the adsorption of H2 is ruled by dispersive forces (van der Waals interactions) while the O2 molecule is strongly adsorbed on the functionalized system.

Equilibrium and heat of adsorption of diethyl phthalate on heterogeneous adsorbents.

PubMed

Zhang, Weiming; Xu, Zhengwen; Pan, Bingcai; Hong, Changhong; Jia, Kun; Jiang, Peijuan; Zhang, Qingjian; Pan, Bingjun

2008-09-01

Removal of phthalate esters from water has been of considerable concern recently. In the present study, the adsorptive removal performance of diethyl phthalate (DEP) from water was investigated with the aminated polystyrene resin (NDA-101) and oxidized polystyrene resin (NDA-702). In addition, the commercial homogeneous polystyrene resin (XAD-4) and acrylic ester resin (Amberlite XAD-7) as well as coal-based granular activated carbon (AC-750) were chosen for comparison. The corresponding equilibrium isotherms are well described by the Freundlich equation and the adsorption capacities for DEP followed the order NDA-702 > NDA-101 > AC-750 > XAD-4 > XAD-7. Analysis of adsorption mechanisms suggested that these adsorbents spontaneously adsorb DEP molecules driven mainly by enthalpy change, and the adsorption process was derived by multiple adsorbent-adsorbate interactions such as hydrogen bonding, pi-pi stacking, and micropore filling. The information related to the adsorbent surface heterogeneity and the adsorbate-adsorbate interaction was obtained by Do's model. All the results indicate that heterogeneous resins NDA-702 and NDA-101 have excellent potential as an adsorption material for the removal of DEP from the contaminated water.

Preparation of weak-light-driven TiO2-based catalysts via adsorbed-layer nanoreactor synthesis and enhancement of their photo-degradation performance in seawater

NASA Astrophysics Data System (ADS)

Wang, Ting; Xu, Zhi-yong; Zhu, Yi-chen; Wu, Li-guang; Yuan, Hao-xuan; Li, Chang-chun; Liu, Ya-yu; Cai, Jing

2017-11-01

Graphene oxide (GO) was first employed as a support in preparing TiO2 nanoparticles by adsorbed-layer nanoreactor synthesis (ALNS). Both TiO2 crystallization and GO reduction simultaneously occurred during solvothermal treatment with alcohol as a solvent. By transmission electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence spectroscopy, the results showed that TiO2 nanoparticles with less than 10 nm of size distributed very homogeneously on the GO surface. Tight interaction between TiO2 particles and GO surface could effectively inhibit the aggregation of TiO2 particles, during solvothermal treatment for anatase TiO2 formation. Alcohol could also reduce oxygenated functional groups on GO surface after solvothermal treatment. TiO2 particles with small size and the decrease in oxygenated functional groups on the GO surface both caused high separation efficiency of photo-generated charge carriers, thus resulting in high photo-degradation performance of catalysts. Strong phenol adsorption on photocatalyst was key to enhancing photo-degradation efficiency for phenol in seawater. Moreover, the change in catalyst structure was minimal at different temperatures of solvothermal treatment. But, the degradation rate and efficiency for phenol in seawater were obviously enhanced because of the sensitive structure-activity relationship of catalysts under weak-light irradiation.

Molecular adsorption study of nicotine and caffeine on single-walled carbon nanotubes from first principles

NASA Astrophysics Data System (ADS)

Lee, Hyung-June; Kim, Gunn; Kwon, Young-Kyun

2013-08-01

Using first-principles calculations, we investigate the electronic structures and binding properties of nicotine and caffeine adsorbed on single-walled carbon nanotubes to determine whether CNTs are appropriate for filtering or sensing nicotine and caffeine molecules. We find that caffeine adsorbs more strongly than nicotine. The different binding characteristics are discussed by analyzing the modification of the electronic structure of the molecule-adsorbed CNTs. We also calculate the quantum conductance of the CNTs in the presence of nicotine or caffeine adsorbates and demonstrate that the influence of caffeine is stronger than nicotine on the conductance of the host CNT.

Chiral Selective Chemistry Induced by Natural Selection of Spin-Polarized Electrons.

PubMed

Rosenberg, Richard A; Mishra, Debabrata; Naaman, Ron

2015-06-15

The search to understand the origin of homochirality in nature has been ongoing since the time of Pasteur. Previous work has shown that DNA can act as a spin filter for low-energy electrons and that spin-polarized secondary electrons produced by X-ray irradiation of a magnetic substrate can induce chiral selective chemistry. In the present work it is demonstrated that secondary electrons from a substrate that are transmitted through a chiral overlayer cause enantiomeric selective chemistry in an adsorbed adlayer. We determine the quantum yields (QYs) for dissociation of (R)- or (S)-epichlorohydrin adsorbed on a chiral self-assembled layer of DNA on gold and on bare gold (for control). The results show that there is a significant difference in the QYs between the two enantiomers when adsorbed on DNA, but none when they are adsorbed on bare Au. We propose that the effect results from natural spin filtering effects cause by the chiral monolayer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable electronic structure and spin splitting in single and multiple Fe-adsorbed g-C2N with different layers: A first-principles study

NASA Astrophysics Data System (ADS)

Zheng, Z. D.; Wang, X. C.; Mi, W. B.

2018-04-01

The electronic structure of Fe adsorbed g-C2N with different layers is investigated by first-principles calculations. The Fe1 and Fe2 represent the Fe adsorptions at Csbnd C and Csbnd N rings, and Fe11 and Fe121 adsorption sites are also considered. The Fe1 adsorbed g-C2N is metallic with layer from n = 1 to 4, and the maximum spin splitting is 515, 428, 46 and 133 meV. The band gap of Fe2 adsorbed g-C2N with different layers is 0, 0, 117 and 6 meV, and the maximum spin splitting is 565, 369, 195 and 146 meV, respectively. All of the Fe11 adsorbed g-C2N are metallic with layer from n = 1 to 4, and the maximum spin splitting is 199, 0, 83 and 203 meV. An indirect band gap of 215 meV appears in Fe121 adsorbed g-C2N at layer n = 3, and the maximum spin splitting is 283, 211, 304 and 153 meV, respectively. Our results show that the electronic structures of Fe adsorbed novel two-dimensional semiconductor g-C2N can be tuned by different layers. Moreover, the spin splitting of Fe2 adsorbed g-C2N decreases monotonically as g-C2N layer increases from n = 1 to 4, which will provide more potential applications in spintronic devices.

Time scale of random sequential adsorption.

PubMed

Erban, Radek; Chapman, S Jonathan

2007-04-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) The kinetics of the chemical reaction between adsorbing molecules and the surface and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modeled in a diffusion-driven context, i.e., the conditional probability of adsorbing a molecule provided that the molecule hits the surface is related to the macroscopic surface reaction rate. The geometrical constraint (ii) is modeled using random sequential adsorption (RSA), which is the sequential addition of molecules at random positions on a surface; one attempt to attach a molecule is made per one RSA simulation time step. By coupling RSA with the diffusion of molecules in the solution above the surface the RSA simulation time step is related to the real physical time. The method is illustrated on a model of chemisorption of reactive polymers to a virus surface.

A surprising way to control the charge transport in molecular electronics: the subtle impact of the coverage of self-assembled monolayers of floppy molecules adsorbed on metallic electrodes.

PubMed

Bâldea, Ioan

2017-10-26

Inspired by earlier attempts in organic electronics aiming at controlling charge injection from metals into organic materials by manipulating the Schottky energy barrier using self-assembled monolayers (SAMs), recent experimental and theoretical work in molecular electronics showed that metal-organic interfaces can be controlled via changes in the metal work function that are induced by SAMs. In this paper we indicate a different route to achieve interface-driven control over the charge transfer/transport at the molecular scale. It is based on the fact that, in floppy molecule based SAMs, the molecular conformation can be tuned by varying the coverage of the adsorbate. We demonstrate this effect with the aid of benchmark molecules that are often used to fabricate nanojunctions and consist of two rings that can easily rotate relative to each other. We show that, by varying the coverage of the SAM, the twisting angle φ of the considered molecular species can be modified by a factor of two. Given the fact that the low bias conductance G scales as cos 2  φ, this results in a change in G of over one order of magnitude for the considered molecular species. Tuning the twisting angle by controlling the SAM coverage may be significant, e.g., for current efforts to fabricate molecular switches. Conversely, the lack of control over the local SAM coverage may be problematic for the reproducibility and interpretation of the STM (scanning tunneling microscope) measurements on repeatedly forming single molecule break junctions.

Charge transfer from TiO2 into adsorbed benzene diazonium compounds

NASA Astrophysics Data System (ADS)

Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

2004-08-01

Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

Bioavailability of Carbon Nanomaterial-Adsorbed Polycyclic Aromatic Hydrocarbons to Pimphales promelas: Influence of Adsorbate Molecular Size and Configuration.

PubMed

Linard, Erica N; Apul, Onur G; Karanfil, Tanju; van den Hurk, Peter; Klaine, Stephen J

2017-08-15

Despite carbon nanomaterials' (CNMs) potential to alter the bioavailability of adsorbed contaminants, information characterizing the relationship between adsorption behavior and bioavailability of CNM-adsorbed contaminants is still limited. To investigate the influence of CNM morphology and organic contaminant (OC) physicochemical properties on this relationship, adsorption isotherms were generated for a suite of polycyclic aromatic hydrocarbons (PAHs) on multiwalled carbon nanotubes (MWCNTs) and exfoliated graphene (GN) in conjunction with determining the bioavailability of the adsorbed PAHs to Pimphales promelas using bile analysis via fluorescence spectroscopy. Although it appeared that GN adsorbed PAHs indiscriminately compared to MWCNTs, the subsequent bioavailability of GN-adsorbed PAHs was more sensitive to PAH morphology than MWCNTs. GN was effective at reducing bioavailability of linear PAHs by ∼70%, but had little impact on angular PAHs. MWCNTs were sensitive to molecular size, where bioavailability of two-ringed naphthalene was reduced by ∼80%, while bioavailability of the larger PAHs was reduced by less than 50%. Furthermore, the reduction in bioavailability of CNM-adsorbed PAHs was negatively correlated with the amount of CNM surface area covered by the adsorbed-PAHs. This study shows that the variability in bioavailability of CNM-adsorbed PAHs is largely driven by PAH size, configuration and surface area coverage.

Nonadiabatic dynamics of electron scattering from adsorbates in surface bands

NASA Astrophysics Data System (ADS)

Gumhalter, Branko; Šiber, Antonio; Buljan, Hrvoje; Fauster, Thomas

2008-10-01

We present a comparative study of nonadiabatic dynamics of electron scattering in quasi-two-dimensional surface band which is induced by the long-range component of the interactions with a random array of adsorbates. Using three complementary model descriptions of intraband spatiotemporal propagation of quasiparticles that go beyond the single-adsorbate scattering approach we are able to identify distinct subsequent regimes of evolution of an electron following its promotion into an unoccupied band state: (i) early quadratic or ballistic decay of the initial-state survival probability within the Heisenberg uncertainty window, (ii) preasymptotic exponential decay governed by the self-consistent Fermi golden rule scattering rate, and (iii) asymptotic decay described by a combined inverse power-law and logarithmic behavior. The developed models are applied to discuss the dynamics of intraband adsorbate-induced scattering of hot electrons excited into the n=1 image-potential band on Cu(100) surface during the first stage of a two-photon photoemission process. Estimates of crossovers between the distinct evolution regimes enable assessments of the lifespan of a standard quasiparticle behavior and thereby of the range of applicability of the widely used Fermi golden rule and optical Bloch equations approach for description of adsorbate-induced quasiparticle decay and dephasing in ultrafast experiments.

Characterization of the bionano interface and mapping extrinsic interactions of the corona of nanomaterials

NASA Astrophysics Data System (ADS)

O'Connell, D. J.; Bombelli, F. Baldelli; Pitek, A. S.; Monopoli, M. P.; Cahill, D. J.; Dawson, K. A.

2015-09-01

Nanoparticles in physiological environments are known to selectively adsorb proteins and other biomolecules forming a tightly bound biomolecular `corona' on their surface. Where the exchange times of the proteins are sufficiently long, it is believed that the protein corona constitutes the particle identity in biological milieu. Here we show that proteins in the corona retain their functional characteristics and can specifically bind to cognate proteins on arrays of thousands of immobilised human proteins. The biological identity of the nanomaterial is seen to be specific to the blood plasma concentration in which they are exposed. We show that the resulting in situ nanoparticle interactome is dependent on the protein concentration in plasma, with the emergence of a small number of dominant protein-protein interactions. These interactions are those driven by proteins that are adsorbed onto the particle surface and whose binding epitopes are subsequently expressed or presented suitably on the particle surface. We suggest that, since specific tailored protein arrays for target systems and organs can be designed, their use may be an important element in an overall study of the biomolecular corona.Nanoparticles in physiological environments are known to selectively adsorb proteins and other biomolecules forming a tightly bound biomolecular `corona' on their surface. Where the exchange times of the proteins are sufficiently long, it is believed that the protein corona constitutes the particle identity in biological milieu. Here we show that proteins in the corona retain their functional characteristics and can specifically bind to cognate proteins on arrays of thousands of immobilised human proteins. The biological identity of the nanomaterial is seen to be specific to the blood plasma concentration in which they are exposed. We show that the resulting in situ nanoparticle interactome is dependent on the protein concentration in plasma, with the emergence of a small number of dominant protein-protein interactions. These interactions are those driven by proteins that are adsorbed onto the particle surface and whose binding epitopes are subsequently expressed or presented suitably on the particle surface. We suggest that, since specific tailored protein arrays for target systems and organs can be designed, their use may be an important element in an overall study of the biomolecular corona. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01970b

Direct electron transfer of glucose oxidase on carbon nanotubes

NASA Astrophysics Data System (ADS)

Guiseppi-Elie, Anthony; Lei, Chenghong; Baughman, Ray H.

2002-10-01

In this report, exploitation of the unique properties of single-walled carbon nanotubes (SWNT) leads to the achievement of direct electron transfer with the redox active centres of adsorbed oxidoreductase enzymes. Flavin adenine dinucleotide (FAD), the redox active prosthetic group of flavoenzymes that catalyses important biological redox reactions and the flavoenzyme glucose oxidase (GOx), were both found to spontaneously adsorb onto carbon nanotube bundles. Both FAD and GOx were found to spontaneously adsorb to unannealed carbon nanotubes that were cast onto glassy carbon electrodes and to display quasi-reversible one-electron transfer. Similarly, GOx was found to spontaneously adsorb to annealed, single-walled carbon nanotube paper and to display quasi-reversible one-electron transfer. In particular, GOx immobilized in this way was shown, in the presence of glucose, to maintain its substrate-specific enzyme activity. It is believed that the tubular fibrils become positioned within tunnelling distance of the cofactors with little consequence to denaturation. The combination of SWNT with redox active enzymes would appear to offer an excellent and convenient platform for a fundamental understanding of biological redox reactions as well as the development of reagentless biosensors and nanobiosensors.

Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

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

Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

2014-01-28

The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

Substrate driven photochemistry of CdSe quantum dot films: charge injection and irreversible transformations on oxide surfaces.

PubMed

Tvrdy, Kevin; Kamat, Prashant V

2009-04-23

The photochemical behavior of CdSe quantum dots anchored to different surfaces was probed through their deposition on glass, SiO2, and TiO2 films. Following visible light irradiation under ambient conditions, CdSe quantum dots deposited on semiconducting TiO2 surface degraded, where no such degradation was observed when deposited on inert SiO2 surface or glass. Fluorescence decay and transient absorption experiments confirmed that charge injection from excited CdSe into TiO2 occurs with an apparent rate constant of 5.62 x 10(8) s(-1) and is the primary event responsible for photodegradation. In the presence of air, injected electrons are scavenged by surface adsorbed oxygen leaving behind reactive holes which induce anodic corrosion of CdSe quantum dots. In a vacuum environment, minimal CdSe degradation was observed as electron scavenging by oxygen is replaced with charge recombination between injected electrons and holes in CdSe nanocrystals. Spectroscopic measurements presented in this study highlight the role of both substrate and medium in dictating the photochemistry of CdSe quantum dots.

Development of an electrically driven molecular motor.

PubMed

Murphy, Colin J; Sykes, E Charles H

2014-10-01

For molecules to be used as components in molecular machinery, methods are required that couple individual molecules to external energy sources in order to selectively excite motion in a given direction. While significant progress has been made in the construction of synthetic molecular motors powered by light and by chemical reactions, there are few experimental examples of electrically driven molecular motors. To this end, we pioneered the use of a new, stable and tunable molecular rotor system based on surface-bound thioethers to comprehensively study many aspects of molecular rotation. As biological molecular motors often operate at interfaces, our synthetic system is especially amenable to microscopic interrogation as compared to solution-based systems. Using scanning tunneling microscopy (STM) and density functional theory, we studied the rotation of surface-bound thioethers, which can be induced either thermally or by electrons from the STM tip in a two-terminal setup. Moreover, the temperature and electron flux can be adjusted to allow each rotational event to be monitored at the molecular scale in real time. This work culminated in the first experimental demonstration of a single-molecule electric motor, where the electrically driven rotation of a butyl methyl sulfide molecule adsorbed on a copper surface could be directionally biased. The direction and rate of the rotation are related to the chirality of both the molecule and the STM tip (which serves as the electrode), illustrating the importance of the symmetry of the metal contacts in atomic-scale electrical devices. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Static and hydrodynamic studies of the conformation of adsorbed macromolecules at the solid/liquid interface

NASA Astrophysics Data System (ADS)

Yavorsky, D. P.

1981-08-01

The structure of an adsorbed macromolecular layer at the solid/liquid interface under both stationary and flow conditions is examined. The conformation of adsorbed bovine serum albumin (BSA) is deduced from the thickness of surface layers formed on the pore walls of track etched (mica) membranes. Changes in membrane permeability due to protein adsorption are related directly to a net reduction in pore size or an equivalent adsorbed layer thickness. Complementary permeability measurements using electrolyte conduction, tracer diffusion, and pressure driven flow have verified the unique structural qualities of the track etched membrane and collectively demonstrate an ability to determine bare pore size with an accuracy of + or - 2A. The average static thickness of an adsorbed BSA layer, as derived from electrolyte conduction and tracer diffusion, was 43 + or - 3A independent of pore size. In comparison with the known BSA solution dimensions, this measured thickness is consistent with a monolayer of structurally unperturbed protein molecules each oriented in a "side-on" position. Pronounced conformational changes in adsorbed BSA layers were observed under conditions of shear flow. Electrostatic interactions were also shown to significantly affect adsorbed protein conformation through changes in solution ionic strength and surface charge.

Charge-transfer excited state in pyrene-1-carboxylic acids adsorbed on titanium dioxide nanoparticles

NASA Astrophysics Data System (ADS)

Krawczyk, S.; Nawrocka, A.; Zdyb, A.

2018-06-01

The electronic structure of excited photosensitizer adsorbed at the surface of a solid is the key factor in the electron transfer processes that underlie the efficiency of dye-sensitized solar cells and photocatalysts. In this work, Stark effect (electroabsorption) spectroscopy has been used to measure the polarizability and dipole moment changes in electronic transitions of pyrene-1-carboxylic (PCA), -acetic (PAA) and -butyric (PBA) acids in ethanol, both free and adsorbed on colloidal TiO2, in glassy ethanol at low temperature. The lack of appreciable increase of dipole moment in the excited state of free and adsorbed PAA and PBA points that two or more single bonds completely prevent the expansion of π-electrons from the aromatic ring towards the carboxylic group, thus excluding the possibility of direct electron injection into TiO2. In free PCA, the pyrene's forbidden S0 → S1 transition has increased intensity, exhibits a long progression in 1400 cm-1 Ag mode and is associated with |Δμ| of 2 D. Adsorption of PCA on TiO2 causes a broadening and red shift of the S0 → S1 absorption band and an increase in dipole moment change on electronic excitation to |Δμ| = 6.5 D. This value increased further to about 15 D when the content of acetic acid in the colloid was changed from 0.2% to 2%, and this effect is ascribed to the surface electric field. The large increase of |Δμ| points that the electric field effect can not only change the energetics of electron transfer from the excited sensitizer into the solid, but can also shift the molecular electronic density, thus directly influencing the electronic coupling factor relevant for electron transfer at the molecule-solid interface.

Experimental demonstration of a single-molecule electric motor.

PubMed

Tierney, Heather L; Murphy, Colin J; Jewell, April D; Baber, Ashleigh E; Iski, Erin V; Khodaverdian, Harout Y; McGuire, Allister F; Klebanov, Nikolai; Sykes, E Charles H

2011-09-04

For molecules to be used as components in molecular machines, methods that couple individual molecules to external energy sources and that selectively excite motion in a given direction are required. Significant progress has been made in the construction of molecular motors powered by light and by chemical reactions, but electrically driven motors have not yet been built, despite several theoretical proposals for such motors. Here we report that a butyl methyl sulphide molecule adsorbed on a copper surface can be operated as a single-molecule electric motor. Electrons from a scanning tunnelling microscope are used to drive the directional motion of the molecule in a two-terminal setup. Moreover, the temperature and electron flux can be adjusted to allow each rotational event to be monitored at the molecular scale in real time. The direction and rate of the rotation are related to the chiralities of both the molecule and the tip of the microscope (which serves as the electrode), illustrating the importance of the symmetry of the metal contacts in atomic-scale electrical devices.

Oxygen adsorption on a Si(1 0 0) substrate: effects on secondary emission properties

NASA Astrophysics Data System (ADS)

Vogan, W. S.; Champion, R. L.

2001-10-01

Secondary anion and electron yields resulting from low-energy (50-500 eV) Na + bombardment of an oxygen-adsorbed Si(1 0 0) substrate have been measured as a function of oxygen exposure and of Na + impact energy. Adsorbate coverage ranges from none to over half a monolayer. The dominant sputtered anion was found to be O - with SiO 2- being a minor constituent. Kinetic energy distributions of the secondary anions and electrons were also measured. The presence of an adsorbate was observed to enhance secondary anion emission to a significant degree whereas secondary electron emission was minor, in sharp contrast to what has been observed for metallic substrates. The mechanism for secondary emission appears to involve electronic excitation of Si xO -; it is suggested that electron emission is governed by a process similar to Penning ionization, in which a vacancy created by the excitation of Si xO - may be filled by an electron from the valence band. The variation in the work function as oxygen accumulated on the surface was observed to be small.

Light-driven water oxidation for solar fuels

PubMed Central

Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

2014-01-01

Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

Theory of vibrationally assisted tunneling for hydroxyl monomer flipping on Cu(110)

NASA Astrophysics Data System (ADS)

Gustafsson, Alexander; Ueba, Hiromu; Paulsson, Magnus

2014-10-01

To describe vibrationally mediated configuration changes of adsorbates on surfaces we have developed a theory to calculate both reaction rates and pathways. The method uses the T-matrix to describe excitations of vibrational states by the electrons of the substrate, adsorbate, and tunneling electrons from a scanning tunneling probe. In addition to reaction rates, the theory also provides the reaction pathways by going beyond the harmonic approximation and using the full potential energy surface of the adsorbate which contains local minima corresponding to the adsorbates different configurations. To describe the theory, we reproduce the experimental results in [T. Kumagai et al., Phys. Rev. B 79, 035423 (2009), 10.1103/PhysRevB.79.035423], where the hydrogen/deuterium atom of an adsorbed hydroxyl (OH/OD) exhibits back and forth flipping between two equivalent configurations on a Cu(110) surface at T =6 K. We estimate the potential energy surface and the reaction barrier, ˜160 meV, from DFT calculations. The calculated flipping processes arise from (i) at low bias, tunneling of the hydrogen through the barrier, (ii) intermediate bias, tunneling electrons excite the vibrations increasing the reaction rate although over the barrier processes are rare, and (iii) higher bias, overtone excitations increase the reaction rate further.

Effect of Li Adsorption on the Electronic and Hydrogen Storage Properties of Acenes: A Dispersion-Corrected TAO-DFT Study

PubMed Central

Seenithurai, Sonai; Chai, Jeng-Da

2016-01-01

Due to the presence of strong static correlation effects and noncovalent interactions, accurate prediction of the electronic and hydrogen storage properties of Li-adsorbed acenes with n linearly fused benzene rings (n = 3–8) has been very challenging for conventional electronic structure methods. To meet the challenge, we study these properties using our recently developed thermally-assisted-occupation density functional theory (TAO-DFT) with dispersion corrections. In contrast to pure acenes, the binding energies of H2 molecules on Li-adsorbed acenes are in the ideal binding energy range (about 20 to 40 kJ/mol per H2). Besides, the H2 gravimetric storage capacities of Li-adsorbed acenes are in the range of 9.9 to 10.7 wt%, satisfying the United States Department of Energy (USDOE) ultimate target of 7.5 wt%. On the basis of our results, Li-adsorbed acenes can be high-capacity hydrogen storage materials for reversible hydrogen uptake and release at ambient conditions. PMID:27609626

Thermodynamics of Indomethacin Adsorption to Phospholipid Membranes.

PubMed

Fearon, Amanda D; Stokes, Grace Y

2017-11-22

Using second-harmonic generation, we directly monitored adsorption of indomethacin, a nonsteroidal anti-inflammatory drug, to supported lipid bilayers composed of phospholipids of varying phase, cholesterol content, and head group charge without the use of extrinsic labels at therapeutically relevant aqueous concentrations. Indomethacin adsorbed to gel-phase lipids with a high binding affinity, suggesting that like other arylacetic acid-containing drugs, it preferentially interacts with ordered lipid domains. We discovered that adsorption of indomethacin to gel-phase phospholipids was endothermic and entropically driven, whereas adsorption to fluid-phase phospholipids was exothermic and enthalpically driven. As temperature increased from 19 to 34 °C, binding affinities to gel-phase lipids increased by 7-fold but relative surface concentration decreased to one-fifth of the original value. We also compared our results to the entropies reported for indomethacin adsorbed to surfactant micelles, which are used in drug delivery systems, and assert that adsorbed water molecules in the phospholipid bilayer may be buried deeper into the acyl chains and less accessible for disruption. The thermodynamic studies reported here provide mechanistic insight into indomethacin interactions with mammalian plasma membranes in the gastrointestinal tract and inform studies of drug delivery, where indomethacin is commonly used as a prototypical, hydrophobic small-molecule drug.

Method and apparatus for atomic imaging

DOEpatents

Saldin, Dilano K.; de Andres Rodriquez, Pedro L.

1993-01-01

A method and apparatus for three dimensional imaging of the atomic environment of disordered adsorbate atoms are disclosed. The method includes detecting and measuring the intensity of a diffuse low energy electron diffraction pattern formed by directing a beam of low energy electrons against the surface of a crystal. Data corresponding to reconstructed amplitudes of a wave form is generated by operating on the intensity data. The data corresponding to the reconstructed amplitudes is capable of being displayed as a three dimensional image of an adsorbate atom. The apparatus includes a source of a beam of low energy electrons and a detector for detecting the intensity distribution of a DLEED pattern formed at the detector when the beam of low energy electrons is directed onto the surface of a crystal. A device responsive to the intensity distribution generates a signal corresponding to the distribution which represents a reconstructed amplitude of a wave form and is capable of being converted into a three dimensional image of the atomic environment of an adsorbate atom on the crystal surface.

Effect of urea and glycerol on the adsorption of ribonuclease A at the air-water interface.

PubMed

Hüsecken, Anne K; Evers, Florian; Czeslik, Claus; Tolan, Metin

2010-08-17

This study reports on the influence of nonionic cosolvents on the interfacial structure of ribonuclease A (RNase) adsorbed at the air-water interface. We applied X-ray reflectometry to obtain detailed volume fraction profiles of the adsorbed layers and to follow the effect of glycerol and urea on the adsorbate structure as a function of cosolvent concentration. Under all conditions studied, the adsorbed RNase layer maintains its compact shape, and the adsorbed RNase molecules adopt a flat-on orientation at the interface. Both kosmotropic glycerol and chaotropic urea exert profound effects on the adsorbate: The surface excess decreases linearly with glycerol content and is also reduced at low urea concentration. However, at high urea concentration, parts of the adsorbed layer are dehydrated and become exposed to air. The electron density and volume fraction profiles of the adsorbed protein provide clear evidence that these effects are ruled by different mechanisms.

Valley filters, accumulators, and switches induced in graphene quantum dots by lines of adsorbed hydrogen atoms

NASA Astrophysics Data System (ADS)

Azari, Mohammadhadi; Kirczenow, George

2018-06-01

We present electronic structure and quantum transport calculations that predict conducting channels induced in graphene quantum dots by lines of adsorbed hydrogen atoms to function as highly efficient, experimentally realizable valley filters, accumulators, and switches. The underlying physics is an interesting property of graphene Dirac point resonances (DPRs) that is revealed here, namely, that an electric current passing through a DPR-mediated conducting channel in a given direction is carried by electrons of only one of the two graphene valleys. Our predictions apply to lines of hydrogen atoms adsorbed on graphene quantum dots that are either free standing or supported on a hexagonal boron nitride substrate.

Complementary Barrier Infrared Detector (CBIRD) Contact Methods

NASA Technical Reports Server (NTRS)

Ting, David Z.; Hill, Cory J.; Gunapala, Sarath D.

2013-01-01

The performance of the CBIRD detector is enhanced by using new device contacting methods that have been developed. The detector structure features a narrow gap adsorber sandwiched between a pair of complementary, unipolar barriers that are, in turn, surrounded by contact layers. In this innovation, the contact adjacent to the hole barrier is doped n-type, while the contact adjacent to the electron barrier is doped p-type. The contact layers can have wider bandgaps than the adsorber layer, so long as good electrical contacts are made to them. If good electrical contacts are made to either (or both) of the barriers, then one could contact the barrier(s) directly, obviating the need for additional contact layers. Both the left and right contacts can be doped either n-type or ptype. Having an n-type contact layer next to the electron barrier creates a second p-n junction (the first being the one between the hole barrier and the adsorber) over which applied bias could drop. This reduces the voltage drop over the adsorber, thereby reducing dark current generation in the adsorber region.

The creation of a biomimetic interface between boron-doped diamond and immobilized proteins.

PubMed

Hoffmann, René; Kriele, Armin; Obloh, Harald; Tokuda, Norio; Smirnov, Waldemar; Yang, Nianjun; Nebel, Christoph E

2011-10-01

Immobilization of proteins on a solid electrode is to date done by chemical cross-linking or by addition of an adjustable intermediate. In this paper we introduce a concept where a solid with variable surface properties is optimized to mediate binding of the electron-transfer protein Cytochrome c (Cyt c) by mimicking the natural binding environment. It is shown that, as a carbon-based material, boron-doped diamond can be adjusted by simple electrochemical surface treatments to the specific biochemical requirements of Cyt c. The structure and functionality of passively adsorbed Cyt c on variously terminated diamond surfaces were characterized in detail using a combination of electrochemical techniques and atomic force microscopy with single-molecule resolution. Partially oxidized diamond allowed stable immobilization of Cyt c together with high electron transfer activity, driven by a combination of electrostatic and hydrophobic interactions. This surface mimics the natural binding partner, where coarse orientation is governed by electrostatic interaction of the protein's dipole and hydrophobic interactions assist in formation of the electron transfer complex. The optimized surface mediated electron transfer kinetics around 100 times faster than those reported for other solids and even faster kinetics than on self-assembled monolayers of alkanethiols. Copyright © 2011 Elsevier Ltd. All rights reserved.

Influence of the adsorption geometry of PTCDA on Ag(111) on the tip-molecule forces in non-contact atomic force microscopy.

PubMed

Langewisch, Gernot; Falter, Jens; Schirmeisen, André; Fuchs, Harald

2014-01-01

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) adsorbed on a metal surface is a prototypical organic-anorganic interface. In the past, scanning tunneling microscopy and scanning tunneling spectroscopy studies of PTCDA adsorbed on Ag(111) have revealed differences in the electronic structure of the molecules depending on their adsorption geometry. In the work presented here, high-resolution 3D force spectroscopy measurements at cryogenic temperatures were performed on a surface area that contained a complete PTCDA unit cell with the two possible geometries. At small tip-molecule separations, deviations in the tip-sample forces were found between the two molecule orientations. These deviations can be explained by a different electron density in both cases. This result demonstrates the capability of 3D force spectroscopy to detect even small effects in the electronic properties of organic adsorbates.

Photoemission into water adsorbed on metals: Probing dissociative electron transfer using theory

NASA Astrophysics Data System (ADS)

Zhang, Yu; Whitten, J. L.

The photoinduced dissociation of water adsorbed on a silver nanoparticle is explored using theory to probe reaction pathways that produce hydrogen. Ab initio configuration theory is used to describe the systems. A formulation that allows excited electronic states embedded in a near continuum of lower energy states to be calculated accurately is described. Electron attachment of a photoemitted electron to adsorbed water can lead to the formation of H2 at a very low energy barrier with oxygen remaining on the Ag surface. A large energy barrier to form H2 plus adsorbed O is found for the ground state. The excited state has a much smaller barrier to OH stretch; however, to dissociate, the system must cross over from the excited state to the ground state potential energy surface. The cross over point is near the transition state for a ground state process. A characteristic feature of the excited state potential curve is an increase in energy in the early stages of OH stretch as the charge transfer state evolves from a state with considerable Rydberg character to one that has a typical OH antibonding molecular orbital. Another pathway releases a H atom leaving OH on the surface. Effects due to doping of a Ag nanoparticle with a K electron donor atom are compared with those caused by a Fermi level shift due to an applied potential. Results are also reported for electron transfer to a solvated lithium ion, Li(H2O) 6+, near the surface of a silver particle. A steering mechanism is found that involves the interaction of a hydridic hydrogen formed after electron transfer with an acidic hydrogen of a second solvated water molecule.

The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

PubMed

Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

2005-03-01

The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and substrate bands. Significant implications are described for density-functional calculations of through-molecule electron transport in molecular electronics.

NOx adsorber and method of regenerating same

DOEpatents

Endicott, Dennis L [Peoria, IL; Verkiel, Maarten [Metamora, IL; Driscoll, James J [Dunlap, IL

2007-01-30

New technologies, such as NOx adsorber catalytic converters, are being used to meet increasingly stringent regulations on undesirable emissions, including NOx emissions. NOx adsorbers must be periodically regenerated, which requires an increased fuel consumption. The present disclosure includes a method of regenerating a NOx adsorber within a NOx adsorber catalytic converter. At least one sensor positioned downstream from the NOx adsorber senses, in the downstream exhaust, at least one of NOx, nitrous oxide and ammonia concentrations a plurality of times during a regeneration phase. The sensor is in communication with an electronic control module that includes a regeneration monitoring algorithm operable to end the regeneration phase when a time rate of change of the at least one of NOx, nitrous oxide and ammonia concentrations is after an expected plateau region begins.

Electronic structures of graphane with vacancies and graphene adsorbed with fluorine atoms

NASA Astrophysics Data System (ADS)

Wu, Bi-Ru; Yang, Chih-Kai

2012-03-01

We investigate the electronic structure of graphane with hydrogen vacancies, which are supposed to occur in the process of hydrogenation of graphene. A variety of configurations is considered and defect states are derived by density functional calculation. We find that a continuous chain-like distribution of hydrogen vacancies will result in conduction of linear dispersion, much like the transport on a superhighway cutting through the jungle of hydrogen. The same conduction also occurs for chain-like vacancies in an otherwise fully fluorine-adsorbed graphene. These results should be very useful in the design of graphene-based electronic circuits.

Removal performance of elemental mercury by low-cost adsorbents prepared through facile methods of carbonisation and activation of coconut husk.

PubMed

Johari, Khairiraihanna; Alias, Afidatul Shazwani; Saman, Norasikin; Song, Shiow Tien; Mat, Hanapi

2015-01-01

The preparation of chars and activated carbon as low-cost elemental mercury adsorbents was carried out through the carbonisation of coconut husk (pith and fibre) and the activation of chars with potassium hydroxide (KOH), respectively. The synthesised adsorbents were characterised by using scanning electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption analysis. The elemental mercury removal performance was measured using a conventional flow type packed-bed adsorber. The physical and chemical properties of the adsorbents changed as a result of the carbonisation and activation process, hence affecting on the extent of elemental mercury adsorption. The highest elemental mercury (Hg°) adsorption capacity was obtained for the CP-CHAR (3142.57 µg g(-1)), which significantly outperformed the pristine and activated carbon adsorbents, as well as higher than some adsorbents reported in the literature. © The Author(s) 2014.

Molecular Electronic Devices Based On Electrooptical Behavior Of Heme-Like Molecules

NASA Astrophysics Data System (ADS)

Simic-Glavaski, B.

1986-02-01

This paper discusses application of the electrically modulated and unusually strong Raman emitted light produced by an adsorbed monolayer of phthalocyanine molecules on silver electrode or silver bromide substrates and on neural membranes. The analysis of electronic energy levels in semiconducting silver bromide and the adsorbed phthalocyanine molecules suggests a lasing mechanism as a possible origin of the high enhancement factor in surface enhanced Raman scattering. Electrically modulated Raman scattering may be used as a carrier of information which is drawn fran the fast intramolecular electron transfer aN,the multiplicity of quantum wells in phthalocyanine molecules. Fast switching times on the order of 10-13 seconds have been measured at room temperature. Multilevel and multioutput optical signals have also been obtained fran such an electrically modulated adsorbed monolayer of phthalocyanine molecules which can be precisely addressed and interrogated. This may be of practical use to develop Nlecular electronic devices with high density memory and fast parallel processing systems with a typical 1020 gate Hz/cm2 capacity at room temperature for use in optical computers. The paper also discusses the electrooptical modulation of Raman signals obtained from adsorbed bio-compatible phthalocyanine molecules on nerve membranes. This optical probe of neural systems can be used in studies of complex information processing in neural nets and provides a possible method for interfacing natural and man-made information processing devices.

Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

PubMed Central

Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

2015-01-01

Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated. PMID:25749635

Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

NASA Astrophysics Data System (ADS)

Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

2015-03-01

Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

FENTON-DRIVEN CHEMICAL REGENERATION OF MTBE-SPENT GAC

EPA Science Inventory

Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was chemically regenerated utilizing the Fenton mechanism. Two successive GAC regeneration cycles were performed involving iterative adsorption and oxidation processes: MTBE was adsorbed to the GAC, oxidized, r...

Ultrafast chemical interface scattering as an additional decay channel for nascent nonthermal electrons in small metal nanoparticles.

PubMed

Bauer, Christophe; Abid, Jean-Pierre; Fermin, David; Girault, Hubert H

2004-05-15

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas.

Photoreduction of Shewanella oneidensis Extracellular Cytochromes by Organic Chromophores and Dye‐Sensitized TiO2

PubMed Central

Ainsworth, Emma V.; Lockwood, Colin W. J.; White, Gaye F.; Hwang, Ee Taek; Sakai, Tsubasa; Gross, Manuela A.; Richardson, David J.; Clarke, Thomas A.

2016-01-01

Abstract The transfer of photoenergized electrons from extracellular photosensitizers across a bacterial cell envelope to drive intracellular chemical transformations represents an attractive way to harness nature's catalytic machinery for solar‐assisted chemical synthesis. In Shewanella oneidensis MR‐1 (MR‐1), trans‐outer‐membrane electron transfer is performed by the extracellular cytochromes MtrC and OmcA acting together with the outer‐membrane‐spanning porin⋅cytochrome complex (MtrAB). Here we demonstrate photoreduction of solutions of MtrC, OmcA, and the MtrCAB complex by soluble photosensitizers: namely, eosin Y, fluorescein, proflavine, flavin, and adenine dinucleotide, as well as by riboflavin and flavin mononucleotide, two compounds secreted by MR‐1. We show photoreduction of MtrC and OmcA adsorbed on RuII‐dye‐sensitized TiO2 nanoparticles and that these protein‐coated particles perform photocatalytic reduction of solutions of MtrC, OmcA, and MtrCAB. These findings provide a framework for informed development of strategies for using the outer‐membrane‐associated cytochromes of MR‐1 for solar‐driven microbial synthesis in natural and engineered bacteria. PMID:27685371

Controlled clockwise and anticlockwise rotational switching of a molecular motor.

PubMed

Perera, U G E; Ample, F; Kersell, H; Zhang, Y; Vives, G; Echeverria, J; Grisolia, M; Rapenne, G; Joachim, C; Hla, S-W

2013-01-01

The design of artificial molecular machines often takes inspiration from macroscopic machines. However, the parallels between the two systems are often only superficial, because most molecular machines are governed by quantum processes. Previously, rotary molecular motors powered by light and chemical energy have been developed. In electrically driven motors, tunnelling electrons from the tip of a scanning tunnelling microscope have been used to drive the rotation of a simple rotor in a single direction and to move a four-wheeled molecule across a surface. Here, we show that a stand-alone molecular motor adsorbed on a gold surface can be made to rotate in a clockwise or anticlockwise direction by selective inelastic electron tunnelling through different subunits of the motor. Our motor is composed of a tripodal stator for vertical positioning, a five-arm rotor for controlled rotations, and a ruthenium atomic ball bearing connecting the static and rotational parts. The directional rotation arises from sawtooth-like rotational potentials, which are solely determined by the internal molecular structure and are independent of the surface adsorption site.

Utilization of fish bone as adsorbent of Fe3+ ion by controllable removal of its carbonaceous component

NASA Astrophysics Data System (ADS)

Nurhadi, M.; Kusumawardani, R.; Widiyowati, I. I.; Wirhanuddin; Nur, H.

2018-05-01

The performance of fish bone to adsorb Fe3+ ion in solution was studied. Powdered fish bone and carbonized fish bone were used as adsorbent. All absorbents were characterized by X-ray diffraction (XRD), IR spectroscopy, nitrogen adsorption, scanning electron microscopy (SEM) and TG analysis. Powdered fish bone and carbonized fish bone were effective as adsorbent for removing Fe3+ ion in solution. The metal adsorptions of Fe3+ ion were 94 and 98% for powdered fish bone and fish bone which carbonized at 400 and 500 °C.

Electron spin resonance and electron spin echo modulation studies of N,N,N prime ,N prime -tetramethylbenzidine photoionization adsorbed at the interface of polymeric latices

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

Baglioni, P.; Rivara-Minten, E.; Kevan, L.

1989-02-23

Electron spin resonance (ESR) and electron spin echo modulation (ESEM) of photoionized N,N,N{prime},N{prime}-tetramethylbenzidine (TMB) cation adsorbed at the interface of butadiene-acrylonitrile-methacrylic acid and butadiene-styrene-acrylic acid polymeric latices have been studied as a function of sodium dodecyl sulfate (SDS) concentration adsorbed at the latex interface. The photoionization yield of TMB in frozen latices mainly depends on the strength of TMB{sup +}-water interactions, which are enhanced by added SDS as measured by ESEM. An increase in the negative surface potential of the latex particles, due to the adsorption of SDS at the latex surface, does not affect the photoionization yield, showing thatmore » the particle surface potential has, for negatively charged systems, a secondary role in promoting the photoionization yield. Differences in the TMB{sup +} yield are found for the two polymeric latices and are attributed to the different latex compositions and/or different interfacial structures.« less

Anomalous Kondo resonance mediated by semiconducting graphene nanoribbons in a molecular heterostructure

DOE PAGES

Li, Yang; Ngo, Anh T.; DiLullo, Andrew; ...

2017-10-16

An unusually large spin-coupling of almost 100% is found in vertically stacked molecular hetrostructures composed of cobalt-porphyrin based magnetic molecules adsorbed on semiconducting armchair graphene nanoribbon on a Au(111) surface. Although the graphene nanoribbons are electronically decoupled from the gold substrate due to their band gaps and weak adsorption, they enable spin coupling between the magnetic moment of the molecule and the electrons from the substrate exhibiting a Kondo resonance. Surprisingly, the Kondo temperatures corresponding to three adsorption sites of the molecules on Au(111) surface are reproduced on the molecules adsorb on the graphene nanoribbons although the molecules are locatedmore » 7.5 Å away from the surface. This finding suggests that the molecules on graphene nanoribbons experience almost the same environment for spin-electron interactions as the ones directly adsorb on Au(111). This puzzling effect is further confirmed by density functional theory calculations that reveal no spin electron interactions if the molecule is left at the same height from the Au(111) surface without the graphene nanoribbon in between.« less

Trap-state-dominated suppression of electron conduction in carbon nanotube thin-film transistors.

PubMed

Qian, Qingkai; Li, Guanhong; Jin, Yuanhao; Liu, Junku; Zou, Yuan; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2014-09-23

The often observed p-type conduction of single carbon nanotube field-effect transistors is usually attributed to the Schottky barriers at the metal contacts induced by the work function differences or by the doping effect of the oxygen adsorption when carbon nanotubes are exposed to air, which cause the asymmetry between electron and hole injections. However, for carbon nanotube thin-film transistors, our contrast experiments between oxygen doping and electrostatic doping demonstrate that the doping-generated transport barriers do not introduce any observable suppression of electron conduction, which is further evidenced by the perfect linear behavior of transfer characteristics with the channel length scaling. On the basis of the above observation, we conclude that the environmental adsorbates work by more than simply shifting the Fermi level of the CNTs; more importantly, these adsorbates cause a poor gate modulation efficiency of electron conduction due to the relatively large trap state density near the conduction band edge of the carbon nanotubes, for which we further propose quantitatively that the adsorbed oxygen-water redox couple is responsible.

Anomalous Kondo resonance mediated by semiconducting graphene nanoribbons in a molecular heterostructure

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

Li, Yang; Ngo, Anh T.; DiLullo, Andrew

An unusually large spin-coupling of almost 100% is found in vertically stacked molecular hetrostructures composed of cobalt-porphyrin based magnetic molecules adsorbed on semiconducting armchair graphene nanoribbon on a Au(111) surface. Although the graphene nanoribbons are electronically decoupled from the gold substrate due to their band gaps and weak adsorption, they enable spin coupling between the magnetic moment of the molecule and the electrons from the substrate exhibiting a Kondo resonance. Surprisingly, the Kondo temperatures corresponding to three adsorption sites of the molecules on Au(111) surface are reproduced on the molecules adsorb on the graphene nanoribbons although the molecules are locatedmore » 7.5 Å away from the surface. This finding suggests that the molecules on graphene nanoribbons experience almost the same environment for spin-electron interactions as the ones directly adsorb on Au(111). This puzzling effect is further confirmed by density functional theory calculations that reveal no spin electron interactions if the molecule is left at the same height from the Au(111) surface without the graphene nanoribbon in between.« less

Improving adsorption and activation of the lipase immobilized in amino-functionalized ordered mesoporous SBA-15

NASA Astrophysics Data System (ADS)

Xu, Yun-qiang; Zhou, Guo-wei; Wu, Cui-cui; Li, Tian-duo; Song, Hong-bin

2011-05-01

Ordered mesoporous SBA-15 was prepared by hydrothermal process and was functionalized with(3-aminopropyl) triethoxysilane (APTES) by post-synthesis-grafting method. The materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectrometer (EDS), small-angle X-ray powder diffraction (SAXRD), N 2 adsorption-desorption and Fourier transform infrared spectroscopy (FT-IR). The results indicated that SBA-15 had a 2-dimensional hexagonal p6 mm mesoscopic structure and the mesoscopic structure was remained after the functionalization procedure. The activities of porcine pancreatic lipase (PPL) immobilized in SBA-15 by physical adsorption and in APTES functionalized SBA-15 by chemical adsorption were studied by hydrolysis of triacetin. Chemically adsorbed PPL showed higher loading amount and catalytic activity comparing with physically adsorbed PPL. The stability of immobilized PPL against thermal and pH of reaction medium was significantly improved. Recycling experiments showed that chemically adsorbed PPL exhibited better reusability than physically adsorbed PPL.

First-principles study of Au–Cu alloy surface changes induced by gas adsorption of CO, NO, or O{sub 2}

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

Dhifallah, Marwa; Université de Gabes, Unité de recherche environnement, Catalyse et Analyse des Procédés, 6072 Gabes; Dhouib, Adnene

2016-07-14

The surface composition of bimetallics can be strongly altered by adsorbing molecules where the metal with the strongest interaction with the adsorbate segregates into the surface. To investigate the effect of reactive gas on the surface composition of Au–Cu alloy, we examined by means of density functional theory to study the segregation behavior of copper in gold matrices. The adsorption mechanisms of CO, NO, and O{sub 2} gas molecules on gold, copper, and gold-copper low index (111), (100), and (110) surfaces were analyzed from energetic and electronic points of view. Our results show a strong segregation of Cu toward themore » (110) surface in the presence of all adsorbed molecules. Interestingly, the Cu segregation toward the (111) and (100) surface could occur only in the presence of CO and at a lower extent in the presence of NO. The analysis of the electronic structure highlights the different binding characters of adsorbates inducing the Cu segregation.« less

Study toward high-performance thermally driven air-conditioning systems

NASA Astrophysics Data System (ADS)

Miyazaki, Takahiko; Miyawaki, Jin; Ohba, Tomonori; Yoon, Seong-Ho; Saha, Bidyut Baran; Koyama, Shigeru

2017-01-01

The Adsorption heat pump is a technology for cooling and heating by using hot water as a driving heat source. It will largely contribute to energy savings when it is driven by solar thermal energy or waste heat. The system is available in the market worldwide, and there are many examples of application to heat recovery in factories and to solar cooling systems. In the present system, silica gel and zeolite are popular adsorbents in combination with water refrigerant. Our study focused on activated carbon-ethanol pair for adsorption cooling system because of the potential to compete with conventional systems in terms of coefficient of performance. In addition, activated-ethanol pair can generally produce larger cooling effect by an adsorption-desorption cycle compared with that of the conventional pairs in terms of cooling effect per unit adsorbent mass. After the potential of a commercially available activated carbon with highest level specific surface area was evaluated, we developed a new activated carbon that has the optimum pore characteristics for the purpose of solar or waste heat driven cooling systems. In this paper, comparison of refrigerants for adsorption heat pump application is presented, and a newly developed activated carbon for ethanol adsorption heat pump is introduced.

Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

PubMed

Nolan, Michael

2012-04-07

The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

An experimental and theoretical study of the adsorption removal of toluene and chlorobenzene on coconut shell derived carbon.

PubMed

Zhao, Xiaoyan; Zeng, Xiaolan; Qin, Yu; Li, Xiang; Zhu, Tianle; Tang, Xiaolong

2018-04-26

The adsorption performance of toluene and chlorobenzene on prepared coconut shell derived carbon (CDC) is investigated and compared with commercial activated carbon (CAC) by experiment and theory calculation. Textural properties of prepared adsorbents are characterized by N 2 adsorption, infrared spectra (FT-IR), Raman spectra and X-ray photoelectron spectra (XPS). Adsorption isotherms of toluene and chlorobenzene are obtained and fitted using structure optimizations, Grand Canonical Monte Carlo (GCMC) simulation and thermodynamic models. The results indicate that CDC shows better volatile organic compounds (VOCs) removal performance than CAC, and chlorobenzene is easily adsorbed than toluene. On the aspect of textural characteristics, CDC possesses more micropores ratio and narrower pore size distribution than CAC. Furthermore, amounts of electron-withdrawing carbonyl groups on the CAC surface reduce the electron density of adsorbents, thus weakening the interaction between VOCs and adsorbents. On the aspect of model fitting, the Yoon and Nelson (Y-N) and Dubinin-Astakhov (D-A) models can well describe the dynamic adsorption and the adsorption equilibrium of toluene and chlorobenzene on CDC respectively. It is believed that substituent groups of adsorbates, making the charge distribution deviate, lead to adsorption potentials of chlorobenzene larger than toluene. In general, both the pore structure and the surface property of adsorbents affect the VOCs adsorption behaviors on CDC. Copyright © 2018. Published by Elsevier Ltd.

First-principles study of adsorption-induced magnetic properties of InSe monolayers

NASA Astrophysics Data System (ADS)

Fu, Zhaoming; Yang, Bowen; Zhang, Na; Ma, Dongwei; Yang, Zongxian

2018-04-01

In this work we studied the adsorption-induced magnetic behaviors on the two-dimensional InSe monolayer. Six kinds of adatoms (H, B, C, N, O and F) are taken into account. It is found that the InSe with adsorbing C and F have nonzero magnetic moments and good stability. Importantly, the magnetism of C and F modified InSe monolayers completely comes from p electrons of adatoms and substrates. The strength of magnetic exchange interaction can be controlled by changing the coverage of adsorbates. This p-electron magnetic material is thought to have obvious advantages compared to conventional d- or f-electron magnets. Our research is meaningful for practical applications in spintronic electronics and two dimensional magnetic semiconductors.

Abaca/polyester nonwoven fabric functionalization for metal ion adsorbent synthesis via electron beam-induced emulsion grafting

NASA Astrophysics Data System (ADS)

Madrid, Jordan F.; Ueki, Yuji; Seko, Noriaki

2013-09-01

A metal ion adsorbent was developed from a nonwoven fabric trunk material composed of both natural and synthetic polymers. A pre-irradiation technique was used for emulsion grafting of glycidyl methacrylate (GMA) onto an electron beam irradiated abaca/polyester nonwoven fabric (APNWF). The dependence of degree of grafting (Dg), calculated from the weight of APNWF before and after grafting, on absorbed dose, reaction time and monomer concentration were evaluated. After 50 kGy irradiation with 2 MeV electron beam and subsequent 3 h reaction with an emulsion consisting of 5% GMA and 0.5% polyoxyethylene sorbitan monolaurate (Tween 20) surfactant in deionized water at 40 °C, a grafted APNWF with a Dg greater than 150% was obtained. The GMA-grafted APNWF was further modified by reaction with ethylenediamine (EDA) in isopropyl alcohol at 60 °C to introduce amine functional groups. After a 3 h reaction with 50% EDA, an amine group density of 2.7 mmole/gram adsorbent was achieved based from elemental analysis. Batch adsorption experiments were performed using Cu2+ and Ni2+ ions in aqueous solutions with initial pH of 5 at 30 °C. Results show that the adsorption capacity of the grafted adsorbent for Cu2+ is four times higher than Ni2+ ions.

Theory of raman scattering from molecules adsorbed at semiconductor surfaces

NASA Astrophysics Data System (ADS)

Ueba, H.

1983-09-01

A theory is presented to calculate the Raman polarizability of an adsorbed molecule at a semiconductor surface, where the electronic excitation in the molecular site interacts with excitons (elementary excitations in the semiconductor) through non-radiative energy transfer between them, in an intermediate state in the Raman scattering process. The Raman polarizability thus calculated is found to exhibit a peak at the energy corresponding to a resonant excitation of excitons, thereby suggesting the possibility of surface enhanced Raman scattering on semiconductor surfaces. The mechanism studied here can also give an explanation of a recent observation of the Raman excitation profiles of p-NDMA and p-DMAAB adsorbed on ZnO or TiO 2, where those profiles were best described by assuming a resonant intermediate state of the exciton transition in the semiconductors. It is also demonstrated that in addition to vibrational Raman scattering, excitonic Raman scattering of adsorbed molecules will occur in the coupled molecule-semiconductor system, where the molecular returns to its ground electronic state by leaving an exciton in the semiconductor. A spectrum of the excitonic Raman scattering is expected to appear in the background of the vibrational Raman band and to be characterized by the electronic structure of excitons. A desirable experiment is suggested for an examination of the theory.

Energy transfer and photochemistry on a metal surface: Mo(CO)/sub 6/ on Rh(100)

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

Germer, T.A.; Ho, W.

1989-05-01

The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO)/sub 6/ on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO)/sub 6/ adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated firstmore » layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO)/sub 6/ adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface.« less

L-Tryptophan on Cu(111): engineering a molecular labyrinth driven by indole groups

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

Yitamben, E. N.; Clayborne, A.; Darling, Seth B.

2015-05-21

The present article investigates the adsorption and molecular orientation of L-Tryptophan, which is both an essential amino acid important for protein synthesis and of particular interest for the development of chiral molecular electronics and biocompatible processes and devices, on Cu(111) using scanning tunneling microscopy and spectroscopy at 55 K and at room temperature. The arrangement of chemisorbed L-Tryptophan on the copper surface varies with both temperature and surface coverage. At low coverage, small clusters form on the surface irrespective of temperature, while at high coverage an ordered chain structure emerges at room temperature, and a tightly packed structure forms amore » molecular labyrinth at low temperature. The dominating superstructure of the adsorbates arises from intermolecular hydrogen bonding, and pi-bonding interactions between the indole groups of neighboring molecules and the Cu surface.« less

Adsorption enhancement of elemental mercury onto sulphur-functionalized silica gel adsorbents.

PubMed

Johari, Khairiraihanna; Saman, Norasikin; Mat, Hanapi

2014-01-01

In this study, elemental mercury (EM) adsorbents were synthesized using tetraethyl orthosilicate (TEOS) and 3-mercaptopropyl trimethoxysilane as silica precursors. The synthesized silica gel (SG)-TEOS was further functionalized through impregnation with elemental sulphur and carbon disulphide (CS2). The SG adsorbents were then characterized by using scanning electron microscope, Fourier transform infra-red spectrophotometer, nitrogen adsorption/desorption, and energy-dispersive X-ray diffractometer. The EM adsorption of the SG adsorbents was determined using fabricated fixed-bed adsorber. The EM adsorption results showed that the sulphur-functionalized SG adsorbents had a greater Hgo breakthrough adsorption capacity, confirming that the presence of sulphur in silica matrices can improve Hgo adsorption performance due to their high affinity towards mercury. The highest Hgo adsorption capacity was observed for SG-TEOS(CS2) (82.62 microg/g), which was approximately 2.9 times higher than SG-TEOS (28.47 microg/g). The rate of Hgo adsorption was observed higher for sulphur-impregnated adsorbents, and decreased with the increase in the bed temperatures.

Synthesis of magnetic ordered mesoporous carbon (Fe-OMC) adsorbent and its evaluation for fuel desulfurization

NASA Astrophysics Data System (ADS)

Farzin Nejad, N.; Shams, E.; Amini, M. K.

2015-09-01

In this work, magnetic ordered mesoporous carbon adsorbent was synthesized using soft templating method to adsorb sulfur from model oil (dibenzothiophene in n-hexane). Through this research, pluronic F-127, resorcinol-formaldehyde and hydrated iron nitrate were respectively used as soft template, carbon source and iron source. The adsorbent was characterized by X-ray diffraction, nitrogen adsorption-desorption isotherm and transmission electron microscopy. Nitrogen adsorption-desorption measurement revealed the high surface area (810 m2 g-1), maxima pore size of 3.3 nm and large pore volume (1.01 cm3 g-1) of the synthesized sample. The adsorbent showed a maximum adsorption capacity of 111 mg dibenzothiophene g-1 of adsorbent. Sorption process was described by the pseudo-second-order rate equation and could be better fitted by the Freundlich model, showing the heterogeneous feature of the adsorption process. In addition, the adsorption capacity of regenerated adsorbent was 78.6% of the initial level, after five regeneration cycles.

Evaluation of Aluminium Dross as Adsorbent for Removal of Carcinogenic Congo Red Dye in Wastewater

NASA Astrophysics Data System (ADS)

Zakaria, Mohamad Zulfika Hazielim b.; Zauzi, Nur Syuhada Ahmad; Baini, Rubiyah; Sutan, Norsuzailina Mohamed; Rezaur Rahman, Md

2017-06-01

In this study, aluminium dross waste generated from aluminium smelting industries was employed as adsorbent in removing of congo red dye in aqueous solution. The raw aluminium dross as adsorbent was characterized using Scanning Electron Microscope (SEM), Brunauer-Emmett-Teller (BET) for surface area and X-Ray Fluorescence (XRF) Spectroscopy. Adsorption experiments were carried out by batch system at different adsorbent mass, pH, and initial dye concentration. The results showed that the per cent removal of dye increased as adsorbent mass increased. It was found that 0.4 gram of adsorbent can remove approximately 100 % of dye at pH 9 for dye concentration 20 and 40 ppm. Therefore, it can be concluded that raw aluminium dross without undergone any treatment can be effectively used for the adsorption of congo red in textile wastewater related industries.

Surfactant modified zeolite as amphiphilic and dual-electronic adsorbent for removal of cationic and oxyanionic metal ions and organic compounds.

PubMed

Tran, Hai Nguyen; Viet, Pham Van; Chao, Huan-Ping

2018-01-01

A hydrophilic Y zeolite was primarily treated with sodium hydroxide to enhance its cation exchange capacity (Na-zeolite). The organo-zeolite (Na-H-zeolite) was prepared by a modification process of the external surface of Na-zeolite with a cationic surfactant (hexadecyltrimethylammonium; HDTMA). Three adsorbents (i.e., pristine zeolite, Na-zeolite, and Na-H-zeolite) were characterized with nitrogen adsorption/desorption isotherms, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, cation exchange capacities, and zeta potential. Results demonstrated that HDTMA can be adsorbed on the surface of Na-zeolite to form patchy bilayers. The adsorption capacity of several hazardous pollutants (i.e., Pb 2+ , Cu 2+ , Ni 2+ , Cr 2 O 7 2- , propylbenzene, ethylbenzene, toluene, benzene, and phenol) onto Na-H-zeolite was investigated in a single system and multiple-components. Adsorption isotherm was measured to further understand the effects of the modification process on the adsorption behaviors of Na-H-zeolite. Adsorption performances indicated that Na-H-zeolite can simultaneously adsorb the metal cations (on the surface not covered by HDTMA), oxyanions (on the surface covered by HDTMA). Na-H-zeolite also exhibited both hydrophilic and hydrophobic surfaces to uptake organic compounds with various water solubilities (from 55 to 75,000mg/L). It was experimentally concluded that Na-H-zeolite is a potential dual-electronic and amphiphilic adsorbent for efficiently removing a wide range of potentially toxic pollutants from aquatic environments. Copyright © 2017 Elsevier Inc. All rights reserved.

Modeling Pressure-Driven Transport of Proteins through a Nanochannel

PubMed Central

Carr, Rogan; Comer, Jeffrey; Ginsberg, Mark D.; Aksimentiev, Aleksei

2012-01-01

Reducing the size of a nanofluidic channel not only creates new opportunities for high-precision manipulation of biological macromolecules, but also makes the performance of the entire nanofluidic system more susceptible to undesirable interactions between the transported biomolecules and the walls of the channel. In this manuscript, we report molecular dynamics simulations of a pressure-driven flow through a silica nanochannel that characterized, with atomic resolution, adsorption of a model protein to its surface. Although the simulated adsorption of the proteins was found to be nonspecific, it had a dramatic effect on the rate of the protein transport. To determine the relative strength of the protein–silica interactions in different adsorbed states, we simulated flow-induced desorption of the proteins from the silica surface. Our analysis of the protein conformations in the adsorbed states did not reveal any simple dependence of the adsorption strength on the size and composition of the protein–silica contact, suggesting that the heterogeneity of the silica surface may be a important factor. PMID:22611338

Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate.

PubMed

Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

2008-10-28

Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hnu approximately 2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hnu approximately 2.2 eV and above hnu approximately 4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate

NASA Astrophysics Data System (ADS)

Hagen, Sebastian; Kate, Peter; Leyssner, Felix; Nandi, Dhananjay; Wolf, Martin; Tegeder, Petra

2008-10-01

Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hν ≈2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hν ≈2.2 eV and above hν ≈4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

Parallel tempering Monte Carlo simulations of lysozyme orientation on charged surfaces

NASA Astrophysics Data System (ADS)

Xie, Yun; Zhou, Jian; Jiang, Shaoyi

2010-02-01

In this work, the parallel tempering Monte Carlo (PTMC) algorithm is applied to accurately and efficiently identify the global-minimum-energy orientation of a protein adsorbed on a surface in a single simulation. When applying the PTMC method to simulate lysozyme orientation on charged surfaces, it is found that lysozyme could easily be adsorbed on negatively charged surfaces with "side-on" and "back-on" orientations. When driven by dominant electrostatic interactions, lysozyme tends to be adsorbed on negatively charged surfaces with the side-on orientation for which the active site of lysozyme faces sideways. The side-on orientation agrees well with the experimental results where the adsorbed orientation of lysozyme is determined by electrostatic interactions. As the contribution from van der Waals interactions gradually dominates, the back-on orientation becomes the preferred one. For this orientation, the active site of lysozyme faces outward, which conforms to the experimental results where the orientation of adsorbed lysozyme is co-determined by electrostatic interactions and van der Waals interactions. It is also found that despite of its net positive charge, lysozyme could be adsorbed on positively charged surfaces with both "end-on" and back-on orientations owing to the nonuniform charge distribution over lysozyme surface and the screening effect from ions in solution. The PTMC simulation method provides a way to determine the preferred orientation of proteins on surfaces for biosensor and biomaterial applications.

Kelvin probe force microscopy studies of the charge effects upon adsorption of carbon nanotubes and C60 fullerenes on hydrogen-terminated diamond

NASA Astrophysics Data System (ADS)

Kölsch, S.; Fritz, F.; Fenner, M. A.; Kurch, S.; Wöhrl, N.; Mayne, A. J.; Dujardin, G.; Meyer, C.

2018-01-01

Hydrogen-terminated diamond is known for its unusually high surface conductivity that is ascribed to its negative electron affinity. In the presence of acceptor molecules, electrons are expected to transfer from the surface to the acceptor, resulting in p-type surface conductivity. Here, we present Kelvin probe force microscopy (KPFM) measurements on carbon nanotubes and C60 adsorbed onto a hydrogen-terminated diamond(001) surface. A clear reduction in the Kelvin signal is observed at the position of the carbon nanotubes and C60 molecules as compared with the bare, air-exposed surface. This result can be explained by the high positive electron affinity of carbon nanotubes and C60, resulting in electron transfer from the surface to the adsorbates. When an oxygen-terminated diamond(001) is used instead, no reduction in the Kelvin signal is obtained. While the presence of a charged adsorbate or a difference in work function could induce a change in the KPFM signal, a charge transfer effect of the hydrogen-terminated diamond surface, by the adsorption of the carbon nanotubes and the C60 fullerenes, is consistent with previous theoretical studies.

Field-induced structural control of COx molecules adsorbed on graphene

NASA Astrophysics Data System (ADS)

Matsubara, Manaho; Okada, Susumu

2018-05-01

Using the density functional theory combined with both the van der Waals correction and the effective screening medium method, we investigate the energetics and electronic structures of CO and CO2 molecules adsorbed on graphene surfaces in the field-effect-transistor structure with respect to the external electric field by the excess electrons/holes. The binding energies of CO and CO2 molecules to graphene monotonically increase with increasing hole and electron concentrations. The increase occurs regardless of the molecular conformations to graphene and the counter electrode, indicating that the carrier injection substantially enhances the molecular adsorption on graphene. Injected carriers also modulate the stable molecular conformation, which is metastable in the absence of an electric field.

A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

NASA Astrophysics Data System (ADS)

Taylor, S. D.; Marcano, M. C.; Becker, U.

2017-01-01

This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

Molecular adsorption on graphene

NASA Astrophysics Data System (ADS)

Kong, Lingmei; Enders, Axel; Rahman, Talat S.; Dowben, Peter A.

2014-11-01

Current studies addressing the engineering of charge carrier concentration and the electronic band gap in epitaxial graphene using molecular adsorbates are reviewed. The focus here is on interactions between the graphene surface and the adsorbed molecules, including small gas molecules (H2O, H2, O2, CO, NO2, NO, and NH3), aromatic, and non-aromatic molecules (F4-TCNQ, PTCDA, TPA, Na-NH2, An-CH3, An-Br, Poly (ethylene imine) (PEI), and diazonium salts), and various biomolecules such as peptides, DNA fragments, and other derivatives. This is followed by a discussion on graphene-based gas sensor concepts. In reviewing the studies of the effects of molecular adsorption on graphene, it is evident that the strong manipulation of graphene’s electronic structure, including p- and n-doping, is not only possible with molecular adsorbates, but that this approach appears to be superior compared to these exploiting edge effects, local defects, or strain. However, graphene-based gas sensors, albeit feasible because huge adsorbate-induced variations in the relative conductivity are possible, generally suffer from the lack of chemical selectivity.

Metallic → Semiconducting transitions in HX(X=F, Br, Cl) adsorbed (5,5) and (7,7) carbon nanotubes: DFT study

NASA Astrophysics Data System (ADS)

Srivastava, Reena; Shrivastava, Sadhana; Srivastava, Anurag

2018-05-01

The edge sensitivity of two different chirality (5,5) and (7,7) armchair carbon nanotubes towards toxic hydrogen halides (HF, HBr and HCl) has been analyzed by using density functional theory based ab-initio approach. The edge sensitivity has been discussed in terms of the variations in the electronic band structure of (5,5) and (7,7) carbon nanotube. The observation shows metallic to semiconducting phase transition in HF and HBr adsorbed (5,5) CNT, whereas for HCl adsorbed, it is more metallic. Whereas HBr and HCl adsorbed (7,7) CNT confirms metallic→semiconducting transition and shows diameter dependence of properties of CNTs.

Adsorption of CO and O2 molecules on Li metal adsorbed graphene: Search for graphene based gas sensors

NASA Astrophysics Data System (ADS)

Kaur, Gagandeep; Gupta, Shuchi; Sachdeva, Ritika; Dharamvir, Keya

2018-05-01

Adsorption of small gas molecules (such as CO and O2) on pristine graphene (PG) and Li-adsorbed graphene (PG-Li) have been investigated using first principles methods within density functional theory (DFT). We also notice that PG-Li has a higher chemical reactivity towards the gas molecules as compared to PG and these molecules have higher adsorption energy on this surface. Moreover, the strong interactions between PG-Li and the adsorbed molecules (as compared to PG and gas molecules) induce dramatic changes to the electronic properties of PG adsorbed with Li and make PG-Li a promising candidate as sensing material for CO and O2 gases.

Anharmonic Effects on the Electron-Energy Spectra of Surface Vibrations

NASA Astrophysics Data System (ADS)

Ariyasu, Janice Carol

First, we consider the effect of lateral interactions on double losses and overtones in electron-energy-loss studies of surface vibrations. We develop a theory of two-phonon losses in the dipole-dominated regime of small -angle scattering. Our calculation employs the simple model of an ordered overlayer of molecules adsorbed on a crystal surface. With this model, we can identify two features; one which corresponds to the double loss and another which corresponds the excitation of an overtone. We then study the role of lateral interactions in each. We find that the presence of lateral interactions affects the position of the overtone relative to the double loss, and influences both its width and shape. The implications of these results are discussed, particularly as they relate to estimates of dissociation energies by the Birge-Sponer procedure. Next, we consider the anharmonic damping of adsorbate vibrations, with specific applications to species (S, O, and CO) adsorbed on the Ni(100) and Ni(111) surfaces. Our attention is restricted to adsorbate modes that can decay by two-phonon processes to one substrate phonon and either another substrate mode phonon or to a phonon of a mode that is localized on the adsorbate. The magnitude and temperature variation of the linewidth of adsorbate modes by this mechanism is explored; we find that near room temperature the calculated linewidths vary linearly with temperature. We also simulate the inhomogeneous broadening produced by disorder by considering the eigenfrequencies of infrared -active modes. Finally, we consider the diffuse scattering of electrons from surfaces by long-wavelength, acoustic phonons. The mechanism that we explore is the modulation of the image potential from ripples induced in the surface profile by thermally-excited surface and bulk phonons. We compare our results with earlier studies, and with the scattering produced by the dynamic-dipole moment of the surface atoms.

Electrostatic interaction between an enzyme and electrodes in the electric double layer examined in a view of direct electron transfer-type bioelectrocatalysis.

PubMed

Sugimoto, Yu; Kitazumi, Yuki; Tsujimura, Seiya; Shirai, Osamu; Yamamoto, Masahiro; Kano, Kenji

2015-01-15

Effects of the electrode poential on the activity of an adsorbed enzyme has been examined by using copper efflux oxidase (CueO) as a model enzyme and by monitoring direct electron transfer (DET)-type bioelectrocatalysis of oxygen reduction. CueO adsorbed on bare Au electrodes at around the point of zero charge (E(pzc)) shows the highest DET activity, and the activity decreases as the adsorption potential (E(ad); at which the enzyme adsorbs) is far from E(pzc). We propose a model to explain the phenomena in which the electrostatic interaction between the enzyme and electrodes in the electric double layer affects the orientation and the stability of the adsorbed enzyme. The self-assembled monolayer of butanethiol on Au electrodes decreases the electric field in the outside of the inner Helmholtz plane and drastically diminishes the E(ad) dependence of the DET activity of CueO. When CueO is adsorbed on bare Au electrodes under open circuit potential and then is held at hold potentials (E(ho)) more positive than E(pzc), the DET activity of the CueO rapidly decreases with the hold time. The strong electric field with positive surface charge density on the metallic electrode (σ(M)) leads to fatal denaturation of the adsorbed CueO. Such denaturation effect is not so serious at E(ho)

Electronic theoretical study of the influences of O adsorption on the electronic structure and optical properties of graphene

NASA Astrophysics Data System (ADS)

Shuang, Zhou; Guili, Liu; Dazhi, Fan

2017-02-01

The electronic structure and optical properties of adsorbing O atoms on graphene with different O coverage are researched using the density functional theory based upon the first-principle study to obtain further insight into properties of graphene. The adsorption energies, band structures, the density of states, light absorption coefficient and reflectivity of each system are calculated theoretically after optimizing structures of each system with different O coverage. Our calculations show that adsorption of O atoms on graphene increases the bond length of C-C which adjacent to the O atoms. When the O coverage is 9.4%, the adsorption energy (3.91 eV) is the maximum, which only increases about 1.6% higher than that of 3.1% O coverage. We find that adsorbed O atoms on pristine graphene opens up indirect gap of about 0.493-0.952 eV. Adsorbing O atoms make pristine graphene from metal into a semiconductor. When the O coverage is 9.4%, the band gap (0.952 eV) is the maximum. Comparing with pristine graphene, we find the density of states at Fermi level of O atoms adsorbing on graphene with different coverage are significantly increased. We also find that light absorption coefficient and reflectivity peaks are significantly reduced, and the larger the coverage, the smaller the absorption coefficient and reflectivity peaks are. And the blue shift phenomenon appears.

Submolecular Structure and Orientation of Oligonucleotide Duplexes Tethered to Gold Electrodes Probed by Infrared Reflection Absorption Spectroscopy: Effect of the Electrode Potentials.

PubMed

Kékedy-Nagy, László; Ferapontova, Elena E; Brand, Izabella

2017-02-23

Unique electronic and ligand recognition properties of the DNA double helix provide basis for DNA applications in biomolecular electronic and biosensor devices. However, the relation between the structure of DNA at electrified interfaces and its electronic properties is still not well understood. Here, potential-driven changes in the submolecular structure of DNA double helices composed of either adenine-thymine (dAdT) 25 or cytosine-guanine (dGdC) 20 base pairs tethered to the gold electrodes are for the first time analyzed by in situ polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) performed under the electrochemical control. It is shown that the conformation of the DNA duplexes tethered to gold electrodes via the C 6 alkanethiol linker strongly depends on the nucleic acid sequence composition. The tilt of purine and pyrimidine rings of the complementary base pairs (dAdT and dGdC) depends on the potential applied to the electrode. By contrast, neither the conformation nor orientation of the ionic in character phosphate-sugar backbone is affected by the electrode potentials. At potentials more positive than the potential of zero charge (pzc), a gradual tilting of the double helix is observed. In this tilted orientation, the planes of the complementary purine and pyrimidine rings lie ideally parallel to each other. These potentials do not affect the integral stability of the DNA double helix at the charged interface. At potentials more negative than the pzc, DNA helices adopt a vertical to the gold surface orientation. Tilt of the purine and pyrimidine rings depends on the composition of the double helix. In monolayers composed of (dAdT) 25 molecules the rings of the complementary base pairs lie parallel to each other. By contrast, the tilt of purine and pyrimidine rings in (dGdC) 20 helices depends on the potential applied to the electrode. Such potential-induced mobility of the complementary base pairs can destabilize the helix structure at a submolecular level. These pioneer results on the potential-driven changes in the submolecular structure of double stranded DNA adsorbed on conductive supports contribute to further understanding of the potential-driven sequence-specific electronic properties of surface-tethered oligonucleotides.

Adsorbing H₂S onto a single graphene sheet: A possible gas sensor

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

Reshak, A. H., E-mail: maalidph@yahoo.co.uk; Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis; Auluck, S.

2014-09-14

The electronic structure of pristine graphene sheet and the resulting structure of adsorbing a single molecule of H₂S on pristine graphene in three different sites (bridge, top, and hollow) are studied using the full potential linearized augmented plane wave method. Our calculations show that the adsorption of H₂S molecule on the bridge site opens up a small direct energy gap of about 0.1 eV at symmetry point M, while adsorption of H₂S on top site opens a gap of 0.3 eV around the symmetry point K. We find that adsorbed H₂S onto the hollow site of pristine graphene sheet causesmore » to push the conduction band minimum and the valence band maximum towards Fermi level resulting in a metallic behavior. Comparing the angular momentum decomposition of the atoms projected electronic density of states of pristine graphene sheet with that of H₂S–graphene for three different cases, we find a significant influence of the location of the H₂S molecule on the electronic properties especially the strong hybridization between H₂S molecule and graphene sheet.« less

Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion

NASA Astrophysics Data System (ADS)

Scholz, Robert; Floß, Gereon; Saalfrank, Peter; Füchsel, Gernot; Lončarić, Ivor; Juaristi, J. I.

2016-10-01

A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 ×2 ):CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.

Adsorbate Diffusion on Transition Metal Nanoparticles

DTIC Science & Technology

2015-01-01

different sizes and shapes using density functional theory calculations. We show that nanoparticles bind adsorbates more strongly than the...structure theoretical methods, a quantitative study with accurate density functional theory (DFT) calculations is still missing. Here, we perform a...functional theory . The projector augmented wave (PAW) potentials29,30 were used for electron- ion interactions and the generalized gradient approximation

Polymer-based adsorbent for heavy metals removal from aqueous solution

NASA Astrophysics Data System (ADS)

Mahmud, H. N. M. E.; Huq, A. K. O.; Yahya, R.

2017-06-01

A novel conducting polymer-based adsorbent, polypyrrole (PPy) fine powder has successfully been prepared as a new adsorbent and utilized in the adsorption of heavy metal ions like arsenic, zinc and cadmium ions from aqueous solution. PPy was chemically synthesized by using FeCl3.6H2O as an oxidant. The prepared PPy adsorbent was characterized by Brunauer-Emmet-Teller (BET) surface analysis, field emission scanning electron microscopy (FESEM) and attenuated total reflectance fourier transform infrared ATR-(FTIR) spectroscopy. The adsorption was conducted by varying different parameters such as, contact time, pH and adsorbent dosage. The concentrations of metal ions were measured by inductively coupled plasma mass spectroscopy (ICP-MS). The results show that PPy acts as an effective sorbent for the removal of arsenic, zinc and cadmium ions from aqueous solution. The as-prepared PPy fine powder is easy to prepare and appeared as an effective adsorbent for heavy metal ions particularly arsenic in wastewater treatment.

The MOF+ Technique: A Significant Synergic Effect Enables High Performance Chromate Removal.

PubMed

Luo, Ming Biao; Xiong, Yang Yang; Wu, Hui Qiong; Feng, Xue Feng; Li, Jian Qiang; Luo, Feng

2017-12-18

A significant synergic effect between a metal-organic framework (MOF) and Fe 2 SO 4 , the so-called MOF + technique, is exploited for the first time to remove toxic chromate from aqueous solutions. The results show that relative to the pristine MOF samples (no detectable chromate removal), the MOF + method enables super performance, giving a 796 Cr mg g -1 adsorption capacity. The value is almost eight-fold higher than the best value of established MOF adsorbents, and the highest value of all reported porous adsorbents for such use. The adsorption mechanism, unlike the anion-exchange process that dominates chromate removal in all other MOF adsorbents, as unveiled by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), is due to the surface formation of Fe 0.75 Cr 0.25 (OH) 3 nanospheres on the MOF samples. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorbate hopping via vibrational-mode coupling induced by femtosecond laser pulses

NASA Astrophysics Data System (ADS)

Ueba, H.; Hayashi, M.; Paulsson, M.; Persson, B. N. J.

2008-09-01

We study the heat transfer from femtosecond laser-heated hot electrons in a metal to adsorbates in the presence of vibrational-mode coupling. The theory is successfully applied to the experimental result of atomic oxygen hopping on a vicinal Pt(111) surface. The effective friction coupling between hot electrons and the vibrational mode relevant to the hopping motion depends on the transient temperature of the partner mode excited by hot electrons. The calculated two-pulse correlation and fluence dependence of the hopping probability reproduce the experimental results, which were previously analyzed using the hot-electron temperature (Te) -dependent friction ηa(Te) in a conventional heat transfer equation. A possible elementary process behind such a hypothetic modeling using ηa(Te) is discussed in terms of an indirect heating of the vibrational mode for hopping at the surface.

Charge-transfer photodissociation of adsorbed molecules via electron image states

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

Jensen, E. T.

The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

Many-body dispersion effects in the binding of adsorbates on metal surfaces

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

Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

2015-09-14

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic–inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding ofmore » adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate–surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.« less

Effect of adsorbed chlorine and oxygen on shear strength of iron and copper junctions

NASA Technical Reports Server (NTRS)

Wheeler, D. R.

1975-01-01

Static friction experiments were performed in ultrahigh vacuum at room temperature on copper, iron, and steel contacts selectively contaminated with oxygen and chlorine in submonolayer amounts. The concentration of the adsorbates was determined with Auger electron spectroscopy and was measured relative to the saturation concentration of oxygen on iron (concentration 1.0). The coefficient of static friction decreased with increasing adsorbate concentration. It was independent of the metal and the adsorbate. The results compared satisfactorily with an extension of the junction growth theory to heterogeneous interfaces. The reduction in interfacial shear strength was measured by the ratio sub a/sub m where sub a is the shear strength of the interface with an adsorbate concentration of 1.0, and sub m is the strength of the clean metal interface. This ratio was 0.835 + or - 0.012 for all the systems tested.

An efficient removal of methyl orange dye from aqueous solution by adsorption onto chitosan/MgO composite: A novel reusable adsorbent

NASA Astrophysics Data System (ADS)

Haldorai, Yuvaraj; Shim, Jae-Jin

2014-02-01

We report a novel multi-functional magnesium oxide (MgO) immobilized chitosan (CS) composite was prepared by chemical precipitation method. The CS-MgO composite was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and zeta potential. The composite was applied as a novel adsorbent for removal of methyl orange model dye and the effect of adsorbent dosage, pH and contact time were studied. The adsorption kinetics followed a pseudo second order reaction. The adsorbent efficiency was unaltered even after five cycles of reuse. In addition, the composite exhibited a superior antibacterial efficacy of 93% within 24 h against Escherichia coli as measured by colony forming units. Based on the data of present investigation the composite being a biocompatible, eco-friendly and low-cost adsorbent with antibacterial activity could find potential applications in variety of fields and in particular environmental applications.

Radiation grafted adsorbents for newly emerging environmental applications

NASA Astrophysics Data System (ADS)

Mahmoud Nasef, Mohamed; Ting, T. M.; Abbasi, Ali; Layeghi-moghaddam, Alireza; Sara Alinezhad, S.; Hashim, Kamaruddin

2016-01-01

Radiation induced grafting (RIG) is acquired to prepare a number of adsorbents for newly emerging environmental applications using a single route involving RIG of glycidymethacrylate (GMA) onto polyethylene-polypropylene (PE-PP) non-woven fabric. The grafted fabric was subjected to one of three functionalization reactions to impart desired ionic characters. This included treatment with (1) N-dimethyl-D-glucamine, (2) triethylamine and (3) triethylamine and alkalisation with KOH. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) were used to study the changes in chemical and physical structures of the obtained fibrous adsorbents. The potential applications of the three adsorbents for removal of boron from solutions, capturing CO2 from CO2/N2 mixtures and catalysing transesterification of triacetin/methanol to methyl acetate (biodiesel) were explored. The obtained fibrous adsorbents provide potential alternatives to granular resins for the investigated applications and require further development.

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

Wei, Chan Yi, E-mail: vicchanyiwei@hotmail.com; Ongkudon, Clarence M., E-mail: clarence@ums.edu.my; Kansil, Tamar, E-mail: tamarkansil87@gmail.com

Modern day synthesis protocols of methacrylate monolithic polymer adsorbent are based on existing polymerization blueprint without a thorough understanding of the dynamics of pore structure and formation. This has resulted in unproductiveness of polymer adsorbent consequently affecting purity and recovery of final product, productivity, retention time and cost effectiveness of the whole process. The problems magnified in monolith scaling-up where internal heat buildup resulting from external heating and high exothermic polymerization reaction was reflected in cracking of the adsorbent. We believe that through careful and precise control of the polymerization kinetics and parameters, it is possible to prepare macroporous methacrylatemore » monolithic adsorbents with controlled pore structures despite being carried out in an unstirred mould. This research involved the study of the effect of scaling-up on pore morphology of monolith, in other words, porous polymethacrylate adsorbents that were prepared via bulk free radical polymerization process by imaging the porous morphology of polymethacrylate with scanning electron microscope.« less

Removal of copper and nickel from water using nanocomposite of magnetic hydroxyapatite nanorods

NASA Astrophysics Data System (ADS)

Thanh, Dong Nguyen; Novák, Pavel; Vejpravova, Jana; Vu, Hong Nguyen; Lederer, Jaromír; Munshi, Tasnim

2018-06-01

A nanocomposite of magnetic hydroxyapatite was synthesized and tested as an adsorbent for the removal of copper (Cu (II)) and nickel (Ni(II)) from aqueous solution. The adsorbent was investigated using Transmission Electron Microscopy (TEM), Scanning Electron Microscopy equipped with an Energy Dispersive Spectrometer (SEM/EDS), X-ray powder diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N2 adsorption). Batch experiments were carried out to determine and compare the adsorption parameters of Fe3O4 and its composite with hydroxyapatite. It was found that the adsorbent is nanostructured and has a specific surface area of 101.2 m2 g-1. The Langmuir adsorption isotherm was found to be an appropriate model to describe the adsorption processes, showing the adsorption capacities of Cu(II) and Ni(II) of 48.78 mg g-1 and 29.07 mg g-1, respectively. In addition to the high adsorption capacity, the fully-adsorbed material could be easily separated from aqueous media using an external magnetic field. These results suggested that the utilization of new hydroxyapatite - Fe3O4 nanocomposite for the removal of Cu(II) and Ni(II) is a promising method in water technology.

Synthesis of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposites as an adsorbent for the fast determination of 16 priority polycyclic aromatic hydrocarbons in aqueous samples.

PubMed

Chen, Kun; Jin, Rongrong; Luo, Chen; Song, Guoxin; Hu, Yaoming; Cheng, Hefa

2018-04-01

A novel adsorbent made of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposite was synthesized and applied to determine 16 priority polycyclic aromatic hydrocarbons by magnetic solid phase extraction in water samples. FTIR spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy consistently indicate that the synthesized adsorbents are made of core-shell nanoparticles well dispersed on the surface of graphene and carbon nanotubes. The major factors affecting the extraction efficiency, including the pH value of samples, the amount of adsorbent, adsorption time and desorption time, type and volume of desorption solvent, were systematically optimized. Under the optimum extraction conditions, a linear response was obtained for polycyclic aromatic hydrocarbons between concentrations of 10 and 500 ng/L with the correlation coefficients ranging from 0.9958 to 0.9989, and the limits of detection (S/N = 3) were between 0.1 and 3.0 ng/L. Satisfactory results were also obtained when applying these magnetic graphene/carbon nanotubes/polydopamine hybrid nanocomposites to detect polycyclic aromatic hydrocarbons in several environmental aqueous samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Designing transition metal surfaces for their adsorption properties and chemical reactivity

NASA Astrophysics Data System (ADS)

Montemore, Matthew M.

Many technological processes, such as catalysis, electrochemistry, corrosion, and some materials synthesis techniques, involve molecules bonding to and/or reacting on surfaces. For many of these applications, transition metals have proven to have excellent chemical reactivity, and this reactivity is strongly tied to the surface's adsorption properties. This thesis focuses on predicting adsorption properties for use in the design of transition metal surfaces for various applications. First, it is shown that adsorption through a particular atom (e.g, C or O) can be treated in a unified way. This allows predictions of all C-bound adsorbates from a single, simple adsorbate, such as CH3. In particular, consideration of the adsorption site can improve the applicability of previous approaches, and gas-phase bond energies correlate with adsorption energies for similarly bound adsorbates. Next, a general framework is presented for understanding and predicting adsorption through any atom. The energy of the adsorbate's highest occupied molecular orbital (HOMO) determines the strength of the repulsion between the adsorbate and the surface. Because adsorbates with similar HOMO energies behave similarly, their adsorption energies correlate. This can improve the efficiency of predictions, but more importantly it constrains catalyst design and suggests strategies for circumventing these constraints. Further, the behavior of adsorbates with dissimilar HOMO energies varies in a systematic way, allowing predictions of adsorption energy differences between any two adsorbates. These differences are also useful in surface design. In both of these cases, the dependence of adsorption energies on surface electronic properties is explored. This dependence is used to justify the unified treatments mentioned above, and is used to gain further insight into adsorption. The properties of the surface's d band and p band control variations in adsorption energy, as does the strength of the adsorbate-surface coupling. A single equation, with only a single adsorbate-dependent fitting parameter as well as a few universal fitting parameters, is developed that can predict the adsorption energy of any radical on any close-packed transition metal surface. The surface electronic properties that are input into this equation can be estimated based on the alloy structure of the surface, improving prospects for high-throughput screening and rational catalyst design. The methods discussed in this thesis are used to design a novel catalyst for ethylene epoxidation, which is experimentally synthesized and tested. Initial tests indicate that this catalyst may have improved selectivity over pure Ag.

Amphiphilic invertible polymers: Self-assembly into functional materials driven by environment polarity

NASA Astrophysics Data System (ADS)

Hevus, Ivan

Stimuli-responsive polymers adapt to environmental changes by adjusting their chain conformation in a fast and reversible way. Responsive polymeric materials have already found use in electronics, coatings industry, personal care, and bio-related areas. The current work aims at the development of novel responsive functional polymeric materials by manipulating environment-dependent self-assembly of a new class of responsive macromolecules strategically designed in this study,—amphiphilic invertible polymers (AIPs). Environment-dependent micellization and self-assembly of three different synthesized AIP types based on poly(ethylene glycol) as a hydrophilic fragment and varying hydrophobic constituents was demonstrated in polar and nonpolar solvents, as well as on the surfaces and interfaces. With increasing concentration, AIP micelles self-assemble into invertible micellar assemblies composed of hydrophilic and hydrophobic domains. Polarity-responsive properties of AIPs make invertible micellar assemblies functional in polar and nonpolar media including at interfaces. Thus, invertible micellar assemblies solubilize poorly soluble substances in their interior in polar and nonpolar solvents. In a polar aqueous medium, a novel stimuli-responsive mechanism of drug release based on response of AIP-based drug delivery system to polarity change upon contact with the target cell has been established using invertible micellar assemblies loaded with curcumin, a phytochemical drug. In a nonpolar medium, invertible micellar assemblies were applied simultaneously as nanoreactors and stabilizers for size-controlled synthesis of silver nanoparticles stable in both polar and nonpolar media. The developed amphiphilic nanosilver was subsequently used as seeds to promote anisotropic growth of CdSe semiconductor nanoparticles that have potential in different applications ranging from physics to medicine. Amphiphilic invertible polymers were shown to adsorb on the surface of silica nanoparticles strongly differing in polarity. AIP modified silica nanoparticles are able to adsolubilize molecules of poorly water-soluble 2-naphthol into the adsorbed polymer layer. The adsolubilization ability of adsorbed invertible macromolecules makes AIP-modified silica nanoparticles potentially useful in wastewater treatment or biomedical applications. Finally, the invertible micellar assemblies were used as functional additives to improve the appearance of electrospun silicon wires based on cyclohexasilane, a liquid silicon precursor. AIP-assisted fabrication of silicon wires from the liquid cyclohexasilane precursor has potential as a scalable method for developing electronic functional materials.

On the nature of the {SO2-4}/{Ag(111) } and {SO2-4}/{Au(111) } surface bonding

NASA Astrophysics Data System (ADS)

Patrito, E. M.; Olivera, P. Paredes; Sellers, Harrell

1997-05-01

The nature of sulfate-Ag(111) and sulfate-Au(111) surface bonding has been investigated at the SCF + MP2 level of theory. Convergence of binding energy with cluster size is investigated and, unlike neutral adsorbates, large clusters are required in order to obtain reliable binding energies. In the most stable adsorption mode, sulfate binds to the surface via three oxygen atoms (C 3v symmetry) with a binding energy of 159.3 kcal/mol on Ag(111) and 143.9 kcal/mol on Au(111). The geometry of adsorbed sulfate was optimized at the SCF level. While the bond length between sulfur and the oxygens coordinated to the surface increases, the sulfur-uncoordinated oxygen bond length decreases. This weakening and strengthening of the bonds, respectively, is consistent with bond order conservation in adsorbates on metal surfaces. Although a charge transfer of 0.4 electrons towards the metal is observed, the adsorbate remains very much sulfate-like. The molecular orbital analysis indicates that there is also some charge back-donation towards unoccupied orbitals of sulfate. This results in an increased electron density around sulfur as revealed in the electron density difference maps. Analysis of the Laplacian of the charge density of free sulfate provides a suitable framework to understand the nature of the different charge transfer processes and allows us to establish some similarities with the CO- and SO 2-metal bondings.

New CO2 adsorbent containing aminated poly(glycidyl methacrylate) grafted onto irradiated PE-PP nonwoven sheet

NASA Astrophysics Data System (ADS)

Mahmoud Nasef, Mohamed; Abbasi, Ali; Ting, T. M.

2014-10-01

A new CO2 adsorbent containing triethylamine (TEA) was prepared by radiation induced grafting of glycidyl methacrylate (GMA) onto polyethylene coated polypropylene (PE-PP) non-woven sheet followed by amination reaction. The degree of grafting (DOG%) was controlled by variation of monomer concentration and absorbed dose. The incorporation of aminated poly(GMA) was investigated by Fourier transform infrared (FTIR) and scanning electron microscope (SEM). The adsorbent with DOG of 350% and amination yield of 60% exhibited CO2 adsorption capacity of 4.52 mol/kg at ambient temperature and pressure.

Development of porous structured polyvinyl alcohol/zeolite/carbon composites as adsorbent

NASA Astrophysics Data System (ADS)

Laksmono, J. A.; Sudibandriyo, M.; Saputra, A. H.; Haryono, A.

2017-05-01

Adsorption is a separation process that has higher energy efficiency than others. Analyzing the nature of the adsorbate and the selection of suitable adsorbent are key success in adsorption. The performance of the adsorbent can be modified either physically or chemically to obtain the efficiency and effectiveness of the adsorption, this can be facilitated by using a composite adsorbent. In this study, we have conducted the preparation process of a polyvinyl alcohol (PVA)/zeolite/carbon composites. The resulting adsorbent composites are dedicated for ethanol - water dehydration proposes. The composites were prepared using cross-linked polymerization method followed by supercritical fluid extraction (SFE) to obtain the porous structured upon drying process. The characterization of the functional groups and morphology were performed by using Fourier Transform Infra-Red (FTIR) and Scanning Electron Microscopy (SEM), respectively. The FTIR analysis showed that composite prepared by SFE method formed hydrogen bonding confirmed by the appearance of peaks at 2950 - 3000 cm-1 compared to composite without SFE method, whereas, the results of SEM study showed the formation of three layered structures. On basis of the obtained results, it can be shown that PVA/zeolite/carbon has high potential to be develop further as an adsorbent composite.

The role of the tunneling matrix element and nuclear reorganization in the design of quantum-dot cellular automata molecules

NASA Astrophysics Data System (ADS)

Henry, Jackson; Blair, Enrique P.

2018-02-01

Mixed-valence molecules provide an implementation for a high-speed, energy-efficient paradigm for classical computing known as quantum-dot cellular automata (QCA). The primitive device in QCA is a cell, a structure with multiple quantum dots and a few mobile charges. A single mixed-valence molecule can function as a cell, with redox centers providing quantum dots. The charge configuration of a molecule encodes binary information, and device switching occurs via intramolecular electron transfer between dots. Arrays of molecular cells adsorbed onto a substrate form QCA logic. Individual cells in the array are coupled locally via the electrostatic electric field. This device networking enables general-purpose computing. Here, a quantum model of a two-dot molecule is built in which the two-state electronic system is coupled to the dominant nuclear vibrational mode via a reorganization energy. This model is used to explore the effects of the electronic inter-dot tunneling (coupling) matrix element and the reorganization energy on device switching. A semi-classical reduction of the model also is made to investigate the competition between field-driven device switching and the electron-vibrational self-trapping. A strong electron-vibrational coupling (high reorganization energy) gives rise to self-trapping, which inhibits the molecule's ability to switch. Nonetheless, there remains an expansive area in the tunneling-reorganization phase space where molecules can support adequate tunneling. Thus, the relationship between the tunneling matrix element and the reorganization energy affords significant leeway in the design of molecules viable for QCA applications.

Fabrication of enzyme-based coatings on intact multi-walled carbon nanotubes as highly effective electrodes in biofuel cells

NASA Astrophysics Data System (ADS)

Kim, Byoung Chan; Lee, Inseon; Kwon, Seok-Joon; Wee, Youngho; Kwon, Ki Young; Jeon, Chulmin; An, Hyo Jin; Jung, Hee-Tae; Ha, Su; Dordick, Jonathan S.; Kim, Jungbae

2017-01-01

CNTs need to be dispersed in aqueous solution for their successful use, and most methods to disperse CNTs rely on tedious and time-consuming acid-based oxidation. Here, we report the simple dispersion of intact multi-walled carbon nanotubes (CNTs) by adding them directly into an aqueous solution of glucose oxidase (GOx), resulting in simultaneous CNT dispersion and facile enzyme immobilization through sequential enzyme adsorption, precipitation, and crosslinking (EAPC). The EAPC achieved high enzyme loading and stability because of crosslinked enzyme coatings on intact CNTs, while obviating the chemical pretreatment that can seriously damage the electron conductivity of CNTs. EAPC-driven GOx activity was 4.5- and 11-times higher than those of covalently-attached GOx (CA) on acid-treated CNTs and simply-adsorbed GOx (ADS) on intact CNTs, respectively. EAPC showed no decrease of GOx activity for 270 days. EAPC was employed to prepare the enzyme anodes for biofuel cells, and the EAPC anode produced 7.5-times higher power output than the CA anode. Even with a higher amount of bound non-conductive enzymes, the EAPC anode showed 1.7-fold higher electron transfer rate than the CA anode. The EAPC on intact CNTs can improve enzyme loading and stability with key routes of improved electron transfer in various biosensing and bioelectronics devices.

Intervalence transfer of ferrocene moieties adsorbed on electrode surfaces by a conjugated linkage

NASA Astrophysics Data System (ADS)

Chen, Wei; Brown, Lauren E.; Konopelski, Joseph P.; Chen, Shaowei

2009-03-01

Effective intervalence transfer occurred between the metal centers of ferrocene moieties that were adsorbed onto a ruthenium thin film surface by ruthenium-carbene π bonds, a direct verification of Hush's four-decade-old prediction. Electrochemical measurements showed two pairs of voltammetric peaks where the separation of the formal potentials suggested a Class II behavior. Additionally, the potential spacing increased with increasing ferrocene surface coverage, most probably as a consequence of the enhanced contribution from through-space electronic interactions between the metal centers. In contrast, the incorporation of a sp 3 carbon spacer into the ferrocene-ruthenium linkage led to the diminishment of interfacial electronic communication.

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

NASA Astrophysics Data System (ADS)

Tremblay, Jean Christophe; Monturet, Serge; Saalfrank, Peter

2010-03-01

The nonadiabatic coupling of an adsorbate close to a metallic surface leads to electronic damping of adsorbate vibrations and line broadening in vibrational spectroscopy. Here, a perturbative treatment of the electronic contribution to the lifetime broadening serves as a building block for a new approach, in which anharmonic vibrational transition rates are calculated from a position-dependent coupling function. Different models for the coupling function will be tested, all related to embedding theory. The first two are models based on a scattering approach with (i) a jellium-type and (ii) a density functional theory based embedding density, respectively. In a third variant a further refined model is used for the embedding density, and a semiempirical approach is taken in which a scaling factor is chosen to match harmonic, single-site, first-principles transition rates, obtained from periodic density functional theory. For the example of hydrogen atoms on (adsorption) and below (subsurface absorption) a Pd(111) surface, lifetimes of and transition rates between vibrational levels are computed. The transition rates emerging from different models serve as input for the selective subsurface adsorption of hydrogen in palladium starting from an adsorption site, by using sequences of infrared laser pulses in a laser distillation scheme.

DFT study on the adsorption behavior and electronic response of AlN nanotube and nanocage toward toxic halothane gas

NASA Astrophysics Data System (ADS)

Mohammadi, R.; Hosseinian, A.; Khosroshahi, E. Saedi; Edjlali, L.; Vessally, E.

2018-04-01

We have investigated the adsorption of a halothane molecule on the AlN nanotube, and nanocage using density functional theory calculations. We predicted that the halothane molecule tends to be physically adsorbed on the surface of AlN nanotube with adsorption energy (Ead) of -4.2 kcal/mol. The electronic properties of AlN nanotube are not affected by the halothane, and it is not a sensor. But the AlN nanocage is more reactive than the AlN nanotube because of its higher curvature. The halothane tends to be adsorbed on a hexagonal ring, an Alsbnd N bond, and a tetragonal ring of the AlN nanocage. The adsorption ability order is as follows: tetragonal ring (Ead = -14.7 kcal/mol) > Alsbnd N bond (Ead = -12.3 kcal/mol) > hexagonal ring (Ead = -10.1 kcal/mol). When a halothane molecule is adsorbed on the AlN nanocage, its electrical conductivity is increased, demonstrating that it can yield an electronic signal at the presence of this molecule, and can be employed in chemical sensors. The AlN nanocage benefits from a short recovery time of about 58 ms at room temperature.

Direct visualization of quasi-ordered oxygen chain structures on Au(110)-(1 × 2)

NASA Astrophysics Data System (ADS)

Hiebel, F.; Montemore, M. M.; Kaxiras, E.; Friend, C. M.

2016-08-01

The Au(110) surface offers unique advantages for atomically-resolved model studies of catalytic oxidation processes on gold. We investigate the adsorption of oxygen on Au(110) using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) methods. We identify the typical (empty-states) STM contrast resulting from adsorbed oxygen as atomic-sized dark features of electronic origin. DFT-based image simulations confirm that chemisorbed oxygen is generally detected indirectly, from the binding-induced electronic structure modification of gold. STM images show that adsorption occurs without affecting the general structure of the pristine Au(110) missing-row reconstruction. The tendency to form one-dimensional structures is observed already at low coverage (< 0.05 ML), with oxygen adsorbing on alternate sides of the reconstruction ridges. Consistently, calculations yield preferred adsorption on the (111) facets of the reconstruction, on a 3-fold coordination site, with increased stability when adsorbed in chains. Gold atoms with two oxygen neighbors exhibit enhanced electronic hybridization with the O states. Finally, the species observed are reactive to CO oxidation at 200 K and desorption of CO2 leaves a clean and ordered gold surface.

STM images and STS for a rectangular quantum corral constructed with δ-function barriers and the effect of an adsorbed atom on STM images and STS

NASA Astrophysics Data System (ADS)

Mitsuoka, Shigenori; Tamura, Akira

2012-04-01

Assuming that an electron confined by double δ-function barriers is in a quasi-stationary state, we derived eigenfunctions and eigenenergies of the electron. Applying this point of view to the electron confined in a rectangular quantum corral (QC), we obtained scanning tunneling microscopic (STM) images and scanning tunneling spectrum (STS). Our results are consistent with experimental ones, which confirms validity of the present model. Comparing with the treatment in which the corral potential is chosen to be of square-barrier type, the present treatment has an advantage that the eigenvalue equations are simple and the number of parameters that specify the potential barrier is only one except the bottom of the potential well. On the basis of a Dyson equation for the Green function we calculated STM images and STS of the QC having an adsorbed atom inside. Our results are consistent with experimental STM images and STS. In contrast to a previous viewpoint that the STS profile is reversed with that of the empty QC, we concluded the STS peaks of the adsorbed QC are shifted downward from those of the empty QC.

Optical impedance spectroscopy with single-mode electro-active-integrated optical waveguides.

PubMed

Han, Xue; Mendes, Sergio B

2014-02-04

An optical impedance spectroscopy (OIS) technique based on a single-mode electro-active-integrated optical waveguide (EA-IOW) was developed to investigate electron-transfer processes of redox adsorbates. A highly sensitive single-mode EA-IOW device was used to optically follow the time-dependent faradaic current originated from a submonolayer of cytochrome c undergoing redox exchanges driven by a harmonic modulation of the electric potential at several dc bias potentials and at several frequencies. To properly retrieve the faradaic current density from the ac-modulated optical signal, we introduce here a mathematical formalism that (i) accounts for intrinsic changes that invariably occur in the optical baseline of the EA-IOW device during potential modulation and (ii) provides accurate results for the electro-chemical parameters. We are able to optically reconstruct the faradaic current density profile against the dc bias potential in the working electrode, identify the formal potential, and determine the energy-width of the electron-transfer process. In addition, by combining the optically reconstructed faradaic signal with simple electrical measurements of impedance across the whole electrochemical cell and the capacitance of the electric double-layer, we are able to determine the time-constant connected to the redox reaction of the adsorbed protein assembly. For cytochrome c directly immobilized onto the indium tin oxide (ITO) surface, we measured a reaction rate constant of 26.5 s(-1). Finally, we calculate the charge-transfer resistance and pseudocapacitance associated with the electron-transfer process and show that the frequency dependence of the redox reaction of the protein submonolayer follows as expected the electrical equivalent of an RC-series admittance diagram. Above all, we show here that OIS with single-mode EA-IOW's provide strong analytical signals that can be readily monitored even for small surface-densities of species involved in the redox process (e.g., fmol/cm(2), 0.1% of a full protein monolayer). This experimental approach, when combined with the analytical formalism described here, brings additional sensitivity, accuracy, and simplicity to electro-chemical analysis and is expected to become a useful tool in investigations of redox processes.

Photoluminescence Probing of Complex H2O Adsorption on InGaN/GaN Nanowires.

PubMed

Maier, Konrad; Helwig, Andreas; Müller, Gerhard; Hille, Pascal; Teubert, Jörg; Eickhoff, Martin

2017-02-08

We demonstrate that the complex adsorption behavior of H 2 O on InGaN/GaN nanowire arrays is directly revealed by their ambient-dependent photoluminescence properties. Under low-humidity, ambient-temperature, and low-excitation-light conditions, H 2 O adsorbates cause a quenching of the photoluminescence. In contrast, for high humidity levels, elevated temperature, and high excitation intensity, H 2 O adsorbates act as efficient photoluminescence enhancers. We show that this behavior, which can only be detected due to the low operation temperature of the InGaN/GaN nanowires, can be explained on the basis of single H 2 O adsorbates forming surface recombination centers and multiple H 2 O adsorbates forming surface passivation layers. Reversible creation of such passivation layers is induced by the photoelectrochemical splitting of adsorbed water molecules and by the interaction of reactive H 3 O + and OH - ions with photoactivated InGaN surfaces. Due to electronic coupling of adsorbing molecules with photoactivated surfaces, InGaN/GaN nanowires act as sensitive nanooptical probes for the analysis of photoelectrochemical surface processes.

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Machado, Fernando M; Bergmann, Carlos P; Fernandes, Thais H M; Lima, Eder C; Royer, Betina; Calvete, Tatiana; Fagan, Solange B

2011-09-15

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N(2) adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298K was fixed at 1h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

A new NH 3 orbital of the NH 3/Ni(110) surface observed by metastable quenching spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Lihwa; Arias, Jose; Hanrahan, Ciaran; Martin, Richard M.; Metiu, Horia

1986-01-01

By using metastable quenching spectroscopy we have found a new NH 3 filled orbital (in the language of one electron theory) for NH 3/Ni(110), located at the Fermi level of the surface. The orbital is not observed when NH 3 is adsorbed on Ni(110), but it is detected for NH 3 adsorbed on polycrystalline Al.

Probing Atomic, Electronic, and Optical Structures of Nanoparticle Photocatalysts Using Fast Electrons

NASA Astrophysics Data System (ADS)

Liu, Qianlang

Graphene has attracted great interest in many fields due to its outstanding electronic and chemical properties. Among them, its surface inertness and high thermal stability makes graphene a promising candidate as a protective material for transition metal surfaces. Recent studies show, however, that small molecules, such as O2, CO and H2O, intercalate between a graphene film and a metal substrate at particular temperatures. The intercalation of O2 between graphene and Ru(0001) is studied with 3 keV helium ion scattering and low energy electron diffraction. It is shown that O2 intercalates between the graphene and the Ru(0001) substrate at a temperature of 650 K and does not adsorb onto the graphene surface. Nevertheless, the graphene layer efficiently avoids both intercalation and adsorption of oxygen at room temperature. It is also found that the intercalated oxygen thermally desorbs from the surface after it is heated to 800 K. Such a desorption is not, however, observed for oxygen dissociatively adsorbed on a bare Ru(0001) surface until 1200 K. It is thus inferred that the oxygen intercalated between graphene and Ru(0001) is in a molecular form. In addition, part of the graphene overlayer is etched by a chemical reaction during the thermal desorption of oxygen. The role of the defects on the graphene layer is also studied. Defects are introduced by 50 eV Ar+ sputtering, which creates single vacancies with a quick sputtering or larger open areas of substrate following a prolonged sputtering. It is found that oxygen molecularly adsorbs at single carbon vacancies even at room temperature, which does not occur on a complete graphene layer. Following post-annealing to 600 K, it is observed that such adsorbed oxygen diffuses to become intercalated between graphene and Ru(0001). Oxygen dissociatively adsorbs in the large open areas of exposed substrate by forming strong oxygen-metal bonds. It is also found that the presence of defects facilitates the intercalation of oxygen and improves the etching efficiency of the graphene during the desorption of oxygen.

Surface chemistry driven actuation in nanoporous gold

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

Biener, J; Wittstock, A; Zepeda-Ruiz, L

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry driven actuation can be realized in high surface area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes in the order of a few tenths of a percent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into amore » mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.« less

Density functional theory study of adsorption geometries and electronic structures of azo-dye-based molecules on anatase TiO2 surface for dye-sensitized solar cell applications.

PubMed

Prajongtat, Pongthep; Suramitr, Songwut; Nokbin, Somkiat; Nakajima, Koichi; Mitsuke, Koichiro; Hannongbua, Supa

2017-09-01

Structural and electronic properties of eight isolated azo dyes (ArNNAr', where Ar and Ar' denote the aryl groups containing benzene and naphthalene skeletons, respectively) were investigated by density functional theory (DFT) based on the B3LYP/6-31G(d,p) and TD-B3LYP/6-311G(d,p) methods The effect of methanol solvent on the structural and electronic properties of the azo dyes was elucidated by employing a polarizable continuum model (PCM). Then, the azo dyes adsorbed onto the anatase TiO 2 (101) slab surface through a carboxyl group. The geometries and electronic structures of the adsorption complexes were determined using periodic DFT based on the PWC/DNP method. The calculated adsorption energies indicate that the adsorbed dyes preferentially take configuration of the bidentate bridging rather than chelating or monodentate ester-type geometries. Furthermore, the azo compounds having two carboxyl groups are coordinated to the TiO 2 surface more preferentially through the carboxyl group connecting to the benzene skeleton than through that connecting to the naphthalene skeleton. The dihedral angles (Φ B-N ) between the benzene- and naphthalene-skeleton moieties are smaller than 10° for the adsorbed azo compounds containing one carboxyl group. In contrast, Φ B-N > 30° are obtained for the adsorbed azo compounds containing two carboxyl groups. The almost planar conformations of the former appear to strengthen both π-electrons conjugation and electronic coupling between low-lying unoccupied molecular orbitals of the azo dyes and the conduction band of TiO 2 . On the other hand, such coupling is very weak for the latter, leading to a shift of the Fermi level of TiO 2 in the lower-energy direction. The obtained results are useful to the design and synthesize novel azo-dye-based molecules that give rise to higher photovoltaic performances of the dye-sensitized solar cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Radioactive Cobalt(II) Removal from Aqueous Solutions Using a Reusable Nanocomposite: Kinetic, Isotherms, and Mechanistic Study

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A lignocellulose/montmorillonite (LMT) nanocomposite was prepared as a reusable adsorbent for cobalt(II) ions, and characterized by nitrogen (N2) adsorption/desorption isotherm, X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). LMT exhibited efficient adsorption of cobalt ions (Co(II)), and the adsorbed Co(II) was readily desorbed by nitric acid (HNO3). All parameters affecting the adsorption and/or desorption of Co(II), including initial Co(II) concentration, pH value, temperature, HNO3 concentration, and time, were optimized. The kinetic data analysis showed that the adsorption followed the pseudo-second-order kinetic model and fit well into the Langmuir isotherm equation. Notably, the nanocomposite can be used four times without significantly losing adsorbent capability. The Energy-Dispersive X-ray (EDX) and FTIR spectra analysis also revealed that the adsorption mechanism may be mainly a chemical adsorption dominated process. PMID:29186794

Theoretical study of adsorption of organic phosphines on transition metal surfaces

NASA Astrophysics Data System (ADS)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

Quantum Chemical Study of Water Adsorption on the Surfaces of SrTiO3 Nanotubes.

PubMed

Bandura, Andrei V; Kuruch, Dmitry D; Evarestov, Robert A

2015-07-20

We have studied the adsorption of water molecules on the inner and outer surfaces of nanotubes generated by rolling (001) layers of SrTiO3 cubic crystals. The stability and the atomic and electronic structures of the adsorbed layers are determined by using hybrid density functional theory. The absorption energy and the preferred adsorbate structure are essentially governed by the nature of the surface of the nanotube. Dissociative adsorption prevails on the outer nanotube surfaces. The stability of the adsorbed layers on the inner surfaces is related to the possibility of the formation of hydrogen bonds between water molecules and surface oxygen atoms, and depends on the surface curvature. The presence of water molecules on the inner surface of the nanotubes leads to an increase of the electronic band gap. Externally TiO2 -terminated nanotubes could be used for the photocatalytic decomposition of water by ultraviolet radiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field.

PubMed

Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

2017-02-23

Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 10 6  A·cm -2 , or about 1 × 10 25 electrons s -1 cm -2 . This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 10 13 electrons per cm 2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions.

Magnetization switching in ferromagnets by adsorbed chiral molecules without current or external magnetic field

PubMed Central

Ben Dor, Oren; Yochelis, Shira; Radko, Anna; Vankayala, Kiran; Capua, Eyal; Capua, Amir; Yang, See-Hun; Baczewski, Lech Tomasz; Parkin, Stuart Stephen Papworth; Naaman, Ron; Paltiel, Yossi

2017-01-01

Ferromagnets are commonly magnetized by either external magnetic fields or spin polarized currents. The manipulation of magnetization by spin-current occurs through the spin-transfer-torque effect, which is applied, for example, in modern magnetoresistive random access memory. However, the current density required for the spin-transfer torque is of the order of 1 × 106 A·cm−2, or about 1 × 1025 electrons s−1 cm−2. This relatively high current density significantly affects the devices' structure and performance. Here we demonstrate magnetization switching of ferromagnetic thin layers that is induced solely by adsorption of chiral molecules. In this case, about 1013 electrons per cm2 are sufficient to induce magnetization reversal. The direction of the magnetization depends on the handedness of the adsorbed chiral molecules. Local magnetization switching is achieved by adsorbing a chiral self-assembled molecular monolayer on a gold-coated ferromagnetic layer with perpendicular magnetic anisotropy. These results present a simple low-power magnetization mechanism when operating at ambient conditions. PMID:28230054

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.

2018-01-01

100 eV electrons are stopped in the H 2 O portion of the isotopically-layered nanoscale film on α-Al 2 O 3 (0001) but D 2 is produced at the D 2 O/alumina interface by mobile electronic excitations and/or hydronium ions.

Co-adsorption of water and oxygen on GaN: Effects of charge transfer and formation of electron depletion layer.

PubMed

Wang, Qi; Puntambekar, Ajinkya; Chakrapani, Vidhya

2017-09-14

Species from ambient atmosphere such as water and oxygen are known to affect electronic and optical properties of GaN, but the underlying mechanism is not clearly known. In this work, we show through careful measurement of electrical resistivity and photoluminescence intensity under various adsorbates that the presence of oxygen or water vapor alone is not sufficient to induce electron transfer to these species. Rather, the presence of both water and oxygen is necessary to induce electron transfer from GaN that leads to the formation of an electron depletion region on the surface. Exposure to acidic gases decreases n-type conductivity due to increased electron transfer from GaN, while basic gases increase n-type conductivity and PL intensity due to reduced charge transfer from GaN. These changes in the electrical and optical properties, as explained using a new electrochemical framework based on the phenomenon of surface transfer doping, suggest that gases interact with the semiconductor surface through electrochemical reactions occurring in an adsorbed water layer present on the surface.

Electron-Scavenging Chemistry of Benzoquinone on TiO2(110)

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

Henderson, Michael A.; Shen, Mingmin

The chemistry of benzoquinone (BQ) on TiO2(110) was examined using temperature programmed desorption (TPD), electron energy loss spectroscopy (EELS) and Auger electron spectroscopy (AES). BQ adsorbs mostly molecularly on the clean surface, although EELS demonstrates that electrons from surface Ti3+ sites at oxygen vacancy sites (VO) are readily oxidized by the high electron scavenging ability of the molecule. In contrast, when the surface is covered with water, subsequently adsorbed BQ molecules that scavenge surface electrons also abstract H from surface OHbr groups to form hydroquinone (HQ), which desorbs at ~450 K. This work was supported by the US Department ofmore » Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

Titanium-incorporated organic–inorganic hybrid adsorbent for improved CO{sub 2} adsorption performance

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

Zhang, Xiaoyun; Qin, Hongyan; Zhang, Sisi

2015-02-15

Highlights: • Titanium-incorporated organic–inorganic hybrid adsorbent was prepared. • The incorporation of Ti to the adsorbent showed significant effect. • The sorbent shows high CO{sub 2} capture capacity both in pure and diluted CO{sub 2} at RT. • The sorbent exhibits a high recycling stability after 15 cycling runs. - Abstract: The CO{sub 2} adsorption performance of acrylonitrile (AN)–tetraethylenepentamine (TEPA) adduct (hereafter referred to as TN) impregnated adsorbent was greatly enhanced by introduction of Titanium atom into the silica matrix. The adsorbents were characterized by X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), transmission electron microscopy (TEM), N{sub 2} adsorption/desorption, UV–vismore » spectroscopy, Fourier transform infrared (FTIR) spectroscopy. The adsorption experiments together with the physicochemical characterization demonstrated that these adsorbents containing an optimal amount of Titanium (Ti/Si ≈ 0.1) remarkably reinforced the CO{sub 2} adsorption capacity and recycling stability. The highest CO{sub 2} uptakes reached 4.65 and 1.80 mmol CO{sub 2}/g adsorbent at 25 °C under 90% CO{sub 2} (CO{sub 2}/N{sub 2}, 90:10 V/V) and 1% CO{sub 2} (CO{sub 2}/N{sub 2}, 1:99 V/V) conditions for sample Ti(0.1)-DMS-TN, respectively. Repeated adsorption/desorption cycles revealed that the Ti-incorporated adsorbent showed only a tiny decrease in adsorption capacity (1.778 mmol CO{sub 2}/g adsorbent after 15 cycles, decreased by 0.95%), significantly enhanced the adsorbent recycling stability.« less

Attosecond time-resolved streaked photoemission from Mg-covered W(110) surfaces

NASA Astrophysics Data System (ADS)

Liao, Qing; Thumm, Uwe

2015-05-01

We formulate a quantum-mechanical model for infrared-streaked photoelectron emission by an ultrashort extreme ultraviolet pulse from adsorbate-covered metal surfaces. Applying this numerical model to ultrathin Mg adsorbates on W(110) substrates, we analyze streaked photoelectron spectra and attosecond streaking time delays for photoemission from the Mg/W(110) conduction band and Mg(2p) and W(4f) core levels. Based on this analysis, we propose the use of attosecond streaking spectroscopy on adsorbate-covered surfaces with variable adsorbate thickness as a method for investigating (a) electron transport in condensed-matter systems and (b) metal-adsorbate-interface properties at subatomic length and time scales. Our calculated streaked photoemission spectra and time delays agree with recently obtained experimental data. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy under Grant No. DE-FG02-86ER13491 and NSF Grant PHY-1068752.

Immobilization of heavy metals on pillared montmorillonite with a grafted chelate ligand.

PubMed

Brown, Loren; Seaton, Kenneth; Mohseni, Ray; Vasiliev, Aleksey

2013-10-15

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring of montmorillonite with silica followed by grafting of a chelate ligand on its surface. Obtained adsorbent was mesoporous with high content of adsorption sites. Its structure was studied by BET adsorption of N2, dynamic light scattering, and scanning electron microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin and soil samples and by analysis of heavy metal contents in leachate. Deionized water and 50% acetic acid were used for leaching of metals from the samples. As it was demonstrated by the experiments, the adsorbent was efficient in immobilization of heavy metals not only in neutral aqueous media but also in the presence of weak acid. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites. Copyright © 2013 Elsevier B.V. All rights reserved.

Razor clam (Ensis directus) shell as a low-cost adsorbent for the removal of Congo red and Rhodamine B dyes from aqueous solution

NASA Astrophysics Data System (ADS)

Areibat, Lila Elamari Mohamed; Kamari, Azlan

2017-05-01

Wastewater originating from industrial effluents contains many types of pollutants including dyes. Anionic and cationic dyes are very toxic and they can cause several problems to aquatic system. In present study, razor clam shell was used as a potential adsorbent to remove two classes of dyes, namely anionic (Congo red, CR) and cationic (Rhodamine B, RB) dyes from aqueous solution. Batch adsorption experiments were performed to study the effects of three experimental parameters, namely solution pH, adsorbent dosage and initial dye concentration, on adsorption capacity of CR and RB onto razor clam shell. Results indicated that pH 2.0 was optimum pH for adsorbent to adsorb both CR and RB. At an initial concentration of 20 mg/L, the removal percentages of CR and RB were 97% and 38%, respectively. The Freundlich and Langmuir isotherm models were used to describe adsorption behaviour of CR and RB, as well as the relationship between adsorbent and adsorbate. The adsorption equilibrium data were well fitted to Freundlich isotherm model. The separation factor (RL) constants suggest that both CR and RB were favourably adsorbed by razor clam shell. Razor clam shell was characterised by using two techniques, namely Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectrometry (FTIR). Overall, this study suggests that razor clam shell has great potential to be an alternative to expensive adsorbents.

A new NH 3 orbital of the NH 3/Ni(110) surface observed by metastable quenching spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Lihwa; Arias, Jose; Hanrahan, Ciaran; Martin, Richard M.; Metiu, Horia

By using metastable quenching spectroscopy we have found a new NH 3 filled orbital (in the language of one electron theory) for NH 3/Ni(110), located at the Fermi level of the surface. The orbital is not observed when NH 3 is adsorbed on Ni(111) and O/Ni(110), but it is detected for NH 3 adsorbed on polycrystalline Al.

Role of Adsorbed Water on Charge Carrier Dynamics in Photoexcited TiO2

PubMed Central

2017-01-01

Overall photocatalytic water splitting is one of the most sought after processes for sustainable solar-to-chemical energy conversion. The efficiency of this process strongly depends on charge carrier recombination and interaction with surface adsorbates at different time scales. Here, we investigated how hydration of TiO2 P25 affects dynamics of photogenerated electrons at the millisecond to minute time scale characteristic for chemical reactions. We used rapid scan diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). The decay of photogenerated electron absorption was substantially slower in the presence of associated water. For hydrated samples, the charge carrier recombination rates followed an Arrhenius-type behavior in the temperature range of 273–423 K; these became temperature-independent when the material was dehydrated at temperatures above 423 K or cooled below 273 K. A DFT+U analysis revealed that hydrogen bonding with adsorbed water stabilizes surface-trapped holes at anatase TiO2(101) facet and lowers the barriers for hole migration. Hence, hole mobility should be higher in the hydrated material than in the dehydrated system. This demonstrates that adsorbed associated water can efficiently stabilize photogenerated charge carriers in nanocrystalline TiO2 and suppress their recombination at the time scale up to minutes. PMID:28413570

A Reliable Hybrid Adsorbent for Efficient Radioactive Cesium Accumulation from Contaminated Wastewater

PubMed Central

Awual, Md. Rabiul; Yaita, Tsuyoshi; Miyazaki, Yuji; Matsumura, Daiju; Shiwaku, Hideaki; Taguchi, Tomitsugu

2016-01-01

Cesium (Cs) removal from nuclear liquid wastewater has become an emerging issue for safeguarding public health after the accident at the Fukushima Daiichi Nuclear Power Plant. A novel macrocyclic ligand of o-benzo-p-xylyl-22-crown-6-ether (OBPX22C6) was developed and successfully immobilized onto mesoporous silica for the preparation of hybrid adsorbent. The benzene ring π electron is the part of crown ether of OBPX22C6 for easy orientation of the macrocyclic compound for making the π electron donation with Cs complexation. The potential and feasibility of the hybrid adsorbent as being Cs selective was evaluated in terms of sensitivity, selectivity and reusability. The results clarified that the Cs removal process was rapid and reached saturation within a short time. Considering the effect of competitive ions, sodium (Na) did not markedly affect the Cs adsorption whereas potassium (K) was slightly affected due to the similar ionic radii. However, the oxygen in long ethylene glycol chain in OBPX22C6 was expected to show strong coordination, including Cs-π interaction with Cs even in the presence of the high amount of K and Na. Due to its high selectivity and reusability, significant volume reduction is expected as this promising hybrid adsorbent is used for Cs removal in Fukushima wastewater. PMID:26818070

A Reliable Hybrid Adsorbent for Efficient Radioactive Cesium Accumulation from Contaminated Wastewater.

PubMed

Awual, Md Rabiul; Yaita, Tsuyoshi; Miyazaki, Yuji; Matsumura, Daiju; Shiwaku, Hideaki; Taguchi, Tomitsugu

2016-01-28

Cesium (Cs) removal from nuclear liquid wastewater has become an emerging issue for safeguarding public health after the accident at the Fukushima Daiichi Nuclear Power Plant. A novel macrocyclic ligand of o-benzo-p-xylyl-22-crown-6-ether (OBPX22C6) was developed and successfully immobilized onto mesoporous silica for the preparation of hybrid adsorbent. The benzene ring π electron is the part of crown ether of OBPX22C6 for easy orientation of the macrocyclic compound for making the π electron donation with Cs complexation. The potential and feasibility of the hybrid adsorbent as being Cs selective was evaluated in terms of sensitivity, selectivity and reusability. The results clarified that the Cs removal process was rapid and reached saturation within a short time. Considering the effect of competitive ions, sodium (Na) did not markedly affect the Cs adsorption whereas potassium (K) was slightly affected due to the similar ionic radii. However, the oxygen in long ethylene glycol chain in OBPX22C6 was expected to show strong coordination, including Cs-π interaction with Cs even in the presence of the high amount of K and Na. Due to its high selectivity and reusability, significant volume reduction is expected as this promising hybrid adsorbent is used for Cs removal in Fukushima wastewater.

First-principles study of Au-decorated carbon nanotubes

NASA Astrophysics Data System (ADS)

Ju, Weiwei; Li, Tongwei; Zhou, Qingxiao; Li, Haisheng; Li, Xiaohong

2018-07-01

The electronic structures and spin-orbit (SO) coupling of carbon nanotubes with adsorbed Au atoms are investigated based on density functional theory. Three kinds of zigzag single-walled CNT (8,0), (10,0) and (12,0) are selected. The Au atoms prefer to adsorb on the top of C atoms. The adsorption of Au atoms can introduce impurity states in the band gap, modifying the electronic properties of systems. Furthermore, the influence of SO coupling on these impurity states is also explored. Considerable SO splitting (∼130 meV) can be obtained. We find that the SO splitting decreases with the increase of the concentration of Au atoms, which can be ascribed to the interaction between Au atoms, suppressing the SO splitting. Our work provides imperative understanding on the electronic properties and SO coupling effect in Au-decorated CNTs.

Electronic energy level alignment at metal-molecule interfaces with a GW approach

NASA Astrophysics Data System (ADS)

Tamblyn, Isaac; Darancet, Pierre; Quek, Su Ying; Bonev, Stanimir A.; Neaton, Jeffrey B.

2011-11-01

Using density functional theory and many-body perturbation theory within a GW approximation, we calculate the electronic structure of a metal-molecule interface consisting of benzene diamine (BDA) adsorbed on Au(111). Through direct comparison with photoemission data, we show that a conventional G0W0 approach can underestimate the energy of the adsorbed molecular resonance relative to the Au Fermi level by up to 0.8 eV. The source of this discrepancy is twofold: a 0.7 eV underestimate of the gas phase ionization energy (IE), and a 0.2 eV overestimate of the Au work function. Refinements to self-energy calculations within the GW framework that account for deviations in both the Au work function and BDA gas-phase IE can result in an interfacial electronic level alignment in quantitative agreement with experiment.

3D morphology of Au and Au@Ag nanobipyramids

NASA Astrophysics Data System (ADS)

Burgin, Julien; Florea, Ileana; Majimel, Jérôme; Dobri, Adam; Ersen, Ovidiu; Tréguer-Delapierre, Mona

2012-02-01

The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance.The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11454b

Highly regenerable carbon-Fe3O4 core-satellite nanospheres as oxygen reduction electrocatalyst and magnetic adsorbent

NASA Astrophysics Data System (ADS)

Zhou, Wenqiang; Liu, Minmin; Cai, Chao; Zhou, Haijun; Liu, Rui

2017-02-01

We present the synthesis and multifunctional utilization of core-satellite carbon-Fe3O4 nanoparticles to serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. Starting from polydopamine (PDA) nanoparticles and Fe(NO3)3, carbon-Fe3O4 core-satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The synergistic combination of Fe3O4 and N-doped carbon endows the nanocomposite with high electrochemical activity in ORR and mainly four electrons transferred in reaction process. Furthermore, carbon-Fe3O4 nanoparticles used as magnetic adsorbent exhibit the efficient removal of Rhodamine B from an aqueous solution. The recovery and reuse of the adsorbent is demonstrated 5 times without any detectible loss in activity.

Monolayer adsorption of noble gases on graphene

NASA Astrophysics Data System (ADS)

Maiga, Sidi M.; Gatica, Silvina M.

2018-02-01

We report our results of simulations of the adsorption of noble gases (Kr, Ar, Xe) on graphene. For Kr, we consider two configurations: supported and free-standing graphene, where atoms are adsorbed only on one or two sides of the graphene. For Ar and Xe, we studied only the case of supported graphene. For the single-side adsorption, we calculated the two-dimensional gas-liquid critical temperature for each adsorbate. We determined the different phases of the monolayers and constructed the phase diagrams. We found two-dimensional incommensurate solid phases for krypton, argon and xenon, and a two-dimensional commensurate solid phase for krypton. For double side adsorption of Kr, we do not see evidence of an ordering transition driven by the interlayer forces.

Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

PubMed

Chayawan; Vikas

2016-11-01

This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment. Copyright © 2016 Elsevier Ltd. All rights reserved.

A key discovery at the TiO2/dye/electrolyte interface: slow local charge compensation and a reversible electric field.

PubMed

Yang, Wenxing; Pazoki, Meysam; Eriksson, Anna I K; Hao, Yan; Boschloo, Gerrit

2015-07-14

Dye-sensitized mesoporous TiO2 films have been widely applied in energy and environmental science related research fields. The interaction between accumulated electrons inside TiO2 and cations in the surrounding electrolyte at the TiO2/dye/electrolyte interface is, however, still poorly understood. This interaction is undoubtedly important for both device performance and fundamental understanding. In the present study, Stark effects of an organic dye, LEG4, adsorbed on TiO2 were well characterized and used as a probe to monitor the local electric field at the TiO2/dye/electrolyte interface. By using time-resolved photo- and potential-induced absorption techniques, we found evidence for a slow (t > 0.1 s) local charge compensation mechanism, which follows electron accumulation inside the mesoporous TiO2. This slow local compensation was attributed to the penetration of cations from the electrolyte into the adsorbed dye layer, leading to a more localized charge compensation of the electrons inside TiO2. Importantly, when the electrons inside TiO2 were extracted, a remarkable reversal of the surface electric field was observed for the first time, which is attributed to the penetrated and/or adsorbed cations now being charge compensated by anions in the bulk electrolyte. A cation electrosorption model is developed to account for the overall process. These findings give new insights into the mesoporous TiO2/dye/electrolyte interface and the electron-cation interaction mechanism. Electrosorbed cations are proposed to act as electrostatic trap states for electrons in the mesoporous TiO2 electrode.

Terahertz-driven linear electron acceleration

PubMed Central

Nanni, Emilio A.; Huang, Wenqian R.; Hong, Kyung-Han; Ravi, Koustuban; Fallahi, Arya; Moriena, Gustavo; Dwayne Miller, R. J.; Kärtner, Franz X.

2015-01-01

The cost, size and availability of electron accelerators are dominated by the achievable accelerating gradient. Conventional high-brightness radio-frequency accelerating structures operate with 30–50 MeV m−1 gradients. Electron accelerators driven with optical or infrared sources have demonstrated accelerating gradients orders of magnitude above that achievable with conventional radio-frequency structures. However, laser-driven wakefield accelerators require intense femtosecond sources and direct laser-driven accelerators suffer from low bunch charge, sub-micron tolerances and sub-femtosecond timing requirements due to the short wavelength of operation. Here we demonstrate linear acceleration of electrons with keV energy gain using optically generated terahertz pulses. Terahertz-driven accelerating structures enable high-gradient electron/proton accelerators with simple accelerating structures, high repetition rates and significant charge per bunch. These ultra-compact terahertz accelerators with extremely short electron bunches hold great potential to have a transformative impact for free electron lasers, linear colliders, ultrafast electron diffraction, X-ray science and medical therapy with X-rays and electron beams. PMID:26439410

Terahertz-driven linear electron acceleration

DOE PAGES

Nanni, Emilio A.; Huang, Wenqian R.; Hong, Kyung-Han; ...

2015-10-06

The cost, size and availability of electron accelerators are dominated by the achievable accelerating gradient. Conventional high-brightness radio-frequency accelerating structures operate with 30–50 MeVm -1 gradients. Electron accelerators driven with optical or infrared sources have demonstrated accelerating gradients orders of magnitude above that achievable with conventional radio-frequency structures. However, laser-driven wakefield accelerators require intense femtosecond sources and direct laser-driven accelerators suffer from low bunch charge, sub-micron tolerances and sub-femtosecond timing requirements due to the short wavelength of operation. Here we demonstrate linear acceleration of electrons with keV energy gain using optically generated terahertz pulses. Terahertz-driven accelerating structures enable high-gradient electron/protonmore » accelerators with simple accelerating structures, high repetition rates and significant charge per bunch. As a result, these ultra-compact terahertz accelerators with extremely short electron bunches hold great potential to have a transformative impact for free electron lasers, linear colliders, ultrafast electron diffraction, X-ray science and medical therapy with X-rays and electron beams.« less

PVDF membranes containing hybrid nanoparticles for adsorbing cationic dyes: physical insights and mechanism

NASA Astrophysics Data System (ADS)

Sharma, Maya; Madras, Giridhar; Bose, Suryasarathi

2016-07-01

In this study, Fe (iron) and Ag (silver) based adsorbents were synthesized using solution combustion and in situ reduction techniques. The synthesized adsorbents were comprehensively characterized by different techniques including electron microscopy, BET, XRD, Zeta potential etc. Three chlorinated cationic dyes used were malachite green, methyl violet and pyronin Y. These dyes were adsorbed on various synthesized adsorbents [iron III oxide (Fe2O3)], iron III oxide decorated silver nanoparticles by combustion synthesis technique [Fe2O3-Ag(C)] and iron III oxide decorated silver nanoparticles using in situ reduction, [Fe2O3-Ag (S)]. The isotherm and the adsorption kinetics have been studied systematically. The kinetic data can be explained by the pseudo second order model and the adsorption equilibrium followed Langmuir isotherm. The equilibrium and kinetics results suggest that Fe2O3-Ag(S) nanoparticles showed the maximum adsorption among all the adsorbents. Hence, Polyvinylidene fluoride based membranes containing Fe2O3-Ag(S) nanoparticles were prepared via phase inversion (precipitation immersion using DMF/water) technique. The adsorption kinetics were studied in detail and it was observed that the composite membrane showed synergistic improvement in dye adsorption. Such membranes can be used for water purification.

Synthesis and characterization of nontoxic chitosan-coated Fe3O4 particles for patulin adsorption in a juice-pH simulation aqueous.

PubMed

Luo, Ying; Zhou, Zhengkun; Yue, Tianli

2017-04-15

Chitosan-coated Fe 3 O 4 particles were prepared as a magnetic adsorbent by reverse oil-in-water micro-emulsion system using Triton X-100 as the emulsifier. Coating chitosan onto the magnetic particles was confirmed by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectra and magnetic measurements. Chitosan-coated Fe 3 O 4 adsorbent was shown to be effective for patulin adsorption with a maximum adsorption capacity of 6.67mg/g within 5h by adding 300μg adsorbents into 10mL 200μg/L patulin aqueous. In addition, the recovery rate of chitosan-coated Fe 3 O 4 adsorbent reached to 99.95% within 60min, showed its excellent recoverable performance. Moreover, in vitro cytotoxicity and acute toxicity evaluation were also conducted, the results suggested that the chitosan-coated Fe 3 O 4 adsorbent was non-cytotoxic, and had no toxic response or histopathological changes on mice. The results of this study demonstrated that chitosan-coated Fe 3 O 4 particles are promising adsorbents for patulin removal in fruit juice industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

The application of textile sludge adsorbents for the removal of Reactive Red 2 dye.

PubMed

Sonai, Gabriela G; de Souza, Selene M A Guelli U; de Oliveira, Débora; de Souza, Antônio Augusto U

2016-03-01

Sludge from the textile industry was used as a low-cost adsorbent to remove the dye Reactive Red 2 from an aqueous solution. Adsorbents were prepared through the thermal and chemical treatment of sludge originating from physical-chemical (PC) and biological (BIO) effluent treatment processes. The adsorbent characterization was carried out through physical-chemical analysis, X-ray fluorescence (XRF) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, pHPZC determination, Boehm titration method, Brunauer-Emmett-Teller (BET) surface area analysis and scanning electron microscopy (SEM). Batch kinetic experiments and adsorption isotherm modeling were conducted under different pH and temperature conditions. The results for the kinetic studies indicate that the adsorption processes associated with these systems can be described by a pseudo-second-order model and for the equilibrium data the Langmuir model provided the best fit. The adsorption was strongly dependent on the pH but not on the temperature within the ranges studied. The maxima adsorption capacities were 159.3 mg g(-1) for the BIO adsorbent and 213.9 mg g(-1) for PC adsorbent at pH of 2 and 25 °C. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solution Adsorption Formation of a π-Conjugated Polymer/Graphene Composite for High-Performance Field-Effect Transistors.

PubMed

Liu, Yun; Hao, Wei; Yao, Huiying; Li, Shuzhou; Wu, Yuchen; Zhu, Jia; Jiang, Lei

2018-01-01

Semiconducting polymers with π-conjugated electronic structures have potential application in the large-scale printable fabrication of high-performance electronic and optoelectronic devices. However, owing to their poor environmental stability and high-cost synthesis, polymer semiconductors possess limited device implementation. Here, an approach for constructing a π-conjugated polymer/graphene composite material to circumvent these limitations is provided, and then this material is patterned into 1D arrays. Driven by the π-π interaction, several-layer polymers can be adsorbed onto the graphene planes. The low consumption of the high-cost semiconductor polymers and the mass production of graphene contribute to the low-cost fabrication of the π-conjugated polymer/graphene composite materials. Based on the π-conjugated system, a reduced π-π stacking distance between graphene and the polymer can be achieved, yielding enhanced charge-transport properties. Owing to the incorporation of graphene, the composite material shows improved thermal stability. More generally, it is believed that the construction of the π-conjugated composite shows clear possibility of integrating organic molecules and 2D materials into microstructure arrays for property-by-design fabrication of functional devices with large area, low cost, and high efficiency. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical Calculation of the Gas-Sensing Properties of Pt-Decorated Carbon Nanotubes

PubMed Central

Zhang, Xiaoxing; Dai, Ziqiang; Wei, Li; Liang, Naifeng; Wu, Xiaoqing

2013-01-01

The gas-sensing properties of Pt-decorated carbon nanotubes (CNTs), which provide a foundation for the fabrication of sensors, have been evaluated. In this study, we calculated the gas adsorption of Pt-decorated (8,0) single-wall CNTs (Pt-SWCNTs) with SO2, H2S, and CO using GGA/PW91 method based on density functional theory. The adsorption energies and the changes in geometric and electronic structures after absorption were comprehensively analyzed to estimate the responses of Pt-SWCNTs. Results indicated that Pt-SWCNTs can respond to the three gases. The electrical characteristics of Pt-SWCNTs show different changes after adsorption. Pt-SWCNTs donate electrons and increase the number of hole carriers after adsorbing SO2, thereby enhancing its conductivity. When H2S is adsorbed on CNTs, electrons are transferred from H2S to Pt-SWCNTs, converting Pt-SWCNTs from p-type to n-type sensors with improved conductivity. However, Pt-SWCNTs obtain electrons and show decreased conductivity when reacted with CO gas. PMID:24201317

Graphene-Supported Spinel CuFe2O4 Composites: Novel Adsorbents for Arsenic Removal in Aqueous Media

PubMed Central

La, Duong Duc; Nguyen, Tuan Anh; Jones, Lathe A.; Bhosale, Sheshanath V.

2017-01-01

A graphene nanoplate-supported spinel CuFe2O4 composite (GNPs/CuFe2O4) was successfully synthesized by using a facile thermal decomposition route. Scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), Electron Dispersive Spectroscopy (EDS), X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to characterize the prepared composite. The arsenic adsorption behavior of the GNPs/CuFe2O4 composite was investigated by carrying out batch experiments. Both the Langmuir and Freundlich models were employed to describe the adsorption isotherm, where the sorption kinetics of arsenic adsorption by the composite were found to be pseudo-second order. The selectivity of the adsorbent toward arsenic over common metal ions in water was also demonstrated. Furthermore, the reusability and regeneration of the adsorbent were investigated by an assembled column filter test. The GNPs/CuFe2O4 composite exhibited significant, fast adsorption of arsenic over a wide range of solution pHs with exceptional durability, selectivity, and recyclability, which could make this composite a very promising candidate for effective removal of arsenic from aqueous solution. The highly sensitive adsorption of the material toward arsenic could be potentially employed for arsenic sensing. PMID:28587257

Around a camphoric-acid boat, is the surfactant adsorbed on to the interface or dissolved in the bulk?

NASA Astrophysics Data System (ADS)

Mandre, Shreyas; Akella, Sathish; Singh, Dhiraj; Singh, Ravi; Bandi, Mahesh

2016-11-01

A camphoric-acid boat (c-boat for short), a cylindrical gel tablet infused with camphoric acid, moves spontaneously when placed on an air-water interface. This system is a classic example of propulsion driven by Marangoni forces. Despite rich history on particles propelled by Marangoni forces, including contributions by figures such as Benjamin Franklin, Allesandro Volta, and Giovanni Venturi, the underlying fluid dynamics remains poorly understood. A key missing piece is the nature of the surfactant; in our case, the question is whether the camphoric acid is dissolved in the bulk or adsorbed on to the interface. We gain insight into this piece by holding the c-boat stationary and measuring the surrounding axisymmetric flow velocity to a precision needed to distinguish between the two possibilities. For soluble surfactants, it is known that the velocity field decays as r - 2 / 3, where r is the distance from the center of the c-boat. Whereas, for surfactant adsorbed on to the air-water interface, we derive that the surrounding velocity fields decays as r - 3 / 5. Based on our measurements we deduce that, even though soluble in water, the Marangoni flow results from a layer of camphoric acid adsorbed to the air-water interface.

Self-consistent field theory of polymer-ionic molecule complexation.

PubMed

Nakamura, Issei; Shi, An-Chang

2010-05-21

A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

Adsorption, aggregation, and desorption of proteins on smectite particles.

PubMed

Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

2014-10-07

We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

Poorly crystalline hydroxyapatite: A novel adsorbent for enhanced fulvic acid removal from aqueous solution

NASA Astrophysics Data System (ADS)

Wei, Wei; Yang, Lei; Zhong, Wenhui; Cui, Jing; Wei, Zhenggui

2015-03-01

In this study, poorly crystalline hydroxyapatite (HAP) was developed as an efficient adsorbent for the removal of fulvic acid (FA) from aqueous solution. Surface functionality, crystallinity, and morphology of the synthetic adsorbent were studied by Fourier-transformation infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of various parameters such as crystallinity of adsorbent, contact time, adsorbent dosage, pH, initial adsorbate concentration, temperature, ionic strength and the presence of alkaline earth metal ions on FA adsorption were investigated. Results indicated that the nanosized HAP calcined at lower temperature was poorly crystalline (Xc = 0.23) and had better adsorption capacity for FA than those (Xc = 0.52, 0.86) calcined at higher temperature. FA removal was increased with increases of adsorbent dosage, temperature, ionic strength and the presence of alkali earth metal ions, but decreased as the pH increased. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Sips models, and the estimated maximum adsorption capacity of poorly crystalline HAP was 90.20 mg/g at 318 K, displaying higher efficiency for FA removal than previously reported adsorbents. FT-IR results revealed that FA adsorption over the adsorbent could be attributed to the surface complexation between the oxygen atom of functional groups of FA and calcium ions of HAP. Regeneration studies indicated that HAP could be recyclable for a long term. Findings of the present work highlight the potential for using poorly crystalline HAP nanoparticles as an effective and recyclable adsorbent for FA removal from aqueous solution.

Quantum impurity models for magnetic adsorbates on superconductor surfaces

NASA Astrophysics Data System (ADS)

Žitko, Rok

2018-05-01

Magnetic atoms adsorbed on surfaces have a quenched orbital moment while their ground-state spin multiplet is partially split as a consequence of the spin-orbit coupling which, even if intrinsically weak, has a large effect due to the abrupt change of the potential at the surface. Such metal adsorbates should be modelled using quantum impurity models that include the relevant internal degrees of freedom and the interaction terms, in particular the magnetic anisotropy and the Kondo exchange coupling. When adsorbed on superconducting surfaces, these impurities have complex spectra of sub-gap excitations due to magnetic anisotropy splitting and Kondo screening. Both anisotropy splitting and Zeeman splitting due to the external magnetic field are significantly renormalized by the coupling to the substrate electrons. In this work I discuss the quantum-to-classical crossover and the applicability of classical static-local-spin picture for discussing magnetic nanostructures on superconductors.

Magnetite nanoparticles coated glass wool for As(V) removal from drinking water

NASA Astrophysics Data System (ADS)

Kango, Sarita; Kumar, Rajesh

2015-08-01

Arsenic (As) removal from contaminated groundwater is a key environmental concern worldwide. In this study, glass wool was coated with magnetite nanoparticles under argon gas flow and magnetite coated glass wool have been investigated for application as an adsorbent for As(V) removal from water. The adsorbent was characterized by using Scanning Electron Microscopy (SEM) and arsenic contaminated water treated with adsorbent was analyzed by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The ICP-MS results showed that 10 g/L of adsorbent removed 99.4% of As(V) within 5 hours at pH-7 and initial arsenic concentration of 360µg/L. Adsorption kinetics data fitted well in pseudo-first-order kinetics model with high correlation coefficient (R2 = 0.995). As magnetite nanoparticles coated glass wool showed favorable adsorption behavior for As(V), it can be a promising tool for water purification.

Framework for scalable adsorbate–adsorbate interaction models

DOE PAGES

Hoffmann, Max J.; Medford, Andrew J.; Bligaard, Thomas

2016-06-02

Here, we present a framework for physically motivated models of adsorbate–adsorbate interaction between small molecules on transition and coinage metals based on modifications to the substrate electronic structure due to adsorption. We use this framework to develop one model for transition and one for coinage metal surfaces. The models for transition metals are based on the d-band center position, and the models for coinage metals are based on partial charges. The models require no empirical parameters, only two first-principles calculations per adsorbate as input, and therefore scale linearly with the number of reaction intermediates. By theory to theory comparison withmore » explicit density functional theory calculations over a wide range of adsorbates and surfaces, we show that the root-mean-squared error for differential adsorption energies is less than 0.2 eV for up to 1 ML coverage.« less

Magnetite nanoparticles coated glass wool for As(V) removal from drinking water

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

Kango, Sarita; Kumar, Rajesh, E-mail: rajesh.kumar@juit.ac.in

2015-08-28

Arsenic (As) removal from contaminated groundwater is a key environmental concern worldwide. In this study, glass wool was coated with magnetite nanoparticles under argon gas flow and magnetite coated glass wool have been investigated for application as an adsorbent for As(V) removal from water. The adsorbent was characterized by using Scanning Electron Microscopy (SEM) and arsenic contaminated water treated with adsorbent was analyzed by Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The ICP-MS results showed that 10 g/L of adsorbent removed 99.4% of As(V) within 5 hours at pH-7 and initial arsenic concentration of 360µg/L. Adsorption kinetics data fitted well inmore » pseudo-first-order kinetics model with high correlation coefficient (R{sup 2} = 0.995). As magnetite nanoparticles coated glass wool showed favorable adsorption behavior for As(V), it can be a promising tool for water purification.« less

Utilization of granular activated carbon adsorber for nitrates removal from groundwater of the Cluj region.

PubMed

Moşneag, Silvia C; Popescu, Violeta; Dinescu, Adrian; Borodi, George

2013-01-01

The level of nitrates from groundwater from Cluj County and other areas from Romania have increased values, exceeding or getting close to the allowed limit values, putting in danger human and animal heath. In this study we used granular activated carbon adsorbent (GAC) for nitrate (NO(-)3) removal for the production of drinking water from groundwater of the Cluj county. The influences of the contact time, nitrate initial concentration, and adsorbent concentration have been studied. We determined the equilibrium adsorption capacity of GAC, used for NO(-)3 removal and we applied the Langmuir and Freundlich isotherm models. Ultraviolet-visible (UV-Vis) and Fourier transform infrared (FTIR) spectroscopy, X ray diffraction (XRD), Scanning Electron Microscopy (SEM) were used for process characterization. We also determined: pH, conductivity, Total Dissolved Solids and Total Hardness. The GAC adsorbents have excellent capacities of removing nitrate from groundwater from Cluj County areas.

Probing long-range structural order in SnPc/Ag(111) by umklapp process assisted low-energy angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Jauernik, Stephan; Hein, Petra; Gurgel, Max; Falke, Julian; Bauer, Michael

2018-03-01

Laser-based angle-resolved photoelectron spectroscopy is performed on tin-phthalocyanine (SnPc) adsorbed on silver Ag(111). Upon adsorption of SnPc, strongly dispersing bands are observed which are identified as secondary Mahan cones formed by surface umklapp processes acting on photoelectrons from the silver substrate as they transit through the ordered adsorbate layer. We show that the photoemission data carry quantitative structural information on the adsorbate layer similar to what can be obtained from a conventional low-energy electron diffraction (LEED) study. More specifically, we compare photoemission data and LEED data probing an incommensurate-to-commensurate structural phase transition of the adsorbate layer. Based on our results we propose that Mahan-cone spectroscopy operated in a pump-probe configuration can be used in the future to probe structural dynamics at surfaces with a temporal resolution in the sub-100-fs regime.

Preparation and Adsorption Property of Imido-acetic Acid Type Chelating Nano-fibers by Electro-spinning Technique

NASA Astrophysics Data System (ADS)

Yang, Jiali; Lu, Lansi; Zhang, Zhu; Liao, Minhui; He, Huirong; Li, Lingxing; Chen, Jida; Chen, Shijin

2017-12-01

A novel nano-fibrous adsorbent from imino-acetic acid (IDA) and polyvinyl alcohol (PVA) mixture solution was prepared by electro-spinning technique. The nano-fibrous adsorbents with imino-acetic acid functional groups were characterized and demonstrated by fourier transform infrared spectrometry (FT-IR) and the scanning electron microscopy (SEM). The effect of the adsorbents to remove heavy metals such as lead (Pb) and copper (Cu) ions from the aqueous solution was studied. The maximum adsorption percentage (SP) of the metal ions can reach 93.08% for Cu (II) and 96.69% for Pb(II), respectively. Furthermore, it shows that the adsorption procedure of the adsorbents is spontaneous and endothermic, and adsorption rate fits well with pseudo-second-order kinetic model. Most importantly, the reusability of the nanofibers for removal of metal ions was also demonstrated to be used at least five times.

In situ study of the electronic structure of atomic layer deposited oxide ultrathin films upon oxygen adsorption using ambient pressure XPS

DOE PAGES

Mao, Bao-Hua; Crumlin, Ethan; Tyo, Eric C.; ...

2016-07-21

In this work, ambient pressure X-ray photoelectron spectroscopy (APXPS) was used to investigate the effect of oxygen adsorption on the band bending and electron affinity of Al 2O 3, ZnO and TiO 2 ultrathin films (~1 nm in thickness) deposited on a Si substrate by atomic layer deposition (ALD). Upon exposure to oxygen at room temperature (RT), upward band bending was observed on all three samples, and a decrease in electron affinity was observed on Al 2O 3 and ZnO ultrathin films at RT. At 80°C, the magnitude of the upward band bending decreased, and the change in the electronmore » affinity vanished. These results indicate the existence of two surface oxygen species: a negatively charged species that is strongly adsorbed and responsible for the observed upward band bending, and a weakly adsorbed species that is polarized, lowering the electron affinity. Based on the extent of upward band bending on the three samples, the surface coverage of the strongly adsorbed species exhibits the following order: Al 2O 3 > ZnO > TiO 2. This finding is in stark contrast to the trend expected on the surface of these bulk oxides, and highlights the unique surface activity of ultrathin oxide films with important implications, for example, in oxidation reactions taking place on these films or in catalyst systems where such oxides are used as a support material.« less

Interfacial charge transfer absorption: Application to metal molecule assemblies

NASA Astrophysics Data System (ADS)

Creutz, Carol; Brunschwig, Bruce S.; Sutin, Norman

2006-05-01

Optically induced charge transfer between adsorbed molecules and a metal electrode was predicted by Hush to lead to new electronic absorption features, but has been only rarely observed experimentally. Interfacial charge transfer absorption (IFCTA) provides information concerning the barriers to charge transfer between molecules and the metal/semiconductor and the magnitude of the electronic coupling and could thus provide a powerful tool for understanding interfacial charge-transfer kinetics. Here, we utilize a previously published model [C. Creutz, B.S. Brunschwig, N. Sutin, J. Phys. Chem. B 109 (2005) 10251] to predict IFCTA spectra of metal-molecule assemblies and compare the literature observations to these predictions. We conclude that, in general, the electronic coupling between molecular adsorbates and the metal levels is so small that IFCTA is not detectable. However, few experiments designed to detect IFCTA have been done. We suggest approaches to optimizing the conditions for observing the process.

Theoretical study on electronic properties of MoS{sub 2} antidot lattices

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

Shao, Li; Chen, Guangde; Ye, Honggang, E-mail: hgye@mail.xjtu.edu.cn

2014-09-21

Motivated by the state of the art method for etching hexagonal array holes in molybdenum disulfide (MoS{sub 2}), the electronic properties of MoS{sub 2} antidot lattices (MoS{sub 2}ALs) with zigzag edge were studied with first-principles calculations. Monolayer MoS{sub 2}ALs are semiconducting and the band gaps converge to constant values as the supercell area increases, which can be attributed to the edge effect. Multilayer MoS{sub 2}ALs and chemical adsorbed MoS{sub 2}ALs by F atoms show metallic behavior, while the structure adsorbed with H atoms remains to be semiconducting with a tiny bandgap. Our results show that forming periodically repeating structures inmore » MoS{sub 2} can develop a promising technique for engineering nano materials and offer new opportunities for designing MoS{sub 2}-based nanoscale electronic devices and chemical sensors.« less

Carbon monoxide sensing properties of B-, Al- and Ga-doped Si nanowires

NASA Astrophysics Data System (ADS)

de Santiago, F.; Trejo, A.; Miranda, A.; Salazar, F.; Carvajal, E.; Pérez, L. A.; Cruz-Irisson, M.

2018-05-01

Silicon nanowires (SiNWs) are considered as potential chemical sensors due to their large surface-to-volume ratio and their possible integration into arrays for nanotechnological applications. Detection of harmful gases like CO has been experimentally demonstrated, however, the influence of doping on the sensing capacity of SiNWs has not yet been reported. For this work, we theoretically studied the surface adsorption of a CO molecule on hydrogen-passivated SiNWs grown along the [111] crystallographic direction and compared it with the adsorption of other molecules such as NO, and O2. Three nanowire diameters and three dopant elements (B, Al and Ga) were considered, and calculations were done within the density functional theory framework. The results indicate that CO molecules are more strongly adsorbed on the doped SiNW than on the pristine SiNW. The following trend was observed for the CO adsorption energies: E A[B-doped] > E A[Al-doped] > E A[Ga-doped] > E A[undoped], for all diameters. The electronic charge transfers between the SiNWs and the adsorbed CO were estimated by using a Voronoi population analysis. The CO adsorbed onto the undoped SiNWs has an electron-acceptor character, while the CO adsorbed onto the B-, Al-, and Ga-doped SiNWs exhibits an electron-donor character. Comparing these results with the ones obtained for the NO and O2 adsorption, the larger CO adsorption energy on B-doped SiNWs indicates their good selectivity towards CO. These results suggest that SiNW-based sensors of toxic gases could represent a clear and advantageous application of nanotechnology in the improvement of human quality of life.

Carbon monoxide sensing properties of B-, Al- and Ga-doped Si nanowires.

PubMed

de Santiago, F; Trejo, A; Miranda, A; Salazar, F; Carvajal, E; Pérez, L A; Cruz-Irisson, M

2018-05-18

Silicon nanowires (SiNWs) are considered as potential chemical sensors due to their large surface-to-volume ratio and their possible integration into arrays for nanotechnological applications. Detection of harmful gases like CO has been experimentally demonstrated, however, the influence of doping on the sensing capacity of SiNWs has not yet been reported. For this work, we theoretically studied the surface adsorption of a CO molecule on hydrogen-passivated SiNWs grown along the [111] crystallographic direction and compared it with the adsorption of other molecules such as NO, and O 2 . Three nanowire diameters and three dopant elements (B, Al and Ga) were considered, and calculations were done within the density functional theory framework. The results indicate that CO molecules are more strongly adsorbed on the doped SiNW than on the pristine SiNW. The following trend was observed for the CO adsorption energies: E A [B-doped] > E A [Al-doped] > E A [Ga-doped] > E A [undoped], for all diameters. The electronic charge transfers between the SiNWs and the adsorbed CO were estimated by using a Voronoi population analysis. The CO adsorbed onto the undoped SiNWs has an electron-acceptor character, while the CO adsorbed onto the B-, Al-, and Ga-doped SiNWs exhibits an electron-donor character. Comparing these results with the ones obtained for the NO and O 2 adsorption, the larger CO adsorption energy on B-doped SiNWs indicates their good selectivity towards CO. These results suggest that SiNW-based sensors of toxic gases could represent a clear and advantageous application of nanotechnology in the improvement of human quality of life.

Adsorption of arsenic by activated carbon, calcium alginate and their composite beads.

PubMed

Hassan, A F; Abdel-Mohsen, A M; Elhadidy, H

2014-07-01

The present investigation deals with preparation of three different adsorbent materials namely; potassium hydroxide activated carbon based apricot stone (C), calcium alginate beads (G) and calcium alginate/activated carbon composite beads (GC) were used for the removal of arsenic. The prepared adsorbent materials were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), N2-adsorption at -196°C and point of zero charge. From the obtained results, it was found that the porosity, surface area and total pore volume of the adsorbent material C>GC>G respectively, however, the G adsorbent has more acidic function group than the other adsorbents. The influence of pH, time, temperature and initial concentration of arsenic(V) were studied and optimized. GC exhibits the maximum As(V) adsorption (66.7mg/g at 30°C). The adsorption of arsenic ions was observed to follow pseudo-second order mechanism as well as the thermodynamic parameters confirm also the endothermic spontaneous and a physisorption process. Copyright © 2014 Elsevier B.V. All rights reserved.

Removal of zearalenone toxin from synthetics gastric and body fluids using talc and diatomite: a batch kinetic study.

PubMed

Sprynskyy, Myroslav; Gadzała-Kopciuch, Renata; Nowak, Karolina; Buszewski, Bogusław

2012-06-01

Adsorption kinetics of zearalenone (ZEA) toxin from synthetic gastric fluid (SGF) and synthetic body fluid (SBF) by talc and diatomite was studied in the batch experiments. Chemical composition, morphology and structure of the used adsorbents were examined by scanning electron microscopy, FTIR spectroscopy and low-temperature nitrogen adsorption/desorption method. High performance liquid chromatography (HPLC) method was used for ZEA determining. The study results showed that ZEA is more effectively adsorbed on the talc (73% and 54% from SGF and SBF respectively). The efficiency on the diatomite was lower (53% and 42% from SGF and SBF respectively). The first order kinetics model was applied to describe the adsorption process. Rate of the ZEA adsorption from SGF is very rapid initially with about 95% of amount of the toxin adsorbed during first 5 min, while ZEA is adsorbed from SBF in two steps. The values of determined Gibbs free energy of adsorption (from -13 to -17 kJ/mol) indicated that adsorption of ZEA toxin by the both adsorbents are spontaneous and exothermic. Copyright © 2012 Elsevier B.V. All rights reserved.

Adsorption of Pb(II) using silica gel composite from rice husk ash modified 3-aminopropyltriethoxysilane (APTES)-activated carbon from coconut shell

NASA Astrophysics Data System (ADS)

Yusmaniar, Purwanto, Agung; Putri, Elfriyana Awalita; Rosyidah, Dzakiyyatur

2017-03-01

Silica gel modified by 3-aminopropyltriethoxysilane (APTES) was synthesized from rice husk ash combined with activated carbon from coconut shell yielded the composite adsorbent. The composite was characterized by Fourier Transform Infra Red spectroscopy (FT-IR), Electron Dispersive X-Ray (EDX), Surface Area Analyzer (SAA) and adsorption test by Atomic Absorption Spectrometry (AAS). This composite adsorbent has been used moderately for the removal of lead ions from metal solutions and compared with silica gel modified APTES and activated carbon. The adsorption experiments of Pb -ions by adsorbents were performed at different pH and contact time with the same metal solutions concentration, volume solution, and adsorbent dosage. The optimum pH for the adsorption was found to be 5.0 and the equilibrium was achieved for Pb with 20 min of contact time. Pb ions adsorption by composite silica gel modified APTES-activated carbon followed by Langmuir isotherm model with qmax value of 46.9483 mg/g that proved an adsorbent mechanism consistent to the mechanism of monolayer formation.

Selective Recovery of Critical Materials from Geothermal Fluid

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

Mayes, Richard T.; Halstenberg, Phillip W.; Moyer, Bruce A.

This project, funded by the DOE Small Business Voucher program, assisted the partner with the development of ion-imprinted adsorbents for the selective extraction of rare earth elements (REE) from geothermal brines. This effort seeks to utilize a currently untapped resource thus diversifying the U. S. REE market. The initial stage of the program focused on the adsorbent developed by partner and optimization of the adsorbent. The adsorbent was based upon an ion imprinted ligand that was copolymerized with a crosslinker to generate the REE selectivity. During this task, the adsorbents were irradiated via electron beam at the NEO Beam Electronmore » Beam Crosslinking Facility (Mercury Plastics, Middlefield, OH) to induce further crosslinking. The irradiation crosslinked adsorbents exhibited no difference in the Fourier transform infrared spectroscopic (FTIR) analysis suggesting inefficiency in the crosslinking. In the later stage of the effort, a new method was proposed and studied at ORNL involving a new partnership between the partner and a commercial polymer vender. This resulted in a new material being developed which allows the partner to utilize a commercial support and integrate the synthesis into a production-ready product stream. This will enhance the route to commercialization for the partner resulting in a quicker market penetration for the product. The new adsorbent exhibits selectivity for REE over transition metals commonly found within geothermal brines. Further optimization is required for enhanced selectivity, capacity, and intra-lanthanide separations.« less

Effect of Yeast Cell Morphology, Cell Wall Physical Structure and Chemical Composition on Patulin Adsorption

PubMed Central

Luo, Ying; Wang, Jianguo; Liu, Bin; Wang, Zhouli; Yuan, Yahong; Yue, Tianli

2015-01-01

The capability of yeast to adsorb patulin in fruit juice can aid in substantially reducing the patulin toxic effect on human health. This study aimed to investigate the capability of yeast cell morphology and cell wall internal structure and composition to adsorb patulin. To compare different yeast cell morphologies, cell wall internal structure and composition, scanning electron microscope, transmission electron microscope and ion chromatography were used. The results indicated that patulin adsorption capability of yeast was influenced by cell surface areas, volume, and cell wall thickness, as well as 1,3-β-glucan content. Among these factors, cell wall thickness and 1,3-β-glucan content serve significant functions. The investigation revealed that patulin adsorption capability was mainly affected by the three-dimensional network structure of the cell wall composed of 1,3-β-glucan. Finally, patulin adsorption in commercial kiwi fruit juice was investigated, and the results indicated that yeast cells could adsorb patulin from commercial kiwi fruit juice efficiently. This study can potentially simulate in vitro cell walls to enhance patulin adsorption capability and successfully apply to fruit juice industry. PMID:26295574

Effect of Yeast Cell Morphology, Cell Wall Physical Structure and Chemical Composition on Patulin Adsorption.

PubMed

Luo, Ying; Wang, Jianguo; Liu, Bin; Wang, Zhouli; Yuan, Yahong; Yue, Tianli

2015-01-01

The capability of yeast to adsorb patulin in fruit juice can aid in substantially reducing the patulin toxic effect on human health. This study aimed to investigate the capability of yeast cell morphology and cell wall internal structure and composition to adsorb patulin. To compare different yeast cell morphologies, cell wall internal structure and composition, scanning electron microscope, transmission electron microscope and ion chromatography were used. The results indicated that patulin adsorption capability of yeast was influenced by cell surface areas, volume, and cell wall thickness, as well as 1,3-β-glucan content. Among these factors, cell wall thickness and 1,3-β-glucan content serve significant functions. The investigation revealed that patulin adsorption capability was mainly affected by the three-dimensional network structure of the cell wall composed of 1,3-β-glucan. Finally, patulin adsorption in commercial kiwi fruit juice was investigated, and the results indicated that yeast cells could adsorb patulin from commercial kiwi fruit juice efficiently. This study can potentially simulate in vitro cell walls to enhance patulin adsorption capability and successfully apply to fruit juice industry.

Highly enhanced adsorption of Congo red by functionalized finger-citron-leaf-based porous carbon.

PubMed

Zhao, Gui-Hua; Fang, Yao-Yao; Dai, Wei; Ma, Na

2018-01-01

A novel high-performance porous carbon material, lanthanum(III)-doped finger-citron-leaf-based porous carbon (La/FPC), has been synthesized and used as an adsorbent for anion dye Congo red (CR). The La/FPC was characterized by nitrogen adsorption and desorption isotherms, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The adsorption performance of CR by the FPC and La/FPC composites with different contents of lanthanum(III) were evaluated in fixed-bed breakthrough experiments and batch tests at room temperature (298 K). The La/FPC had a high CR uptake capacity, which was superior to those previously reported for other adsorbents. The La/FPC sorbents can be easily regenerated using an ethanol elution technique, and after five cycles the reused La/FPC maintained about 98% of its original CR adsorption capacity. The adsorption kinetics of CR onto the lanthanum(III)-doped FPCs followed a pseudo-second-order kinetic model and fitted well with a Langmuir adsorption isotherm. La/FPC is a promising adsorbent for the removal of the anionic dyes from wastewater.

A study of surface enhanced Raman scattering for furfural adsorbed on silver surface

NASA Astrophysics Data System (ADS)

Jia, Ting-jian; Li, Peng-wei; Shang, Zhi-guo; Zhang, Ling; He, Ting-chao; Mo, Yu-jun

2008-02-01

The normal Raman spectrum (NRS) and the surface enhanced Raman scattering (SERS) spectrum of furfural in silver colloid were recorded and analyzed in this paper. The assignment of these bands to furfural molecules was performed by density functional theory (DFT) calculation. The data of the SERS by comparing with the one of NRS show that furfural molecules are adsorbed on the silver surface via the nonbonding electrons of the carbonyl oxygen.

Current status and future perspectives of electron interactions with molecules, clusters, surfaces, and interfaces [Workshop on Fundamental challenges in electron-driven chemistry; Workshop on Electron-driven processes: Scientific challenges and technological opportunities

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

Becker, Kurt H.; McCurdy, C. William; Orlando, Thomas M.

2000-09-01

This report is based largely on presentations and discussions at two workshops and contributions from workshop participants. The workshop on Fundamental Challenges in Electron-Driven Chemistry was held in Berkeley, October 9-10, 1998, and addressed questions regarding theory, computation, and simulation. The workshop on Electron-Driven Processes: Scientific Challenges and Technological Opportunities was held at Stevens Institute of Technology, March 16-17, 2000, and focused largely on experiments. Electron-molecule and electron-atom collisions initiate and drive almost all the relevant chemical processes associated with radiation chemistry, environmental chemistry, stability of waste repositories, plasma-enhanced chemical vapor deposition, plasma processing of materials for microelectronic devices andmore » other applications, and novel light sources for research purposes (e.g. excimer lamps in the extreme ultraviolet) and in everyday lighting applications. The life sciences are a rapidly advancing field where the important role of electron-driven processes is only now beginning to be recognized. Many of the applications of electron-initiated chemical processes require results in the near term. A large-scale, multidisciplinary and collaborative effort should be mounted to solve these problems in a timely way so that their solution will have the needed impact on the urgent questions of understanding the physico-chemical processes initiated and driven by electron interactions.« less

Adsorptive removal of Lead from water by the effective and reusable magnetic cellulose nanocomposite beads entrapping activated bentonite.

PubMed

Luo, Xiaogang; Lei, Xiaojuan; Xie, Xiuping; Yu, Bo; Cai, Ning; Yu, Faquan

2016-10-20

Many efforts have been driven to decontaminate the drinking water, and the development of efficient adsorbents with the advantages of cost-effectiveness and operating convenience for the removal of Pb(2+) from water is a major challenge. This work was aimed to explore the possibility of using cellulose-based adsorbents for efficient adsorption of Pb(2+). The millimeter-scale magnetic cellulose-based nanocomposite beads were fabricated via an optimal extrusion dropping technology by blending cellulose with the carboxyl-functionalized magnetite nanoparticles and acid-activated bentonite in NaOH/urea aqueous solution, and then they had been tested to evaluate the effectiveness in the removal of Pb(2+) from water. The effects of contact time, initial heavy metal ion concentrations, adsorption isotherms and solution pH on the sorption behavior were studied. The thermodynamic parameters (ΔG, ΔH and ΔS) indicated that the adsorption processes were feasible, spontaneous, endothermic and mainly controlled by chemical mechanisms. The reusability of the adsorbent was also studied. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evidence and implications of direct charge excitation as the dominant mechanism in plasmon-mediated photocatalysis

DOE PAGES

Boerigter, Calvin; Campana, Robert; Morabito, Matthew; ...

2016-01-28

Plasmonic metal nanoparticles enhance chemical reactions on their surface when illuminated with light of particular frequencies. It has been shown that these processes are driven by excitation of localized surface plasmon resonance (LSPR). The interaction of LSPR with adsorbate orbitals can lead to the injection of energized charge carriers into the adsorbate, which can result in chemical transformations. The mechanism of the charge injection process (and role of LSPR) is not well understood. Here we shed light on the specifics of this mechanism by coupling optical characterization methods, mainly wavelength-dependent Stokes and anti-Stokes SERS, with kinetic analysis of photocatalytic reactionsmore » in an Ag nanocube–methylene blue plasmonic system. We propose that localized LSPR-induced electric fields result in a direct charge transfer within the molecule–adsorbate system. Lastly, these observations provide a foundation for the development of plasmonic catalysts that can selectively activate targeted chemical bonds, since the mechanism allows for tuning plasmonic nanomaterials in such a way that illumination can selectively enhance desired chemical pathways.« less

Graphene-diamond interface: Gap opening and electronic spin injection

NASA Astrophysics Data System (ADS)

Ma, Yandong; Dai, Ying; Guo, Meng; Huang, Baibiao

2012-06-01

Creating a finite band gap, injecting electronic spin, and finding a suitable substrate are the three important challenges for building graphene-based devices. Here, first-principles calculations are performed to investigate the electronic and magnetic properties of graphene adsorbed on the (111) surface of diamond, which is synthesized experimentally [Nature10.1038/nature09979 472, 74 (2011); J. Appl. Phys.10.1063/1.3627370 110, 044324 (2011); Nano Lett.10.1021/nl204545q 12, 1603 (2012); ACS Nano10.1021/nn204362p 6, 1018 (2012)]. Our results reveal that the graphene adsorbed on the diamond surface is a semiconductor with a finite gap depending on the adsorption arrangements due to the variation of on-site energy induced by the diamond surface, with the extra advantage of maintaining main characters of the linear band dispersion of graphene. More interestingly, different from typical graphene/semiconductor hybrid systems, we find that electronic spin can arise ``intrinsically'' in graphene owing to the exchange proximity interaction between electrons in graphene and localized electrons in the diamond surface rather than the characteristic graphene states. These predications strongly revive this new synthesized system as a viable candidate to overcome all the aforementioned challenges, providing an ideal platform for future graphene-based electronics.

Nanotransition Materials (NTMs): Photocatalysis, Validated High Effective Sorbent Models Study for Organic Dye Degradation and Precise Mathematical Data’s at Standardized Level

PubMed Central

Khan, Farheen; Wahab, Rizwan; Hagar, Mohamed; Alnoman, Rua; Lutfullah; Rashid, Mohd

2018-01-01

The present work describes the synthesis of copper oxide nanoparticles (CuONPs) via a solution process with the aim of applying the nano-adsorbent for the reduction of methylene blue (MB) dye in alkaline media. These NPs were characterized via Field emission scanning electron microscopy (FE-SEM), X-ray diffraction, high-resolution Transmission electron microscopy (TEM), and ultra violet UV-visible spectroscopy to confirm their morphology and crystalline and optical properties in order to design an adsorption-degradation process. The photocatalytic CuONPs exhibited dynamic properties, great adsorption affinity during the chemisorption process, and operated at various modes with a strong interaction between the adsorbent and the adsorptive species, and equilibrium isotherm, kinetic isotherm, and thermodynamic activities in the presence of UV light. All basic quantities, such as concentration, pH, adsorbent dose, time, and temperature, were determined by an optimization process. The best-fitted adsorption Langmuir model (R2 = 0.9988) and performance, including adsorption capacity (350.87 mg/g), photocatalytic efficiency (90.74%), and degradation rate constant (Ks = 2.23 ×10−2 min−1), illustrate good feasibility with respect to sorption-reduction reactions but followed a pseudo-second-order kinetic on the adsorbent surface, reaching an equilibrium point in 80 min. The thermodynamic analysis suggests that the adsorption reaction is spontaneous and endothermic in nature. The thermodynamic parameters such as enthalpy (∆H°), entropy (∆S°), and Gibbs free energy (∆G°) give effective results to support a chemical reduction reaction at 303 K temperature. The equilibrium isotherm and kinetic and thermodynamic models with error function analysis explore the potential, acceptability, accuracy, access to adsorbents, and novelty of an unrivaled-sorption system. PMID:29495511

Development of a new adsorbent from agro-industrial waste and its potential use in endocrine disruptor compound removal.

PubMed

Rovani, Suzimara; Censi, Monique T; Pedrotti, Sidnei L; Lima, Eder C; Cataluña, Renato; Fernandes, Andreia N

2014-04-30

A new activated carbon (AC) material was prepared by pyrolysis of a mixture of coffee grounds, eucalyptus sawdust, calcium hydroxide and soybean oil at 800°C. This material was used as adsorbent for the removal of the endocrine disruptor compounds 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solutions. The carbon material was characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR), N2 adsorption/desorption curves and point of zero charge (pHPZC). Variables including the initial pH of the adsorbate solutions, adsorbent masses and contact time were optimized. The optimum range of initial pH for removal of endocrine disruptor compounds (EDC) was 2.0-11.0. The kinetics of adsorption were investigated using general order, pseudo first-order and pseudo-second order kinetic models. The Sips isotherm model gave the best fits of the equilibrium data (298K). The maximum amounts of E2 and EE2 removed at 298K were 7.584 (E2) and 7.883mgg(-1) (EE2) using the AC as adsorbent. The carbon adsorbent was employed in SPE (solid phase extraction) of E2 and EE2 from aqueous solutions. Copyright © 2014 Elsevier B.V. All rights reserved.

Paraquat adsorption on NaX and Al-MCM-41.

PubMed

Rongchapo, Wina; Deekamwong, Krittanun; Loiha, Sirinuch; Prayoonpokarach, Sanchai; Wittayakun, Jatuporn

2015-01-01

The aim of this work is to determine paraquat adsorption capacity of zeolite NaX and Al-MCM-41. All adsorbents were synthesized by hydrothermal method using rice husk silica. For Al-MCM-41, aluminum (Al) was added to the synthesis gel of MCM-41 with Al content of 10, 15, 20 and 25 wt%. The faujasite framework type of NaX and mesoporous characteristic of Al-MCM-41 were confirmed by X-ray diffraction. Surface area of all adsorbents determined by N2 adsorption-desorption analysis was higher than 650 m2/g. Al content and geometry were determined by X-ray fluorescence and 27Al nuclear magnetic resonance, respectively. Morphology of Al-MCM-41 were studied by transmission electron microscopy; macropores and defects were observed. The paraquat adsorption experiments were conducted using a concentration range of 80-720 mg/L for NaX and 80-560 mg/L for Al-MCM-41. The paraquat adsorption isotherms from all adsorbents fit well with the Langmuir model. The adsorption capacity of NaX was 120 mg/g-adsorbent. Regarding Al-MCM-41, the 10% Al-MCM-41 exhibited the lowest capacity of 52 mg/g-adsorbent while the other samples had adsorption capacity of 66 mg/g-adsorbent.

Thermoelectric transport properties of Ti doped/adsorbed monolayer blue phosphorene.

PubMed

Zhu, Lin; Li, Bowen; Yao, Kailun

2018-08-10

Thermoelectric transport properties of Ti doped or adsorbed monolayer blue phosphorene are investigated by density functional theory combined with the nonequilibrium Green's function formalism. The thermal giant magnetoresistance and a nearly 100% spin polarization which solely relies on the temperature gradient of electrodes without bias or gate voltage are observed. Moreover, the spin Seebeck effect is also found. Furthermore, taking into account the electronic and phonon dispersion, the thermoelectric merit for Ti doping in the monolayer blue phosphorene at room temperature is also studied, the maximum value of thermoelectric merit can reach 1.01 near the Fermi level. The results indicate that Ti doped or adsorbed monolayer blue phosphorene has potential application in both spintronics and spin caloritronics.

Effects of surface imperfections on the binding of CH 3OH and H 2O on FeS 2(100): using adsorbed Xe as a probe of mineral surface structure

NASA Astrophysics Data System (ADS)

Guevremont, J. M.; Strongin, D. R.; Schoonen, M. A. A.

1997-11-01

Studies are presented that investigate the adsorption and binding of CH 3OH and H 2O on the atomically clean (100) crystallographic plane of pyrite, FeS 2. Temperature programmed desorption suggests that both reactants adsorb molecularly at 90 K and desorb thermally between 170 and 400 K depending on the surface coverage. Photoemission of adsorbed xenon (PAX) suggests that the surface of pyrite is heterogeneous and contains a significant fraction of defect sites that are believed to be, at least in part, anion vacancy or sulfur-deficient sites. An upper limit of 0.2 is proposed for the fraction of surface sites that are defects on FeS 2(100). PAX indicates that these defect sites at low adsorbate coverage serve as the exclusive binding sites for H 2O and CH 3OH adsorbate. We speculate, on the basis of our ability to interpret PAX data for pyrite, that PAX may be of use for understanding the effect of short range order on adsorbate binding on other complex mineral surfaces. On the basis of high resolution electron energy loss spectroscopy, it is found that some dissociation of the adsorbate occurs on the pyrite. Vibrational data obtained with this technique suggests that FeO species result from the adsorbate decomposition. After saturation of the defect sites, further molecular adsorption is accommodated on the less reactive surface that we postulate is largely disulfide, the characteristic structural group of pyrite.

Phthalocyanine adsorption to graphene on Ir(111): Evidence for decoupling from vibrational spectroscopy

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

Endlich, M., E-mail: michael.endlich@tu-ilmenau.de; Gozdzik, S.; Néel, N.

2014-11-14

Phthalocyanine molecules have been adsorbed to Ir(111) and to graphene on Ir(111). From a comparison of scanning tunneling microscopy images of individual molecules adsorbed to the different surfaces alone it is difficult to discern potential differences in the molecular adsorption geometry. In contrast, vibrational spectroscopy using inelastic electron scattering unequivocally hints at strong molecule deformations on Ir(111) and at a planar adsorption geometry on graphene. The spectroscopic evidence for the different adsorption configurations is supported by density functional calculations.

Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

PubMed

Xiao, Jie; Dowben, Peter A

2009-02-04

In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

A study of vibrating nanotubes with additional adsorbed masses

NASA Astrophysics Data System (ADS)

Adler, Joan; Adler, Omri

2017-11-01

We describe calculations of the electronic density surrounding strained nanotubes. These are then used to estimate the nanotube wall width. This width is an essential parameter for the analysis of the nanotube vibrations. By studying the effect of additional adsorbed molecules on the nanotubes’ vibrations and their frequency changes we can deduce the molecules’ mass. Our calculations show that the strain does not greatly affect the nanotube width, but the vibrations change sufficiently for the mass to be detected.

Graphene symmetry-breaking with molecular adsorbates: modeling and experiment

NASA Astrophysics Data System (ADS)

Groce, M. A.; Hawkins, M. K.; Wang, Y. L.; Cullen, W. G.; Einstein, T. L.

2012-02-01

Graphene's structure and electronic properties provide a framework for understanding molecule-substrate interactions and developing techniques for band gap engineering. Controlled deposition of molecular adsorbates can create superlattices which break the degeneracy of graphene's two-atom unit cell, opening a band gap. We simulate scanning tunneling microscopy and spectroscopy measurements for a variety of organic molecule/graphene systems, including pyridine, trimesic acid, and isonicotinic acid, based on density functional theory calculations using VASP. We also compare our simulations to ultra-high vacuum STM and STS results.

Controlling the Electronic Structure of Graphene Using Surface-adsorbate Interactions

DTIC Science & Technology

2015-07-21

substrate via n doping, with or without intercalation, suggests that the graphene-to-substrate interaction could be controlled dynamically. DOI : 10.1103...which form a Dirac cone and are degenerate at the Fermi level [1]. These states change in response to atoms adsorbed on top of graphene (doping) or when...coupling to the substrate is strong. In the case of graphene on metals, the energy of the Dirac cone can change as a result of interfacial doping, or

Controlling the Electronic Structure of Graphene Using Surface-Adsorbate Interactions

DTIC Science & Technology

2015-07-21

after adsorption of Na the propensity of graphene bonding to Ni is much lower due to reduced overlap of atomic orbitals, which results from n- doping of...subse- quent intercalation of the Na underneath graphene. The ability to partially decouple graphene from a Ni substrate via n- doping (with or without...interactions with the substrate or adsorbates, which can modify the energy of the Dirac cone through doping , or cause a band gap to open at the K

Magnetic graphene coated inorganic-organic hybrid nanocomposite for enhanced preconcentration of selected pesticides in tomato and grape.

PubMed

Rashidi Nodeh, Hamid; Sereshti, Hassan; Gaikani, Hamid; Kamboh, Muhammad Afzal; Afsharsaveh, Zahra

2017-08-04

The new magnetic graphene based hybrid silica-N-[3-(trimethoxysilyl)propyl]ethylenediamine (MG@SiO 2 -TMSPED) nanocomposite was synthesized via sol-gel process, and used as an effective adsorbent in magnetic solid phase extraction (MSPE) of three selected pesticides followed by gas chromatography micro-electron capture detection (GC-μECD). The adsorbent was characterized using Fourier transform-infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDXS) techniques. The analytical validity of the developed method was evaluated under optimized conditions and the following figures of merit were obtained: linearity, 1-20μgkg -1 with good determination coefficients (R 2 =0.995-0.999); limits of detection (LODs), 0.23-0.30μgkg -1 (3×SD/m, n=3); and limits of quantitation (LOQ), 0.76-1.0μgkg -1 (10×SD/m, n=3). The precision (RSD%) of the proposed MSPE method was studied based on intra-day (3.43-8.83%, n=3) and inter-day (6.68-8.37%, n=12) precisions. Finally, the adsorbent was applied to determination of pesticides in tomato and grape samples and good recoveries were obtained in the range from 82 to 113% (RSDs 5.1-8.1%, n=3). Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

NASA Astrophysics Data System (ADS)

Maurer, Reinhard J.; Ruiz, Victor G.; Camarillo-Cisneros, Javier; Liu, Wei; Ferri, Nicola; Reuter, Karsten; Tkatchenko, Alexandre

2016-05-01

Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdWsurf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdWsurf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

Thermodynamics of adsorption of dithiocarbamates at the hanging mercury drop.

PubMed

Giannakopoulos, Evangelos; Deligiannakis, Yiannis

2007-02-27

Two dimethyldithiocarbamate (DMDTC) pesticides, thiram and ziram, are adsorbed onto a Hg drop via an entropically driven process. The adsorption isotherms are described by the Frumkin equation. For both molecules, the adsorption is characterized by a nonlinear pseudosigmoid temperature dependence of the Gibbs free energy. For the temperature range of 273-313 K, DeltaGADS varies between -43.4 and -56.71 kJ/mol for thiram and -42.60 and -55.67 kJ/mol for ziram. This variation of DeltaGADS reveals that the adsorption strength is increased at higher temperatures. During the adsorption of either molecule, strong lateral interactions are developed between neighboring adsorbates, which are severely weakened as the temperature increases. A unified reaction scheme is suggested for both ziram and thiram that predicts the formation and adsorption of a surface complex, (DMDTC)2Hg. In the case of thiram, two DMDTC molecules are formed by the cleavage of the disulfide S-S bond near the Hg electrode. The thermodynamic and structural parameters reveal that there are two limiting thermodynamic regimes for the adsorbed (DMDTC)2Hg species that originate from two limiting adsorption conformations of the adsorbates on the Hg surface. A transition occurs between these two conformations at temperatures in the region of 285-295 K. This transition is accompanied by large entropic and enthalpic changes.

Graphene for amino acid biosensing: Theoretical study of the electronic transport

NASA Astrophysics Data System (ADS)

Rodríguez, S. J.; Makinistian, L.; Albanesi, E. A.

2017-10-01

The study of biosensors based on graphene has increased in the last years, the combination of excellent electrical properties and low noise makes graphene a material for next generation electronic devices. This work discusses the application of a graphene-based biosensor for the detection of amino acids histidine (His), alanine (Ala), aspartic acid (Asp), and tyrosine (Tyr). First, we present the results of modeling from first principles the adsorption of the four amino acids on a graphene sheet, we calculate adsorption energy, substrate-adsorbate distance, equilibrium geometrical configurations (upon relaxation) and densities of states (DOS) for each biomolecule adsorbed. Furthermore, in order to evaluate the effects of amino acid adsorption on the electronic transport of graphene, we modeled a device using first-principles calculations with a combination of Density Functional Theory (DFT) and Nonequilibrium Greens Functions (NEGF). We provide with a detailed discussion in terms of transmission, current-voltage curves, and charge transfer. We found evidence of differences in the electronic transport through the graphene sheet due to amino acid adsorption, reinforcing the possibility of graphene-based sensors for amino acid sequencing of proteins.

Binding energies of benzene on coinage metal surfaces: Equal stability on different metals

NASA Astrophysics Data System (ADS)

Maaß, Friedrich; Jiang, Yingda; Liu, Wei; Tkatchenko, Alexandre; Tegeder, Petra

2018-06-01

Interfaces between organic molecules and inorganic solids adapt a prominent role in fundamental science, catalysis, molecular sensors, and molecular electronics. The molecular adsorption geometry, which is dictated by the strength of lateral and vertical interactions, determines the electronic structure of the molecule/substrate system. In this study, we investigate the binding properties of benzene on the noble metal surfaces Au(111), Ag(111), and Cu(111), respectively, using temperature-programmed desorption and first-principles calculations that account for non-locality of both electronic exchange and correlation effects. In the monolayer regime, we observed for all three systems a decrease of the binding energy with increasing coverage due to repulsive adsorbate/adsorbate interactions. Although the electronic properties of the noble metal surfaces are rather different, the binding strength of benzene on these surfaces is equal within the experimental error (accuracy of 0.05 eV), in excellent agreement with our calculations. This points toward the existence of a universal trend for the binding energy of aromatic molecules resulting from a subtle balance between Pauli repulsion and many-body van der Waals attraction.

Tuning electronic properties of graphene nanoflake polyaromatic hydrocarbon through molecular charge-transfer interactions

NASA Astrophysics Data System (ADS)

Sharma, Vaishali; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

2018-05-01

By means of first principles calculation we have tuned the electronic properties of graphene nanoflake polyaromatic hydrocarbon via molecular charge transfer. Acceptor/donor Tetracyanoquinodimethane (TCNQ) and Tetrathiafulvalene (TTF) organic molecules are adsorbed on polyaromatic hydrocarbons (PAH) in order to introduce the charge transfer. The substrate's n- or p- type nature depends on the accepting/donating behavior of dopant molecules. Two different classes of PAH (extended form of triangulene) namely Bow-tie graphene nanoflake (BTGNF) and triangular zigzag graphene nanoflake (TZGNF). It is revealed that all the TCNQ and TTF modified graphene nanoflakes exhibit significant changes in HOMO-LUMO gap in range from 0.58 eV to 0.64 eV and 0.01 eV to 0.05 eV respectively. The adsorption energies are in the range of -0.05 kcal/mol to -2.6 kcal/mol. The change in work function is also calculated and discussed, the maximum charge transfer is for TCNQ adsorbed BTGNF. These alluring findings in the tuning of electronic properties will be advantageous for promoting graphene nanoflake polyaromatic hydrocarbon for their applications in electronic devices.

Electronic and structural properties of vacancies and hydrogen adsorbates on trilayer graphene

NASA Astrophysics Data System (ADS)

Menezes, Marcos G.; Capaz, Rodrigo B.

2015-08-01

Using ab initio calculations, we study the electronic and structural properties of vacancies and hydrogen adsorbates on trilayer graphene. Those defects are found to share similar low-energy electronic features, since they both remove a pz electron from the honeycomb lattice and induce a defect level near the Fermi energy. However, a vacancy also leaves unpaired σ electrons on the lattice, which lead to important structural differences and also contribute to magnetism. We explore both ABA and ABC stackings and compare properties such as formation energies, magnetic moments, spin density and the local density of states (LDOS) of the defect levels. These properties show a strong sensitivity to the layer in which the defect is placed and smaller sensitivities to sublattice placing and stacking type. Finally, for the ABC trilayer, we also study how these states behave in the presence of an external field, which opens a tunable gap in the band structure of the non-defective system. The pz defect states show a strong hybridization with band states as the field increases, with reduction and eventually loss of magnetization, and a non-magnetic, midgap-like state is found when the defect is at the middle layer.

Electronic and Structural Properties of Vacancies and Hydrogen Adsorbates on Trilayer Graphene

NASA Astrophysics Data System (ADS)

Menezes, Marcos; Capaz, Rodrigo

2015-03-01

Using ab initio calculations, we study the electronic and structural properties of vacancies and hydrogen adsorbates on trilayer graphene. Those defects are found to share similar low-energy electronic features, since they both remove a pz electron from the honeycomb lattice and induce a defect level near the Fermi energy. However, a vacancy also leaves unpaired σ electrons on the lattice, which lead to important structural differences and also contribute to magnetism. We explore both ABA and ABC stackings and compare properties such as formation energies, magnetic moments, spin density and the local density of states (LDOS) of the defect levels. These properties show a strong sensitivity to the layer in which the defect is placed and smaller sensitivities to sublattice placing and stacking type. Finally, for the ABC trilayer, we also study how these states behave in the presence of an external electrical field, which opens a tunable gap in the band structure of the non-defective system. The pz defect states show a strong hybridization with band states as the field increases, with reduction and eventually loss of magnetization, and a non-magnetic, midgap-like state is found when the defect is at the middle layer.

Rational design of a molecularly imprinted polymer for dinotefuran: theoretical and experimental studies aimed at the development of an efficient adsorbent for microextraction by packed sorbent.

PubMed

Silva, Camilla Fonseca; Borges, Keyller Bastos; do Nascimento, Clebio Soares

2017-12-18

In this work, we studied theoretically the formation process of a molecularly imprinted polymer (MIP) for dinotefuran (DNF), testing distinct functional monomers (FM) in various solvents through density functional theory calculations. The results revealed that the best conditions for MIP synthesis were established with methacrylic acid (MAA) as FM in a 1 : 4 stoichiometry and with chloroform as the solvent. This protocol showed the most favourable stabilization energies for the pre-polymerization complexes. Furthermore, the formation of the FM/template complex is enthalpy driven and the occurrence of hydrogen bonds between the DNF and MAA plays a major role in the complex stability. To confirm the theoretical results, MIP was experimentally synthesized considering the best conditions found at the molecular level and characterized by scanning electron microscopy and thermogravimetric analysis. After that, the synthesized material was efficiently employed in microextraction by packed sorbent combined with high-performance liquid chromatography in a preliminary study of the recovery of DNF from water and artificial saliva samples.

Spectroscopic Studies of Abiotic and Biological Nanomaterials: Silver Nanoparticles, Rhodamine 6G Adsorbed on Graphene, and c-Type Cytochromes and Type IV Pili in Geobacter sulfurreducens

NASA Astrophysics Data System (ADS)

Thrall, Elizabeth S.

This thesis describes spectroscopic studies of three different systems: silver nanoparticles, the dye molecule rhodamine 6G adsorbed on graphene, and the type IV pili and c-type cytochromes produced by the dissimilatory metal-reducing bacterium Geobacter sulfurreducens. Although these systems are quite different in some ways, they can all be considered examples of nanomaterials. A nanomaterial is generally defined as having at least one dimension below 100 nm in size. Silver nanoparticles, with sub-100 nm size in all dimensions, are examples of zero-dimensional nanomaterials. Graphene, a single atomic layer of carbon atoms, is the paradigmatic two-dimensional nanomaterial. And although bacterial cells are on the order of 1 μm in size, the type IV pili and multiheme c-type cytochromes produced by G. sulfurreducens can be considered to be one- and zero-dimensional nanomaterials respectively. A further connection between these systems is their strong interaction with visible light, allowing us to study them using similar spectroscopic tools. The first chapter of this thesis describes research on the plasmon-mediated photochemistry of silver nanoparticles. Silver nanoparticles support coherent electron oscillations, known as localized surface plasmons, at resonance frequencies that depend on the particle size and shape and the local dielectric environment. Nanoparticle absorption and scattering cross-sections are maximized at surface plasmon resonance frequencies, and the electromagnetic field is amplified near the particle surface. Plasmonic effects can enhance the photochemistry of silver particles alone or in conjunction with semiconductors according to several mechanisms. We study the photooxidation of citrate by silver nanoparticles in a photoelectrochemical cell, focusing on the wavelength-dependence of the reaction rate and the role of the semiconductor substrate. We find that the citrate photooxidation rate does not track the plasmon resonance of the silver nanoparticles but instead rises monotonically with photon energy. These results are discussed in terms of plasmonic enhancement mechanisms and a theoretical model describing hot carrier photochemistry. The second chapter explores the electronic absorption and resonance Raman scattering of the dye molecule rhodamine 6G (R6G) adsorbed on graphene. Graphene has been shown to quench the fluorescence of adsorbed molecules and quantum dots, and some previous studies have reported that the Raman scattering from molecules adsorbed on graphene is enhanced. We show that reflective contrast spectroscopy can be used to obtain the electronic absorption spectrum of R6G adsorbed on graphene, allowing us to estimate the surface concentration of the dye molecule. From these results we are able to calculate the absolute Raman scattering cross-section for R6G adsorbed on bilayer graphene. We find that there is no evidence of enhancement but instead that the cross-section is reduced by more than three-fold from its value in solution. We further show that a model incorporating electromagnetic interference effects can reproduce the observed dependence of the R6G Raman intensity on the number of graphene layers. The third and final chapter describes the preliminary results from studies of the dissimilatory metal-reducing bacterium Geobacter sulfurreducens . This anaerobic bacterium couples the oxidation of organic carbon sources to the reduction of iron oxides and other extracellular electron acceptors, a type of anaerobic respiration that necessitates an electron transport chain that can move electrons from the interior of the cell to the extracellular environment. The electron transport chain in G. sulfurreducens has not been completely characterized and two competing mechanisms for the charge transport have been proposed. The first holds that G. sulfurreducens produces type IV pili, protein filaments several nanometers in width, with intrinsic metallic-like conductivity. According to this mechanism, the conductive pili mediate electron transport to extracellular acceptors. The second proposed mechanism is that charge transport proceeds by electron hopping between the heme groups in the many c-type cytochromes produced by G. sulfurreducens. In this picture, the observed conductivity of the pili is due to hopping through associated cytochrome proteins. Our aim is to explore these alternative mechanisms for electron transport in G. sulfurreducens through electrical and optical studies. We report the work we have done thus far to culture and characterize G. sulfurreducens , and we show that preliminary micro-Raman studies of G. sulfurreducens cells confirm that we can detect the spectroscopic signature of c-type cytochrome proteins. Future directions for this ongoing work are briefly discussed.

Separation of acid blue 25 from aqueous solution using water lettuce and agro-wastes by batch adsorption studies

NASA Astrophysics Data System (ADS)

Kooh, Muhammad Raziq Rahimi; Dahri, Muhammad Khairud; Lim, Linda B. L.; Lim, Lee Hoon; Chan, Chin Mei

2018-05-01

Three plant-based materials, namely water lettuce (WL), tarap peel (TP) and cempedak peel (CP), were used to investigate their potentials as adsorbents using acid blue 25 (AB25) dye as a model for acidic dye. The adsorbents were characterised using Fourier transform infrared spectroscopy, X-ray fluorescence and scanning electron microscope. Batch experiments involving parameters such as pH, temperature, contact time, and initial dye concentration were done to investigate the optimal conditions for the adsorption of AB25 onto the adsorbents. Thermodynamics study showed that the uptake of AB25 by the three adsorbents was feasible and endothermic in nature. Both the Langmuir and Freundlich isotherm models can be used to describe the adsorption process of AB25 onto WL and CP while pseudo-second-order fitted the kinetics data, suggesting that chemisorptions were majorly involved. The use of 0.1 M of NaOH showed the best results in regenerating of the WL, TP and CP's adsorption ability after AB25 treatment.

The oxygen-rich pentaerythritol modified multi-walled carbon nanotube as an efficient adsorbent for aqueous removal of alizarin yellow R and alizarin red S

NASA Astrophysics Data System (ADS)

Yang, Jia-Ying; Jiang, Xin-Yu; Jiao, Fei-Peng; Yu, Jin-Gang

2018-04-01

A contrastive work on the removal of two organic dyes, alizarin yellow R (AYR) and alizarin red S (ARS), was carried out by utilizing pentaerythritol modified multi-walled carbon nanotubes (ox-MWCNT-PER) as a highly efficient adsorbent. Various characterization methods such as scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, the Brunauer-Emmett-Teller (BET) analysis and X-ray photoelectron spectroscopy (XPS), were applied for revealing the physical and chemical properties of the as-prepared material. In addition, the adsorption kinetics, isotherms and thermodynamic parameters were also discussed. The results showed that the time required to achieve the adsorption equilibrium for both dyes was about 30 min, and the increase in temperature was not favorable to the adsorption process. It was worth noting that the adsorption capacity of ox-MWCNT-PER towards ARS dye was more significant than that towards AYR dye. And the maximum adsorption capacities for ARS and AYR were 257.73 mg g-1 and 45.39 mg g-1, respectively. The possible adsorption mechanism was also proposed, and the synergistic effects of the hydrogen bonding and the π-π electron stacking interactions between the adsorbents and adsorbates both contributed to the adsorption. It could be proposed that the ox-MWCNT-PER nanocomposite might have some positive effects in removing organic dyes from water treatment in the future.

A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

NASA Astrophysics Data System (ADS)

Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

2017-02-01

Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt4 (-2.11 eV) > Pd4 (-2.05 eV) > Ag4 (-1.53 eV) > Au4 (-1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

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

Ma, Hongwei; Shen, Jianfeng; Shi, Min

Graphical abstract: . The as-obtained ({alpha}-MnO{sub 2}) nanomaterials could act as an adsorbent to remove Conge red. More significantly, the nanomaterials are nontoxic and environmentally friendly though a biological MTT assay experiment. Plots of the capacity to remove Conge red with time by the commercial and new-prepared {alpha}-MnO{sub 2}. Inset shows absorption of Congo Red with time by new-prepared rod-clusters {alpha}-MnO{sub 2} (0, 10, 20, 40 and 60 min, respectively). Highlights: {yields} Nanostructured {alpha}-MnO{sub 2} was prepared through a template-free hydrothermal method. {yields} The obtained {alpha}-MnO{sub 2} could act as effective adsorbents to remove organic dyes. {yields} The obtained adsorbentsmore » are environmentally friendly. -- Abstract: In this paper, nanostructured MnO{sub 2} materials were successfully prepared through a simple and template-free hydrothermal method. X-ray diffraction pattern indicates that the as-prepared nanomaterials are {alpha}-MnO{sub 2}. Transmission Electron Microscopy and Scanning Electron Microscopy images demonstrate that nanostructured rod-clusters {alpha}-MnO{sub 2} could be evolved from the nanorods. Brunauer-Emmett-Teller (BET) surface area measurement was employed to characterize the surface property. Moreover, the as-obtained ({alpha}-MnO{sub 2}) nanomaterials could act as an efficient adsorbent to remove Congo Red and Methlylene Blue. More significantly, the nanomaterials are nontoxic and environmentally friendly via biological methylthiazolyldiphenyltetrazoliumbromide assay experiments. Its nontoxic and enhanced adsorbability properties guarantee their safe applications in environmental protection and industrial aspects.« less

Hydroquinone and Quinone-Grafted Porous Carbons for Highly Selective CO2 Capture from Flue Gases and Natural Gas Upgrading.

PubMed

Wang, Jun; Krishna, Rajamani; Yang, Jiangfeng; Deng, Shuguang

2015-08-04

Hydroquinone and quinone functional groups were grafted onto a hierarchical porous carbon framework via the Friedel-Crafts reaction to develop more efficient adsorbents for the selective capture and removal of carbon dioxide from flue gases and natural gas. The oxygen-doped porous carbons were characterized with scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. CO2, CH4, and N2 adsorption isotherms were measured and correlated with the Langmuir model. An ideal adsorbed solution theory (IAST) selectivity for the CO2/N2 separation of 26.5 (298 K, 1 atm) was obtained on the hydroquinone-grafted carbon, which is 58.7% higher than that of the pristine porous carbon, and a CO2/CH4 selectivity value of 4.6 (298 K, 1 atm) was obtained on the quinone-grafted carbon (OAC-2), which represents a 28.4% improvement over the pristine porous carbon. The highest CO2 adsorption capacity on the oxygen-doped carbon adsorbents is 3.46 mmol g(-1) at 298 K and 1 atm. In addition, transient breakthrough simulations for CO2/CH4/N2 mixture separation were conducted to demonstrate the good separation performance of the oxygen-doped carbons in fixed bed adsorbers. Combining excellent adsorption separation properties and low heats of adsorption, the oxygen-doped carbons developed in this work appear to be very promising for flue gas treatment and natural gas upgrading.

Selective removal of organochlorine pesticides (OCPs) from aqueous solution by triolein-embedded composite adsorbent.

PubMed

Ru, J; Liu, H J; Qu, J H; Wang, A M; Dai, R H; Wang, Z J

2007-01-01

A novel composite adsorbent (CA-T) was used for the selective removal of organochlorine pesticides (OCPs) from aqueous solution. The adsorbent was composed of the supporting activated carbon and the surrounding triolein-embedded cellulose acetate membrane. Scanning electron microscopy (SEM), N2 adsorption isotherms and fluorescence methods were used to characterize the physicochemical properties of CA-T. Triolein was perfectly embedded in the cellulose acetate membrane and deposited on the surface of activated carbon. The adsorbent was stable in water and no triolein leakage was detected during the test periods. Some organochlorine pesticides (OCPs), such as dieldrin, endrin, aldrin, and heptachlor epoxide, were used as model contaminants and removed by CA-T in laboratory batch experiments. The adsorption isotherm followed the Freundlich equation and the kinetic data fitted well to the pseudo-second-order reaction model. Results also indicated that CA-T appeared to be a promising adsorbent with good selectivity and satisfactory removal rate for lipophilic OCPs from aqueous solutions when present in trace amounts. The adsorption rate and removal efficiency for lipophilic OCPs were positively related to their octanol-water partition coefficients (log K(ow)). Lower residual concentrations of OCPs were achieved when compared to granular activated carbon (GAC).

Arsenic removal from water using a novel amorphous adsorbent developed from coal fly ash.

PubMed

Zhang, Kaihua; Zhang, Dongxue; Zhang, Kai

2016-01-01

A novel effective adsorbent of alumina/silica oxide hydrate (ASOH) for arsenic removal was developed through simple chemical reactions using coal fly ash. The iron-modified ASOH with enhancing adsorption activity was further developed from raw fly ash based on the in situ technique. The adsorbents were characterized by X-ray diffraction, Fourier transform infrared spectrometry, scanning electron micrograph, laser particle size and Brunauer-Emmet-Teller surface area. The results show that the adsorbents are in amorphous and porous structure, the surface areas of which are 8-12 times that of the raw ash. The acidic hydrothermal treatment acts an important role in the formation of the amorphous structure of ASOH rather than zeolite crystal. A series of adsorption experiments for arsenic on them were studied. ASOH can achieve a high removal efficiency for arsenic of 96.4% from water, which is more than 2.5 times that of the raw ash. Iron-modified ASOH can enhance the removal efficiency to reach 99.8% due to the in situ loading of iron (Fe). The condition of synthesis pH = 2-4 is better for iron-modified ASOH to adsorb arsenic from water.

Removal of Emulsified Oil from Water by Fruiting Bodies of Macro-Fungus (Auricularia polytricha)

PubMed Central

Yang, Xunan; Guo, Mengting; Wu, Yinghai; Wu, Qunhe; Zhang, Renduo

2014-01-01

The aim of this study was to investigate the feasibility of utilizing the fruiting bodies of a jelly macro-fungus Auricularia polytricha as adsorbents to remove emulsified oil from water. The effects of several factors, including temperature, initial pH, agitation speed, and adsorbent dosage, were taken into account. Results showed that the optimized conditions for adsorption of A. polytricha were a temperature of 35°C, pH of 7.5, and agitation speed of 100 rpm. The adsorption kinetics were characterized by the pseudo-first order model, which showed the adsorption to be a fast physical process. The Langmuir-Freundlich isotherm described the adsorption very well and predicted the maximum adsorption capacity of 398 mg g−1, under optimized conditions. As illustrated by scanning electron micrographs, the oil particles were adsorbed onto the hairs covering the bottom surface and could be desorbed by normal temperature volatilization. The material could be used as an emulsified oil adsorbent at least three times, retaining more than 95% of the maximum adsorption capacity. The results demonstrated that the fruiting bodies of A. polytricha can be a useful adsorbent to remove emulsified oil from water. PMID:24743498

Watching adsorption and electron beam induced decomposition on the model system Mo(CO)6/Cu(1 1 1) by X-ray absorption and photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Paufert, Pierre; Fonda, Emiliano; Li, Zheshen; Domenichini, Bruno; Bourgeois, Sylvie

2013-11-01

An in-depth study of the first steps of electron beam assisted growth of Mo from molybdenum hexacarbonyl on Cu(1 1 1) has been carried out exploiting the complementarity of X-ray photoemission and X-ray absorption spectroscopies. Frank van der Merwe (2D) growth mode has been observed for the completion of the two first monolayers of adsorbed molecules through a simple physisorption process. Irradiation of the Mo(CO)6 deposit by 1 keV electron beam induces a modification of molybdenum coordination, the average number of C-neighbors decreasing from 6 to 3. Decomposed molecules remain on the surface after annealing at 520 K and organize themselves, the molybdenum atoms moving in Cu(1 1 1) surface fcc hollow sites. After annealing at 670 K, metallic molybdenum growth begins, if the total amount of adsorbed Mo atoms exceeds 1.2 monolayers.

Surface Reactivity Enhancement on a Pd/Bi2Te3 Heterostructure through Robust Topological Surface States

PubMed Central

He, Qing Lin; Lai, Ying Hoi; Lu, Yao; Law, Kam Tuen; Sou, Iam Keong

2013-01-01

We present a study of the surface reactivity of a Pd/Bi2Te3 thin film heterostructure. The topological surface states from Bi2Te3, being delocalized and robust owing to their topological natures, were found to act as an effective electron bath that significantly enhances the surface reactivity of palladium in the presence of two oxidizing agents, oxygen and tellurium respectively, which is consistent with a theoretical calculation. The surface reactivity of the adsorbed tellurium on this heterostructure is also intensified possibly benefitted from the effective transfer of the bath electrons. A partially inserted iron ferromagnetic layer at the interface of this heterostructure was found to play two competing roles arising from the higher-lying d-band center of the Pd/Fe bilayer and the interaction between the ferromagnetism and the surface spin texture of Bi2Te3 on the surface reactivity and their characteristics also demonstrate that the electron bath effect is long-lasting against accumulated thickness of adsorbates. PMID:23970163

Molecular dynamics study of the adsorption of anionic surfactant in a nonionic polymer brush.

PubMed

Wang, Hua; Zhang, Heng; Yuan, Shiling; Liu, Chengbu; Xu, Zhen

2014-06-01

The adsorption of the anionic surfactant, sodium dodecylsulfate (SDS) in poly(ethylene oxide) (PEO) brush was studied by molecular dynamics simulations. Our simulations revealed that surfactant can adsorb in polymer brush as micellar aggregates and the polymer would reside at the hydrocarbon-water interface of SDS micelles. This association between surfactant and polymer was mainly driven by the hydrophobic interaction between the polymer and surfactant tails. In the simulation, with the increasing of surfactant concentration, a plateau value representing saturated adsorption was observed. The height of polymer brush was mainly affected by the adsorbed surfactant at low grafting density of polymer; however, it was primarily controlled by the grafting density at high grafting density. Our conclusions at the molecular level were in close agreement with experiment about the adsorption of surfactant in polymer brushes.

Label-free, real-time interaction and adsorption analysis 2: quartz crystal microbalance.

PubMed

Fee, Conan J

2013-01-01

In this chapter, a second biosensor technique is described: the quartz crystal microbalance (QCM). The quartz crystal microbalance is a physical technique that detects changes in the resonance frequency of an electrically driven quartz crystal with changes in mass. Unlike surface plasmon resonance (SPR), QCM is affected by both the water that may be associated with the adsorbed layer and by conformational changes in the adsorbed species, while SPR is insensitive to both effects. Thus QCM can both corroborate the findings of an SPR experiment and provide some complementary information. Also, the QCM surface is highly versatile and can range from plain quartz, through gold and other metal surfaces (e.g., titanium or stainless steel) to polymeric materials. Thus, the QCM technique has wide utility in tracking interactions with a variety of materials.

Light modulated electron beam driven radiofrequency emitter

DOEpatents

Wilson, M.T.; Tallerico, P.J.

1979-10-10

The disclosure relates to a light modulated electron beam-driven radiofrequency emitter. Pulses of light impinge on a photoemissive device which generates an electron beam having the pulse characteristics of the light. The electron beam is accelerated through a radiofrequency resonator which produces radiofrequency emission in accordance with the electron, hence, the light pulses.

Delayed electron emission in strong-field driven tunnelling from a metallic nanotip in the multi-electron regime

PubMed Central

Yanagisawa, Hirofumi; Schnepp, Sascha; Hafner, Christian; Hengsberger, Matthias; Kim, Dong Eon; Kling, Matthias F.; Landsman, Alexandra; Gallmann, Lukas; Osterwalder, Jürg

2016-01-01

Illuminating a nano-sized metallic tip with ultrashort laser pulses leads to the emission of electrons due to multiphoton excitations. As optical fields become stronger, tunnelling emission directly from the Fermi level becomes prevalent. This can generate coherent electron waves in vacuum leading to a variety of attosecond phenomena. Working at high emission currents where multi-electron effects are significant, we were able to characterize the transition from one regime to the other. Specifically, we found that the onset of laser-driven tunnelling emission is heralded by the appearance of a peculiar delayed emission channel. In this channel, the electrons emitted via laser-driven tunnelling emission are driven back into the metal, and some of the electrons reappear in the vacuum with some delay time after undergoing inelastic scattering and cascading processes inside the metal. Our understanding of these processes gives insights on attosecond tunnelling emission from solids and should prove useful in designing new types of pulsed electron sources. PMID:27786287

Phenol adsorption on surface-functionalized iron oxide nanoparticles: modeling of the kinetics, isotherm, and mechanism

NASA Astrophysics Data System (ADS)

Yoon, Soon Uk; Mahanty, Biswanath; Ha, Hun Moon; Kim, Chang Gyun

2016-06-01

Phenol adsorption from aqueous solution was carried out using uncoated and methyl acrylic acid (MAA)-coated iron oxide nanoparticles (NPs), having size <10 nm, as adsorbents. Batch adsorption studies revealed that the phenol removal efficiency of MAA-coated NPs (950 mg g-1) is significantly higher than that of uncoated NPs (550 mg g-1) under neutral to acidic conditions. However, this improvement disappears above pH 9. The adsorption data under optimized conditions (pH 7) were modeled with pseudo-first- and pseudo-second-order kinetics and subjected to Freundlich and Langmuir isotherms. The analysis determined that pseudo-second-order kinetics and the Freundlich model are appropriate for both uncoated and MAA-coated NPs (all R 2 > 0.98). X-ray photoelectron spectroscopy analysis of pristine and phenol-adsorbed NPs revealed core-level binding energy and charge for Fe(2 s) and O(1 s) on the NP surfaces. The calculations suggest that phenol adsorption onto MAA-coated NPs is a charge transfer process, where the adsorbate (phenol) acts as an electron donor and the NP surface (Fe, O) as an electron acceptor. However, a physisorption process appears to be the relevant mechanism for uncoated NPs.

Polyvinyl alcohol-based nanocomposite hydrogels containing magnetic laponite RD to remove cadmium.

PubMed

Mola Ali Abasiyan, Sara; Mahdavinia, Gholam Reza

2018-05-01

In this study, magnetic nanocomposite hydrogels based on polyvinyl alcohol were synthesized. Magnetic polyvinyl alcohol/laponite RD (PVA-mLap) nanocomposites were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. The results indicated that PVA-mLap had desirable magnetic-sorption properties and magnetic-laponite nanoparticles were successfully synthesized and added to polyvinyl alcohol. The present nanocomposites were applied to remove Cd 2+ from aqueous solution. The influence of initial Cd 2+ concentration, magnetic-laponite concentration, pH, and ionic strength on adsorption isotherm was investigated. Heterogeneity of adsorption sites was intensified by increasing magnetic concentration of adsorbents and by rising pH value. Results of ionic strength studies indicated that by increasing ionic strength more than four times, the adsorption of Cd 2+ has only decreased around 15%. According to the results, the dominant mechanism of Cd 2+ sorption by the present adsorbents was determined chemical and specific sorption. Therefore, the use of the present nanocomposites as a powerful adsorbent of Cd 2+ in the wastewater treatment is suggested. Isotherm data were described by using Freundlich and Langmuir models, and better fitting was introduced Langmuir model.

A spin transition mechanism for cooperative adsorption in metal-organic frameworks

NASA Astrophysics Data System (ADS)

Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

2017-10-01

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

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

Das, Sadananda; Brown, Suree S.; Mayes, Richard T.

A new series of amidoxime-based polymer adsorbents were synthesized at the Oak Ridge National Laboratory (ORNL) by electron beam induced grafting of acrylonitrile and itaconic acid onto polyethylene fiber. Hydroxylamine derivatives of poly(acrylonitrile) (PAN) moiety are demonstrated to possess two kinds of functional groups: open-chain amidoxime and cyclic imide dioxime. The open-chain amidoxime is shown to convert to imide dioxime on heat treatment in the presence of an aprotic solvent, like dimethylsulfoxide (DMSO). The formation of amidoxime and imide dioxime was confirmed by 13-C CPMAS spectra. The adsorbents were evaluated for uranium adsorption efficiency at ORNL with simulated seawater spikedmore » with 8 ppm uranium and 5 gallon seawater in a batch reactor, and in flow-through columns with natural seawater at the Marine Science Laboratory (MSL) of Pacific Northwest National Laboratory (PNNL) at Sequim Bay, WA. The DMSO-heat-treated sorbents adsorbed uranium as high as 4.48 g-U/kg-ads. from seawater. Experimental evidence is presented that the poly(imide dioxime) is primarily responsible for enhanced uranium adsorption capacity from natural seawater. The conjugated system in the imide dioxime ligand possesses increased electron donation ability, which is believed to significantly enhance the uranyl coordination in seawater« less

Ferrihydrite-associated organic matter (OM) stimulates reduction by Shewanella oneidensis MR-1 and a complex microbial consortia

NASA Astrophysics Data System (ADS)

Cooper, Rebecca Elizabeth; Eusterhues, Karin; Wegner, Carl-Eric; Totsche, Kai Uwe; Küsel, Kirsten

2017-11-01

The formation of Fe(III) oxides in natural environments occurs in the presence of natural organic matter (OM), resulting in the formation of OM-mineral complexes that form through adsorption or coprecipitation processes. Thus, microbial Fe(III) reduction in natural environments most often occurs in the presence of OM-mineral complexes rather than pure Fe(III) minerals. This study investigated to what extent does the content of adsorbed or coprecipitated OM on ferrihydrite influence the rate of Fe(III) reduction by Shewanella oneidensis MR-1, a model Fe(III)-reducing microorganism, in comparison to a microbial consortium extracted from the acidic, Fe-rich Schlöppnerbrunnen fen. We found that increased OM content led to increased rates of microbial Fe(III) reduction by S. oneidensis MR-1 in contrast to earlier findings with the model organism Geobacter bremensis. Ferrihydrite-OM coprecipitates were reduced slightly faster than ferrihydrites with adsorbed OM. Surprisingly, the complex microbial consortia stimulated by a mixture of electrons donors (lactate, acetate, and glucose) mimics S. oneidensis under the same experimental Fe(III)-reducing conditions suggesting similar mechanisms of electron transfer whether or not the OM is adsorbed or coprecipitated to the mineral surfaces. We also followed potential shifts of the microbial community during the incubation via 16S rRNA gene sequence analyses to determine variations due to the presence of adsorbed or coprecipitated OM-ferrihydrite complexes in contrast to pure ferrihydrite. Community profile analyses showed no enrichment of typical model Fe(III)-reducing bacteria, such as Shewanella or Geobacter sp., but an enrichment of fermenters (e.g., Enterobacteria) during pure ferrihydrite incubations which are known to use Fe(III) as an electron sink. Instead, OM-mineral complexes favored the enrichment of microbes including Desulfobacteria and Pelosinus sp., both of which can utilize lactate and acetate as an electron donor under Fe(III)-reducing conditions. In summary, this study shows that increasing concentrations of OM in OM-mineral complexes determines microbial Fe(III) reduction rates and shapes the microbial community structure involved in the reductive dissolution of ferrihydrite. Similarities observed between the complex Fe(III)-reducing microbial consortia and the model Fe(III)-reducer S. oneidensis MR-1 suggest electron-shuttling mechanisms dominate in OM-rich environments, including soils, sediments, and fens, where natural OM interacts with Fe(III) oxides during mineral formation.

Evidence for protein conformational change at a Au(110)/protein interface

NASA Astrophysics Data System (ADS)

Messiha, H. L.; Smith, C. I.; Scrutton, N. S.; Weightman, P.

2008-07-01

Evidence is presented that reflection anisotropy spectroscopy (RAS) can provide real-time measurements of conformational change in proteins induced by electron transfer reactions. A bacterial electron transferring flavoprotein (ETF) has been modified so as to adsorb on an Au(110) electrode and enable reversible electron transfer to the protein cofactor in the absence of mediators. Reversible changes are observed in the RAS of this protein that are interpreted as arising from conformational changes accompanying the transfer of electrons.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers

NASA Astrophysics Data System (ADS)

Del Rosso, T.; Rey, N. A.; Rosado, T.; Landi, S.; Larrude, D. G.; Romani, E. C.; Freire Junior, F. L.; Quinteiro, S. M.; Cremona, M.; Aucelio, R. Q.; Margheri, G.; Pandoli, O.

2016-06-01

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers.

PubMed

Del Rosso, T; Rey, N A; Rosado, T; Landi, S; Larrude, D G; Romani, E C; Junior, F L Freire; Quinteiro, S M; Cremona, M; Aucelio, R Q; Margheri, G; Pandoli, O

2016-06-24

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Carbon vacancy-induced enhancement of the visible light-driven photocatalytic oxidation of NO over g-C3N4 nanosheets

NASA Astrophysics Data System (ADS)

Li, Yuhan; Ho, Wingkei; Lv, Kangle; Zhu, Bicheng; Lee, Shun Cheng

2018-02-01

g-C3N4 (gCN) with carbon vacancy has been extensively investigated and applied in (photo)catalysis. Engineering the carbon vacancy in gCN is of great importance, but it remains a challenging task. In this work, we report for the first time the fabrication of gCN with carbon vacancy (Cv-gCN) via thermal treatment of pristine gCN in CO2 atmosphere. The photocatalytic performance of Cv-gCN is evaluated on the basis of NO oxidization under visible light irradiation (λ > 400 nm) in a continual reactor. The successful formation of carbon vacancy in gCN is confirmed through electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic oxidation removal rate of NO over Cv-gCN is 59.0%, which is two times higher than that over pristine gCN (24.2%). The results of the quenching experiment show that superoxide radicals (O2rad -) act as the main reactive oxygen species, which is responsible for the oxidation of NO. The enlarged BET surface areas and negatively shifted conduction band (CB) potential enhance the photocatalytic activity of Cv-gCN, which facilitates the efficient electron transfer from the CB of Cv-gCN to the surface adsorbed oxygen, resulting in the formation of O2rad - that can oxidize NO.

Consequences of plasma oxidation and vacuum annealing on the chemical properties and electron accumulation of In2O3 surfaces

NASA Astrophysics Data System (ADS)

Berthold, Theresa; Rombach, Julius; Stauden, Thomas; Polyakov, Vladimir; Cimalla, Volker; Krischok, Stefan; Bierwagen, Oliver; Himmerlich, Marcel

2016-12-01

The influence of oxygen plasma treatments on the surface chemistry and electronic properties of unintentionally doped and Mg-doped In2O3(111) films grown by plasma-assisted molecular beam epitaxy or metal-organic chemical vapor deposition is studied by photoelectron spectroscopy. We evaluate the impact of semiconductor processing technology relevant treatments by an inductively coupled oxygen plasma on the electronic surface properties. In order to determine the underlying reaction processes and chemical changes during film surface-oxygen plasma interaction and to identify reasons for the induced electron depletion, in situ characterization was performed implementing a dielectric barrier discharge oxygen plasma as well as vacuum annealing. The strong depletion of the initial surface electron accumulation layer is identified to be caused by adsorption of reactive oxygen species, which induce an electron transfer from the semiconductor to localized adsorbate states. The chemical modification is found to be restricted to the topmost surface and adsorbate layers. The change in band bending mainly depends on the amount of attached oxygen adatoms and the film bulk electron concentration as confirmed by calculations of the influence of surface state density on the electron concentration and band edge profile using coupled Schrödinger-Poisson calculations. During plasma oxidation, hydrocarbon surface impurities are effectively removed and surface defect states, attributed to oxygen vacancies, vanish. The recurring surface electron accumulation after subsequent vacuum annealing can be consequently explained by surface oxygen vacancies.

Regeneration of Waste Edible Oil by the Use of Virgin and Calcined Magnesium Hydroxide as Adsorbents.

PubMed

Ogata, Fumihiko; Kawasaki, Naohito

2016-01-01

In this study, we prepared virgin (S, L) and calcined (S-380, S-1000, L-380, L-1000) magnesium hydroxide for regeneration of waste edible oil. Deterioration of soybean oil, rapeseed oil, and olive oil was achieved by heat and aeration treatment. The properties of the different adsorbents were investigated using specific surface area measurements, scanning electron microscopy, X-ray diffraction analysis, thermogravimetric-differential thermal analysis, and surface pH measurement. Moreover, the relationship between the changes in acid value (AV) and carbonyl value (CV) and the adsorbent properties were evaluated. The specific surface areas of S-380 and L-380 were greater than that of other adsorbents. In addition, the XRD results show that S-380 and L-380 contain both magnesium hydroxide and magnesium oxide structures. The decreases in AV and CV using S-380 and L-380 were greater than achieved using other adsorbents. The correlation coefficients between the decrease in AV and CV and specific surface area were 0.947 for soybean oil, 0.649 for rapeseed oil, and 0.773 for olive oil, respectively. The results obtained in this study suggest that a physical property of the adsorbent, namely specific surface area, was primarily responsible for the observed decreases in AV and CV. Overall, the results suggest that S-380 and L-380 are useful for the regeneration of waste edible oil.

Preparation and Evaluation of Adsorbents from Coal and Irvingia gabonensis Seed Shell

NASA Astrophysics Data System (ADS)

Ezeokonkwo, Mercy A.; Ofor, Okechukwu F.; Ani, Julius U.

2017-12-01

The adsorption of Cd(II) and Pb(II) ions on adsorbents prepared from sub-bituminous coal, lignite and a blend of coal and Irvingia gabonensis seed shells was investigated. Fourier transform infrared, scanning electron microscope and X-ray fluorescence analyses implicated hydroxyl, carbonyl, Al2O3 and SiO2 as being responsible for binding the metal ions on the porous adsorbents. The optimum adsorption of carbonized lignite for the removal of Cd(II) and Pb(II) ions from aqueous media were 80.93% and 87.85%, respectively. Batch adsorption was done by effect of adsorbent dosage, pH, contact time, temperature, particle size, and initial concentration. Equilibrium for the removal of Pb(II) and Cd(II) was established within 100 and 120 min respectively. Blending the lignite-derived adsorbent with Irvingia gabonensis seed shell improved the performance significantly. More improvement was observed on modification of the blend using NaOH and H3PO4. Pb(II) was preferentially adsorbed than Cd(II) in all cases. Adsorption of Cd(II) and Pb(II) ions followed Langmuir isotherm. The kinetics of adsorption was best described by pseudo-second order model. The potential for using a blend of coal and agricultural byproduct (Irvingia gabonensis seed shell) was found to be a viable alternative for removal of toxic heavy metals from aqueous solutions.

Removal of uranium from aqueous solution by a low cost and high-efficient adsorbent

NASA Astrophysics Data System (ADS)

Liu, Yun-Hai; Wang, You-Qun; Zhang, Zhi-Bin; Cao, Xiao-Hong; Nie, Wen-Bin; Li, Qin; Hua, Rong

2013-05-01

In this study, a low-cost and high-efficient carbonaceous adsorbent (HTC-COOH) with carboxylic groups was developed for U(VI) removal from aqueous solution compared with the pristine hydrothermal carbon (HTC). The structure and chemical properties of resultant adsorbents were characterized by Scanning electron microscope (SEM), N2 adsorption-desorption, Fourier transform-infrared spectra (FT-IR) and acid-base titration. The key factors (solution pH, contact time, initial U(VI) concentrations and temperature) affected the adsorption of U(VI) on adsorbents were investigated using batch experiments. The adsorption of U(VI) on HTC and HTC-COOH was pH-dependent, and increased with temperature and initial ion concentration. The adsorption equilibrium of U(VI) on adsorbents was well defined by the Langmuir isothermal equation, and the monolayer adsorption capacity of HTC-COOH was found to be 205.8 mg/g. The kinetics of adsorption was very in accordance with the pseudo-second-order rate model. The adsorption processes of U(VI) on HTC and HTC-COOH were endothermic and spontaneous in nature according to the thermodynamics of adsorption. Furthermore, HTC-COOH could selectively adsorption of U(VI) in aqueous solution containing co-existing ions (Mg2+, Co2+, Ni2+, Zn2+ and Mn2+). From the results of the experiments, it is found that the HTC-COOH is a potential adsorbent for effective removal of U(VI) from polluted water.

Removal of heavy metals from artificial metals contaminated water samples based on micelle-templated silica modified with pyoverdin I.

PubMed

Tansupo, Panadda; Worakarn, Chamonkolpradit; Saksit, Chanthai; Ruangviriyachai, Chalerm

2009-01-01

The micelle-templated silica (MTS) was firstly chemically modified with 3-glycidoxypropyl-trimethoxysilane (GPTMS) before immobilized with pyoverdin I. The characteristics of pyoverdin I-anchored onto the modified MTS were investigated using fluorescence, infrared spectra and scanning electron microscopy. The specific surface area of all materials was calculated by Brunauer, Emmett and Teller (BET) method using nitrogen isotherm adsorption data. As the results, the surface area of commercial silica gel decreased from 609.2 to 405.4 m2/g, it indicated that the pyoverdin I could be immobilized onto the surface of silica solid support. This adsorbent was used for extraction of Fe(III), Cu(II), Zn(II), and Pb(II) in artificial metals contaminated water. Experimental conditions for effective adsorption of trace levels of metal ions were optimized with respect to different experimental parameters using batch procedure. The optimum pH value for the removal of metal ions simultaneously on this adsorbent was 4.0. Complete desorption of the adsorbed metal ions from the adsorbent was carried out using 0.25 mol/L of EDTA. The effect of different cations and anions on the adsorption of these metals on adsorbent was studied and the results showed that the proposed adsorbent could be applied to the highly saline samples and the sample which contains some transition metals.

Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS2.

PubMed

Zhou, Changjie; Yang, Weihuang; Zhu, Huili

2015-06-07

Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS2 upon adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO). The most stable configuration of the adsorbed molecules, the adsorption energy, and the degree of charge transfer between adsorbate and substrate were determined. All evaluated molecules were physisorbed on monolayer WS2 with a low degree of charge transfer and accept charge from the monolayer, except for NH3, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS2 are not significantly altered upon adsorption of H2, H2O, NH3, and CO, whereas the lowest unoccupied molecular orbitals of O2, NO, and NO2 are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS2. The phenomenon of Fermi-level pinning was discussed in light of the traditional and orbital mixing charge transfer theories. The impacts of the charge transfer mechanism on Fermi-level pinning were confirmed for the gas molecules adsorbed on monolayer WS2. The proposed mechanism governing Fermi-level pinning is applicable to the systems of adsorbates on recently developed two-dimensional materials, such as graphene and transition metal dichalcogenides.

Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters

NASA Astrophysics Data System (ADS)

Curotto, E.; Mella, M.

2018-03-01

We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D2(H2)n and HD(H2)n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D2 from the adsorbed clusters is always much higher than that of H2 from both pure and doped aggregates. Radial distributions of D2 and H2 are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H2, and at the periphery of the aggregate, H2 molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D2-(H2)n clusters with n ≥12 , such preference leads to the desorption of D2 from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H2)12. The same happens for (H2)13, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.

Regulation of electron temperature gradient turbulence by zonal flows driven by trapped electron modes

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

Asahi, Y., E-mail: y.asahi@nr.titech.ac.jp; Tsutsui, H.; Tsuji-Iio, S.

2014-05-15

Turbulent transport caused by electron temperature gradient (ETG) modes was investigated by means of gyrokinetic simulations. It was found that the ETG turbulence can be regulated by meso-scale zonal flows driven by trapped electron modes (TEMs), which are excited with much smaller growth rates than those of ETG modes. The zonal flows of which radial wavelengths are in between the ion and the electron banana widths are not shielded by trapped ions nor electrons, and hence they are effectively driven by the TEMs. It was also shown that an E × B shearing rate of the TEM-driven zonal flows is larger thanmore » or comparable to the growth rates of long-wavelength ETG modes and TEMs, which make a main contribution to the turbulent transport before excitation of the zonal flows.« less

Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

PubMed

Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

2005-01-01

The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer.

PubMed

Zhong, Hongying; Fu, Jieying; Wang, Xiaoli; Zheng, Shi

2012-06-04

Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355 nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO(2) nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry. Copyright © 2012 Elsevier B.V. All rights reserved.

Real-time investigation of protein unfolding at an air–water interface at the 1 s time scale

PubMed Central

Yano, Yohko F.; Arakawa, Etsuo; Voegeli, Wolfgang; Matsushita, Tadashi

2013-01-01

Protein unfolding at an air–water interface has been demonstrated such that the X-ray reflectivity can be measured with an acquisition time of 1 s using a recently developed simultaneous multiple-angle–wavelength-dispersive X-ray reflectometer. This has enabled the electron density profile of the adsorbed protein molecules to be obtained in real time. A globular protein, lysozyme, adsorbed at the air–water interface is found to unfold into a flat shape within 1 s. PMID:24121352

Influence of hydrogen oxidation kinetics on hydrogen environment embrittlement

NASA Technical Reports Server (NTRS)

Walter, R. J.; Kendig, M. W.; Meisels, A. P.

1992-01-01

Results are presented from experiments performed to determine the roles of hydrogen absorption and hydrogen electron transfer on the susceptibility of Fe- and Ni-base alloys to ambient-temperature hydroen embrittlement. An apparent independence is noted between hydrogen environment embrittlement and internal hydrogen embrittlement. The experiments were performed on Inconel 718, Incoloy 903, and A286. The electrochemical results obtained indicate that Inconel 718 either adsorbs hydrogen more rapidly and/or the electrochemical oxidation of the adsorbed hydrogen occurred more rapidly than in the other two materials.

Silica-gelatin hybrid sol-gel coatings: a proteomic study with biocompatibility implications.

PubMed

Araújo-Gomes, N; Romero-Gavilán, F; Lara-Sáez, I; Elortza, F; Azkargorta, M; Iloro, I; Martínez-Ibañez, M; Martín de Llano, J J; Gurruchaga, M; Goñi, I; Suay, J; Sánchez-Pérez, A M

2018-05-21

Osseointegration, including the foreign body reaction to biomaterials, is an immune-modulated, multifactorial, and complex healing process in which various cells and mediators are involved. The buildup of the osseointegration process is immunological and inflammation-driven, often triggered by the adsorption of proteins on the surfaces of the biomaterials and complement activation. New strategies for improving osseointegration use coatings as vehicles for osteogenic biomolecules delivery from implants. Natural polymers, such as gelatin, can mimic collagen I and enhance the biocompatibility of a material. In this experimental study, two different base sol-gel formulations and their combination with gelatin, were applied as coatings on sandblasted, acid-etched titanium (SAE-Ti) substrates and their biological potential as osteogenic biomaterials was tested. We examined the proteins adsorbed onto each surface and their in vitro and in vivo effects. In vitro results showed an improvement in cell proliferation and mineralization in gelatin-containing samples. In vivo testing showed the presence of a looser connective tissue layer in those coatings with substantially more complement activation proteins adsorbed, especially those containing gelatin. Vitronectin and FETUA, proteins associated with mineralization process, were significantly more adsorbed in gelatin coatings. This article is protected by copyright. All rights reserved.

Comparison of the adsorbed conformation of barley lipid transfer protein at the decane-water and vacuum-water interface: a molecular dynamics simulation.

PubMed

Euston, S R; Hughes, P; Naser, Md A; Westacott, R E

2008-05-01

Molecular dynamics simulation is used to model the adsorption of the barley lipid transfer protein (LTP) at the decane-water and vacuum-water interfaces. Adsorption at both surfaces is driven by displacement of water molecules from the interfacial region. LTP adsorbed at the decane surface exhibits significant changes in its tertiary structure, and penetrates a considerable distance into the decane phase. At the vacuum-water interface LTP shows small conformational changes away from its native structure and does not penetrate into the vacuum space. Modification of the conformational stability of LTP by reduction of its four disulphide bonds leads to an increase in conformational entropy of the molecules, which reduces the driving force for adsorption. Evidence for changes in the secondary structure are also observed for native LTP at the decane-water interface and reduced LTP at the vacuum-water interface. In particular, intermittent formation of short (six-residue) regions of beta-sheet is found in these two systems. Formation of interfacial beta-sheet in adsorbed proteins has been observed experimentally, notably in the globular milk protein beta-lactoglobulin and lysozyme.

Preferred Molecular Orientation of Coumarin 343 on TiO 2 Surfaces: Application to Dye-Sensitized Solar Cells

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

McCree-Grey, Jonathan; Cole, Jacqueline M.; Evans, Peter J.

2015-07-21

The dye…TiO2 interfacial structure in working electrodes of dye-sensitized solar cells (DSCs) is known to influence its photovoltaic device performance. Despite this, direct and quantitative reports of such structure remain sparse. This case study presents the application of X-ray reflectometry to determine the preferred structural orientation and molecular packing of the organic dye, coumarin 343, adsorbed onto amorphous TiO2. Results show that the dye molecules are, on average, tilted by 61.1° relative to the TiO2 surface, and are separated from each other by 8.2 Å. These findings emulate the molecular packing arrangement of a monolayer of coumarin 343 within itsmore » crystal structure. This suggests that the dye adsorbs onto TiO2 in one of its lowest energy configurations, i.e. dye…TiO2 self assembly is driven more by thermodynamic rather than kinetic means. Complementary DSC device tests illustrate that this interfacial structure compromises photovoltaic performance, unless a suitably sized co-adsorbant is interdispersed between the coumarin 343 chromophores on the TiO2 surface.« less

Removal of salicylic acid as an emerging contaminant by a polar nano-dendritic adsorbent from aqueous media.

PubMed

Arshadi, M; Mousavinia, F; Abdolmaleki, M K; Amiri, M J; Khalafi-Nezhad, A

2017-05-01

A polar nano-dendritic adsorbent containing amine groups (SAPAMAA) was synthesized onto the nanoparticles of SiO 2 Al 2 O 3 and its uptake of salicylic acid (SA) from the synthetic and real water was investigated. The synthesized nanomaterials were fully studied by nuclear magnetic resonance spectrum ( 1 H NMR and 13 C NMR), Fourier transform infrared spectroscopy (FT-IR), zeta potential (ζ), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) and elemental analysis. Various parameters such as the effect of the contact time, adsorbent dosage, initial SA concentrations, effect of solution's temperature, interfering ions, the hydrophobicity of the nanoadsorbent and initial pH were assessed. The contact time to approach equilibrium for higher adsorption was 15min (252.8mgg -1 ). The isotherms could be fitted by Sips model (with the average relative error of 6.6) and the kinetic data could be characterized by pseudo-second-order rate equation (with the average relative error of 13.0), implying chemical adsorption as the ratelimiting step of uptake process which was supported by the experimental data from the effect of interfering ions, zeta potential, and altering of the adsorbent's hydrophobicity. The uptake capacities decreased with temperature increasing, and showed that the uptake of SA was chemically exothermic in nature between 15 and 80°C. In addition, the spent SAPAMAA could be regenerated by the removal of adsorbed SA with NaOH and ethanol to regain the original SAPAMAA, the regenerated SAPAMAA also exhibited the high adsorption capacity after 10 runs. Moreover, SAPAMAA could also be applied to uptake SA from a real water (Anzali lagoon water). We envisage that the prepared nano-dendritic with remarkable characteristics such as environmentally friendly, low-cost, easy preparation in large quantity, high mechanical and chemical stability will play a significant role in developing a new generation of emerging contaminants adsorbent. Copyright © 2017 Elsevier Inc. All rights reserved.

Self-assembly properties of semiconducting donor-acceptor-donor bithienyl derivatives of tetrazine and thiadiazole-effect of the electron accepting central ring.

PubMed

Zapala, Joanna; Knor, Marek; Jaroch, Tomasz; Maranda-Niedbala, Agnieszka; Kurach, Ewa; Kotwica, Kamil; Nowakowski, Robert; Djurado, David; Pecaut, Jacques; Zagorska, Malgorzata; Pron, Adam

2013-11-26

Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates.

Modulating the magnetic behavior of Fe(II)-MOF-74 by the high electron affinity of the guest molecule.

PubMed

Han, Sungmin; Kim, Heejin; Kim, Jaehoon; Jung, Yousung

2015-07-14

As a new class of magnetic materials, metal-organic framework (MOF) has received a significant attention due to their functionality and porosity that can provide diverse magnetic phenomena by utilizing host-guest chemistry. For Fe-MOF-74, we here find using density functional calculations that the O2 and C2H4 adsorptions result in the ferromagnetic (FM) and antiferromagnetic (AFM) orderings along the 1D chain of an hexagonal MOF framework, respectively, while their adsorption energies, pi-complexation, and geometrical changes are all similar upon binding. We reveal that this different magnetism behavior is attributed to the different electronic effects, where the adsorbed O2 greatly withdraws a minor spin electron from the Fe centers. The latter significant back donation opens a new channel for superexchange interactions that can enhance the FM coupling between Fe centers, where the strength of calculated intrachain FM coupling constrant (Jin) in O2 adsorbed Fe-MOF-74 is more than 10 times enhanced compared to bare Fe-MOF-74. This prediction suggests a possibility for the conceptual usage of Fe-MOF-74 as a gas sensor based on its magnetic changes caused by the adsorbed gases. Furthermore, the suggested mechanism might be used to control the magnetic properties of MOFs using the guest molecules, although concrete strategies to enhance such magnetic interactions to be used in practical applications would require further significant investigation.

Tunable electronic and optical properties of gas molecules adsorbed monolayer graphitic ZnO: Implications for gas sensor and environment monitoring

NASA Astrophysics Data System (ADS)

Zhang, Wei; Du, Qikui; Zhang, Lifa

2017-12-01

Due to the large surface area and the peculiar electronic characters, great attention has been paid to 2D materials for the gas sensing applications. Here, using the hybrid density functional calculations, we systematically study the adsorptions of gas molecules on the monolayer graphitic ZnO (g-ZnO), including CO, H2, H2O, H2S, NH3, NO, NO2, O2, and SO2. For most of the molecules, g-ZnO shows superior sensing performance to the well-known MoS2, black phosphorus, blue phosphorus, antimonene, and germanene. H2S, NO, NO2, and SO2 act as charge acceptors, and CO, H2, H2O, and NH3 serve as charge donors. These molecules also induce distinct modifications to the electronic structures, work functions, and optical adsorptions. NO, NO2, and O2 form flat bands in the bandgaps of the spin-up or spin-down states, whereas other molecules mainly tune the bandgaps and the orbital couplings. In particular, g-ZnO is most likely to adsorb the atmospheric pollutant SO2, which has the strongest interaction through hybridizing its widely broadened 2p orbitals with the 3d orbitals of g-ZnO. Moreover, the improved visible light absorption is demonstrated in the NO2 adsorbed g-ZnO. Our results not only confirm that the electronic and optical properties of g-ZnO can be effectively tuned by the selective adsorption of gas molecules but also provide insightful guidance for the potential application of g-ZnO in the field of gas sensors.

Evaluation of magnetic- and carbon-based nano-adsorbents application in pre-purification of paclitaxel from needles of Taxus baccata

NASA Astrophysics Data System (ADS)

Naghavi, M. R.; Motamedi, E.; Nasiri, J.; Alizadeh, H.; Fattahi Moghadam, M. R.; Mashouf, A.

2015-01-01

In this investigation, the proficiency of a number of magnetic carbon-based nano-adsorbents is evaluated in pre-purification process of the crude paclitaxel extract obtained from fresh needles of yew tree ( Taxus baccata L.). The effectiveness and removal ability of color and impurities from crude extracts, for three novel candidate nano-adsorbents (i.e., Fe3O4 nanoparticles (Fe3O4Nps), graphite oxide (GO), and their hybrids Fe3O4Nps/GO) are compared with commercial graphite in three different solvents. In general, both HPLC and UV-Vis spectroscopy results demonstrate that in less polar solvent (i.e., dichloromethane), the adsorption is greatly affected by the electrostatic attractions, while in more polar solvents (i.e., acetone and ethanol) π-π electron interactions taking place between adsorbent and adsorbate are the most dominant factors in sorption. Considering decolorization efficiency, purity of taxol, recovery and reusability of adsorbents, Fe3O4Nps/GO (50 g/L) in dichloromethane is selected as the best medium for pre-purification of paclitaxel. Additionally, in kinetic studies the sorption equilibrium can be reached within 120 min, and the experimental data are well fitted by the pseudo-second-order model. The Langmuir sorption isotherm model correlates well with the sorption equilibrium data for the crude extract concentration (500-2,000 mg/L). Our findings display promising applications of Fe3O4Nps/GO, as a cost-effective nano-adsorbent, to provide a suitable vehicle toward improvement of paclitaxel pre-purification.

Preparation of a new adsorbent from activated carbon and carbon nanofiber (AC/CNF) for manufacturing organic-vacbpour respirator cartridge

PubMed Central

2013-01-01

In this study a composite of activated carbon and carbon nanofiber (AC/CNF) was prepared to improve the performance of activated carbon (AC) for adsorption of volatile organic compounds (VOCs) and its utilization for respirator cartridges. Activated carbon was impregnated with a nickel nitrate catalyst precursor and carbon nanofibers (CNF) were deposited directly on the AC surface using catalytic chemical vapor deposition. Deposited CNFs on catalyst particles in AC micropores, were activated by CO2 to recover the surface area and micropores. Surface and textural characterizations of the prepared composites were investigated using Brunauer, Emmett and Teller’s (BET) technique and electron microscopy respectively. Prepared composite adsorbent was tested for benzene, toluene and xylene (BTX) adsorption and then employed in an organic respirator cartridge in granular form. Adsorption studies were conducted by passing air samples through the adsorbents in a glass column at an adjustable flow rate. Finally, any adsorbed species not retained by the adsorbents in the column were trapped in a charcoal sorbent tube and analyzed by gas chromatography. CNFs with a very thin diameter of about 10-20 nm were formed uniformly on the AC/CNF. The breakthrough time for cartridges prepared with CO2 activated AC/CNF was 117 minutes which are significantly longer than for those cartridges prepared with walnut shell- based activated carbon with the same weight of adsorbents. This study showed that a granular form CO2 activated AC/CNF composite could be a very effective alternate adsorbent for respirator cartridges due to its larger adsorption capacities and lower weight. PMID:23369424

Comment on "Cosmic-ray-driven reaction and greenhouse effect of halogenated molecules: Culprits for atmospheric ozone depletion and global climate change"

NASA Astrophysics Data System (ADS)

Müller, Rolf; Grooß, Jens-Uwe

2014-04-01

Lu's "cosmic-ray-driven electron-induced reaction (CRE) theory" is based on the assumption that the CRE reaction of halogenated molecules (e.g., chlorofluorocarbons (CFCs), HCl, ClONO2) adsorbed or trapped in polar stratospheric clouds in the winter polar stratosphere is the key step in forming photoactive halogen species that are the cause of the springtime ozone hole. This theory has been extended to a warming theory of halogenated molecules for climate change. In this comment, we discuss the chemical and physical foundations of these theories and the conclusions derived from the theories. First, it is unclear whether the loss rates of halogenated molecules induced by dissociative electron attachment (DEA) observed in the laboratory can also be interpreted as atmospheric loss rates, but even if this were the case, the impact of DEA-induced reactions on polar chlorine activation and ozone loss in the stratosphere is limited. Second, we falsify several conclusions that are reported on the basis of the CRE theory: There is no polar ozone loss in darkness, there is no apparent 11-year periodicity in polar total ozone measurements, the age of air in the polar lower stratosphere is much older than 1-2 years, and the reported detection of a pronounced recovery (by about 20-25%) in Antarctic total ozone measurements by the year 2010 is in error. There are also conclusions about the future development of sea ice and global sea level which are fundamentally flawed because Archimedes' principle is neglected. Many elements of the CRE theory are based solely on correlations between certain datasets which are no substitute for providing physical and chemical mechanisms causing a particular behavior noticeable in observations. In summary, the CRE theory cannot be considered as an independent, alternative mechanism for polar stratospheric ozone loss and the conclusions on recent and future surface temperature and global sea level change do not have a physical basis.

Analysis of electron beam induced deposition (EBID) of residual hydrocarbons in electron microscopy

NASA Astrophysics Data System (ADS)

Rykaczewski, Konrad; White, William B.; Fedorov, Andrei G.

2007-03-01

In this work we have developed a comprehensive dynamic model of electron beam induced deposition (EBID) of residual hydrocarbon coupling mass transport, electron transport and scattering, and species decomposition to predict the deposition of carbon nanopillars. The simulations predict the local species and electron density distributions, as well as the three-demensional morphology and the growth rate of the deposit. Since the process occurs in a high vacuum environment, surface diffusion is considered as the primary transport mode of surface-adsorbed hydrocarbon precursor. The governing surface transport equation (STE) of the adsorbed species is derived and solved numerically. The transport, scattering, and absorption of primary electron as well as secondary electron generation are treated using the Monte Carlo method. Low energy secondary electrons are the major contributors to hydrocarbon decomposition due to their energy range matching peak dissociation reaction cross section energies for precursor molecules. The deposit and substrate are treated as a continuous entity allowing the simulation of the growth of a realistically sized deposit rather than a large number of cells representing each individual atom as in previously published simulations [Mitsuishi et al., Ultramicroscopy 103, 17 (2005); Silvis-Cividjian, Ph.D. thesis, University of Delft, 2002]. Such formulation allows for simple coupling of the STE with the dynamic growth of the nanopillar. Three different growth regimes occurring in EBID are identified using scaling analysis, and simulations are used to describe the deposit morphology and precursor surface concentration specific for each growth regime.

The effect of sputter temperature on vacancy island behavior on Ni(111) measured by photoemission of adsorbed xenon

NASA Astrophysics Data System (ADS)

Malafsky, Geoffrey P.

1994-04-01

The temperature dependence of vacancy coalescence on an ion bombarded Ni(111) surface is measured by photoemission of adsorbed xenon (PAX). The Ni(111) crystal is sputtered by a low fluence (0.06 ML incident ions) Ar + ion beam with incident kinetic energies of 500-3000 eV. The Xe coverage decreases rapidly with increasing temperature between 88 and 375 K with little additional change from 375 to 775 K. The PAX spectra are acquired with a Xe chamber pressure of 8 × 10 -10 Torr and at a temperature of 88 K. Under these conditions, the Xe is selectively adsorbed at defect sites which would make the Xe coverage proportional to the surface defect density on simple defect structures but the large size of the Xe atom relative to the Ni atom prevents the direct relationship of Xe coverage to the defect density when complex and varying defect structures are present. The decrease in Xe coverage is not attributed to the loss of defect sites by adatom-vacancy recombination but the changing vacancy island shape and size with temperature which alters the ratio of adsorbed Xe atoms to surface vacancy sites. This ratio decreases with increasing temperature as the vacancy islands progress from small and irregularly shaped islands to larger and hexagonally shaped islands. This transition is seen in Monte Carlo simulations of the kinetically driven atomic diffusion on the sputtered surface.

Enhanced removal of methylene blue and methyl violet dyes from aqueous solution using a nanocomposite of hydrolyzed polyacrylamide grafted xanthan gum and incorporated nanosilica.

PubMed

Ghorai, Soumitra; Sarkar, Asish; Raoufi, Mohammad; Panda, Asit Baran; Schönherr, Holger; Pal, Sagar

2014-04-09

The synthesis and characterization of a novel nanocomposite is reported that was developed as an efficient adsorbent for the removal of toxic methylene blue (MB) and methyl violet (MV) from aqueous solution. The nanocomposite comprises hydrolyzed polyacrylamide grafted onto xanthan gum as well as incorporated nanosilica. The synthesis exploits the saponification of the grafted polyacrylamide and the in situ formation of nanoscale SiO2 by a sol-gel reaction, in which the biopolymer matrix promotes the silica polymerization and therefore acts as a novel template for nanosilica formation. The detailed investigation of the kinetics and the adsorption isotherms of MB and MV from aqueous solution showed that the dyes adsorb rapidly, in accordance with a pseudo-second-order kinetics and a Langmuir adsorption isotherm. The entropy driven process was furthermore found to strongly depend on the point of zero charge (pzc) of the adsorbent. The remarkably high adsorption capacity of dyes on the nanocomposites (efficiency of MB removal, 99.4%; maximum specific removal Qmax, 497.5 mg g(-1); and efficiency of MV removal, 99.1%; Qmax, 378.8 mg g(-1)) is rationalized on the basis of H-bonding interactions as well as dipole-dipole and electrostatic interactions between anionic adsorbent and cationic dye molecules. Because of the excellent regeneration capacity the nanocomposites are considered interesting materials for the uptake of, for instance, toxic dyes from wastewater.

The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

DOE PAGES

An, Wei; Liu, Ping

2016-09-07

When using the TiO 2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd 7-3D/TiO 2(110) at low coverage to Pd 7-2D/TiO 2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO 2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O 2 dissociation and CO oxidation via bifunctional synergy.

The impact of adsorption on the localization of spins in graphene oxide and reduced graphene oxide, observed with electron paramagnetic resonance

NASA Astrophysics Data System (ADS)

Kempiński, Mateusz; Florczak, Patryk; Jurga, Stefan; Śliwińska-Bartkowiak, Małgorzata; Kempiński, Wojciech

2017-08-01

We report the observations of electronic properties of graphene oxide and reduced graphene oxide, performed with electron paramagnetic resonance technique in a broad temperature range. Both materials were examined in pure form and saturated with air, helium, and heavy water molecules. We show that spin localization strongly depends on the type and amount of molecules adsorbed at the graphene layer edges (and possible in-plane defects). Physical and chemical states of edges play crucial role in electrical transport within graphene-based materials, with hopping as the leading mechanism of charge carrier transport. Presented results are a good basis to understand the electronic properties of other carbon structures made of graphene-like building blocks. Most active carbons show some degree of functionalization and are known of having good adsorptive properties; thus, controlling both phenomena is important for many applications. Sample treatment with temperature, vacuum, and various adsorbents allowed for the observation of a possible metal-insulator transition and sorption pumping effects. The influence of adsorption on the localization phenomena in graphene would be very important if to consider the graphene-based material as possible candidates for the future spintronics that works in ambient conditions.

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Unraveling the charge transfer/electron transport in mesoporous semiconductive TiO2 films by voltabsorptometry.

PubMed

Renault, Christophe; Nicole, Lionel; Sanchez, Clément; Costentin, Cyrille; Balland, Véronique; Limoges, Benoît

2015-04-28

In this work, we demonstrate that chronoabsorptometry and more specifically cyclic voltabsorptometry are particularly well suited techniques for acquiring a comprehensive understanding of the dynamics of electron transfer/charge transport within a transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye. This is illustrated with the quantitative analysis of the spectroelectrochemical responses of two distinct heme-based redox probes adsorbed in highly-ordered mesoporous TiO2 thin films (prepared from evaporation-induced self-assembly, EISA). On the basis of a finite linear diffusion-reaction model as well as the establishment of the analytical expressions governing the limiting cases, it was possible to quantitatively analyse, predict and interpret the unusual voltabsorptometric responses of the adsorbed redox species as a function of the potential applied to the semiconductive film (i.e., as a function of the transition from an insulating to a conductive state or vice versa). In particular, we were able to accurately determine the interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor. Another important and unexpected finding, inferred from the voltabsorptograms, is an interfacial electron transfer process predominantly governed by the extended conduction band states of the EISA TiO2 film and not by the localized traps in the bandgap. This is a significant result that contrasts those previously observed for dye-sensitized solar cells formed of randomly sintered TiO2 nanoparticles, a behaviour that was ascribed to a particularly low density of localized surface states in EISA TiO2. The present methodology also provides a unique and straightforward access to an activation-driving force relationship according to the Marcus theory, thus opening new opportunities not only to investigate the driving-force effects on electron recombination dynamics in dye-sensitized solar cells but also to study the electron transfer/transport mechanisms in heterogeneous photoelectrocatalytic systems combining nanostructured semiconductor electrodes and heterogeneous redox-active catalysts.

Rethinking chemisorption: New insights into the factors controlling the binding energy

NASA Astrophysics Data System (ADS)

Alcantara Ortigoza, Marisol; Stolbov, Sergey

2015-03-01

Chemisorption of atomic and molecular species on a substrate induces electronic charge redistribution upon which substrate nuclei respond by adjusting their positions. This lattice distortion has been linked to the binding energy EB of the adsorbed species and attached to the so-called surface relaxation energy, Erx. We have found, however, that for transition metals the energy associated with the mere charge redistribution Eelec is much larger than Erx and thus both contributions must be considered [1]. In this work, we quantify the electronic and structural perturbation energy EP brought by various adsorbates on surfaces to understand anomalous adsorbate binding energies, i.e., those in which EP strongly influences the magnitude of EB. For example, for O adsorption on Au(111), while Erx is only 0.25 eV, the overall perturbation energy EP affecting EB(O) is ~ 1 eV [1]. This indicates that EP cannot be ignored but also that local bonds may not be as weak as portrayed by EB, even though EB is significantly reduced. We expose cases in which EP is really dominated by the lattice distortion energy, as well as a rationale for its trends as a function of the substrate and adsorbate. We discuss the implications of the fact that EB is not always predominately controlled by the bond-strength on heterogeneous catalysis, as well as the applications of the same fact. M. Alcántara Ortigoza and S. Stolbov; ``The Perturbation Energy: The missing key to understand gold `nobleness.' '' Submitted in October 2014 This work was supported the NSF under Grant CBET-1249134.

Mustard plant ash: a source of micronutrient and an adsorbent for removal of 2,4-dichlorophenoxyacetic acid.

PubMed

Trivedi, Nikhilesh S; Mandavgane, Sachin A; Kulkarni, Bhaskar D

2016-10-01

The work highlights the utilization of an agricultural waste mustard plant ash (MPA) as a soil additive and an adsorbent. MPA was characterized by X-ray fluorescence (XRF), energy-dispersive X-ray spectroscopy (EDX), proximate analysis, CHNS analysis, Brunauer-Emmett-Teller (BET) surface area analysis, zeta potential measurements, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRF analysis confirmed the presence of CaO (31.35 %), K 2 O (18.55 %), and P 2 O 5 (6.99 %), all of which act as micronutrients to plants. EDX also confirms high amount of elemental O, Ca, K, and P. The adsorptive ability of MPA was investigated using a commonly used herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), as a representative chemical. Batch adsorption experiments were conducted to study the effect of different operational parameters such as adsorbent dose, initial 2,4-D concentration, contact time, and temperature on the adsorption process. Data from experiments were fitted to various kinetic and isothermal models. The pseudo-second-order kinetic model was found to show the best fit (R 2  > 0.99), with the highest k 2 value of the order 10 5 . Based on the study results, dosage of MPA/hectare for different crops has been recommended for effective removal of 2,4-D. To our knowledge, this is the first study in which MPA has been characterized in detail and investigated for dual applications (as an adsorbent and as a soil additive).

The adsorption properties of titanium dioxide

NASA Astrophysics Data System (ADS)

Lanin, S. N.; Vlasenko, E. V.; Kovaleva, N. V.; Zung, Fam Tien

2008-12-01

The adsorption properties of titanium dioxide were studied by gas chromatography. We used organic compounds from different classes, namely, n-alkanes, n-alkenes (C6-C8), and polar compounds (electron donors and acceptors) as test adsorbates. The differential heats of adsorption and the contributions of dispersion and specific intermolecular interaction energies were determined for the systems from the experimental retention data. The electron-donor and electron-acceptor characteristics of the ultimately hydroxylated surface of TiO2 were evaluated.

Toluene and acetaldehyde removal from air on to graphene-based adsorbents with microsized pores.

PubMed

Kim, Ji Min; Kim, Ji Hoon; Lee, Chang Yeon; Jerng, Dong Wook; Ahn, Ho Seon

2018-02-15

Volatile organic compound (VOC) gases can cause harm to the human body with exposure over the long term even at very low concentrations (ppmv levels); thus, effective absorbents for VOC gas removal are an important issue. In this study, accordingly, graphene-based adsorbents with microsized pores were used as adsorbents to remove toluene and acetaldehyde gases at low concentrations (30ppm). Sufficient amounts of the adsorbents were prepared for use on filters and were loaded uniformly at 0.1-0.5g on a 50×50mm 2 area, to evaluate their adsorption features with low gas concentrations. The morphology and chemical composition of the adsorbents were characterized using scanning electron microscopy, N 2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and Raman spectroscopy. Microwave irradiation and heat treatment near 800°C under KOH activation resulted in enlargement of the pristine graphene surface and its specific surface area; maximum volume capacities of 3510m 3 /g and 630m 3 /g were observed for toluene and acetaldehyde gas. The high removal efficiency for toluene (98%) versus acetaldehyde (30%) gas was attributed to π-π interactions between the pristine graphene surface and toluene molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of banana peels waste as adsorbents for the removal of CO2, NO, NOx, and SO2 gases from motorcycle emissions

NASA Astrophysics Data System (ADS)

Viena, V.; Elvitriana; Wardani, S.

2018-03-01

The aims of the study were to investigate the application of banana peels as adsorbent for the removal of CO, NO, NOx and SO2 gases from motorcycles emissions. The effect of differents thermal activation on the characteristics of banana peels adsorbent (BPA) such as moisture content, ash content, volatile matter and fixed carbon has been studied using proximate analysis. The study of Iodine adsorption capacity of BPA was obtained at 952 mg/g adsorbent. Structure and morphology of BPA were characterized by Fourier transform infrared (FTIR) and field emission scanning electron microscopy (SEM). The results showed that BPA could significantly adsorbed the CO and SO2 gases emissions from motorcycles, but not applicable for NO, NOx gases. After 10 minutes of flue gas analysis at idle mode using BPA adsorption tube, CO gas could be totally removed, from initial 19618 ppm to 0 ppm, while SO2 gas could also be totally removed from 24523 ppm to 0 ppm. SEM test showed that temperature of activation had significant effect on the size of pores of BPA formed. BPA was suitable for application in removing CO and SO2 gases emissions from motorcycles and it helps to reduce the green house gas effects of fossil fuel to the environment.

Site-dependent atomic and molecular affinities of hydrocarbons, amines and thiols on diamond nanoparticles

NASA Astrophysics Data System (ADS)

Lai, Lin; Barnard, Amanda S.

2016-04-01

Like many of the useful nanomaterials being produced on the industrial scale, the surface of diamond nanoparticles includes a complicated mixture of various atomic and molecular adsorbates, attaching to the facets following synthesis. Some of these adsorbates may be functional, and adsorption is encouraged to promote applications in biotechnology and nanomedicine, but others are purely adventurous and must be removed prior to use. In order to devise more effective treatments it is advantageous to know the relative strength of the interactions of the adsorbates with the surface, and ideally how abundant they are likely to be under different conditions. In this paper we use a series of explicit electronic structure simulations to map the distribution of small hydrocarbons, amines and thiols on a 2.9 nm diamond nanoparticle, with atomic level resolution, in 3-D. We find a clear relationship between surface reconstructions, facet orientation, and the distribution of the different adsorbates; with a greater concentration expected on the (100) and (110) facets, particularly when the supersaturation in the reservoir is high. Adsorption on the (111) facets is highly unlikely, suggesting that controlled graphitization may be a useful stage in the cleaning and treatment of nanodiamonds, prior to the deliberate coating with functional adsorbates needed for drug delivery applications.

Structure and adsorption properties of a porous cooper hexacyanoferrate polymorph

NASA Astrophysics Data System (ADS)

Roque-Malherbe, R.; Carballo, E.; Polanco, R.; Lugo, F.; Lozano, C.

2015-11-01

The key questions addressed here were: the structure elucidation and the investigation of the adsorption space and framework expansion effect of a Cu(II) hexacyanoferrate (III) polymorph (labeled Cu-PBA-I). The structural analysis was performed with a broad set of characterization methods. Additionally, a low and high pressure carbon dioxide adsorption investigation was performed, assuming, to comprehend the adsorption experiments, that the adsorbent plus the adsorbed phase were a solid solution. We concluded: that the Cu-PBA-I presented the following composition, K1/4 Cu (II)[ Fe (III)(CN)6 ] 3 / 4⋄1/4 nH2 O , exhibited an antiferromagnetic behavior and displayed a thermally stable I 4 bar m 2 space group lattice in the degassed state. Moreover, the low pressure adsorption study allowed the calculation of the micropore volume, W=0.09 cm3/g and the isosteric heat of adsorption, qiso=19 kJ/mol; further, the high pressure adsorption data revealed an extremely high adsorption capacity owing to a framework expansion effect. Finally, the DRIFTS spectrum of adsorbed CO2 displayed peaks corresponding to carbon dioxide physically adsorbed and interacting with electron accepting Lewis acid sites. Hence, was produced an excellent adsorbent which combine porosity and anti-ferromagnetism, antagonist properties rarely found together.

Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca- and Fe-doped MgO(001) surface basic sites.

PubMed

Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

2012-08-02

The electronic properties of undoped and Ca- or Fe-doped MgO(001) surfaces, as well as their propensity toward atmospheric acidic gas (CO2, SO2, and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, O(surf), using periodic density functional theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the O(surf) sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe-doped MgO(001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca-doped MgO(001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces.

Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca and Fe doped MgO (001) surface basic sites

PubMed Central

Hatch, Courtney; Orlando, Roberto

2012-01-01

The electronic properties of undoped and Ca or Fe doped MgO (001) surfaces, as well as their propensity towards atmospheric acidic gas (CO2, SO2 and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, Osurf, using periodic Density Functional Theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the Osurf sites than the undoped MgO for a given adsorbate molecule. Charge transfer from the iron atom in Fe doped MgO (001) to NO2 was shown to increase the binding interaction between adsorbate by an order of magnitude, when compared to that of undoped and Ca doped MgO (001) surfaces. Secondary binding interactions of adsorbate oxygen atoms were observed with surface magnesium sites at distances close to those of the Mg-O bond within the crystal. These interactions may serve as a preliminary step for adsorption and facilitate further adsorbate transformations into other binding configurations. Impacts on global atmospheric chemistry are discussed as these adsorption phenomena can affect atmospheric gas budgets via altered partitioning and retention on mineral aerosol surfaces. PMID:22775293

A theoretical study on metal atom-modified BC3 sheets for effects of gas molecule adsorptions

NASA Astrophysics Data System (ADS)

Tang, Yanan; Cui, Xiao; Chen, Weiguang; Zhu, Dalei; Chai, Huaduo; Dai, Xianqi

2018-06-01

Based on the first-principle calculations, the chemical reactivity of transition metal (Fe, Co, Ni, and Cu) dopants within BC3 sheets toward toxic gas molecules (CO, NO, NO2, SO2, and HCN) is comparably investigated. First, the adsorbed gases on metal-modified BC3 sheets exhibit the different stability. Compared with other gases, the metal-modified BC3 substrates exhibit the stronger affinity toward the NO and NO2 molecules (> 1.0 eV), while the adsorbed HCN has the smallest adsorption energy, illustrating that the NO and NO2 as specific toxic gas molecule can be easily detected. Second, the adsorbed gas molecules can effectively regulate the electronic structure and magnetic property of BC3 systems. Fox example, the strong adsorption of NO and NO2 on Fe-modified BC3 systems exhibits non-magnetic property, yet these gases on Co modified BC3 systems exhibit the magnetic character. In addition, the adsorbed NO and SO2 can induce and turn the degree of magnetic moments of Ni- and Cu-modified BC3 systems. Therefore, the different kinds of adsorbed gases on metal-modified BC3 sheets can be distinguished through investigating the changed magnetic moments of system, which would provide important information for designing the functional BC3-based materials.

Magnetic dendritic materials for highly efficient adsorption of dyes and drugs.

PubMed

Zhou, Li; Gao, Chao; Xu, Weijian

2010-05-01

A versatile and robust adsorbent with both magnetic property and very high adsorption capacity is presented on the basis of functionalization of iron oxide-silica magnetic particles with carboxylic hyperbranched polyglycerol (Fe(3)O(4)/SiO(2)/HPG-COOH). The structure of the resulting product was confirmed by Fourier transform infrared (FTIR) spectra, thermo gravimetric analysis (TGA), zeta-potential, and transmission electron microscopy (TEM). According to the TGA results, the density of the carboxylic groups on the surface of Fe(3)O(4)/SiO(2)/HPG-COOH is calculated to be as high as 3.0 mmol/g, posing a powerful base for adsorbing dyes and drugs. Five kinds of dyes and one representative anticancer drug were chosen to investigate the adsorption capacity of the as-prepared magnetic adsorbent. The adsorbent shows highly efficient adsorption performance for all of the adsorbates especially for the cationic dyes and drug. For example, the saturated adsorption capacity of the Fe(3)O(4)/SiO(2)/HPG-COOH for methyl violet (MV) can reach 0.60 mmol/g, which is much higher than the previous magnetic adsorbents (usually lower than 0.30 mmol/g). 95% of MV and 90% of R6G could be adsorbed within 5 min, and both of the adsorptions reached equilibrium in about 15 min. The adsorption kinetics and isotherm of the adsorbents were investigated in detail and found that the kinetic and equilibrium adsorptions are well-modeled using pseudo-second-order kinetics and Langmuir isotherm model, respectively. In addition, the influences of pH and ionic strength on the adsorption capacity were also examined and found that pH has much greater effect on the adsorption capacity compared with the ionic strength. Regeneration experiments showed that the Fe(3)O(4)/SiO(2)/HPG-COOH can be well-regenerated in ethanol and partially regenerated in 1 M HCl aqueous solution. After regeneration, the magnetic adsorbents can still show high adsorption capacity even for 10 cycles of desorption-adsorption. No obvious decreases of magnetic intensity and aggregation of adsorbents can be observed even after 10 cycles of adsorption-desorption.

The effect of adsorbates on the electrical stability of graphene studied by transient photocurrent spectroscopy

NASA Astrophysics Data System (ADS)

Kalkan, S. B.; Aydın, H.; Özkendir, D.; ćelebi, C.

2018-01-01

Adsorbate induced variations in the electrical conductivity of graphene layers with two different types of charge carriers are investigated by using the Transient Photocurrent Spectroscopy (TPS) measurement technique. In-vacuum TPS measurements taken for a duration of 5 ks revealed that the adsorption/desorption of atmospheric adsorbates leads to more than a 110% increment and a 45% decrement in the conductivity of epitaxial graphene (n-type) and chemical vapor deposition graphene (p-type) layers on semi-insulating silicon carbide (SiC) substrates, respectively. The graphene layers on SiC are encapsulated and passivated with a thin SiO2 film grown by the Pulsed Electron Deposition method. The measurements conducted for short periods and a few cycles showed that the encapsulation process completely suppresses the time dependent conductivity instability of graphene independent of its charge carrier type. The obtained results are used to construct an experimental model for identifying adsorbate related conductivity variations in graphene and also in other 2D materials with an inherently high surface-to-volume ratio.

Removal of toxic zinc from water/wastewater using eucalyptus seeds activated carbon: non-linear regression analysis.

PubMed

Senthil Kumar, Ponnusamy; Saravanan, Anbalagan; Anish Kumar, Kodyingil; Yashwanth, Ramesh; Visvesh, Sridharan

2016-08-01

In the present study, a novel activated carbon was prepared from low-cost eucalyptus seeds, which was utilised for the effectively removal of toxic zinc from the water/wastewater. The prepared adsorbent was studied by Fourier transform infrared spectroscopy and scanning electron microscopic characterisation studies. Adsorption process was experimentally performed for optimising the influencing factors such as adsorbent dosage, solution pH, contact time, initial zinc concentration, and temperature for the maximum removal of zinc from aqueous solution. Adsorption isotherm of zinc removal was ensued Freundlich model, and the kinetic model ensued pseudo-second order model. Langmuir monolayer adsorption capacity of the adsorbent for zinc removal was evaluated as 80.37 mg/g. The results of the thermodynamic studies suggested that the adsorption process was exothermic, thermodynamically feasible and impulsive process. Finally, a batch adsorber was planned to remove zinc from known volume and known concentration of wastewater using best obeyed model such as Freundlich. The experimental details showed the newly prepared material can be effectively utilised as a cheap material for the adsorption of toxic metal ions from the contaminated water.

Orientation of N-benzoyl glycine on silver nanoparticles: SERS and DFT studies

NASA Astrophysics Data System (ADS)

Parameswari, A.; Asath, R. Mohamed; Premkumar, R.; Benial, A. Milton Franklin

2017-05-01

Surface enhanced Raman scattering (SERS) studies of N-benzoyl glycine (NBG) adsorbed on silver nanoparticles (AgNPs) was studied by experimental and density functional theory (DFT) approach. Single crystals of NBG were prepared using slow evaporation method. The AgNPs were prepared and characterized. The DFT/ B3PW91 method with LanL2DZ basis set was used to optimize the molecular structure of NBG and NBG adsorbed on silver cluster. The calculated and observed vibrational frequencies were assingned on the basis of potential energy distribution calculation. The reduced band gap value was obtained for NBG adsorbed on silver nanoparticles from the frontier molecular orbitals analysis. Natural bond orbital analysis was carried out to inspect the intra-molecular stabilization interactions, which are responsible for the bio activity and nonlinear optical property of the molecule. The spectral analysis was also evidenced that NBG would adsorb tilted orientation on the silver surface over the binding sites such as lone pair electron of N atom in amine group and through phenyl ring π system.

Treatment of Refinery Waste Water Using Environmental Friendly Adsorbent

NASA Astrophysics Data System (ADS)

Devi, M. Geetha; Al-Moshrafi, Samira Mohammed Khamis; Al Hudaifi, Alaa; Al Aisari, Buthaina Hamood

2017-12-01

This research evaluates the effectiveness of activated carbon prepared from walnut shell in the removal of pollutants from refinery waste water by adsorption technique. A series of batch experiments were carried out by varying the effluent solution pH, stirring time, stirring speed and adsorbent dosage in the reduction of pollutants from refinery effluent. Characterization of the adsorbent was performed using Scanning Electron Microscopy (SEM), Brunauer Emmett and Teller (BET) isotherm and Fourier Transform Infrared (FTIR) Spectroscopy. The best quality activated carbon was obtained with a particle size of 0.75 µm, activation temperature of 800 °C and activation time 24 h. The maximum BET surface area obtained was 165.2653 m2/g. The experimental results demonstrates that the highest percentage reduction in COD was 79%, using 0.6 g walnut shell powder at an optimum stirring speed of 100 rpm, at pH 6 and 120 min of contact time. The outcome of the result shows that walnut shell carbon is a potentially useful adsorbent for the removal of pollutants from refinery waste water.

Adsorption of Direct Blue 53 dye from aqueous solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Prola, Lizie D T; Machado, Fernando M; Bergmann, Carlos P; de Souza, Felipe E; Gally, Caline R; Lima, Eder C; Adebayo, Matthew A; Dias, Silvio L P; Calvete, Tatiana

2013-11-30

Multi-walled carbon nanotubes (MWCNT) and powder activated carbon (PAC) were used as adsorbents for adsorption of Direct Blue 53 dye (DB-53) from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, N2 adsorption/desorption isotherms, and scanning and transmission electron microscopy. The effects of initial pH, contact time and temperature on adsorption capacity of the adsorbents were investigated. At pH 2.0, optimum adsorption of the dye was achieved by both adsorbents. Equilibrium contact times of 3 and 4 h were achieved by MWCNT and PAC adsorbents, respectively. The general order kinetic model provided the best fit of the experimental data compared to pseudo-first order and pseudo-second order kinetic adsorption models. For DB-53 dye, the equilibrium data (298-323 K) were best fitted to the Sips isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, with the values of 409.4 and 135.2 mg g(-1) for MWCNT and PAC, respectively. Studies of adsorption/desorption were conducted and the results showed that DB-53 loaded MWCNT could be regenerated (97.85%) using a mixture 50% acetone + 50% of 3 mol L(-1) NaOH. Simulated dye house effluents were used to evaluate the application of the adsorbents for effluent treatment (removal of 99.87% and 97.00% for MWCNT and PAC, respectively, were recorded). Copyright © 2013 Elsevier Ltd. All rights reserved.

Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT).

PubMed

Maurer, Reinhard J; Reuter, Karsten

2013-07-07

Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion Δ-self-consistent field method by Gavnholt et al. [Phys. Rev. B 78, 075441 (2008)] presents an efficient alternative to time consuming quasi-particle calculations. In this method, the standard Kohn-Sham equations of density-functional theory are solved with the constraint of a non-equilibrium occupation in a region of Hilbert-space resembling gas-phase orbitals of the adsorbate. In this work, we discuss the applicability of this method for the excited-state dynamics of metal-surface mounted organic adsorbates, specifically in the context of molecular switching. We present necessary advancements to allow for a consistent quality description of excited-state potential-energy surfaces (PESs), and illustrate the concept with the application to Azobenzene adsorbed on Ag(111) and Au(111) surfaces. We find that the explicit inclusion of substrate electronic states modifies the topologies of intra-molecular excited-state PESs of the molecule due to image charge and hybridization effects. While the molecule in gas phase shows a clear energetic separation of resonances that induce isomerization and backreaction, the surface-adsorbed molecule does not. The concomitant possibly simultaneous induction of both processes would lead to a significantly reduced switching efficiency of such a mechanism.

Adsorption of organic chemicals in soils.

PubMed Central

Calvet, R

1989-01-01

This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

Configuration-specific electronic structure of strongly interacting interfaces: TiOPc on Cu(110)

NASA Astrophysics Data System (ADS)

Maughan, Bret; Zahl, Percy; Sutter, Peter; Monti, Oliver L. A.

2017-12-01

We use low-temperature scanning tunneling microscopy in combination with angle-resolved ultraviolet and two-photon photoemission spectroscopy to investigate the interfacial electronic structure of titanyl phthalocyanine (TiOPc) on Cu(110). We show that the presence of two unique molecular adsorption configurations is crucial for a molecular-level analysis of the hybridized interfacial electronic structure. Specifically, thermally induced self-assembly exposes marked adsorbate-configuration-specific contributions to the interfacial electronic structure. The results of this work demonstrate an avenue towards understanding and controlling interfacial electronic structure in chemisorbed films even for the case of complex film structure.

Vibrational dynamics of adsorbed molecules under conditions of photodesorption: pump-probe SFG spectra of CO/Pt(111).

PubMed

Fournier, Frédéric; Zheng, Wanquan; Carrez, Serge; Dubost, Henri; Bourguignon, Bernard

2004-09-08

Interaction of CO adsorbed on Pt(111) with electrons and phonons is studied experimentally by means of a pump-probe experiment where CO is probed by IR + visible sum frequency generation under a pump laser intensity that allows photodesorption. Vibrational spectra of CO internal stretch are obtained as a function of pump-probe delay. A two-temperature and anharmonic coupling model is used to extract from the spectra the real time variations of CO peak frequency and dephasing time. The main conclusions are the following: (i) The CO stretch is perturbed by two low-frequency modes, assigned to frustrated rotation and frustrated translation. (ii) The frustrated rotation is directly coupled to electrons photoexcited in Pt(111) by the pump laser. (iii) There is no evidence of Pt-CO stretch excitation in the spectra. The implications for the photodesorption dynamics are discussed. Copyright 2004 American Institute of Physics

Vibrational dynamics of adsorbed molecules under conditions of photodesorption: Pump-probe SFG spectra of CO/Pt(111)

NASA Astrophysics Data System (ADS)

Fournier, Frédéric; Zheng, Wanquan; Carrez, Serge; Dubost, Henri; Bourguignon, Bernard

2004-09-01

Interaction of CO adsorbed on Pt(111) with electrons and phonons is studied experimentally by means of a pump-probe experiment where CO is probed by IR+visible sum frequency generation under a pump laser intensity that allows photodesorption. Vibrational spectra of CO internal stretch are obtained as a function of pump-probe delay. A two-temperature and anharmonic coupling model is used to extract from the spectra the real time variations of CO peak frequency and dephasing time. The main conclusions are the following: (i) The CO stretch is perturbed by two low-frequency modes, assigned to frustrated rotation and frustrated translation. (ii) The frustrated rotation is directly coupled to electrons photoexcited in Pt(111) by the pump laser. (iii) There is no evidence of Pt-CO stretch excitation in the spectra. The implications for the photodesorption dynamics are discussed.

Study program to develop and evaluate die and container materials for the growth of silicon ribbons. [for development of low cost solar cells

NASA Technical Reports Server (NTRS)

Addington, L. A.; Ownby, P. D.; Yu, B. B.; Barsoum, M. W.; Romero, H. V.; Zealer, B. G.

1979-01-01

The development and evaluation of proprietary coatings of pure silicon carbide, silicon nitride, and aluminum nitride on less pure hot pressed substrates of the respective ceramic materials, is described. Silicon sessile drop experiments were performed on coated test specimens under controlled oxygen partial pressure. Prior to testing, X-ray diffraction and SEM characterization was performed. The reaction interfaces were characterized after testing with optical and scanning electron microscopy and Auger electron spectroscopy. Increasing the oxygen partial pressure was found to increase the molten silicon contact angle, apparently because adsorbed oxygen lowers the solid-vapor interfacial free energy. It was also found that adsorbed oxygen increased the degree of attack of molten silicon upon the chemical vapor deposited coatings. Cost projections show that reasonably priced, coated, molten silicon resistant refractory material shapes are obtainable.

Routine single particle CryoEM sample and grid characterization by tomography

PubMed Central

Noble, Alex J; Brasch, Julia; Chase, Jillian; Acharya, Priyamvada; Tan, Yong Zi; Zhang, Zhening; Kim, Laura Y; Scapin, Giovanna; Rapp, Micah; Eng, Edward T; Rice, William J; Cheng, Anchi; Negro, Carl J; Shapiro, Lawrence; Kwong, Peter D; Jeruzalmi, David; des Georges, Amedee; Potter, Clinton S

2018-01-01

Single particle cryo-electron microscopy (cryoEM) is often performed under the assumption that particles are not adsorbed to the air-water interfaces and in thin, vitreous ice. In this study, we performed fiducial-less tomography on over 50 different cryoEM grid/sample preparations to determine the particle distribution within the ice and the overall geometry of the ice in grid holes. Surprisingly, by studying particles in holes in 3D from over 1000 tomograms, we have determined that the vast majority of particles (approximately 90%) are adsorbed to an air-water interface. The implications of this observation are wide-ranging, with potential ramifications regarding protein denaturation, conformational change, and preferred orientation. We also show that fiducial-less cryo-electron tomography on single particle grids may be used to determine ice thickness, optimal single particle collection areas and strategies, particle heterogeneity, and de novo models for template picking and single particle alignment. PMID:29809143

Charge transfer at organic-inorganic interfaces—Indoline layers on semiconductor substrates

NASA Astrophysics Data System (ADS)

Meyenburg, I.; Falgenhauer, J.; Rosemann, N. W.; Chatterjee, S.; Schlettwein, D.; Heimbrodt, W.

2016-12-01

We studied the electron transfer from excitons in adsorbed indoline dye layers across the organic-inorganic interface. The hybrids consist of indoline derivatives on the one hand and different inorganic substrates (TiO2, ZnO, SiO2(0001), fused silica) on the other. We reveal the electron transfer times from excitons in dye layers to the organic-inorganic interface by analyzing the photoluminescence transients of the dye layers after femtosecond excitation and applying kinetic model calculations. A correlation between the transfer times and four parameters have been found: (i) the number of anchoring groups, (ii) the distance between the dye and the organic-inorganic interface, which was varied by the alkyl-chain lengths between the carboxylate anchoring group and the dye, (iii) the thickness of the adsorbed dye layer, and (iv) the level alignment between the excited dye ( π* -level) and the conduction band minimum of the inorganic semiconductor.

Adsorption and mineralization of REE-lanthanum onto bacterial cell surface.

PubMed

Cheng, Yangjian; Zhang, Li; Bian, Xiaojing; Zuo, Hongyang; Dong, Hailiang

2017-07-11

A large number of rare earth element mining and application resulted in a series of problems of soil and water pollution. Environmental remediation of these REE-contaminated sites has become a top priority. This paper explores the use of Bacillus licheniformis to adsorb lanthanum and subsequent mineralization process in contaminated water. The maximum adsorption capacity of lanthanum on bacteria was 113.98 mg/g (dry weight) biomass. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated that adsorbed lanthanum on bacterial cell surface occurred in an amorphous form at the initial stage. Scanning electron microscopy with X-ray energy-dispersive spectroscopy (SEM/EDS) results indicated that lanthanum adsorption was correlated with phosphate. The amorphous material was converted into scorpion-like monazite (LaPO 4 nanoparticles) in a month. The above results provide a method of using bacterial surface as adsorption and nucleation sites to treat REE-contaminated water.

Polycyclic Aromatic Hydrocarbons Adsorption onto Graphene: A DFT and AIMD Study.

PubMed

Li, Bing; Ou, Pengfei; Wei, Yulan; Zhang, Xu; Song, Jun

2018-05-03

Density functional theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations were performed to understand graphene and its interaction with polycyclic aromatic hydrocarbons (PAHs) molecules. The adsorption energy was predicted to increase with the number of aromatic rings in the adsorbates, and linearly correlate with the hydrophobicity of PAHs. Additionally, the analysis of the electronic properties showed that PAHs behave as mild n-dopants and introduce electrons into graphene; but do not remarkably modify the band gap of graphene, indicating that the interaction between PAHs and graphene is physisorption. We have also discovered highly sensitive strain dependence on the adsorption strength of PAHs onto graphene surface. The AIMD simulation indicated that a sensitive and fast adsorption process of PAHs can be achieved by choosing graphene as the adsorbent. These findings are anticipated to shed light on the future development of graphene-based materials with potential applications in the capture and removal of persistent aromatic pollutants.

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.

Separation of enantiomers by their enantiospecific interaction with achiral magnetic substrates.

PubMed

Banerjee-Ghosh, Koyel; Ben Dor, Oren; Tassinari, Francesco; Capua, Eyal; Yochelis, Shira; Capua, Amir; Yang, See-Hun; Parkin, Stuart S P; Sarkar, Soumyajit; Kronik, Leeor; Baczewski, Lech Tomasz; Naaman, Ron; Paltiel, Yossi

2018-06-22

It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Surface studies on scandate cathodes and synthesized scandates

NASA Technical Reports Server (NTRS)

Lesny, Gary; Forman, Ralph

1990-01-01

Auger, ESCA, electron emission, evaporation, and desorption measurements were made on three different types of scandate surfaces. They are: (1) an impregnated top layer scandate cathode, (2) an unimpregnated top layer scandate cathode with a deposited barium or barium oxide adsorbate surface layer, and (3) a synthesized scandate surface, which replicates a scandate cathode surface. The purpose of these experiments was to determine the role that Sc2O3 plays in making the scandate cathode a more copious electron emitter than the conventional impregnated-type cathode. The synthesized scandate surface experiments consisted of depositing multilayer scandium on a tungsten surface, oxidizing the scandium, and then depositing either Ba or BaO on the scandium oxide surface. The results of these measurements showed that the low work function portions of the thin-film scandate cathode are where the Sc2O3 is the substrate and BaO is the adsorbate.

Preparation and characterization of poly(AA co PVP)/PGS composite and its application for methylene blue adsorption.

PubMed

Yang, Cai-xia; Lei, Lei; Zhou, Peng-xin; Zhang, Zhe; Lei, Zi-qiang

2015-04-01

Poly (AA co PVP)/PGS (PAPP) composite adsorbent was prepared by radical polymerization from Acrylic acid (AA), Polyvinylpyrrolidone (PVP) and Palygorskite (PGS), using N,N-methylenebisacrylamide (MBA) as cross-linker and potassium persulfate (KPS) as initiator. The PAPP was characterized with Fourier transform infrared (FT-IR), thermogravimetric analysis (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). PAPP was used as adsorbent for the removal of methylene blue from aqueous solutions. The influences of pH, adsorption temperature and adsorption time on the adsorption properties of the composite to the dye were also investigated. Meanwhile, the adsorption rate data and adsorption equilibrium date were analyzed based on the pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models, respectively. The results indicating that the kinetic behavior better fit with the pseudo-second-order kinetic model. The maximum equilibrium adsorption capacity (q(m)) is 1815 mg/g at 289 K. The isotherm behavior can be explained by the Langmuir isotherm models. The activation energy was also evaluated for the removal of methylene blue onto PAPP. These results demonstrate that this composite material could be used as a good adsorbent for the removal of cationic dyes from wastewater. Copyright © 2014 Elsevier Inc. All rights reserved.

Adsorption of benzene on low index surfaces of platinum in the presence of van der Waals interactions

NASA Astrophysics Data System (ADS)

K, Ayishabi P.; Chatanathodi, Raghu

2017-10-01

We have studied the adsorption of benzene on three low index surfaces of platinum using plane-wave Density Functional Theory (DFT) calculations, taking into consideration van der Waals (vdW) interaction. Experimentally, it is known that benzene adsorbs at the bridge site on the (111) surface, but in case of (110) and (100), this is not known yet. Our calculations show that benzene preferably adsorbs on bridge position on Pt(111) surface, whereas on Pt(110) and Pt(100) surfaces, the hollow position is energetically more favoured. The structural and electronic modifications of molecule and the surfaces are also examined. In all cases, adsorption-induced distortions of adsorbate-substrate complex are found to be modest in character, but relatively maximum in case of the (110) facet. The molecule is bound most strongly to the (110) surface. Importantly, we find that adsorption at bridge and atop positions are energetically feasible on the (110) surface, with the canting of benzene ring at a small angle from the metal plane. We study changes in electronic structure and the net charge transfer upon adsorption of benzene on all three low index planes. Inclusion of vdW interactions is important for obtaining realistic adsorption strengths for benzene on various Pt facets.

Novel poly(imide dioxime) sorbents: Development and testing for enhanced extraction of uranium from natural seawater

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

Das, Sadananda; Brown, Suree; Mayes, Richard T.

2016-04-09

We synthesized a new series of amidoxime-based polymer adsorbents at the Oak Ridge National Laboratory (ORNL) by electron beam induced grafting of acrylonitrile and itaconic acid onto polyethylene fiber. We also demonstrate hydroxylamine derivatives of poly(acrylonitrile) (PAN) moiety to possess two kinds of functional groups: open-chain amidoxime and cyclic imide dioxime. The open-chain amidoxime is shown to convert to imide dioxime on heat treatment in the presence of an aprotic solvent, like dimethylsulfoxide (DMSO). Furthermore, the formation of amidoxime and imide dioxime was confirmed by 13C CP-MAS spectra. The adsorbents were evaluated for uranium adsorption efficiency at ORNL with simulatedmore » seawater spiked with 8 ppm uranium and 5 gallon seawater in a batch reactor, and in flow-through columns with natural seawater at the Marine Science Laboratory (MSL) of Pacific Northwest National Laboratory (PNNL) at Sequim Bay, WA. The DMSO-heat-treated sorbents adsorbed uranium as high as 4.48 g-U/kg-ads. from seawater. Experimental evidence is presented that the poly(imide dioxime) is primarily responsible for enhanced uranium adsorption capacity from natural seawater. The conjugated system in the imide dioxime ligand possesses increased electron donation ability, which is believed to significantly enhance the uranyl coordination in seawater.« less

MgO-based adsorbents for CO2 adsorption: Influence of structural and textural properties on the CO2 adsorption performance.

PubMed

Elvira, Gutiérrez-Bonilla; Francisco, Granados-Correa; Víctor, Sánchez-Mendieta; Alberto, Morales-Luckie Raúl

2017-07-01

A series of MgO-based adsorbents were prepared through solution-combustion synthesis and ball-milling process. The prepared MgO-based powders were characterized using X-ray diffraction, scanning electron microscopy, N 2 physisorption measurements, and employed as potential adsorbents for CO 2 adsorption. The influence of structural and textural properties of these adsorbents over the CO 2 adsorption behaviour was also investigated. The results showed that MgO-based products prepared by solution-combustion and ball-milling processes, were highly porous, fluffy, nanocrystalline structures in nature, which are unique physico-chemical properties that significantly contribute to enhance their CO 2 adsorption. It was found that the MgO synthesized by solution combustion process, using a molar ratio of urea to magnesium nitrate (2:1), and treated by ball-milling during 2.5hr (MgO-BM2.5h), exhibited the maximum CO 2 adsorption capacity of 1.611mmol/g at 25°C and 1atm, mainly via chemisorption. The CO 2 adsorption behaviour on the MgO-based adsorbents was correlated to their improved specific surface area, total pore volume, pore size distribution and crystallinity. The reusability of synthesized MgO-BM2.5h was confirmed by five consecutive CO 2 adsorption-desorption times, without any significant loss of performance, that supports the potential of MgO-based adsorbent. The results confirmed that the special features of MgO prepared by solution-combustion and treated by ball-milling during 2.5hr are favorable to be used as effective MgO-based adsorbent in post-combustion CO 2 capture technologies. Copyright © 2016. Published by Elsevier B.V.

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

Li, Jingcheng; Wang, Yu; Li, Bin, E-mail: libin@mail.ustc.edu.cn, E-mail: bwang@ustc.edu.cn

We investigate the modification of electronic properties of single cobalt phthalocyanine (CoPc) molecule by an extra Co atom co-adsorbed on Au (111) surface using scanning tunneling microscopy (STM), joint with density functional theory (DFT) calculations. By manipulating CoPc molecules using the STM tip to contact individually adsorbed Co atom, two types of relatively stable complexes can be formed, denoted as CoPc-Co(I) and CoPc-Co(II). In CoPc-Co(I), the Co atom is at an intramolecular site close to aza-N atom of CoPc, which induces significant modifications of the electronic states of CoPc, such as energy shifts and splitting of nonlocal molecular orbitals. However,more » in CoPc-Co(II) where the Co atom is underneath a benzene lobe of CoPc, it only slightly modifies the electronic states of CoPc, and mainly local characteristics of specific molecular orbitals are affected, even though CoPc-Co(II) is more stable than CoPc-Co(I). Our DFT calculations give consistent results with the experiments, and related analyses based on the molecular orbital theory reveal mechanism behind the experimental observations.« less

Electronic and magnetic properties of Fe-, Co-, and Ni-decorated BC3: A first-principles study

NASA Astrophysics Data System (ADS)

Zhu, Jingzhong; Zhao, Yinchang; Zulfiqar, Muhammad; Zeng, Shuming; Ni, Jun

2018-05-01

The electronic and magnetic properties of Fe-, Co-, and Ni-decorated two dimensional (2D) BC3 are systematically investigated by first-principles calculations. We find that the Fe, Co, and Ni atoms can be strongly adsorbed on the hollow sites of 2D BC3. Fe and Co adatoms are more stable when adsorbed on the hollow sites of the carbon rings in the 2D BC3, while the hollow sites of boron-carbon rings in the 2D BC3 are the most stable sites for the adsorption of Ni adatoms. These proposed metal-BC3 complexes exhibit interesting electronic and magnetic behaviors. In particular, the Fe-BC3 and Co-BC3 complexes are metals with magnetic ground states , while the Ni-BC3 complex behaves as a nonmagnetic semiconductor with a direct bandgap. Furthermore, our magnetic analysis reveals that induced magnetism in the Fe-BC3 and Co-BC3 complexes arises from their local magnetic moments. Functionalization of 2D BC3 through these metal-adatom adsorption appears to be a promising way to extend its applications.

Light-field-driven currents in graphene

NASA Astrophysics Data System (ADS)

Higuchi, Takuya; Heide, Christian; Ullmann, Konrad; Weber, Heiko B.; Hommelhoff, Peter

2017-10-01

The ability to steer electrons using the strong electromagnetic field of light has opened up the possibility of controlling electron dynamics on the sub-femtosecond (less than 10-15 seconds) timescale. In dielectrics and semiconductors, various light-field-driven effects have been explored, including high-harmonic generation, sub-optical-cycle interband population transfer and the non-perturbative change of the transient polarizability. In contrast, much less is known about light-field-driven electron dynamics in narrow-bandgap systems or in conductors, in which screening due to free carriers or light absorption hinders the application of strong optical fields. Graphene is a promising platform with which to achieve light-field-driven control of electrons in a conducting material, because of its broadband and ultrafast optical response, weak screening and high damage threshold. Here we show that a current induced in monolayer graphene by two-cycle laser pulses is sensitive to the electric-field waveform, that is, to the exact shape of the optical carrier field of the pulse, which is controlled by the carrier-envelope phase, with a precision on the attosecond (10-18 seconds) timescale. Such a current, dependent on the carrier-envelope phase, shows a striking reversal of the direction of the current as a function of the driving field amplitude at about two volts per nanometre. This reversal indicates a transition of light-matter interaction from the weak-field (photon-driven) regime to the strong-field (light-field-driven) regime, where the intraband dynamics influence interband transitions. We show that in this strong-field regime the electron dynamics are governed by sub-optical-cycle Landau-Zener-Stückelberg interference, composed of coherent repeated Landau-Zener transitions on the femtosecond timescale. Furthermore, the influence of this sub-optical-cycle interference can be controlled with the laser polarization state. These coherent electron dynamics in graphene take place on a hitherto unexplored timescale, faster than electron-electron scattering (tens of femtoseconds) and electron-phonon scattering (hundreds of femtoseconds). We expect these results to have direct ramifications for band-structure tomography and light-field-driven petahertz electronics.

Light-field-driven currents in graphene.

PubMed

Higuchi, Takuya; Heide, Christian; Ullmann, Konrad; Weber, Heiko B; Hommelhoff, Peter

2017-10-12

The ability to steer electrons using the strong electromagnetic field of light has opened up the possibility of controlling electron dynamics on the sub-femtosecond (less than 10 -15 seconds) timescale. In dielectrics and semiconductors, various light-field-driven effects have been explored, including high-harmonic generation, sub-optical-cycle interband population transfer and the non-perturbative change of the transient polarizability. In contrast, much less is known about light-field-driven electron dynamics in narrow-bandgap systems or in conductors, in which screening due to free carriers or light absorption hinders the application of strong optical fields. Graphene is a promising platform with which to achieve light-field-driven control of electrons in a conducting material, because of its broadband and ultrafast optical response, weak screening and high damage threshold. Here we show that a current induced in monolayer graphene by two-cycle laser pulses is sensitive to the electric-field waveform, that is, to the exact shape of the optical carrier field of the pulse, which is controlled by the carrier-envelope phase, with a precision on the attosecond (10 -18 seconds) timescale. Such a current, dependent on the carrier-envelope phase, shows a striking reversal of the direction of the current as a function of the driving field amplitude at about two volts per nanometre. This reversal indicates a transition of light-matter interaction from the weak-field (photon-driven) regime to the strong-field (light-field-driven) regime, where the intraband dynamics influence interband transitions. We show that in this strong-field regime the electron dynamics are governed by sub-optical-cycle Landau-Zener-Stückelberg interference, composed of coherent repeated Landau-Zener transitions on the femtosecond timescale. Furthermore, the influence of this sub-optical-cycle interference can be controlled with the laser polarization state. These coherent electron dynamics in graphene take place on a hitherto unexplored timescale, faster than electron-electron scattering (tens of femtoseconds) and electron-phonon scattering (hundreds of femtoseconds). We expect these results to have direct ramifications for band-structure tomography and light-field-driven petahertz electronics.

Electrostatic energy and screened charge interaction near the surface of metals with different Fermi surface shape

NASA Astrophysics Data System (ADS)

Gabovich, A. M.; Il'chenko, L. G.; Pashitskii, E. A.; Romanov, Yu. A.

1980-04-01

Using the Poisson equation Green function for a self-consistent field in a spatially inhomogeneous system, expressions for the electrostatic energy and screened charge interaction near the surface of a semi-infinite metal and a thin quantizing film are derived. It is shown that the decrease law and Friedel oscillation amplitude of adsorbed atom indirect interaction are determined by the electron spectrum character and the Fermi surface shape. The results obtained enable us to explain, in particular, the submonolayer adsorbed film structure on the W and Mo surfaces.

Photo-induced free radicals on a simulated Martian surface

NASA Technical Reports Server (NTRS)

Tseng, S.-S.; Chang, S.

1974-01-01

Results of an electron spin resonance study of free radicals in the ultraviolet irradiation of a simulated Martian surface suggest that the ultraviolet photolysis of CO or CO2, or a mixture of both, adsorbed on silica gel at minus 170 C involves the formation of OH radicals and possibly of H atoms as the primary process, followed by the formation of CO2H radicals. It is concluded that the photochemical synthesis of organic compounds could occur on Mars if the siliceous surface dust contains enough silanol groups and/or adsorbed H2O in the form of bound water.

Field emission energy distributions of hydrogen and deuterium on the /100/ and /110/ planes of tungsten.

NASA Technical Reports Server (NTRS)

Plummer, E. W.; Bell, A. E.

1972-01-01

Total energy distributions of field emitted electrons from the tungsten (110) and (100) planes as a function of coverage by hydrogen and deuterium have been recorded utilizing a spherical deflection energy analyzer. The elastic tunneling resonance spectrum gives a plot of the 'local density of states' in the adsorbate. The inelastic tunneling spectrum reveals those discrete excitation energies available in the adsorbate-substrate complex. These spectroscopic data have been used to infer the chemical nature of the binding states which have been observed in the flash desorption spectrum of hydrogen from tungsten.

Phantom force induced by tunneling current: a characterization on Si(111).

PubMed

Weymouth, A J; Wutscher, T; Welker, J; Hofmann, T; Giessibl, F J

2011-06-03

Simultaneous measurements of tunneling current and atomic forces provide complementary atomic-scale data of the electronic and structural properties of surfaces and adsorbates. With these data, we characterize a strong impact of the tunneling current on the measured force on samples with limited conductivity. The effect is a lowering of the effective gap voltage through sample resistance which in turn lowers the electrostatic attraction, resulting in an apparently repulsive force. This effect is expected to occur on other low-conductance samples, such as adsorbed molecules, and to strongly affect Kelvin probe measurements when tunneling occurs.

Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces

NASA Astrophysics Data System (ADS)

Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.

2017-07-01

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.

Synthesis, characterization and computational chemical study of novel pyrazole derivatives as anticorrosion and antiscalant agents

NASA Astrophysics Data System (ADS)

El-Taib Heakal, F.; Attia, S. K.; Rizk, S. A.; Abou Essa, M. A.; Elkholy, A. E.

2017-11-01

Metals corrosion and scales deposition are two serious problems of heavy burden in most industries. Both problems can be mitigated by adding special chemicals capable of being adsorbed on metallic surfaces as well as on scale growing crystal surfaces. Efficient materials should be rich in functional groups containing heteroatoms and/or π bonds for supporting their adsorbability on surfaces. In the present work, four novel pyrazole derivatives were synthesized and characterized for their structures using elemental analysis and spectroscopic tools. The tested compounds were fabricated by treating 2,3-diaryloxirane-2,3-dicarbonitriles with different nitrogen nucleophiles. The density functional theory (DFT) was then applied to explore the structural and electronic characteristics of these materials. Molecular dynamics simulation was also run to scrutinize the ability of the prepared compounds to act as corrosion inhibitors and antiscalant agents by adsorbing on Fe and CaSO4 surfaces.

Removal of cadmium ions from wastewater using innovative electronic waste-derived material.

PubMed

Xu, Meng; Hadi, Pejman; Chen, Guohua; McKay, Gordon

2014-05-30

Cadmium is a highly toxic heavy metal even at a trace level. In this study, a novel material derived from waste PCBs has been applied as an adsorbent to remove cadmium ions from aqueous solutions. The effects of various factors including contact time, initial cadmium ion concentration, pH and adsorbent dosage have been evaluated. The maximum uptake capacity of the newly derived material for cadmium ions has reached 2.1mmol/g at an initial pH 4. This value shows that this material can effectively remove cadmium ions from effluent. The equilibrium isotherm has been analyzed using several isotherm equations and is best described by the Redlich-Peterson model. Furthermore, different commercial adsorbent resins have been studied for comparison purposes. The results further confirm that this activated material is highly competitive with its commercial counterparts. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of novel nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric.

PubMed

Bondar, Yuliia; Kuzenko, Svetlana; Han, Do-Hung; Cho, Hyun-Kug

2014-01-01

A nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric was synthesized for selective removal of Cs ions from contaminated waters by a two-stage synthesis: radiation-induced graft polymerization of acrylic acid monomer onto the nonwoven polypropylene fabric surface with subsequent in situ formation of potassium nickel hexacyanoferrate (KNiHCF) nanoparticles within the grafted chains. Data of scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy confirmed the formation of KNiHCF homogeneous phase on the fabric surface, which consisted of crystalline cubic-shaped nanoparticles (70 to 100 nm). The efficiency of the synthesized adsorbent for removal of cesium ions was evaluated under various experimental conditions. It has demonstrated a rapid adsorption process, high adsorption capacity over a wide pH range, and selectivity in Cs ion removal from model solutions with high concentration of sodium ions.

Surface spectators and their role in relationships between activity and selectivity of the oxygen reduction reaction in acid environments.

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

Ciapina, Eduardo G.; Lopes, Pietro P.; Subbaraman, Ram

2015-11-01

We use the rotating ring disk (RRDE) method to study activity-selectivity relationships for the oxygen reduction reaction (ORR) on Pt(111) modified by various surface coverages of adsorbed CNad (ΘCNad). The results demonstrate that small variations in ΘCNad have dramatic effect on the ORR activity and peroxide production, resulting in “volcano-like” dependence with an optimal surface coverage of ΘCNad = 0.3 ML. These relationships can be simply explained by balancing electronic and ensemble effects of co-adsorbed CNad and adsorbed spectator species from the supporting electrolytes, without the need for intermediate adsorption energy arguments. Although this study has focused on the Pt(111)-CNad/H2SO4more » interface, the results and insight gained here are invaluable for controlling another dimension in the properties of electrochemical interfaces.« less

Preparation of Chitosan Coated Magnetic Hydroxyapatite Nanoparticles and Application for Adsorption of Reactive Blue 19 and Ni2+ Ions

PubMed Central

Nguyen, Van Cuong; Pho, Quoc Hue

2014-01-01

An adsorbent called chitosan coated magnetic hydroxyapatite nanoparticles (CS-MHAP) was prepared with the purpose of improvement for the removal of Ni2+ ions and textile dye by coprecipitation. Structure and properties of CS-MHAP were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM). Weight percent of chitosan was investigated by thermal gravimetric analysis (TGA). The prepared CS-MHAP presents a significant improvement on the removal efficiency of Ni2+ ions and reactive blue 19 dye (RB19) in comparison with chitosan and magnetic hydroxyapatite nanoparticles. Moreover, the adsorption capacities were affected by several parameters such as contact time, initial concentration, adsorbent dosage, and initial pH. Interestingly, the prepared adsorbent could be easily recycled from an aqueous solution by an external magnet and reused for adsorption with high removal efficiency. PMID:24592158

Development of novel nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric

PubMed Central

2014-01-01

A nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric was synthesized for selective removal of Cs ions from contaminated waters by a two-stage synthesis: radiation-induced graft polymerization of acrylic acid monomer onto the nonwoven polypropylene fabric surface with subsequent in situ formation of potassium nickel hexacyanoferrate (KNiHCF) nanoparticles within the grafted chains. Data of scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy confirmed the formation of KNiHCF homogeneous phase on the fabric surface, which consisted of crystalline cubic-shaped nanoparticles (70 to 100 nm). The efficiency of the synthesized adsorbent for removal of cesium ions was evaluated under various experimental conditions. It has demonstrated a rapid adsorption process, high adsorption capacity over a wide pH range, and selectivity in Cs ion removal from model solutions with high concentration of sodium ions. PMID:24725367

Adsorption Studies of Gadolinium ion on Graphitic Carbon Nitride

NASA Astrophysics Data System (ADS)

Kuila, S. K.; Kundu, T. K.

2018-03-01

Bulk graphitic carbon nitride (g-C3N4) is synthesized by thermal decomposition of urea and used as an adsorbent for gadolinium ion (Gd3+) from aqueous solution. Adsorption capacity of g-C3N4 is found to be influenced by initial Gd3+ concentration, solution pH and contact time. Adsorbed Gd3+is separated from g-C3N4 by ultracentrifuge. Initial and Gd ion accumulated g-C3N4 adsorbent are characterized by X-ray diffraction technique (XRD) for phase identification, UV-visible and Fourier transform infrared (FTIR) spectroscopy for adsorption characteristics and optical property, scanning electron microscopy (SEM) for morphological behaviour along with energy dispersive X-ray spectroscopy (EDS) for elemental study. HNO3(0.1M), NaOH (0.1M) and de-ionized water are used for desorption and around 97% quantitative recovery of Gd ion is observed.

Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions

NASA Astrophysics Data System (ADS)

Li, Song; Li, Duanyang; Su, Fei; Ren, Yuping; Qin, Gaowu

2014-10-01

A novel method to produce composite sorbent material compromising porous diatomaceous earth (DE) and surface functionalized amorphous MnO2 is reported. Via a simple in situ redox reaction over the carbonized DE powders, a uniform layer of amorphous MnO2 was anchored onto the DE surface. The hybrid adsorbent was characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The batch method has been employed to investigate the effects of surface coating on adsorption performance of DE. According to the equilibrium studies, the adsorption capacity of DE for adsorbing lead ions after MnO2 modification increased more than six times. And the adsorption of Pb2+ on the MnO2 surface is based on ion-exchange mechanism. The developed strategy presents a novel opportunity to prepare composite adsorbent materials by integrating nanocrystals with porous matrix.

Nonlinearity, resonance, charging, and motion at the atomic scale studied with scanning tunneling microscopes

NASA Astrophysics Data System (ADS)

Tu, Xiuwen

2008-10-01

Several novel phenomena at the single-atom and single-molecule level occurring on the surfaces of single crystals were studied with home-built low temperature scanning tunneling microscopes. The results revealed intriguing properties of single atoms and single molecules, including nonlinearity, resonance, charging, and motion. First, negative differential resistance (NDR) was observed in the dI/dV spectra for single copper-phthalocyanine (CuPc) molecules adsorbed on one- and two-layer sodium bromide (NaBr), but not for single CuPc molecules adsorbed on three-layer NaBr, all grown on a NiAl(110) surface. This transition from NDR to the absence of NDR was explained as the result of competing effects in the double-barrier tunnel junction (DBTJ) and was reproduced in a calculation based on a resonant-tunneling model. Second, the nonlinearity of the STM junction due to a single manganese (Mn) atom or MnCO molecule adsorbed on a NiAl(110) surface was used to rectify microwave irradiation. The resulting rectification current was shown to be sensitive to the spin-splitting of the electronic states of the Mn atom and to the vibrations of the MnCO molecule. Next, the ordering of cesium (Cs) atoms adsorbed on a Au(111) surface and a NiAl(110) surface was imaged in real space. Because of charge transfer to the substrates, Cs adatoms were positively charged on both surfaces. Even at 12 K, Cs adatoms were able to move and adjust according to coverage. On Au(111), the Cs first layer had a quasi-hexagonal lattice and islands of the second Cs layer did not appear until the first was completed. On NiAl(110), a locally disordered Cs first layer was observed before a locally ordered layer appeared at higher coverages. The cation-pi interactions were then studied at the single molecular level. We were able to form cation-pi complexes such as Cs···DSB, Cs···DSB···Cs, Rb···DSB, and Rb···ZnEtiol controllably by manipulation with the STM tip. We could also separate these complexes controllably by voltage pulses. STM imaging and spectroscopy revealed precise information about the atomic and electronic structure of these cation-pi complexes. Finally, electron transport through single atoms and molecules in a double-barrier tunnel junction (DBTJ) was examined. Charge bistability was observed for single ZnEtioI molecules adsorbed in several different conformations on ultrathin aluminum oxide. A sudden decrease in local apparent barrier height (LABH) was observed at the onset of an adsorbate electronic orbital for single ZnEtioI molecules and Cs atoms supported by the ultrathin aluminum oxide. The resonant-tunneling model, which was proposed to explain the transition from NDR to the absence of NDR, was found useful in explaining the sudden decrease in LABH, too. NDR, bipolar tunneling, and vibronic states were also observed and discussed in the context of DBTJ.

Radiation synthesis of a new amidoximated UHMWPE fibrous adsorbent with high adsorption selectivity for uranium over vanadium in simulated seawater

NASA Astrophysics Data System (ADS)

Gao, Qianhong; Hu, Jiangtao; Li, Rong; Xing, Zhe; Xu, Lu; Wang, Mouhua; Guo, Xiaojing; Wu, Guozhong

2016-05-01

A new kind of highly efficient adsorbent material has been fabricated in this study for the purpose of extracting uranium from seawater. Ultra-high molecular weight polyethylene (UHMWPE) fiber was used as a trunk material for the adsorbent, which was prepared by a series of modification reactions, as follows: (1) grafting of glycidyl methacrylate (GMA) and methyl acrylate (MA) onto UHMWPE fibers via 60Co γ-ray pre-irradiation; (2) aminolyzation of UHMWPE fiber by the ring-opening reaction between of epoxy groups PGMA and ethylene diamine (EDA); (3) Michael addition of amino groups with acrylonitrile (AN) to yield nitrile groups; (4) amidoximation of the attached nitrile moieties by hydroxylamine in dimethyl sulfoxide-water mixture. Modified UHMWPE fibers were characterized by means of attenuated total reflectance-Fourier transformed infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) to confirm the attachment of amidoxime (AO) groups onto the UHMWPE fibers. The results of X-ray diffraction (XRD) and single fiber tensile strength verified that the modified UHMWPE fiber retained excellent mechanical properties at a low absorbed radiation dose. The adsorption performance of the UHMWPE fibrous adsorbent was evaluated by subjecting it to an adsorption test in simulated seawater using a continuous-flow mode. The amount of uranium adsorbed by this AO-based UHMWPE fibrous adsorbent was 1.97 mg-U/g after 42 days. This new adsorbent also showed high selectivity for the uranyl ion, and its selectivity for metal ions was found to decrease in the following order: U>Cu>Fe>Ca>Mg>Ni>Zn>Pb>V>Co. The adsorption selectivity for uranium is significantly higher than that for vanadium. In addition, preparation of this modified adsorbent consumes much smaller amounts of the toxic acrylonitrile monomer than the conventional preparation methods of AO-based polyethylene fibers.

Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

NASA Astrophysics Data System (ADS)

Petit, Camille

Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism involves dissolution of ammonia in water when moisture is present in the system. Even though this process increases the breakthrough capacity of a material, it provides rather weak retention forces since ammonia dissolved in water is easily desorbed from the adsorbent's surface.

Radiobiological Effectiveness of Ultrashort Laser-Driven Electron Bunches: Micronucleus Frequency, Telomere Shortening and Cell Viability.

PubMed

Andreassi, Maria Grazia; Borghini, Andrea; Pulignani, Silvia; Baffigi, Federica; Fulgentini, Lorenzo; Koester, Petra; Cresci, Monica; Vecoli, Cecilia; Lamia, Debora; Russo, Giorgio; Panetta, Daniele; Tripodi, Maria; Gizzi, Leonida A; Labate, Luca

2016-09-01

Laser-driven electron accelerators are capable of producing high-energy electron bunches in shorter distances than conventional radiofrequency accelerators. To date, our knowledge of the radiobiological effects in cells exposed to electrons using a laser-plasma accelerator is still very limited. In this study, we compared the dose-response curves for micronucleus (MN) frequency and telomere length in peripheral blood lymphocytes exposed to laser-driven electron pulse and X-ray radiations. Additionally, we evaluated the effects on cell survival of in vitro tumor cells after exposure to laser-driven electron pulse compared to electron beams produced by a conventional radiofrequency accelerator used for intraoperative radiation therapy. Blood samples from two different donors were exposed to six radiation doses ranging from 0 to 2 Gy. Relative biological effectiveness (RBE) for micronucleus induction was calculated from the alpha coefficients for electrons compared to X rays (RBE = alpha laser/alpha X rays). Cell viability was monitored in the OVCAR-3 ovarian cancer cell line using trypan blue exclusion assay at day 3, 5 and 7 postirradiation (2, 4, 6, 8 and 10 Gy). The RBE values obtained by comparing the alpha values were 1.3 and 1.2 for the two donors. Mean telomere length was also found to be reduced in a significant dose-dependent manner after irradiation with both electrons and X rays in both donors studied. Our findings showed a radiobiological response as mirrored by the induction of micronuclei and shortening of telomere as well as by the reduction of cell survival in blood samples and cancer cells exposed in vitro to laser-generated electron bunches. Additional studies are needed to improve preclinical validation of the radiobiological characteristics and efficacy of laser-driven electron accelerators in the future.

Shewanella secretes flavins that mediate extracellular electron transfer

PubMed Central

Marsili, Enrico; Baron, Daniel B.; Shikhare, Indraneel D.; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

2008-01-01

Bacteria able to transfer electrons to metals are key agents in biogeochemical metal cycling, subsurface bioremediation, and corrosion processes. More recently, these bacteria have gained attention as the transfer of electrons from the cell surface to conductive materials can be used in multiple applications. In this work, we adapted electrochemical techniques to probe intact biofilms of Shewanella oneidensis MR-1 and Shewanella sp. MR-4 grown by using a poised electrode as an electron acceptor. This approach detected redox-active molecules within biofilms, which were involved in electron transfer to the electrode. A combination of methods identified a mixture of riboflavin and riboflavin-5′-phosphate in supernatants from biofilm reactors, with riboflavin representing the dominant component during sustained incubations (>72 h). Removal of riboflavin from biofilms reduced the rate of electron transfer to electrodes by >70%, consistent with a role as a soluble redox shuttle carrying electrons from the cell surface to external acceptors. Differential pulse voltammetry and cyclic voltammetry revealed a layer of flavins adsorbed to electrodes, even after soluble components were removed, especially in older biofilms. Riboflavin adsorbed quickly to other surfaces of geochemical interest, such as Fe(III) and Mn(IV) oxy(hydr)oxides. This in situ demonstration of flavin production, and sequestration at surfaces, requires the paradigm of soluble redox shuttles in geochemistry to be adjusted to include binding and modification of surfaces. Moreover, the known ability of isoalloxazine rings to act as metal chelators, along with their electron shuttling capacity, suggests that extracellular respiration of minerals by Shewanella is more complex than originally conceived. PMID:18316736

Seebeck coefficient of one electron

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

Durrani, Zahid A. K., E-mail: z.durrani@imperial.ac.uk

2014-03-07

The Seebeck coefficient of one electron, driven thermally into a semiconductor single-electron box, is investigated theoretically. With a finite temperature difference ΔT between the source and charging island, a single electron can charge the island in equilibrium, directly generating a Seebeck effect. Seebeck coefficients for small and finite ΔT are calculated and a thermally driven Coulomb staircase is predicted. Single-electron Seebeck oscillations occur with increasing ΔT, as one electron at a time charges the box. A method is proposed for experimental verification of these effects.

Molecular dynamics studies of water deposition on hematite surfaces

NASA Astrophysics Data System (ADS)

Kvamme, Bjørn; Kuznetsova, Tatiana; Haynes, Martin

2012-12-01

The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decrease in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide to the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures which may lead to the formation of hydrate between residual water dissolved in carbon dioxide. The critical question is whether the water at some condition of temperature and pressure will drop out as liquid droplets or as water adsorbed on the surfaces of the pipeline and then subsequently form hydrates heterogeneously. In this work we have used the 6-311G basis set with B3LYP to estimate the charge distribution of different sizes of hematite crystals. The obtained surface charge distribution were kept unchanged while the inner charge distribution where scaled so as to result in an overall neutral crystal. These rust particles were embedded in water and chemical potential for adsorbed water molecules were estimated through thermodynamic integration and compared to similar estimates for same size water cluster. Estimated values of water chemical potentials indicate that it is thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based this sequence of processes.

Adsorption and Detection of Hazardous Trace Gases by Metal-Organic Frameworks.

PubMed

Woellner, Michelle; Hausdorf, Steffen; Klein, Nicole; Mueller, Philipp; Smith, Martin W; Kaskel, Stefan

2018-06-19

The quest for advanced designer adsorbents for air filtration and monitoring hazardous trace gases has recently been more and more driven by the need to ensure clean air in indoor, outdoor, and industrial environments. How to increase safety with regard to personal protection in the event of hazardous gas exposure is a critical question for an ever-growing population spending most of their lifetime indoors, but is also crucial for the chemical industry in order to protect future generations of employees from potential hazards. Metal-organic frameworks (MOFs) are already quite advanced and promising in terms of capacity and specific affinity to overcome limitations of current adsorbent materials for trace and toxic gas adsorption. Due to their advantageous features (e.g., high specific surface area, catalytic activity, tailorable pore sizes, structural diversity, and range of chemical and physical properties), MOFs offer a high potential as adsorbents for air filtration and monitoring of hazardous trace gases. Three advanced topics are considered here, in applying MOFs for selective adsorption: (i) toxic gas adsorption toward filtration for respiratory protection as well as indoor and cabin air, (ii) enrichment of hazardous gases using MOFs, and (iii) MOFs as sensors for toxic trace gases and explosives. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

PubMed

Buron, Cédric C; Callegari, Vincent; Nysten, Bernard; Jonas, Alain M

2007-09-11

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.

The adsorption of methyl, acetylide, chlorine and phosphorus trifluoride on zinc oxide: A quantum-chemical study

NASA Astrophysics Data System (ADS)

Rodriguez, JoséA.

1989-11-01

The chemisorptions of methyl (CH 3), acetylide (H-CC), chlorine (Cl) and phosphorus trifluoride (PF 3) on ZnO(0001) and of Cl on ZnO(101¯0) have been examined employing semi-em- pirical quantum-chemical calculations (INDO/S) and neutral clusters of limited size (Zn 13O 13). CH 3, H-CC and Cl appear as strong electron acceptors when adsorbed on Zn sites of ZnO. The chemisorption bonds of these molecules are almost pure σ-bonds and are largely localized on the adsorption site. An increase in the work function of ZnO surfaces upon adsorption of CH 3, H-CC and Cl is predicted. The PF 3 molecule is a very weak acceptor of electrons when adsorbed on a-top sites of ZnO(0001). The bonding mechanism of CH 3, H-CC, Cl and PF 3 on the ZnO(0001) surface involves primarily the HOMO and LUMO of the adsorbate and the Zn(4s,4p) orbitals of the substrate. The effects of chemisorption on the C-H bonds of CH 3 and H-CC, the C-C bond of H-CC, and the P-F bonds of PF 3 are examined. On the basis of these INDO/S results, the possible UPS spectra for CH 3, H-CC and PF 3 adsorbed on ZnO(0001) are discussed and compared with results for adsorption on transition-metal surfaces. A general picture of the chemisorption bond of alkyls, acetylides, alkoxides, carboxylates and halogens on a-top sites of ZnO(0001) is obtained by comparing our results for adsorption of CH 3, H-CC and Cl with those previously reported for adsorption of methoxy, OH and formate.

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

Petrik, Nikolay G.; Kimmel, Gregory A.

Weakly bound (physisorbed) atoms and molecules such as Ar, Kr, Xe, CO, CH4, CH3OH, CO2 and N2 are used to probe the photochemical interactions of O2 on rutile TiO2(110). UV irradiation of chemisorbed O2 along with the physisorbed probe species leads to photon-stimulated desorption (PSD) of Ar, Kr, CO, CH4 and N2. Without co-adsorbed O2, the PSD yields of the probe species are very low or not observed. No PSD was observed for CO2, N2O, CH3OH and the PSD yield for Xe is very low compared to the other probe atoms or molecules. The angular distribution of the photo-desorbing Kr,more » which is broad and cosine, is quite different from the O2 PSD angular distribution, which is sharply peaked along the surface normal. The Kr PSD yields increase with increasing coverage of Kr and of chemisorbed O2. We propose a mechanism for the observed phenomena where the chemisorbed O2 serves as photoactive center, excited via electronic excitations (electrons and/or holes) created in the TiO2 substrate by UV photon irradiation. The photo-excited O2 may transfer its energy to neighboring co-adsorbed atom or molecule resulting in desorption of the latter. Simple momentum transfer considerations suggest that heavier adsorbates (like Xe) and adsorbates with higher binding energy (like CO2) should desorb less efficiently according to the proposed mechanism. Various forms of chemisorbed O2 appeared photoactive in such stimulated desorption of Kr atoms: molecular anions (O22-, O2-), adatoms (Oa), and others. The observed phenomenon provides a new tool for study of photocatalysis.« less

Nanocomposite of exfoliated bentonite/g-C3N4/Ag3PO4 for enhanced visible-light photocatalytic decomposition of Rhodamine B.

PubMed

Ma, Jianfeng; Huang, Daiqin; Zhang, Wenyi; Zou, Jing; Kong, Yong; Zhu, Jianxi; Komarneni, Sridhar

2016-11-01

Novel visible-light-driven heterojunction photocatalyst comprising exfoliated bentonite, g-C3N4 and Ag3PO4 (EB/g-C3N4/Ag3PO4) was synthesized by a facile and green method. The composites EB/g-C3N4/Ag3PO4 were characterized by X-ray diffraction, Transmission electron microscopy, Fourier transform infrared spectroscopy, UV-Vis diffuse reflectance spectroscopy and the Brunauer, Emmett, and Teller (BET) surface area method. Under visible light irradiation, EB/g-C3N4/Ag3PO4 composites displayed much higher photocatalytic activity than that of either pure g-C3N4 or pure Ag3PO4 in the degradation of Rhodamine B (RhB). Among the hybrid photocatalysts, EB/g-C3N4/Ag3PO4 composite containing 20 wt% Ag3PO4 exhibited the highest photocatalytic activity for the decolorization of RhB. Under the visible-light irradiation, the RhB dye was completely decolorized in less than 60 min. The enhanced photocatalytic performance is attributed to the stable structure, enlarged surface area, strong adsorbability, strong light absorption ability, and high-efficiency separation rate of photoinduced electron-hole pairs. Our finding paves a way to design highly efficient and stable visible-light-induced photocatalysts for practical applications in wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Programmable ion-sensitive transistor interfaces. II. Biomolecular sensing and manipulation.

PubMed

Jayant, Krishna; Auluck, Kshitij; Funke, Mary; Anwar, Sharlin; Phelps, Joshua B; Gordon, Philip H; Rajwade, Shantanu R; Kan, Edwin C

2013-07-01

The chemoreceptive neuron metal-oxide-semiconductor transistor described in the preceding paper is further used to monitor the adsorption and interaction of DNA molecules and subsequently manipulate the adsorbed biomolecules with injected static charge. Adsorption of DNA molecules onto poly-L-lysine-coated sensing gates (SGs) modulates the floating gate (FG) potential ψ(O), which is reflected as a threshold voltage shift measured from the control gate (CG) V(th_CG). The asymmetric capacitive coupling between the CG and SG to the FG results in V(th_CG) amplification. The electric field in the SG oxide E(SG_ox) is fundamentally different when we drive the current readout with V(CG) and V(ref) (i.e., the potential applied to the CG and reference electrode, respectively). The V(CG)-driven readout induces a larger E(SG_ox), leading to a larger V(th_CG) shift when DNA is present. Simulation studies indicate that the counterion screening within the DNA membrane is responsible for this effect. The DNA manipulation mechanism is enabled by tunneling electrons (program) or holes (erase) onto FGs to produce repulsive or attractive forces. Programming leads to repulsion and eventual desorption of DNA, while erasing reestablishes adsorption. We further show that injected holes or electrons prior to DNA addition either aids or disrupts the immobilization process, which can be used for addressable sensor interfaces. To further substantiate DNA manipulation, we used impedance spectroscopy with a split ac-dc technique to reveal the net interface impedance before and after charge injection.

Photoinduced charge separation in a colloidal system of exfoliated layered semiconductor controlled by coexisting aluminosilicate clay.

PubMed

Nakato, Teruyuki; Yamada, Yoshimi; Miyamoto, Nobuyoshi

2009-02-05

We investigated photoinduced charge separation occurring in a multicomponent colloidal system composed of oxide nanosheets of photocatalytically active niobate and photochemically inert clay and electron accepting methylviologen dications (MV2+). The inorganic nanosheets were obtained by exfoliation of layered hexaniobate and hectorite clay. The niobate and clay nanosheets were spatially separated in the colloidally dispersed state, and the MV2+ molecules were selectively adsorbed on the clay platelets. UV irradiation of the colloids led to electron transfer from the niobate nanosheets to the MV2+ molecules adsorbed on clay. The photoinduced electron transfer produced methylviologen radical cations (MV*+), which was characterized by high yield and long lifetime. The yield and stability of the MV*+ species were found to depend strongly on the clay content of the colloid: from a few mol % to approximately 70 mol % of the yield and several tens of minutes to more than 40 h of the lifetime. The contents of the niobate nanosheets and MV2+ molecules and the aging of the colloid also affected the photoinduced charge separation. In the absence of MV2+ molecules in the colloid, UV irradiation induced electron accumulation in the niobate nanosheets. The stability of the electron-accumulated state also depended on the clay content. The variation in the photochemical behavior is discussed in relation to the viscosity of the colloid.

Guiding of relativistic electron beams in dense matter by laser-driven magnetostatic fields.

PubMed

Bailly-Grandvaux, M; Santos, J J; Bellei, C; Forestier-Colleoni, P; Fujioka, S; Giuffrida, L; Honrubia, J J; Batani, D; Bouillaud, R; Chevrot, M; Cross, J E; Crowston, R; Dorard, S; Dubois, J-L; Ehret, M; Gregori, G; Hulin, S; Kojima, S; Loyez, E; Marquès, J-R; Morace, A; Nicolaï, Ph; Roth, M; Sakata, S; Schaumann, G; Serres, F; Servel, J; Tikhonchuk, V T; Woolsey, N; Zhang, Z

2018-01-09

Intense lasers interacting with dense targets accelerate relativistic electron beams, which transport part of the laser energy into the target depth. However, the overall laser-to-target energy coupling efficiency is impaired by the large divergence of the electron beam, intrinsic to the laser-plasma interaction. Here we demonstrate that an efficient guiding of MeV electrons with about 30 MA current in solid matter is obtained by imposing a laser-driven longitudinal magnetostatic field of 600 T. In the magnetized conditions the transported energy density and the peak background electron temperature at the 60-μm-thick target's rear surface rise by about a factor of five, as unfolded from benchmarked simulations. Such an improvement of energy-density flux through dense matter paves the ground for advances in laser-driven intense sources of energetic particles and radiation, driving matter to extreme temperatures, reaching states relevant for planetary or stellar science as yet inaccessible at the laboratory scale and achieving high-gain laser-driven thermonuclear fusion.

Synthesis and characterization of Silica/polyvinyl imidazole/H2PO4-core-shell nanoparticles as recyclable adsorbent for efficient scavenging of Sm(III) and Dy(III) from water.

PubMed

Ettehadi Gargari, Jafar; Sid Kalal, Hossein; Shakeri, Alireza; Khanchi, Alireza

2017-11-01

In this study, we used Silica/polyvinyl imidazole core-shell nanoparticles impregnated with sodium dihydrogen phosphate (SiO 2 /PVI/H 2 PO 4 - NPs) for adsorption of samarium and dysprosium ions from aqueous solutions. The effects of the pH, adsorbent dose, contact time, and initial concentration of the adsorbate on the Core-shell nanoparticles adsorption capacity have been studied. The pH value for maximum removal of Sm (III) and Dy (III) on the core-shell nanoparticles surface were found to be 4. The saturated capacity of SiO 2 /PVI/H 2 PO 4 - NPs was up to 160mg.g -1 and 150mg.g -1 at 25°C for Sm (III) and Dy (III) ions respectively. The obtained uptake data were analyzed by the Langmuir and Freundlich equations using a linearized correlation coefficient at room temperature. The Freundlich isotherm was found to fit well with the equilibrium data. The adsorption kinetics could be modeled by a pseudo-second-order rate expression. Thermodynamic investigation revealed the adsorption process of the studied ions is entropy driven. Furthermore, the performance of regeneration and reutilization were studied. The adsorbed Sm (III) and Dy (III) can be desorbed by 0.5mol/L HCl, with the desorption percentage of 90% for Sm (III) and Dy (III). After five adsorption-desorption cycles, the adsorption capacity shows a slight decrease (about 15%), implying that the SiO 2 /PVI/H 2 PO 4 - NPs can be used as an effective adsorbent for the removal and recovery of Sm(III) and Dy(III) from aqueous solution. The colloid stability of the SiO 2 /PVI/H 2 PO 4 - NPs was investigated by dynamic light scattering measurements. The SiO 2 /PVI/H 2 PO 4 - NPs are stable in adsorption media after five adsorption - desorption cycles. The high stability of SiO 2 /PVI/H 2 PO 4 - NPs can be attributed to steric stabilization by polyvinyl imidazole adsorbed on SiO 2 nanoparticle surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

PubMed

Ji, Liangliang; Chen, Wei; Xu, Zhaoyi; Zheng, Shourong; Zhu, Dongqiang

2013-01-01

Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Development and Testing of Molecular Adsorber Coatings

NASA Technical Reports Server (NTRS)

Abraham, Nithin; Hasegawa, Mark; Straka, Sharon

2012-01-01

The effect of on-orbit molecular contamination has the potential to degrade the performance of spaceflight hardware and diminish the lifetime of the spacecraft. For example, sensitive surfaces, such as optical surfaces, electronics, detectors, and thermal control surfaces, are vulnerable to the damaging effects of contamination from outgassed materials. The current solution to protect these surfaces is through the use of zeolite coated ceramic adsorber pucks. However, these pucks and its additional complex mounting hardware requirements result in several disadvantages, such as size, weight, and cost related concerns, that impact the spacecraft design and the integration and test schedule. As a result, a new innovative molecular adsorber coating was developed as a sprayable alternative to mitigate the risk of on-orbit molecular contamination. In this study, the formulation for molecular adsorber coatings was optimized using various binders, pigment treatment methods, binder to pigment ratios, thicknesses, and spray application techniques. The formulations that passed coating adhesion and vacuum thermal cycling tests were further tested for its adsorptive capacity. Accelerated molecular capacitance tests were performed in an innovatively designed multi-unit system containing idealized contaminant sources. This novel system significantly increased the productivity of the testing phase for the various formulations that were developed. Work performed during the development and testing phases has demonstrated successful application of molecular adsorber coatings onto metallic substrates, as well as, very promising results for the adhesion performance and the molecular capacitance of the coating. Continued testing will assist in the qualification of molecular adsorber coatings for use on future contamination sensitive spaceflight missions.

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Performance evaluation of oxygen adsorbents using negative corona discharge-ion mobility spectrometry.

PubMed

Azadkish, Kamal; Jafari, Mohammad T; Ghaziaskar, Hassan S

2017-02-08

Trace amounts of oxygen was determined using negative corona discharge as an ionization source for ion mobility spectrometry. A point-in-cylinder geometry with novel design was used to establish the corona discharge without interferences of negative ions such as NO X - . The desirable background spectrum shows only electrons peak, providing the instrument capable of trace analysis of oxygen in gaseous samples. The limit of detection and linear dynamic range with high coefficient of determination (r 2  = 0.9997), were obtained for oxygen as 8.5 and 28-14204 ppm, respectively. The relative standard deviations of the method for intraday and interday were obtained 4 and 11%, respectively. The satisfactory results revealed the ability of the negative corona discharge ion mobility spectrometry for investigating the performance of synthesized oxygen adsorbents in nitrogen streams. Two oxygen scavengers of MnO and Cu powder were prepared and the optimum temperature of the reactor containing MnO and Cu powder were obtained as 180 and 230 °C, respectively. Due to higher lifetime of copper powder, it was selected as the oxygen scavenger and some parameters such as: the type of adsorbent support, the size of adsorbent particles, and the amount of copper were studied for preparation of more efficient oxygen adsorbent. Copyright © 2016 Elsevier B.V. All rights reserved.

Electron shuttle-mediated biotransformation of hexahydro-1,3,5-trinitro-1,3,5-triazine adsorbed to granular activated carbon.

PubMed

Millerick, Kayleigh; Drew, Scott R; Finneran, Kevin T

2013-08-06

Granular activated carbon (GAC) effectively removes hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from groundwater but generates RDX-laden GAC that must be disposed of or regenerated. Batch reactors containing GAC to which RDX was preadsorbed were used in experiments to test the potential for adsorbed RDX reduction and daughter product formation using (i) chemically reduced anthrahydroquinone-2,6-disulfonate (AH2QDS), (ii) resting Geobacter metallireducens strain GS-15, and (iii) a combined system containing AQDS and GS-15. Approximately 97.0% of the adsorbed RDX was transformed in each of these experimental systems by 90 h. Chemically reduced AQDS (AH2QDS) transformed 99.2% of adsorbed RDX; formaldehyde was produced rapidly and was stoichiometric (3 mol HCHO per mol RDX). Geobacter metallireducens also reduced RDX with and without AQDS present. This is the first study to demonstrate biological transformation of RDX adsorbed to GAC. Formaldehyde increased and then decreased in biological systems, suggesting a previously unreported capacity for G. metallireducens to oxidize formaldehyde, which was confirmed with resting cell suspensions. These data suggest the masses of GAC waste currently produced by activated carbon at RDX remediation sites can be minimized, decreasing the carbon footprint of the treatment technology. Alternatively, this strategy may be used to develop a Bio-GAC system for ex situ RDX treatment.

Adsorption geometry and core excitation spectra of three phenylpropene isomers on Cu(111)

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

Kolczewski, C.; Williams, F. J.; Cropley, R. L.

Theoretical C 1s near edge x-ray absorption fine structure (NEXAFS) spectra for the C{sub 9}H{sub 10} isomers trans-methylstyrene, {alpha}-methylstyrene, and allylbenzene in gas phase and adsorbed at Cu(111) surfaces have been obtained from density functional theory calculations where adsorbate geometries were determined by corresponding total energy optimizations. The three species show characteristic differences in widths and peak shapes of the lowest C 1s{yields}{pi}* transitions which are explained by different coupling of the {pi}-electron system of the C{sub 6} ring with that of the side chain in the molecules as well as by the existence of nonequivalent carbon centers. The adsorbedmore » molecules bind only weakly with the substrate which makes the use of theoretical NEXAFS spectra of the oriented free molecules meaningful for an interpretation of experimental angle-resolved NEXAFS spectra of the adsorbate systems obtained in this work. However, a detailed quantitative account of relative peak intensities requires theoretical angle-resolved NEXAFS spectra of the complete adsorbate systems which have been evaluated within the surface cluster approach. The comparison with experiment yields almost perfect agreement and confirms the reliability of the calculated equilibrium geometries of the adsorbates. This can help to explain observed differences in the catalytic epoxidation of the three molecules on Cu(111) based on purely geometric considerations.« less

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.

Characteristics of electron transport chain and affecting factors for thiosulfate-driven perchlorate reduction.

PubMed

Zhang, Chao; Guo, Jianbo; Lian, Jing; Lu, Caicai; Ngo, Huu Hao; Guo, Wenshan; Song, Yuanyuan; Guo, Yankai

2017-10-01

The mechanism for perchlorate reduction was investigated using thiosulfate-driven (T-driven) perchlorate reduction bacteria. The influences of various environmental conditions on perchlorate reduction, including pH, temperature and electron acceptors were examined. The maximum perchlorate removal rate was observed at pH 7.5 and 40 °C. Perchlorate reduction was delayed due to the coexistence of perchlorate-chlorate and perchlorate-nitrate. The mechanism of the T-driven perchlorate reduction electron transport chain (ETC) was also investigated by utilizing different inhibitors. The results were as follows: firstly, the NADH dehydrogenase was not involved in the ETC; secondly, the FAD dehydrogenase and quinone loop participated in the ETC; and thirdly, cytochrome oxidase was the main pathway in the ETC. Meanwhile, microbial consortium structure analysis indicated that Sulfurovum which can oxidize sulfur compounds coupled to the reduction of nitrate or perchlorate was the primary bacterium in the T-driven and sulfur-driven consortium. This study generates a better understanding of the mechanism of T-driven perchlorate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon Nanotube-Based Membrane for Light-Driven, Simultaneous Proton and Electron Transport

DOE PAGES

Pilgrim, Gregory A.; Amori, Amanda R.; Hou, Zhentao; ...

2016-12-07

Here we discuss the photon driven transport of protons and electrons over hundreds of microns through a membrane based on vertically aligned single walled carbon nanotubes (SWNTs). Electrons are photogenerated in colloidal CdSe quantum dots that have been noncovalently attached to the carbon nanotube membrane and can be delivered at potentials capable of reducing earth-abundant molecular catalysts that perform proton reduction. Proton transport is driven by the electron photocurrent and is shown to be faster through the SWNT based membrane than through the commercial polymer Nafion. Furthermore, the potential utility of SWNT membranes for solar water splitting applications is demonstratedmore » through their excellent proton and electron transport properties as well as their ability to interact with other components of water splitting systems, such as small molecule electron acceptors.« less

Tip-Enhanced Photoinduced Electron Transfer and Ionization on Vertical Silicon Nanowires.

PubMed

Chen, Xiaoming; Wang, Tao; Lin, Leimiao; Wo, Fangjie; Liu, Yaqin; Liang, Xiao; Ye, Hui; Wu, Jianmin

2018-05-02

Nanostructured semiconductors are one of the most potent candidates for matrix-free laser desorption/ionization mass spectrometric (LDI-MS) analysis of low-molecular-weight molecules. Herein, the enhanced photoinduced electron transfer and LDI on the tip of a vertical silicon nanowire (SiNW) array were investigated. Theoretical simulation and LDI detection of indigo and isatin molecules in negative ion mode revealed that the electric field can be enhanced on the tip end of SiNWs, thereby promoting the energy and electron transfer to the analytes adsorbed on the tip of SiNWs. On the basis of this finding, a tip-contact sampling method coupled with LDI-MS detection was established. In this strategy, the tip of SiNWs can be regarded as microextraction heads for the sampling of molecules when they come in contact with analytes. Impression of skin, tissue, and pericarp on the vertical SiNW array can effectively transfer endogenous metabolites or exogenous substances onto the tip. Upon laser irradiation, the adsorbed molecules on the SiNW tip can be efficiently ionized and detected in negative ion mode because of the tip-enhanced electron transfer and LDI effect. We believe this work may significantly expand the application of LDI-MS in various fields.

Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach.

PubMed

Prucker, V; Bockstedte, M; Thoss, M; Coto, P B

2018-03-28

A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface. The results show a significant dependence of the ET on the orbital symmetry of the donor state and on the molecular and electronic structure of the spacer.

Cooperative inter- and intra-layer lattice dynamics of photoexcited multi-walled carbon nanotubes studied by ultrafast electron diffraction.

PubMed

Sun, Shuaishuai; Li, Zhongwen; Li, Zi-An; Xiao, Ruijuan; Zhang, Ming; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

2018-04-26

Optical tuning and probing ultrafast structural response of nanomaterials driven by electronic excitation constitute a challenging but promising approach for understanding microscopic mechanisms and applications in microelectromechanical systems and optoelectrical devices. Here we use pulsed electron diffraction in a transmission electron microscope to investigate laser-induced tubular lattice dynamics of multi-walled carbon nanotubes (MWCNTs) with varying laser fluence and initial specimen temperature. Our photoexcitation experiments demonstrate cooperative and inverse collective atomic motions in intralayer and interlayer directions, whose strengths and rates depend on pump fluence. The electron-driven and thermally driven structural responses with opposite amplitudes cause a crossover between intralayer and interlayer directions. Our ab initio calculations support these findings and reveal that electrons excited from π to π* orbitals in a carbon tube weaken the intralayer bonds while strengthening the interlayer bonds along the radial direction. Moreover, by probing the structural dynamics of MWCNTs at initial temperatures of 300 and 100 K, we uncover the concomitance of thermal and nonthermal dynamical processes and their mutual influence in MWCNTs. Our results illustrate the nature of electron-driven nonthermal process and electron-phonon thermalization in the MWCNTs, and bear implications for the intricate energy conversion and transfer in materials at the nanoscale.

The preparation of uranium-adsorbed silica particles as a reference material for the fission track analysis

NASA Astrophysics Data System (ADS)

Park, Y. J.; Lee, M. H.; Pyo, H. Y.; Kim, H. A.; Sohn, S. C.; Jee, K. Y.; Kim, W. H.

2005-06-01

Uranium-adsorbed silica particles were prepared as a reference material for the fission track analysis (FTA) of swipe samples. A modified instrumental setup for particle generation, based on a commercial vibrating orifice aerosol generator to produce various sizes of droplets from a SiO 2 solution, is described. The droplets were transferred into a weak acidic solution bath to produce spherical solid silica particles. The classification of the silica particles in the range from 5 to 20 μm was carried out by the gravitational sedimentation method. The size distribution and morphology of the classified silica particles were investigated by scanning electron microscopy. The physicochemical properties of the classified silica particles such as the surface area, pore size and pore volume were measured. After an adsorption of 5% 235U on the silica particles in a solution adjusted to pH 4.5, the uranium-adsorbed silica particles were calcined up to 950 °C in a furnace to fix the uranium strongly onto the silica particles. The various sizes of uranium-adsorbed silica particles were applied to the FTA for use as a reference material.

Radiation induced emulsion graft polymerization of 4-vinylpyridine onto PE/PP nonwoven fabric for As(V) adsorption

NASA Astrophysics Data System (ADS)

Akkaş Kavaklı, Pınar; Kavaklı, Cengiz; Seko, Noriaki; Tamada, Masao; Güven, Olgun

2016-10-01

A novel nonwoven fabric adsorbent having 4-vinylpyridine functional groups was prepared by using radiation-induced emulsion graft polymerization method and grafting 4-vinylpyridine monomer onto a polyethylene-coated polypropylene nonwoven fabric (NWF) in aqueous emulsion solution. The grafting conditions of the 4-vinylpyridine monomer onto the NWF were optimised and 150% Dg VP-g-NWF was prepared using 30 kGy pre-irradiation dose, 5% VP monomer concentration and 0.5% (w/w) Tween 20 in aqueous emulsion. Grafted 4-vinylpyridine chains on the NWF were then quaternized for the preparation of QVP-g-NWF adsorbent. All fabric structures were characterized by using Fourier-transform infrared spectrometer, x-ray photoelectron spectrometer and scanning electron microscope. QVP-g-NWF adsorbent was used in batch adsorption experiments for As(V) ions by studying the pH, contact time, and initial As(V) ion concentration parameters. Results showed that QVP-g-NWF adsorbent has significant As(V) adsorption and experimental As(V) adsorption capacity was 98.04 mg As(V)/g polymer from 500 mg/L initial As(V) concentration at pH 7.00.

DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

NASA Astrophysics Data System (ADS)

Shokuhi Rad, Ali; Sani, Emad; Binaeian, Ehsan; Peyravi, Majid; Jahanshahi, Mohsen

2017-04-01

In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; -123.5, -120, and -118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

First-principles studies on 3d transition metal atom adsorbed twin graphene

NASA Astrophysics Data System (ADS)

Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

2018-05-01

Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

Surface area of vermiculite with nitrogen and carbon dioxide as adsorbates

USGS Publications Warehouse

Thomas, Josephus; Bohor, Bruce F.

1969-01-01

Surface-area studies were made on several homoionic vermiculites with both nitrogen and carbon dioxide as adsorbates. These studies show that only very slight penetration occurs between individual vermiculite platelets. This is in contrast to an earlier investigation of montmorillonite where it was found that the degree of penetration between layers is quite high, particularly for carbon dioxide, and is governed by the size and charge of the interlayer cation. The inability of these adsorbates to penetrate substantially between vermiculite platelets is due primarily to this mineral's high surface-charge density.The extent of penetration of nitrogen and carbon dioxide at the edges of vermiculite platelets, though slight, is influenced by the coordinated water retained within the sample at a given degassing temperature. Forces between layers are weakened with increasing water content, which permits slightly greater penetration by adsorbate gases. Thus, the surface area of vermiculite, as determined by gas adsorption, is larger than the calculated external surface area based upon particle size and shape considerations. In addition, "extra" surface is provided by the lifting and scrolling of terminal platelets. These morphological features are shown in scanning electron micrographs of a naturally occuring vermiculite.

Hexadimethrine-montmorillonite nanocomposite: Characterization and application as a pesticide adsorbent

NASA Astrophysics Data System (ADS)

Gámiz, B.; Hermosín, M. C.; Cornejo, J.; Celis, R.

2015-03-01

The goal of this work was to prepare and characterize a novel functional material by the modification of SAz-1 montmorillonite with the cationic polymer hexadimethrine (SA-HEXAD), and to explore the potential use of this nanocomposite as a pesticide adsorbent. Comparative preparation and characterization with the well-known hexadecyltrimethylammonium-modified SAz-1 montmorillonite (SA-HDTMA) was also assessed. The characterization was performed by elemental analysis, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), physisorption of N2, scanning electron microscopy (SEM) and Z potential measurements. The characterization and adsorption experiments showed that the extent of pesticide adsorption was markedly subjected to the structure and features of the surface of each organo-clay and also to the nature of the considered pesticide. SA-HEXAD displayed a high affinity for anionic pesticides which, presumably, were adsorbed by electrostatic attraction on positively-charged ammonium groups of the polymer not directly interacting with the clay. In contrast, SA-HDTMA displayed great adsorption of both uncharged and anionic pesticides with predominance of hydrophobic interactions. This work provided information about the surface properties of a new organic-inorganic nanohybrid material, SA-HEXAD, and its potential as an adsorbent for the removal of anionic organic pollutants from aqueous solutions.

Electronic Paint: Understanding Children's Representation through Their Interactions with Digital Paint

ERIC Educational Resources Information Center

Matthews, John; Seow, Peter

2007-01-01

This article investigates very young children's use of a stylus-driven, electronic painting and drawing on the tablet PC. The authors compare their development in the use of this device with their use of other mark-making media, including those which derive from pencil and paper technologies and also with mouse-driven electronic paintbox programs.…

Electron Driven Processes in Atmospheric Behaviour

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Teubner, P. J. O.

2006-11-01

Electron impact plays an important role in many atmospheric processes. Calculation of these is important for basic understanding, atmospheric modeling and remote sensing. Accurate atomic and molecular data, including electron impact cross sections, are required for such calculations. Five electron-driven processes are considered: auroral and dayglow emissions, the reduction of atmospheric electron density by vibrationally excited N2, NO production and infrared emission from NO. In most cases the predictions are compared with measurements. The dependence on experimental atomic and molecular data is also investigated.

Investigations of fungal fruiting bodies as biosorbents for the removal of heavy metals from industrial processing streams

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

Muraleedharan, T.R.; Venkobachar, C.; Leela, I.

1994-09-01

The revival of interest in biotechnology has fueled research in many sectors of environmental biotechnology. The present paper describes research utilizing adsorbents prepared from wood-rotting mushrooms growing wild in tropical forests. Nine species of mushrooms were screened using copper(II) as the model adsorbate. While may species showed excellent potential, comparable to biosorbents reported in literature, Ganodernma lucidum emerged as the best biosorbent. This biosorbent was further developed for use in a packed-bed bioreactor for treatment of rare earth processing effluents. Electron paramagnetic studies confirmed that adsorption is by chemical binding to the biosorbent.

Sulfur-vacancy-dependent geometric and electronic structure of bismuth adsorbed on Mo S2

NASA Astrophysics Data System (ADS)

Park, Youngsin; Li, Nannan; Lee, Geunsik; Kim, Kwang S.; Kim, Ki-Jeong; Hong, Soon Cheol; Han, Sang Wook

2018-03-01

Through Bi deposition on the single-crystalline Mo S2 surface, we find that the density of the sulfur vacancy is a critical parameter for the growth of the crystalline Bi overlayer or cluster at room temperature. Also, the Mo S2 band structure is significantly modified near Γ due to the orbital hybridization with an adsorbed Bi monolayer. Our experimental observations and analysis in combination with density functional theory calculation suggest the importance of controlling the sulfur vacancy concentration in realizing an exotic quantum phase based on the van der Waals interface of Bi and Mo S2 .

Magnetic coupling of Fe-porphyrin molecules adsorbed on clean and c(2×2) oxygen-reconstructed Co(100) investigated by spin-polarized photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Weber, A. P.; Caruso, A. N.; Vescovo, E.; Ali, Md. E.; Tarafder, K.; Janjua, S. Z.; Sadowski, J. T.; Oppeneer, P. M.

2013-05-01

The spin-polarized electronic structure of iron octaethylporphyrin (FeOEP) molecules adsorbed on a pristine and on a c(2×2) oxygen-reconstructed Co(100) surface has been analyzed by means of spin-polarized photoemission spectroscopy (SPPES) and first-principles density functional theory with the on-site Coulomb repulsion U term (DFT+U) calculations with and without Van der Waals corrections. The aim is to examine the magnetic exchange mechanism between the FeOEP molecules and the Co(100) substrate in the presence or absence of the oxygen mediator. The results demonstrate that the magnetic coupling from the ferromagnetic substrate to the adsorbed FeOEP molecules is ferromagnetic, whereas, the coupling is antiferromagnetic for the FeOEP on the c(2×2)O/Co(100) system. Spin-resolved partial densities of states extracted from ab initio DFT+U modeling are in fairly good comparison with the electronic spectral densities seen in angle-integrated SPPES energy dispersion curves for submonolayer coverages of FeOEP. Through combined analysis of these spectra and theoretical results, we determine that hybridization of 2p orbitals of N and O with Co 3d orbitals facilitates indirect magnetic exchange interactions between Fe and Co, whereas, a direct Fe-Co interaction involving the Fe dz2 orbital is also found for FeOEP on Co. It is observed through SPPES that the spin polarization of the photoemission-visible molecular overlayers decreases to zero as coverage is increased beyond the submonolayer regime, indicating that only interfacial magnetic coupling is at work. Microspot low-energy electron diffraction and low-energy electron microscopy were performed to characterize the physical order of the molecular coverage, revealing that FeOEP structural domains are orders of magnitude greater in size on c(2×2)O/Co(100) than on clean Co(100), which coincides with reduced scattering from the disorder and sharper features seen in SPPES.

Electrostatic waves driven by electron beam in lunar wake plasma

NASA Astrophysics Data System (ADS)

Sreeraj, T.; Singh, S. V.; Lakhina, G. S.

2018-05-01

A linear analysis of electrostatic waves propagating parallel to the ambient field in a four component homogeneous, collisionless, magnetised plasma comprising fluid protons, fluid He++, electron beam, and suprathermal electrons following kappa distribution is presented. In the absence of electron beam streaming, numerical analysis of the dispersion relation shows six modes: two electron acoustic modes (modes 1 and 6), two fast ion acoustic modes (modes 2 and 5), and two slow ion acoustic modes (modes 3 and 4). The modes 1, 2 and 3 and modes 4, 5, and 6 have positive and negative phase speeds, respectively. With an increase in electron beam speed, the mode 6 gets affected the most and the phase speed turns positive from negative. The mode 6 thus starts to merge with modes 2 and 3 and generates the electron beam driven fast and slow ion acoustic waves unstable with a finite growth. The electron beam driven slow ion-acoustic waves occur at lower wavenumbers, whereas fast ion-acoustic waves occur at a large value of wavenumbers. The effect of various other parameters has also been studied. We have applied this analysis to the electrostatic waves observed in lunar wake during the first flyby of the ARTEMIS mission. The analysis shows that the low (high) frequency waves observed in the lunar wake could be the electron beam driven slow (fast) ion-acoustic modes.

Phosphate Remediation and Recovery using Iron Oxide-based Adsorbents

EPA Science Inventory

E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese and nanoparticles. Characterization was done by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-...

One-pot preparation of magnetic carbon adsorbent derived from pomelo peel for magnetic solid-phase extraction of pollutants in environmental waters.

PubMed

Huang, Youfang; Peng, Jinghe; Huang, Xiaojia

2018-04-20

In this work, magnetic carbon material derived from pomelo peels (MCMPs) was conveniently fabricated utilizing one-pot synthesis method and employed as adsorbent of magnetic solid-phase extraction (MSPE). Several characterized measures including infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer were used to investigate the morphology, spectroscopic and magnetic properties of prepared adsorbent. Apolar parabens and polar fluoroquinolones (FQs) were used to investigate the extraction performance of MCMPs. Under the optimized extraction conditions, the MCMPs displayed satisfactory extraction performance for target analytes. At the same time, the MCMPs/MSPE was combined with HPLC-DAD for the sensitive determination of parabens and FQs in real-life water samples. Results showed that the limits of detection (S/N = 3) for parabens and FQs were in the ranges of 0.011-0.053 μg/L and 0.012-0.46 μg/L, respectively. The spiked recoveries were in the range of 76.6-116% for parabens and 80.2-114% for FQs with good repeatability (relative standard deviations less than 10%). In comparison to reported methods, the developed MCMPs/MSPE-HPLC-DAD showed some merits including low-cost, simplicity, satisfactory sensitivity and green non-pollution. Copyright © 2018 Elsevier B.V. All rights reserved.

The impact of urea-induced unfolding on the redox process of immobilised cytochrome c.

PubMed

Monari, Stefano; Millo, Diego; Ranieri, Antonio; Di Rocco, Giulia; van der Zwan, Gert; Gooijer, Cees; Peressini, Silvia; Tavagnacco, Claudio; Hildebrandt, Peter; Borsari, Marco

2010-11-01

We have studied the effect of urea-induced unfolding on the electron transfer process of yeast iso-1-cytochrome c and its mutant K72AK73AK79A adsorbed on electrodes coated by mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol self-assembled monolayers. Electrochemical measurements, complemented by surface enhanced resonance Raman studies, indicate two distinct states of the adsorbed proteins that mainly differ with respect to the ligation pattern of the haem. The native state, in which the haem is axially coordinated by Met80 and His18, displays a reduction potential that slightly shifts to negative values with increasing urea concentration. At urea concentrations higher than 6 M, a second state prevails in which the Met80 ligand is replaced by an additional histidine residue. This structural change in the haem pocket is associated with an approximately 0.4 V shift of the reduction potential to negative values. These two states were found for both the wild-type protein and the mutant in which lysine residues 72, 73 and 79 had been substituted by alanines. The analysis of the reduction potentials, the reaction enthalpies and entropies as well as the rate constants indicates that these three lysine residues have an important effect on stabilising the protein structure in the adsorbed state and facilitating the electron transfer dynamics.

Laser-induced modification of graphene in the presence of ethanol on a graphene - substrate interface

NASA Astrophysics Data System (ADS)

Pivovarov, P. A.; Frolov, V. D.; Zavedeev, E. V.; Konov, V. I.

2017-12-01

We have studied the effect that the substitution of an organic substance (ethanol) for water adsorbate on a CVD graphene-SiO2/Si interface has on the laser-induced modification of graphene and graphene structures on the SiO2 film. Scanning probe microscopy has been used to analyse changes in the electronic properties of graphene structures on a hydrophilic substrate in the presence of ethanol and as a result of a laser-induced spatial redistribution of a water-alcohol adsorbate on the interface. It has been demonstrated experimentally that ethanol substitution for water adsorbate leads to an increase in the surface potential of the graphene, which is equivalent to a reduction in its work function with respect to the original level under normal conditions at a relative humidity of air from 30% to 60%. In the laser irradiation zone, we observe an additional increase in surface potential by 30-50 mV. Thus, ethanol makes it possible to tune the laser-induced electronic properties of graphene on a substrate. In addition, it has been shown that the intercalation of ethanol molecules leads to severe temporal instability of the physical properties of graphene structures produced by local laser irradiation. We have demonstrated the possibility of information ‘rewriting’ by low-intensity laser pulses in microregions with a changed surface potential in the presence of ethanol.

Ab initio study of gold-doped zigzag graphene nanoribbons

NASA Astrophysics Data System (ADS)

Srivastava, Pankaj; Dhar, Subhra; Jaiswal, Neeraj K.

2014-12-01

The electronic transport properties of zigzag graphene nanoribbons (ZGNRs) through covalent functionalization of gold (Au) atoms is investigated by using non-equilibrium Green's function combined with density functional theory. It is revealed that the electronic properties of Au-doped ZGNRs vary significantly due to spin and its non-inclusion. We find that the DOS profiles of Au-adsorbed ZGNR due to spin reveal very less number of states available for conduction, whereas non-inclusion of spin results in higher DOS across the Fermi level. Edge Au-doped ribbons exhibit stable structure and are energetically more favorable than the center Au-doped ZGNRs. Though the chemical interaction at the ZGNR-Au interface modifies the Fermi level, Au-adsorbed ZGNR reveals semimetallic properties. A prominent qualitative change of the I-V curve from linear to nonlinear is observed as the Au atom shifts from center toward the edges of the ribbon. Number of peaks present near the Fermi level ensures conductance channels available for charge transport in case of Au-center-substituted ZGNR. We predict semimetallic nature of the Au-adsorbed ZGNR with a high DOS peak distributed over a narrow energy region at the Fermi level and fewer conductance channels. Our calculations for the magnetic properties predict that Au functionalization leads to semiconducting nature with different band gaps for spin up and spin down. The outcomes are compared with the experimental and theoretical results available for other materials.

Protein Electrochemistry: Questions and Answers.

PubMed

Fourmond, V; Léger, C

This chapter presents the fundamentals of electrochemistry in the context of protein electrochemistry. We discuss redox proteins and enzymes that are not photoactive. Of course, the principles described herein also apply to photobioelectrochemistry, as discussed in later chapters of this book. Depending on which experiment is considered, electron transfer between proteins and electrodes can be either direct or mediated, and achieved in a variety of configurations: with the protein and/or the mediator free to diffuse in solution, immobilized in a thick, hydrated film, or adsorbed as a sub-monolayer on the electrode. The experiments can be performed with the goal to study the protein or to use it. Here emphasis is on mechanistic studies, which are easier in the configuration where the protein is adsorbed and electron transfer is direct, but we also explain the interpretation of signals obtained when diffusion processes affect the response.This chapter is organized as a series of responses to questions. Questions 1-5 are related to the basics of electrochemistry: what does "potential" or "current" mean, what does an electrochemical set-up look like? Questions 6-9 are related to the distinction between adsorbed and diffusive redox species. The answers to questions 10-13 explain the interpretation of slow and fast scan voltammetry with redox proteins. Questions 14-19 deal with catalytic electrochemistry, when the protein studied is actually an enzyme. Questions 20, 21 and 22 are general.

Femtosecond manipulation of spins, charges, and ions in nanostructures, thin films, and surfaces

PubMed Central

Carbone, F.; Hengsberger, M.; Castiglioni, L.; Osterwalder, J.

2017-01-01

Modern ultrafast techniques provide new insights into the dynamics of ions, charges, and spins in photoexcited nanostructures. In this review, we describe the use of time-resolved electron-based methods to address specific questions such as the ordering properties of self-assembled nanoparticles supracrystals, the interplay between electronic and structural dynamics in surfaces and adsorbate layers, the light-induced control of collective electronic modes in nanowires and thin films, and the real-space/real-time evolution of the skyrmion lattice in topological magnets. PMID:29308416

Influence of field ionization effect on the divergence of laser-driven fast electrons

NASA Astrophysics Data System (ADS)

Lang, Y.; Yang, X. H.; Xu, H.; Jin, Z.; Zhuo, H. B.

2018-07-01

The effect of field ionization on the divergence of fast electrons (E k ≥ 50 keV), driven by ultrashort-ultraintense laser pulse interaction with plasma, is studied by using 2D3V particle-in-cell simulations. It is found that, due to temperature anisotropy of the fast electrons in the ionizing target, strong fluctuant magnetic fields in the preplasma region is generated through Weibel instability. In turn, the field induces an enhancement of the hot electron divergence for the target with ionization process. Meanwhile, compared with the target without an ionization process, larger divergence of hot electrons can also be seen in the ionizing target with laser intensity varying from 5 × 1019 W/cm2 to 5 × 1020 W/cm2 and the divergence is weakly dependent on target materials for a fixed profile of preplasma. The results here are useful for the application of laser-driven fast electron beams.

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations.

PubMed

Mendt, Matthias; Barth, Benjamin; Hartmann, Martin; Pöppl, Andreas

2017-12-14

The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an 27 Al atom and all its relevant 14 N and 27 Al hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al 3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al 3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules.

Effect of transverse nonuniformity of the rf field on the efficiency of microwave sources driven by linear electron beams

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

Nusinovich, G.S.; Sinitsyn, O.V.

This paper contains a simple analytical theory that allows one to evaluate the effect of transverse nonuniformity of the rf field on the interaction efficiency in various microwave sources driven by linear electron beams. The theory is, first, applied to the systems where the beams of cylindrical symmetry interact with rf fields of microwave circuits having Cartesian geometry. Also, various kinds of microwave devices driven by sheet electron beams (orotrons, clinotrons) are considered. The theory can be used for evaluating the efficiency of novel sources of coherent terahertz radiation.

Start-to-end simulation of the shot-noise driven microbunching instability experiment at the Linac Coherent Light Source

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

Qiang, J.; Ding, Y.; Emma, P.

The shot-noise driven microbunching instability can significantly degrade electron beam quality in x-ray free electron laser light sources. Experiments were carried out at the Linac Coherent Light Source (LCLS) to study this instability. Here in this paper, we present start-to-end simulations of the shot-noise driven microbunching instability experiment at the LCLS using the real number of electrons. The simulation results reproduce the measurements quite well. A microbunching self-heating mechanism is also illustrated in the simulation, which helps explain the experimental observation.

Start-to-end simulation of the shot-noise driven microbunching instability experiment at the Linac Coherent Light Source

DOE PAGES

Qiang, J.; Ding, Y.; Emma, P.; ...

2017-05-23

The shot-noise driven microbunching instability can significantly degrade electron beam quality in x-ray free electron laser light sources. Experiments were carried out at the Linac Coherent Light Source (LCLS) to study this instability. Here in this paper, we present start-to-end simulations of the shot-noise driven microbunching instability experiment at the LCLS using the real number of electrons. The simulation results reproduce the measurements quite well. A microbunching self-heating mechanism is also illustrated in the simulation, which helps explain the experimental observation.

H 2 Adsorbed Site-to-Site Electronic Delocalization within IRMOF-1: Understanding Non-Negligible Interactions at High Pressure

DOE PAGES

Wu, Jian; Kucukkal, Mustafa U.; Clark, Aurora E.

2016-07-15

Isoreticular metal organic frameworks (IRMOFs) have shown high uptake capabilities for storage of H 2 (11.5 wt % at 77 K and 170 bar). A significant literature has employed fragment models and a single adsorbed H 2 to identify adsorption sites within IRMOFs, as well as the necessary adsorbate–adsorbent interactions needed to reach sufficient adsorption enthalpy for practical usage, however at high pressures it remains to be seen if H 2···H 2 intermolecular interactions may influence the energetics. This study focuses upon IRMOF-1 (also known as MOF-5), and examines the individual H 2 stabilization energies at different sites using Möller–Plessetmore » perturbation theory and density functional theory alongside chemical models that consist of isolated fragment models and a cubic super cell cluster consisting of both the face- and edge-cube’s of IRMOF-1. Optimization of twenty stable configurations of singly adsorbed H 2 in the super-cell cluster is observed to be essential to obtain energy ordering of the five primary sites consistent with experiment and prior benchmark calculations (α >> β > γ > δ ≈ ε). To examine site-to-site interactions that may occur in the high-pressure regime, 64 co-adsorbed H2 within a super-cell cluster have been studied (a theoretical maximum of all adsorption sites, 14 wt %). There, delocalization and/or charge transfer of electrons is observed from the σ orbitals of the H 2 bound at the γ positions into the σ* orbitals of H 2 bound at the α sites leads to stabilization of the interaction of H 2 at the γ, by 1.4 kJ/mol, respectively (using M06-2X/LANL2DZ). Furthermore, this effect has been confirmed to be charge transfer, and not a manifestation of enhanced dispersion at high loading, through natural bond order (NBO) analysis and by comparisons of the square of off-diagonal NBO Fock matrix elements for both density functionals that account for dispersion interactions and Hartree–Fock calculations that ignore dispersion.« less

Fabrication of a novel NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite and its adsorption behavior for Cr(VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Deng, Lin; Shi, Zhou; Wang, Li; Zhou, Shiqing

2017-05-01

A novel magnetic NiFe2O4/Zn-Al layered double hydroxide intercalated with EDTA composite (NiFe2O4/ZnAl-EDTA LDH) was prepared through modified coprecipitation method and employed for adsorptive removal of Cr(VI) from aqueous solution. The adsorbents were characterized using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS). Factors affecting the Cr(VI) adsorption, such as initial solution pH, adsorbent dosage, contact time, initial Cr(VI) concentration, temperature and coexisting ions, were studied systematically. Experiments results show that the magnetic NiFe2O4/ZnAl-EDTA LDH exhibits high adsorption efficiency within a wide pH range of 3.0-7.0 (R>80% at Cr(VI) concentration 50 mg L-1, contact time 360 min, and adsorbent dosage 2 g/L) and quick separation property. The adsorption process is fitted well with the Langmuir isotherm and pseudo-second-order kinetic model. The maximum theoretical adsorption capacity is found to be 77.22 mg g-1 at pH 6.0 and 318 K. The positive ΔH value (2.907 kJ mol-1) and negative ΔG value (-4.722 kJ mol-1) at 298-318 K reveals that the adsorption process is feasible, spontaneous and endothermic. Coexisting anions (PO43-, SO42-, CO32-, HCO3-, Cl-, and NO3-) have no significant effect on Cr(VI) removal. The mechanism study indicates that the adsorption of Cr(VI) onto NiFe2O4/ZnAl-EDTA LDH mainly involves electrostatic attraction and ion exchange interaction. It is interesting to note that a proportion of Cr(VI) adsorbed on the adsorbent surface are reduced to Cr(III) during the adsorption process. Results from this study demonstrate the potential utility of the magnetic NiFe2O4/ZnAl-EDTA LDH that could be developed into a viable technology for efficient removal of Cr(VI) from aqueous solution.

Controlled surface chemistry of diamond/β-SiC composite films for preferential protein adsorption.

PubMed

Wang, Tao; Handschuh-Wang, Stephan; Yang, Yang; Zhuang, Hao; Schlemper, Christoph; Wesner, Daniel; Schönherr, Holger; Zhang, Wenjun; Jiang, Xin

2014-02-04

Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/β-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/β-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/β-SiC ratio of the composite films shows a continuous change from pure diamond to β-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/β-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on β-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/β-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on β-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/β-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/β-SiC gradient film can be a promising material for biomedical applications which require good biocompatibility and selective adsorption of proteins and cells to direct cell migration.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

Simple theoretical determination of the thickness of an alkali monolayer adsorbed on a jellium surface

NASA Astrophysics Data System (ADS)

Wojciechowski, K. F.; Rogowska, J. M.; Bogdanów, H.

1991-05-01

The thickness of a jellium slab representing an alkali monolayer on a jellium surface has been calculated, using parametrized trial functions for the electron density profile at the surface fulfilling the Budd-Vannimenus theorem and the charge neutrality condition. Reasonable values of the thicknesses of potassium, sodium, rubidium and caesium monolayers are obtained, which, contrary to earlier assumptions, depend on the bulk electron density of the substrate.

Adsorption and photodecomposition of Mo(CO)[sub 6] on Si(111) 7[times]7: An infrared reflection absorption spectroscopy study

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

Richter, L.J.; Buntin, S.A.; Chu, P.M.

1994-02-15

The adsorption and photodecomposition of Mo(CO)[sub 6] adsorbed on Si(111) 7[times]7 surfaces has been studied with Auger electron spectroscopy, temperature programmed desorption, low energy electron diffraction and infrared reflection absorption spectroscopy in a single external reflection configuration. The external-reflection technique is demonstrated to have adequate sensitivity to characterize submonolayer coverages of photogenerated Mo(CO)[sub [ital x

Properties of Carbon Nanotubes: Defects, Adsorbates, and Gas Sensing

NASA Astrophysics Data System (ADS)

Eastman, Micah C.

Carbon naotubes and graphene have been a trending research topic in the past decade. These graphitic compounds exhibit numerous advantageous properties (electronic, mechanical, thermal, optical, etc) which industry and researchers alike are excited to take advantage of. Beyond the challenges of yield and controlled growth, there are a number of standing questions which govern some of the more fundamental characteristics of these materials: What role do lattice defects play in the adsorption of gas molecules on the surface of carbon nanotubes? How are the electronic states of the carbon nanotubes influenced by these adsorbed molecules? And how can we develop models to predict useful applications of this knowledge? In order to address these questions, this study combines Raman spectroscopy and electronic measurements carried out in highly controlled environments of carbon nanotube transistors. Assessing these data in conjunction shows that the defect density of a carbon nanotube channel has no correlation with observed threshold voltage shifts, or change in Schottky barrier, due to the presence of ambient oxygen. With these insights in mind, a dynamic adsorption-desorption model is proposed which addresses the oxygen sensitivity of carbon nanotube transistors. Instrumentation and computational developments which facilitated these measurements are also disclosed.

XPS of oxygen atoms on Ag(111) and Ag(110) surfaces: accurate study with SAC/SAC-CI combined with dipped adcluster model.

PubMed

Ishikawa, Atsushi; Nakatsuji, Hiroshi

2013-08-05

O1s core-electron binding energies (CEBE) of the atomic oxygens on different Ag surfaces were investigated by the symmetry adapted cluster-configuration interaction (SAC-CI) method combined with the dipped adcluster model, in which the electron exchange between bulk metal and adsorbate is taken into account properly. Electrophilic and nucleophilic oxygens (O(elec) and O(nuc)) that might be important for olefin epoxidation in a low-oxygen coverage condition were focused here. We consider the O1s CEBE as a key property to distinguish the surface oxygen states, and series of calculation was carried out by the Hartree-Fock, Density functional theory, and SAC/SAC-CI methods. The experimental information and our SAC/SAC-CI results indicate that O(elec) is the atomic oxygen adsorbed on the fcc site of Ag(111) and that O(nuc) is the one on the reconstructed added-row site of Ag(110) and that one- and two-electron transfers occur, respectively, to the O(elec) and O(nuc) adclusters from the silver surface. Copyright © 2013 Wiley Periodicals, Inc.

[Research on fibrinogen adsorption and its transformation response in hemocompatibility].

PubMed

Jin, Jian; Wan, Guojiang; Zhao, Ansha; Lei, Yuechang; Yang, Ying; Huang, Nan; Wu, Xi; Yang, Ping; Leng, Yongxiang; Chen, Junying; Hou, Mingyong

2010-10-01

In this research,enzyme linked immunoassay (ELISA) was used to assay the fibrinogen (FIG) adsorbed on the Ti-O films and on the low temperature isotropic carbon (LTIC) films which were planted in the femoral arteries of 6 mongrel dogs for six months, respectively. The Ti-O films were planted in the dogs' left femoral arteries; the LTIC films as controls were planted in the dogs' right femoral arteries. The contents adsorbed in these two kinds of films were examined by scanning electron microscopy (SEM). The quantities of FIG adhered or denatured on the Ti-O films or LTIC films determined by ELISA, and the platelets adhered on the two kinds of films examined by SEM were of significant difference between the two groups. In the blood vessel, the amount of FIG adhered on biomaterial was related to its component and construction. FIG released electron to the biomaterial and induced the unfolding of C term of the gamma-chain of FIG, and the conjugation point and effect point were exposed. In conclusion, the biomaterial, which has the capability for resisting the electron release from FIG as well as for maintaining the invariable electric condition, will have excellent hemocompatibility.

Elucidating the electron transport in semiconductors via Monte Carlo simulations: an inquiry-driven learning path for engineering undergraduates

NASA Astrophysics Data System (ADS)

Persano Adorno, Dominique; Pizzolato, Nicola; Fazio, Claudio

2015-09-01

Within the context of higher education for science or engineering undergraduates, we present an inquiry-driven learning path aimed at developing a more meaningful conceptual understanding of the electron dynamics in semiconductors in the presence of applied electric fields. The electron transport in a nondegenerate n-type indium phosphide bulk semiconductor is modelled using a multivalley Monte Carlo approach. The main characteristics of the electron dynamics are explored under different values of the driving electric field, lattice temperature and impurity density. Simulation results are presented by following a question-driven path of exploration, starting from the validation of the model and moving up to reasoned inquiries about the observed characteristics of electron dynamics. Our inquiry-driven learning path, based on numerical simulations, represents a viable example of how to integrate a traditional lecture-based teaching approach with effective learning strategies, providing science or engineering undergraduates with practical opportunities to enhance their comprehension of the physics governing the electron dynamics in semiconductors. Finally, we present a general discussion about the advantages and disadvantages of using an inquiry-based teaching approach within a learning environment based on semiconductor simulations.

Growth of aragonite calcium carbonate nanorods in the biomimetic anodic aluminum oxide template

NASA Astrophysics Data System (ADS)

Lee, Inho; Han, Haksoo; Lee, Sang-Yup

2010-04-01

In this study, a biomimetic template was prepared and applied for growing calcium carbonate (CaCO 3) nanorods whose shape and polymorphism were controlled. A biomimetic template was prepared by adsorbing catalytic dipeptides into the pores of an anodic aluminum oxide (AAO) membrane. Using this peptide-adsorbed template, mineralization and aggregation of CaCO 3 was carried out to form large nanorods in the pores. The nanorods were aragonite and had a structure similar to nanoneedle assembly. This aragonite nanorod formation was driven by both the AAO template and catalytic function of dipeptides. The AAO membrane pores promoted generation of aragonite polymorph and guided nanorod formation by guiding the nanorod growth. The catalytic dipeptides promoted the aggregation and further dehydration of calcium species to form large nanorods. Functions of the AAO template and catalytic dipeptides were verified through several control experiments. This biomimetic approach makes possible the production of functional inorganic materials with controlled shapes and crystalline structures.

Treatment of aqueous diethyl phthalate by adsorption using a functional polymer resin.

PubMed

Xu, Zhengwen; Zhang, Weiming; Pan, Bingcai; Lv, Lu; Jiang, Zhengmao

2011-01-01

To study the adsorptive separation efficiency, adsorption and desorption performances of diethyl phthalate (DEP) were investigated with a functional polymer resin (NDA-702). A macroporous polymer resin (XAD-4) and a coal-based granular activated carbon (AC-750) were chosen for comparison. The kinetic adsorption data obeyed the pseudo-second-order rate model, and the adsorption processes were limited by both film and intraparticle diffusions. Adsorption equilibrium data were well fitted by the Freundlich equation, and the larger uptake and higher selection of NDA-702 than AC-750 and XAD-4 was probably due to the microporous structure, phenyl rings and polar groups on NDA-702. Thermodynamic adsorption studies indicated that the test adsorbents spontaneously adsorbed DEP, driven mainly by enthalpy change. Continuous fixed-bed runs demonstrated that there no significant loss of the resin's adsorption capacity and there was complete regeneration of NDA-702. The results suggest that NDA-702 has excellent potential as an adsorption material for water treatment.

Effective adsorption of malachite green using magnetic barium phosphate composite from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Fan; Wei, Zhong; Zhang, Wanning; Cui, Haiyan

2017-07-01

Magnetic Ba3(PO4)2/Fe3O4-nanoparticle (called BPFN) was prepared, characterized, and developed as a low-cost adsorbent for malachite green (MG) from aqueous solution. Factors such as adsorption temperature, pH of solution, dosage of adsorbent, adsorption kinetics and isotherms were investigated. The maximum adsorption capacity obtained in this work was 1639 mg g- 1 at 45 °C and pH 6. The adsorption process fitted the pseudo-first-order kinetic model and Langmuir isotherm model. Evidences from zeta potential, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) data revealed that the adsorption process was driven by electrostatic attraction, the interaction between Lewis base sbnd N(CH3)2 in MG and Lewis acid Ba sites of BPFN. In addition, the BPFN could be easily regenerated by a magnet and the adsorption capacity maintained at 70% after five cycles. The present study suggests that the BPFN had high potential of removing MG from wastewater.

Xenon adsorption on geological media and implications for radionuclide signatures

DOE PAGES

Paul, M. J.; Biegalski, S. R.; Haas, D. A.; ...

2018-02-13

Here, the detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isothermmore » measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures.« less

Xenon adsorption on geological media and implications for radionuclide signatures

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

Paul, M. J.; Biegalski, S. R.; Haas, D. A.

Here, the detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isothermmore » measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures.« less

Xenon adsorption on geological media and implications for radionuclide signatures.

PubMed

Paul, M J; Biegalski, S R; Haas, D A; Jiang, H; Daigle, H; Lowrey, J D

2018-07-01

The detection of radioactive noble gases is a primary technology for verifying compliance with the pending Comprehensive Nuclear-Test-Ban Treaty. A fundamental challenge in applying this technology for detecting underground nuclear explosions is estimating the timing and magnitude of the radionuclide signatures. While the primary mechanism for transport is advective transport, either through barometric pumping or thermally driven advection, diffusive transport in the surrounding matrix also plays a secondary role. From the study of primordial noble gas signatures, it is known that xenon has a strong physical adsorption affinity in shale formations. Given the unselective nature of physical adsorption, isotherm measurements reported here show that non-trivial amounts of xenon adsorb on a variety of media, in addition to shale. A dual-porosity model is then discussed demonstrating that sorption amplifies the diffusive uptake of an adsorbing matrix from a fracture. This effect may reduce the radioxenon signature down to approximately one-tenth, similar to primordial xenon isotopic signatures. Copyright © 2018 Elsevier Ltd. All rights reserved.

Intertwined electron-nuclear motion in frustrated double ionization in driven heteronuclear molecules

NASA Astrophysics Data System (ADS)

Vilà, A.; Zhu, J.; Scrinzi, A.; Emmanouilidou, A.

2018-03-01

We study frustrated double ionization (FDI) in a strongly-driven heteronuclear molecule HeH+ and compare with H2. We compute the probability distribution of the sum of the final kinetic energies of the nuclei for strongly-driven HeH+. We find that this distribution has more than one peak for strongly-driven HeH+, a feature we do not find to be present for strongly-driven H2. Moreover, we compute the probability distribution of the principal quantum number n of FDI. We find that this distribution has several peaks for strongly-driven HeH+, while the respective distribution has one main peak and a ‘shoulder’ at lower principal quantum numbers n for strongly-driven H2. Surprisingly, we find this feature to be a clear signature of the intertwined electron-nuclear motion.

Seasonal carbon dioxide exchange between the regolith and atmosphere of Mars - Experimental and theoretical studies

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Salvail, J. R.; Banerdt, W. B.; Saunders, R. S.; Johansen, L. A.

1982-01-01

CO2 penetration rate measurements have been made through basalt-clay soils under conditions simulating the penetration of the cap-induced seasonal CO2 pressure wave through the topmost regolith of Mars, and results suggest that existing theoretical models for the diffusion of a gas through a porous and highly adsorbing medium may be used to assess the importance of the Martian seasonal regolith-atmosphere CO2 exchange. The maximum effect of thermally driven exchange between the topmost seasonally (thermally) affected regolith and the atmosphere shows that, while this may be of greater importance than the isothermal exchange, the thermally driven exchange would be recognizable only if the pressure wave from CO2 exchanged at high latitudes did not propagate atmospherically faster than the rate at which the exchange itself occurred. This is an unreasonable assumption.

Frontier molecular orbitals of a single molecule adsorbed on thin insulating films supported by a metal substrate: electron and hole attachment energies.

PubMed

Scivetti, Iván; Persson, Mats

2017-09-06

We present calculations of vertical electron and hole attachment energies to the frontier orbitals of a pentacene molecule absorbed on multi-layer sodium chloride films supported by a copper substrate using a simplified density functional theory (DFT) method. The adsorbate and the film are treated fully within DFT, whereas the metal is treated implicitly by a perfect conductor model. We find that the computed energy gap between the highest and lowest unoccupied molecular orbitals-HOMO and LUMO -from the vertical attachment energies increases with the thickness of the insulating film, in agreement with experiments. This increase of the gap can be rationalised in a simple dielectric model with parameters determined from DFT calculations and is found to be dominated by the image interaction with the metal. We find, however, that this simplified model overestimates the downward shift of the energy gap in the limit of an infinitely thick film.

Frontier molecular orbitals of a single molecule adsorbed on thin insulating films supported by a metal substrate: electron and hole attachment energies

NASA Astrophysics Data System (ADS)

Scivetti, Iván; Persson, Mats

2017-09-01

We present calculations of vertical electron and hole attachment energies to the frontier orbitals of a pentacene molecule absorbed on multi-layer sodium chloride films supported by a copper substrate using a simplified density functional theory (DFT) method. The adsorbate and the film are treated fully within DFT, whereas the metal is treated implicitly by a perfect conductor model. We find that the computed energy gap between the highest and lowest unoccupied molecular orbitals—HOMO and LUMO -from the vertical attachment energies increases with the thickness of the insulating film, in agreement with experiments. This increase of the gap can be rationalised in a simple dielectric model with parameters determined from DFT calculations and is found to be dominated by the image interaction with the metal. We find, however, that this simplified model overestimates the downward shift of the energy gap in the limit of an infinitely thick film.

Imaging the wave functions of adsorbed molecules

PubMed Central

Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

2014-01-01

The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust. PMID:24344291

Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni( 1 1 1 )

NASA Astrophysics Data System (ADS)

Bürgi, T.; Trautman, T. R.; Gostein, M.; Lahr, D. L.; Haug, K. L.; Ceyer, S. T.

2002-03-01

The products of the reaction of the most energetic form of hydrogen, gas phase H atoms, with ethylene, acetylene and ethane adsorbed on a Ni(1 1 1) surface at 60 K are probed. Adsorbed ethylidyne (CCH 3) is identified by high resolution electron energy loss spectroscopy to be the major product (30% yield) in all three cases. Adsorbed acetylene is a minor product (3% yield) and arises as a consequence of a dynamic equilibrium between CCH 3 and C 2H 2 in the presence of gas phase H atoms. The observation of the same product for the reaction of H atoms with all three hydrocarbons implies that CCH 3 is the most stable C 2 species in the presence of coadsorbed hydrogen. The rates of CCH 3 production are measured as a function of the time of exposure of H atoms to each hydrocarbon. A simple kinetic model treating each reaction as a pseudo-first order reaction in the hydrocarbon coverage is fit to these data. A mechanism for the formation of CCH 3 via a CHCH 2 intermediate common to all three reactants is proposed to describe this model. The observed instability of the CH 2CH 3 species relative to C 2H 4 plays a role in the formulation of this mechanism as does the observed stability of CHCH 2 species in the presence of coadsorbed hydrogen. The CH 2CH 3 and the CHCH 2 species are produced by the translational activation of ethane and the dissociative ionization of ethane and ethylene, respectively. In addition, the binding energy and the vibrational spectrum of ethane adsorbed on Ni(1 1 1) are determined and exceptionally high resolution vibrational spectra of adsorbed ethylene and acetylene are presented.

Preparation of Silver Nanoparticles from Synthetic and Natural Sources: Remediation Model for PAHs

NASA Astrophysics Data System (ADS)

Abbasi, Maryam; Saeed, Fatima; Rafique, Uzaira

2014-06-01

The emergence of nanoscience and technology is gaining popularity with an increasing demand for metal nanoparticles applicability in various areas such as electronics, catalysis, chemistry, energy and medicine. Metallic nanoparticles are traditionally synthesized by wet chemical techniques, where the chemicals used are quite often toxic and flammable. In this work, an attempt is made to compare the efficiency of two different synthesis methods and application of each for the remediation of poly aromatic hydrocarbons (PAHs). In this regard, silver nanoparticles are prepared by green and wet chemical method using plant extract of garlic (Allium sativum). The extract is known to reduce the metal during synthesis and acts as stabilizing ligand. These synthesized silver nanoparticles (Agp) and (AgW) were applied as adsorbents in synthetic batch mode experiments at varying parameters of pH and temperature. A concentration of 0.01mg/L of Phenanthrene, Anthracene, and Pyrene were induced at fixed dosage of 1mg/Kg of adsorbent. Residual concentration of each PAH was analyzed on UV-Visible spectrophotometer. The results indicated that both adsorbents follow the sequence of Phenanthrene>Pyrene>Anthracene with optimal removal of higher than 85% in each case. A distinguishing privilege is attained by Agp adsorbent showing 3, 3 and 11 orders of magnitude higher efficiency than Agw. It may be attributed to more functional groups in the plant extract participating in binding of PAH to the surface. Each synthesized adsorbents was characterized by FTIR, SEM and EDX. The average particle size was determined to be of the order of 13-26 nm. The study concludes the use of alternate economical and green adsorbents for control of poly aromatic hydrocarbons (PAHs).

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Amino-functionalized mesoporous MCM-41 silica as an efficient adsorbent for water treatment: batch and fixed-bed column adsorption of the nitrate anion

NASA Astrophysics Data System (ADS)

Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava

2017-07-01

In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.

Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: a potential material for the treatment of various toxic heavy metals and its toxicity.

PubMed

Chung, Seung-Gun; Ryu, Jae-Chun; Song, Mi-Kyung; An, Byungryul; Kim, Song-Bae; Lee, Sang-Hyup; Choi, Jae-Woo

2014-02-28

The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1mgg(-1)) and arsenic (71.9mgg(-1)) compared with other adsorbents, such as DABs (158.1 and 0.0mgg(-1)), SZIB (42.9 and 0.0mgg(-1)) and SZMIOIB (54.0 and 5.9mgg(-1)) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer-Emmett-Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for heavy metal treatment than the powdered form. This research provides promising results for the application of MIOIBs as an adsorbent for various heavy metals from wastewater and sewage. Copyright © 2013 Elsevier B.V. All rights reserved.

Laser-driven electron beam and radiation sources for basic, medical and industrial sciences.

PubMed

Nakajima, Kazuhisa

2015-01-01

To date active research on laser-driven plasma-based accelerators have achieved great progress on production of high-energy, high-quality electron and photon beams in a compact scale. Such laser plasma accelerators have been envisaged bringing a wide range of applications in basic, medical and industrial sciences. Here inheriting the groundbreaker's review article on "Laser Acceleration and its future" [Toshiki Tajima, (2010)],(1)) we would like to review recent progress of producing such electron beams due to relativistic laser-plasma interactions followed by laser wakefield acceleration and lead to the scaling formulas that are useful to design laser plasma accelerators with controllability of beam energy and charge. Lastly specific examples of such laser-driven electron/photon beam sources are illustrated.

Removal of Cd(II), Pb(II) and Cr(III) from water using modified residues of Anacardium occidentale L.

NASA Astrophysics Data System (ADS)

Coelho, Gustavo Ferreira; Gonçalves, Affonso Celso; Schwantes, Daniel; Rodríguez, Esperanza Álvarez; Tarley, César Ricardo Teixeira; Dragunski, Douglas; Conradi Junior, Élio

2018-06-01

The pollution of water has been one of the greatest problems faced by the modern society, due to industrialization and urban growth. Rivers, lakes and seas have been continually suffering from the rising concentration of various pollutants, especially toxic elements. This study aimed to evaluate the use of cashew nut shell ( Anacardium occidentale) (CNS), after chemical modification with H2O2, H2SO4 and NaOH, as an new and renewable adsorbent material, for the removal of metals Cd2+, Pb2+ and Cr3+ in aqueous medium. The adsorbents were characterized by its chemical constitution, structure, infrared spectroscopy, morphology, by means of scanning electron microscopy, determination of the point of zero charge, thermogravimetrical analysis and porosimetry assessments. Tests were conducted to determine the optimal conditions (pH vs. adsorbent mass) for adsorption, by means of multivariate analysis using a central composite design. The adsorption kinetics was evaluated by models of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion, while adsorption isotherms were linearized by Langmuir, Freundlich and Dubinin-Radushkevich. The effect of initial concentration, temperature and desorption was also performed. The adsorbents exhibited irregular, spongy and heterogeneous structure. FTIR analysis confirms the presence of hydroxyl, aliphatic, phenolic and carboxylic acid groups, which are favorable adsorption characteristics. The pHPZC of adsorbent is 4.35, 2.50 e 6.92, respectively, for CNS H2O2, H2SO4 and NaOH. The optimum adsorption conditions were as follows: pH 5.0; relation of adsorbent mass/volume of water: 4 g L-1; 40 min of contact time for reaching the equilibration. Results suggest the predominance of chemisorption of Cd2+ and Cr3+. Most of biosorbents exhibited good fit by Langmuir and Freundlich, suggesting the occurrence of adsorption on mono- and multilayers. The adsorbents of cashew nut shell exhibited high removal efficiency of Cd, Pb and Cr from waters.

Controlling the surface photovoltage on WSe2 by surface chemical modification

NASA Astrophysics Data System (ADS)

Liu, Ro-Ya; Ozawa, Kenichi; Terashima, Naoya; Natsui, Yuto; Feng, Baojie; Ito, Suguru; Chen, Wei-Chuan; Cheng, Cheng-Maw; Yamamoto, Susumu; Kato, Hiroo; Chiang, Tai-Chang; Matsuda, Iwao

2018-05-01

The surface photovoltage (SPV) effect is key to the development of opto-electronic devices such as solar-cells and photo-detectors. For the prototypical transition metal dichalcogenide WSe2, core level and valence band photoemission measurements show that the surface band bending of pristine cleaved surfaces can be readily modified by adsorption with K (an electron donor) or C60 (an electron acceptor). Time-resolved pump-probe photoemission measurements reveal that the SPV for pristine cleaved surfaces is enhanced by K adsorption, but suppressed by C60 adsorption, and yet the SPV relaxation time is substantially shortened in both cases. Evidently, adsorbate-induced electronic states act as electron-hole recombination centers that shorten the carrier lifetime.

The Strongest 40 keV Electron Acceleration By ICME-driven Shocks At 1 AU

NASA Astrophysics Data System (ADS)

Yang, L.; Wang, L.; Li, G.; Wimmer-Schweingruber, R. F.; He, J.; Tu, C. Y.; Bale, S. D.

2017-12-01

Here we present a comprehensive case study of the in situ electron acceleration at the two ICME-driven shocks observed by WIND/3DP on February 11, 2000 and July 22, 2004. For the 11 February 2000 shock (the 22 July 2004 shock), the shocked electrons in the downstream show significant flux enhancements over the ambient solar wind electrons at energies up to 40 keV (66 keV) with a 6.0 times (1.9 times) ehancment at 40 keV, the strongest among all the quasi-perpendicular (quasi-parallel) ICME-driven shocks observed by the WIND spacecraft at 1 AU from 1995 through 2014. We find that in both shocks, the shocked electron fluxes at 0.5-40 keV fit well to a double power-law spectrum, J ˜ E-β, bending up at ˜2 keV. In the downstream, these shocked electrons show stronger fluxes in the anti-sunward direction, but their enhancement over the ambient fluxes peaks near 90° pitch angle (PA). For the 11 February 2000 shock, the electron spectral index, β, appears to not vary with the electron PA, while for the 22 July 2004 shock, β roughly decreases from the anti-sunward PA direction to the sunward PA direction. All of these spectral indexes are strongly larger than the theoretical prediction of diffusive shock acceleration. At energies above (below) 2 keV, however, the shocked electron β is similar to the solar wind superhalo (halo) electrons observed at quiet times. These results suggest that the electron acceleration at the ICME-driven shocks at 1 AU may favor the shock drift acceleration, and the superthermal electrons accelerated by the interplanetary shocks may contribute to the formation of the halo and superhalo electron populations in the solar wind.

An ultrafast electron microscope gun driven by two-photon photoemission from a nanotip cathode

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

Bormann, Reiner; Strauch, Stefanie; Schäfer, Sascha, E-mail: schaefer@ph4.physik.uni-goettingen.de

We experimentally and numerically investigate the performance of an advanced ultrafast electron source, based on two-photon photoemission from a tungsten needle cathode incorporated in an electron microscope gun geometry. Emission properties are characterized as a function of the electrostatic gun settings, and operating conditions leading to laser-triggered electron beams of very low emittance (below 20 nm mrad) are identified. The results highlight the excellent suitability of optically driven nano-cathodes for the further development of ultrafast transmission electron microscopy.

Surface modified mesostructured iron oxyhydroxide: synthesis, ecotoxicity, and application.

PubMed

Choi, Jae-Woo; Mahendran, Basuvaraj; Chung, Seung-Gun; Kim, Song-Bae; Lee, Sang-Hyup

2014-12-01

Mesoporous iron oxide, particularly amine-functionalized FeO(x) and FeO(x), was investigated for the removal of toxic heavy metal anions of arsenic and chromium from an aqueous solution. As a control experiment for these toxic compounds, adsorption tests were also performed on Fe3O4 as their counterpart bulk chemical. The mesostructures were confirmed by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscopy (TEM). In addition, we prepared stock suspensions of meso-FeO(x), amine-functionalized meso-FeO(x) and Fe3O4 particles, and compared their acute toxicity against Daphnia magna. The 24 h-EC50 values of the amine-functionalized meso-FeO(x), meso-FeO(x) and Fe particle suspensions used in this study were 1682, 2549 and 95 mg/L, respectively. Organism toxicity caused by spills of adsorbents can be negated when the amine-functionalized meso-FeO(x), up to 1500 mg/L, is used as the adsorbent for heavy metal treatment. The adsorption of arsenic and chromium by the three adsorbents were examined, and different adsorption models were used to describe the equilibrium and kinetic data. The amine-functionalized meso-FeO(x) adsorbent was found to give the maximum adsorption capacities for arsenic and chromium (33.51 and 25.05 mg/g, respectively). This research gives promising results for the application of modified meso-FeO(x) as an adsorbent of toxic heavy metal anions from aqueous solutions.

A potential low cost adsorbent for the removal of cationic dyes from aqueous solutions

NASA Astrophysics Data System (ADS)

Uddin, Md. Tamez; Rahman, Md. Arifur; Rukanuzzaman, Md.; Islam, Md. Akhtarul

2017-10-01

This study was aimed at using mango leaf powder (MLP) as a potential adsorbent for the removal of methylene blue (MB) from aqueous solutions. Characterization of the adsorbent was carried out with scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption analysis. The pH at the point of zero charge of the adsorbent was determined by titration method and was found a value to be 5.6 ± 0.2. Batch studies were performed to evaluate the influence of various experimental parameters like initial solution pH, contact time, initial concentration of dye and adsorbent dosage on the removal of MB. An adsorption-desorption study was carried out resulting the mechanism of adsorption was carried out by electrostatic force of attraction. The adsorption equilibrium time required for the adsorption of MB on MLP was almost 2 h and 85 ± 5% of the total amount of dye uptake was found to occur in the first rapid phase (30 min). The Langmuir and Freundlich isotherm models were used for modeling the adsorption equilibrium. The experimental equilibrium data could be well interpreted by Langmuir isotherm with maximum adsorption capacity of 156 mg/g. To state the sorption kinetics, the fits of pseudo-first-order and pseudo-second-order kinetic models were investigated. It was obtained that the adsorption process followed the pseudo-second-order rate kinetics. The above findings suggest that MLP can be effectively used for decontamination of dye containing wastewater.

Equilibrium, kinetics and mechanism of Au3+, Pd2+ and Ag+ ions adsorption from aqueous solutions by graphene oxide functionalized persimmon tannin.

PubMed

Wang, Zhongmin; Li, Xiaojuan; Liang, Haijun; Ning, Jingliang; Zhou, Zhide; Li, Guiyin

2017-10-01

In this study, a novel bio-adsorbent (PT-GO) was prepared by functionalization persimmon tannin (PT) with graphene oxide (GO) and the effective adsorption behaviors of Au 3+ , Pd 2+ and Ag + ions from aqueous solution was investigated. The PT-GO was characterized by Fourier transform infrared spectrometer (FTIR), scanning electronic microscope (SEM), thermogravimetric analysis (TGA) and Zeta potential. Many influence factors such as pH value, bio-adsorbent dosage, initial concentration of metal ions and contact time were optimized. The maximum adsorption capacity for Au 3+ , Pd 2+ and Ag + was 1325.09mg/g, 797.66mg/g and 421.01mg/g, respectively. The equilibrium isotherm for the adsorption of Au 3+ and Ag + on PT-GO were found to obey the Langmuir model, while the Freundlich model fitted better for Pd 2+ . The adsorption process of Au 3+ , Pd 2+ presented relatively fast adsorption kinetics with pseudo-second-order equation as the best fitting model, while the pseudo-first-order kinetic model was suitable for describing the adsorption of Ag + . Combination of ion exchange, electrostatic interaction and physical adsorption was the mechanism for adsorption of Au 3+ , Pd 2+ and Ag + onto PT-GO bio-adsorbent. Therefore, the PT-GO bio-adsorbent would be an ideal adsorbent for removal of precious metal ions and broaden the potential applications of persimmon tannin in environmental research. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced encapsulation of metoprolol tartrate with carbon nanotubes as adsorbent

NASA Astrophysics Data System (ADS)

Garala, Kevin; Patel, Jaydeep; Patel, Anjali; Dharamsi, Abhay

2011-12-01

A highly water-soluble antihypertensive drug, metoprolol tartrate (MT), was selected as a model drug for preparation of multi-walled carbon nanotubes (MWCNTs)-impregnated ethyl cellulose (EC) microspheres. The present investigation was aimed to increase encapsulation efficiency of MT with excellent adsorbent properties of MWCNTs. The unique surface area, stiffness, strength and resilience of MWCNTs have drawn much anticipation as carrier for highly water-soluble drugs. Carbon nanotubes drug adsorbate (MWCNTs:MT)-loaded EC microspheres were further optimized by the central composite design of the experiment. The effects of independent variables (MWCNTs:MT and EC:adsorbate) were evaluated on responses like entrapment efficiency (EE) and t 50 (time required for 50% drug release). The optimized batch was compared with drug alone EC microspheres. The results revealed high degree of improvement in encapsulation efficiency for MWCNTs:MT-loaded EC microspheres. In vitro drug release study exhibited complete release form drug alone microspheres within 15 h, while by the same time only 50-60% drug was released for MWCNTs-impregnated EC microspheres. The optimized batch was further characterized by various instrumental analyses such as scanning electron microscopy, powder X-ray diffraction and differential scanning calorimetry. The results endorse encapsulation of MWCNTs:MT adsorbate inside the matrix of EC microspheres, which might have resulted in enhanced encapsulation and sustained effect of MT. Hence, MWCNTs can be utilized as novel carriers for extended drug release and enhanced encapsulation of highly water-soluble drug, MT.

State-selective optimization of local excited electronic states in extended systems

NASA Astrophysics Data System (ADS)

Kovyrshin, Arseny; Neugebauer, Johannes

2010-11-01

Standard implementations of time-dependent density-functional theory (TDDFT) for the calculation of excitation energies give access to a number of the lowest-lying electronic excitations of a molecule under study. For extended systems, this can become cumbersome if a particular excited state is sought-after because many electronic transitions may be present. This often means that even for systems of moderate size, a multitude of excited states needs to be calculated to cover a certain energy range. Here, we present an algorithm for the selective determination of predefined excited electronic states in an extended system. A guess transition density in terms of orbital transitions has to be provided for the excitation that shall be optimized. The approach employs root-homing techniques together with iterative subspace diagonalization methods to optimize the electronic transition. We illustrate the advantages of this method for solvated molecules, core-excitations of metal complexes, and adsorbates at cluster surfaces. In particular, we study the local π →π∗ excitation of a pyridine molecule adsorbed at a silver cluster. It is shown that the method works very efficiently even for high-lying excited states. We demonstrate that the assumption of a single, well-defined local excitation is, in general, not justified for extended systems, which can lead to root-switching during optimization. In those cases, the method can give important information about the spectral distribution of the orbital transition employed as a guess.

Removal of lead from aqueous solution using polyacrylonitrile/magnetite nanofibers.

PubMed

Malik, Hammad; Qureshi, Umair Ahmed; Muqeet, Muhammad; Mahar, Rasool Bux; Ahmed, Farooq; Khatri, Zeeshan

2018-02-01

Lead is known for its toxic and non-biodegradable behavior. The consumption of lead-contaminated water is one of the major threat the world is facing nowadays. In this study, polyacrylonitrile (PAN) and magnetite (Fe 3 O 4 ) composite nanofiber adsorbent was developed for Pb 2+ removal in batch mode. The synthesis was done by a simple and scalable process of electrospinning followed by chemical precipitation of Fe 3 O 4 . The nanofibers thus obtained were characterized through FTIR, zeta potential analyzer, and scanning electron microscope (SEM) and were analyzed for their adsorption capability for Pb 2+ ions. The amount of metal ion adsorbed was influenced by the initial metal ion concentration, the time the adsorbent was in contact, the amount of nanofiber, and the pH of the solution. The experimental data fitted well with pseudo 2nd-order and Langmuir adsorption isotherm model. The nanofibers showed high adsorption capability and could be recommended for Pb 2+ removal successfully.

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

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

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.

2015-09-01

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminalmore » hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Graphene-encapsulated silica as matrix solid-phase dispersion extraction sorbents for the analysis of poly-methoxylated flavonoids in the leaves of Murraya panaculata (L.) Jack.

PubMed

Sun, Ting; Li, Xuwen; Yang, Jie; Li, Lanjie; Jin, Yongri; Shi, Xiaolei

2015-06-01

In this study, graphene-encapsulated silica was synthesized by a hydrothermal reduction strategy. The presence of silica in graphene was identified by Fourier-transform infrared spectrometry, X-ray diffraction and scanning electron microscopy. The graphene-encapsulated silica subsequently was used as adsorbent for matrix solid-phase dispersion extraction of poly-methoxylated flavonoids from the dried leaves of Murraya panaculata (L.) Jack. Compared with the other adsorbents (graphene, silica gel, C18 silica, neutral alumina, diatomaceous earth) and without any adsorbents, better results were obtained. Then a method for analysis of poly-methoxylated flavonoids was established by coupling matrix solid-phase dispersion extraction with ultra high performance liquid chromatography and UV detection. Compared with reflux extraction and ultrasonic extraction, the proposed method is quicker, more efficient and more environmental protection. Less than 10 min is needed from extraction to detection. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

DOE PAGES

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.; ...

2015-09-01

For the noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The fi ndings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. Moreover, the structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogenmore » bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Fe-FeS2 adsorbent prepared with iron powder and pyrite by facile ball milling and its application for arsenic removal.

PubMed

Min, Xiaobo; Li, Yangwenjun; Ke, Yong; Shi, Meiqing; Chai, Liyuan; Xue, Ke

2017-07-01

Arsenic is one of the major pollutants and a worldwide concern because of its toxicity and chronic effects on human health. An adsorbent of Fe-FeS 2 mixture for effective arsenic removal was successfully prepared by mechanical ball milling. The products before and after arsenic adsorption were characterized with scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent shows high arsenic removal efficiency when molar ratio of iron to pyrite is 5:5. The experimental data of As(III) adsorption are fitted well with the Langmuir isotherm model with a maximal adsorption capacity of 101.123 mg/g. And As(V) data were described perfectly by the Freundlich model with a maximal adsorption capacity of 58.341 L/mg. As(III) is partial oxidized to As(V) during the adsorption process. High arsenic uptake capability and cost-effectiveness of waste make it potentially attractive for arsenic removal.

Simulation Study on Understanding the Spin Transport in MgO Adsorbed Graphene Based Magnetic Tunnel Junction

NASA Astrophysics Data System (ADS)

Raturi, Ashish; Choudhary, Sudhanshu

2016-11-01

First principles calculations of spin-dependent electronic transport properties of magnetic tunnel junction (MTJ) consisting of MgO adsorbed graphene nanosheet sandwiched between two CrO2 half-metallic ferromagnetic (HMF) electrodes is reported. MgO adsorption on graphene opens bandgap in graphene nanosheet which makes it more suitable for use as a tunnel barrier in MTJs. It was found that MgO adsorption suppresses transmission probabilities for spin-down channel in case of parallel configuration (PC) and also suppresses transmission in antiparallel configuration (APC) for both spin-up and spin-down channel. Tunnel magneto-resistance (TMR) of 100% is obtained at all bias voltages in MgO adsorbed graphene-based MTJ which is higher than that reported in pristine graphene-based MTJ. HMF electrodes were found suitable to achieve perfect spin filtration effect and high TMR. I-V characteristics for both parallel and antiparallel magnetization states of junction are calculated. High TMR suggests its usefulness in spin valves and other spintronics-based applications.

Work Functions for Models of Scandate Surfaces

NASA Technical Reports Server (NTRS)

Mueller, Wolfgang

1997-01-01

The electronic structure, surface dipole properties, and work functions of scandate surfaces have been investigated using the fully relativistic scattered-wave cluster approach. Three different types of model surfaces are considered: (1) a monolayer of Ba-Sc-O on W(100), (2) Ba or BaO adsorbed on Sc2O3 + W, and (3) BaO on SC2O3 + WO3. Changes in the work function due to Ba or BaO adsorption on the different surfaces are calculated by employing the depolarization model of interacting surface dipoles. The largest work function change and the lowest work function of 1.54 eV are obtained for Ba adsorbed on the Sc-O monolayer on W(100). The adsorption of Ba on Sc2O3 + W does not lead to a low work function, but the adsorption of BaO results in a work function of about 1.6-1.9 eV. BaO adsorbed on Sc2O3 + WO3, or scandium tungstates, may also lead to low work functions.

Removal of methyl orange and methylene blue dyes from aqueous solution using lala clam (Orbicularia orbiculata) shell

NASA Astrophysics Data System (ADS)

Eljiedi, Arwa Alseddig Ahmed; Kamari, Azlan

2017-05-01

Textile effluents are considered as potential sources of water pollution because they contain toxic dyes. In the present study, lala clam shell was used as an alternative low-cost adsorbent for the removal of two harmful dyes, namely methyl orange (MO) and methylene blue (MB) from aqueous solution. Batch adsorption studies were carried out by varying experimental parameters such as solution pH, initial concentration and adsorbent dosage. The optimum pH values for MO and MB removal were pH 2.0 and pH 8.0, respectively. At an initial MO and MB concentration of 20 mg/L, the maximum removal percentage of MO and MB were 18.9 % and 81.3 %, respectively. The adsorption equilibrium data were correlated with both Langmuir and Freundlich isotherm models. The biomass adsorbent was characterised using Field Emission Scanning Electron Microscope (FESEM) and Fourier Transform Infrared Spectrometer (FTIR). Results from this study suggest that lala clam shell, a fishery waste, can be beneficial for water treatment.

Numerical analysis on the synergy between electron cyclotron current drive and lower hybrid current drive in tokamak plasmas

NASA Astrophysics Data System (ADS)

Chen, S. Y.; Hong, B. B.; Liu, Y.; Lu, W.; Huang, J.; Tang, C. J.; Ding, X. T.; Zhang, X. J.; Hu, Y. J.

2012-11-01

The synergy between electron cyclotron current drive (ECCD) and lower hybrid current drive (LHCD) is investigated numerically with the parameters of the HL-2A tokamak. Based on the understanding of the synergy mechanisms, a high current driven efficiency or a desired radial current profile can be achieved through properly matching the parameters of ECCD and LHCD due to the flexibility of ECCD. Meanwhile, it is found that the total current driven by the electron cyclotron wave (ECW) and the lower hybrid wave (LHW) simultaneously can be smaller than the sum of the currents driven by the ECW and LHW separately, when the power of the ECW is much larger than the LHW power. One of the reasons leading to this phenomenon (referred to as negative synergy in this context) is that fast current-carrying electrons tend to be trapped, when the perpendicular velocity driven by the ECW is large and the parallel velocity decided by the LHW is correspondingly small.

Electron-rich driven electrochemical solid-state amorphization in Li-Si alloys.

PubMed

Wang, Zhiguo; Gu, Meng; Zhou, Yungang; Zu, Xiaotao; Connell, Justin G; Xiao, Jie; Perea, Daniel; Lauhon, Lincoln J; Bang, Junhyeok; Zhang, Shengbai; Wang, Chongmin; Gao, Fei

2013-09-11

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governs the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability, and phase equilibrium.

Electron-Rich Driven Electrochemical Solid-State Amorphization in Li-Si Alloys

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

Wang, Zhiguo; Gu, Meng; Zhou, Yungang

2013-08-14

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governsmore » the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability and phase equilibrium.« less

Time-dependent deformation of gas shales - role of rock framework versus reservoir fluids

NASA Astrophysics Data System (ADS)

Hol, Sander; Zoback, Mark

2013-04-01

Hydraulic fracturing operations are generally performed to achieve a fast, drastic increase of permeability and production rates. Although modeling of the underlying short-term mechanical response has proven successful via conventional geomechanical approaches, predicting long-term behavior is still challenging as the formation interacts physically and chemically with the fluids present in-situ. Recent experimental work has shown that shale samples subjected to a change in effective stress deform in a time-dependent manner ("creep"). Although the magnitude and nature of this behavior is strongly related to the composition and texture of the sample, also the choice of fluid used in the experiments affects the total strain response - strongly adsorbing fluids result in more, recoverable creep. The processes underlying time-dependent deformation of shales under in-situ stresses, and the long-term impact on reservoir performance, are at present poorly understood. In this contribution, we report triaxial mechanical tests, and theoretical/thermodynamic modeling work with the aim to identify and describe the main mechanisms that control time-dependent deformation of gas shales. In particular, we focus on the role of the shale solid framework versus the type and pressure of the present pore fluid. Our experiments were mainly performed on Eagle Ford Shale samples. The samples were subjected to cycles of loading and unloading, first in the dry state, and then again after equilibrating them with (adsorbing) CO2 and (non-adsorbing) He at fluid pressures of 4 MPa. Stresses were chosen close to those persisting under in-situ conditions. The results of our tests demonstrate that likely two main types of deformation mechanisms operate that relate to a) the presence of microfractures as a dominating feature in the solid framework of the shale, and b) the adsorbing potential of fluids present in the nanoscale voids of the shale. To explain the role of adsorption in the observed compaction creep, we postulate a serial coupling between 1) stress-driven desorption of the fluid species, 2) diffusion of the desorbed species out of the solid, and 3) consequent shrinkage. We propose a model in which the total shrinkage of the solid (Step 3) that is measured as bulk compaction, is driven by a change in stress state (Step 1), and evolves in time controlled by the diffusion characteristics of the system (Step 2). Our experimental and modeling study shows that both the nature of the solid framework of the shale, as well as the type and pressure of pore fluids affect the long-term in-situ mechanical behavior of gas shale reservoirs.

EXAFS Reveals the Mechanism of U Isotope Fractionation During Adsorption to Mn Oxyhydroxide

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.; Brennecka, G.; Bargar, J.; Weyer, S.; Anbar, A. D.

2010-12-01

Natural variations in the ratio of 238U/235U due to “stable” isotope fractionation have now been reported for a range of geological samples [1-3]. Among the observed variations are a small difference in 238U/235U between seawater and ferromanganese sediments (seawater slightly heavier) and a larger difference, with opposite sense, between seawater and black shales (seawater lighter). These variations suggest that long-term changes in the proportions of oxic and anoxic/sulfidic sinks for U in the ocean over Earth’s history may be recorded as shifts in the isotopic compositions of marine sediments. Thus U isotopes are a potential paleoredox proxy for the oceans, as suggested by [4]. In order to investigate the mechanism behind fractionation of U isotopes in oxidizing marine environments, we previously conducted simple adsorption experiments in which an isotopically known pool of dissolved U partly adsorbed onto synthetic birnessite, a common Mn oxyhydroxide in hydrogenetic ferromanganese crusts. Our experimental result agreed very well with that observed between seawater and natural ferromanganese sediments: δ238U/235U of adsorbed U was 0.2‰ lighter than δ238U/235U of dissolved U [5]. The magnitude of fractionation is constant as a function of experimental duration and fraction of U adsorbed, suggesting an equilibrium isotope effect. Many metal isotope effects are driven by changes in oxidation state for the metal of interest. Because both dissolved and adsorbed U are hexavalent in this system, a redox reaction cannot be causing isotope fractionation. We therefore hypothesized that a difference in uranium’s coordination environment between dissolved and adsorbed U is likely responsible for the isotope effect. We analyzed a sample from our experimental study with extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparison of the EXAFS spectrum of U adsorbed on birnessite with the spectra of aqueous U species (UO22+ and UO2(CO3)34-) reveals subtle, but important differences in the U-O coordination shell between dissolved and adsorbed U. In particular, there is an increase in disorder in the bond distances to equatorial oxygens in the adsorbed complex. Our EXAFS data support our hypothesis that a difference in coordination chemistry drives the isotope effect observed in our experiments. The same mechanism may well explain the U isotope fractionation observed between seawater and hydrogenetic ferromanganese nodules, although a similar investigation of U isotope behavior during adsorption to Fe oxyhydroxides should be undertaken. [1] Weyer et al. (2008) GCA 72, 345. [2] Stirling et al. (2007) EPSL 264, 208. [3] Bopp et al. (2009) Geology, 37, 611. [4] Montoya-Pino et al. (2010) Geology 38, 315. [5] Brennecka et al. (2008) GCA 72(12) Suppl., A114.

Adsorptive Separation of Methanol-Acetone on Isostructural Series of Metal-Organic Frameworks M-BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts.

PubMed

Wu, Ying; Chen, Huiyong; Xiao, Jing; Liu, Defei; Liu, Zewei; Qian, Yu; Xi, Hongxia

2015-12-09

The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.

Orienting proteins by nanostructured surfaces: evidence of a curvature-driven geometrical resonance.

PubMed

Messina, Grazia M L; Bocchinfuso, Gianfranco; Giamblanco, Nicoletta; Mazzuca, Claudia; Palleschi, Antonio; Marletta, Giovanni

2018-04-26

Experimental and theoretical reports have shown that nanostructured surfaces have a dramatic effect on the amount of protein adsorbed and the conformational state and, in turn, on the performances of the related devices in tissue engineering strategies. Here we report an innovative method to prepare silica-based nanostructured surfaces with a reproducible, well-defined local curvature, consisting of ordered hexagonally packed arrays of curved hemispheres, from nanoparticles of different diameters (respectively 147 nm, 235 nm and 403 nm). The nanostructured surfaces have been made chemically homogeneous by partially embedding silica nanoparticles in poly(hydroxymethylsiloxane) films, further modified by means of UV-O3 treatments. This paper has been focused on the experimental and theoretical study of laminin, taken as a model protein, to study the nanocurvature effects on the protein configuration at nanostructured surfaces. A simple model, based on the interplay of electrostatic interactions between the charged terminal domains of laminin and the nanocurved charged surfaces, closely reproduces the experimental findings. In particular, the model suggests that nanocurvature drives the orientation of rigid proteins by means of a "geometrical resonance" effect, involving the matching of dimensions, charge distribution and spatial arrangement of both adsorbed molecules and adsorbent nanostructures. Overall, the results pave the way to unravel the nanostructured surface effects on the intra- and inter-molecular organization processes of proteins.

First-principles study of structure, electronic properties and stability of tungsten adsorption on TiC(111) surface with disordered vacancies

NASA Astrophysics Data System (ADS)

Ilyasov, Victor V.; Pham, Khang D.; Zhdanova, Tatiana P.; Phuc, Huynh V.; Hieu, Nguyen N.; Nguyen, Chuong V.

2017-12-01

In this paper, we systematically investigate the atomic structure, electronic and thermodynamic properties of adsorbed W atoms on the polar Ti-terminated TixCy (111) surface with different configurations of adsorptions using first principle calculations. The bond length, adsorption energy, and formation energy for different reconstructions of the atomic structure of the W/TixCy (111) systems were established. The effect of the tungsten coverage on the electronic structure and the adsorption mechanism of tungsten atom on the TixCy (111) are also investigated. We also suggest the possible mechanisms of W nucleation on the TixCy (111) surface. The effective charges on W atoms and nearest-neighbor atoms in the examined reconstructions were identified. Additionally, we have established the charge transfer from titanium atom to tungsten and carbon atoms which determine by the reconstruction of the local atomic and electronic structures. Our calculations showed that the charge transfer correlates with the electronegativity of tungsten and nearest-neighbor atoms. We also determined the effective charge per atom of titanium, carbon atoms, and neighboring adsorbed tungsten atom in different binding configurations. We found that, with reduction of the lattice symmetry associated with titanium and carbon vacancies, the adsorption energy increases by 1.2 times in the binding site A of W/TixCy systems.

Complementary roles of benzylpiperazine and iodine 'vapor' in the strong enhancement of orange photoluminescence from CuI(1 1 1) thin film.

PubMed

Rawal, Takat B; Turkowski, Volodymyr; Rahman, Talat S

2014-05-07

We have employed density functional theory, corrected by the on-site electron-electron repulsion energy U, to clarify the mechanism behind the enhanced orange photoluminescence (PL) of a CuI(1 1 1) thin film conjugated with a benzylpiperazine (BZP) molecule in the presence of an iodine 'vapor' atom. Our results demonstrated that the adsorbed molecule and the 'vapor' atom play complementary roles in producing the PL. The latter, in attaching to the film surface, creates a hole-trapping surface state located ~0.25 eV above the valence band-edge of the film, in good agreement with ~0.2 eV reported in experiments. Upon photo-excitation of the BZP/CuI(1 1 1) system in the presence of surface iodine 'vapor' atoms, excited electrons are transferred into the conduction band of CuI, and holes are trapped by the 'vapor' atoms. These holes, in turn, quickly relax into the HOMO state of the BZP molecule, owing to the fact that the molecule adsorbs on the film surface in the immediate vicinity of a 'vapor' atom. Relaxed holes subsequently recombine with excited electrons in the conduction band of the CuI film, thereby producing a luminescence peak at ~2.1 eV, in qualitative agreement with experimental findings.

Functional exploration of extracellular polymeric substances (EPS) in the bioleaching of obsolete electric vehicle LiNixCoyMn1-x-yO2 Li-ion batteries.

PubMed

Wang, Jia; Tian, Bingyang; Bao, Yihui; Qian, Can; Yang, Yiran; Niu, Tianqi; Xin, Baoping

2018-07-15

As a fairly new concept, the recovery of valuable metals from urban mining by using bioleaching has become a hotspot. However, the function of extracellular polymeric substances (EPS) in the bioleaching of urban mining gains little attention. The current study used spent EV LIBs to represent urban mining products and systematically explored the function and role of EPS in the attachment of cells to the cathodes, formation of aggregates (cell-EPS-cathode), variation in the electrical and surface properties of the aggregates, concentration of both Fe 2+ and Fe 3+ surrounding the aggregates, electron transfer inside the aggregates and metals released from the aggregates. The results indicated that a strong adhesion of cells to the cathodes occurs mediated by EPS via both hydrophobic force as a main role and electrostatic force as a minor role. Second, the EPS not only adsorb Fe 3+ but also more strongly adsorb Fe 2+ to concentrate the Fe 2+ /Fe 3+ cycle inside the aggregates, witnessing stronger reductive attack on the high valence state of metals as a contact reductive mechanism. Third, the retention or addition of EPS elevated the electronic potential and reduced the electronic resistance to lift the corrosion electric current, thereby boosting the electron transfer and metal dissolution. Copyright © 2018 Elsevier B.V. All rights reserved.

Probing plasma wakefields using electron bunches generated from a laser wakefield accelerator

NASA Astrophysics Data System (ADS)

Zhang, C. J.; Wan, Y.; Guo, B.; Hua, J. F.; Pai, C.-H.; Li, F.; Zhang, J.; Ma, Y.; Wu, Y. P.; Xu, X. L.; Mori, W. B.; Chu, H.-H.; Wang, J.; Lu, W.; Joshi, C.

2018-04-01

We show experimental results of probing the electric field structure of plasma wakes by using femtosecond relativistic electron bunches generated from a laser wakefield accelerator. Snapshots of laser-driven linear wakes in plasmas with different densities and density gradients are captured. The spatiotemporal evolution of the wake in a plasma density up-ramp is recorded. Two parallel wakes driven by a laser with a main spot and sidelobes are identified in the experiment and reproduced in simulations. The capability of this new method for capturing the electron- and positron-driven wakes is also shown via 3D particle-in-cell simulations.

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism

NASA Astrophysics Data System (ADS)

Lunkenheimer, Peter; Müller, Jens; Krohns, Stephan; Schrettle, Florian; Loidl, Alois; Hartmann, Benedikt; Rommel, Robert; de Souza, Mariano; Hotta, Chisa; Schlueter, John A.; Lang, Michael

2012-09-01

Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, as for conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerable interest. Here we provide evidence for ferroelectricity, accompanied by antiferromagnetic spin order, in a two-dimensional organic charge-transfer salt, thus representing a new class of multiferroics. We propose a charge-order-driven mechanism leading to electronic ferroelectricity in this material. Quite unexpectedly for electronic ferroelectrics, dipolar and spin order arise nearly simultaneously. This can be ascribed to the loss of spin frustration induced by the ferroelectric ordering. Hence, here the spin order is driven by the ferroelectricity, in marked contrast to the spin-driven ferroelectricity in helical magnets.

Cation–hydroxide–water coadsorption inhibits the alkaline hydrogen oxidation reaction

DOE PAGES

Chung, Hoon Taek; Martinez, Ulises; Matanovic, Ivana; ...

2016-10-24

Rotating disk electrode voltammograms and infrared reflection absorption spectra indicate that the hydrogen oxidation reaction of platinum in 0.1 M tetramethylammonium hydroxide solution is adversely impacted by time-dependent and potential-driven cation–hydroxide–water coadsorption. Impedance analysis suggests that the hydrogen oxidation reaction inhibition is mainly caused by the hydrogen diffusion barrier of the coadsorbed trilayer rather than intuitive catalyst site blocking by the adsorbed cation species. Finally, these results give useful insights on how to design ionomeric binders for advanced alkaline membrane fuel cells.

M4FT-15OR03100421: Status Report on Alkaline Conditioning Studies

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

Tsouris, Costas; Brown, Suree; Janke, Christopher James

2015-05-01

Significant progress in understanding the role of alkaline conditioning of polyethylene-fiber adsorbent, developed at the Oak Ridge National Laboratory (ORNL), is demonstrated in this report, which is essentially a manuscript prepared for publication in the journal Industrial & Engineering Chemistry Research of the American Chemical Society. The manuscript describes the influence of various parameters involved in adsorbent alkaline conditioning, including base concentration and duration and temperature of conditioning, on the uranium uptake history by the adsorbent. Various solutions have been used to determine the influence of conditioning parameters including (i) a screening solution containing uranyl nitrate at approximately 8 ppmmore » and sodium bicarbonate and sodium chloride at concentrations similar to those found in seawater, (ii) seawater spiked with approximately 75 ppb uranium, and (iii) natural seawater. In addition to concentration measurements by inductively coupled plasma (ICP) spectroscopy to determine the uranium uptake capacity and kinetics, spectroscopic methods such as Fourier transformed infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy were employed to investigate the effect of base treatment on the various chemical bonds of the adsorbent. Scanning electron microscopy (SEM) has also been employed to determine structural effects of the alkali on the adsorbent. The results are summarized as follows: 1. Alkali conditioning is necessary to prepare the adsorbent for uranium uptake. ICP analysis showed that without alkali conditioning, no appreciable uranium adsorption occurs. 2. FTIR showed that the base converts amidoxime to carboxylate groups. 3. FTIR showed that formation of carboxylate groups is irreversible and reduces the selectivity of the adsorbent toward uranium. 4. NMR showed that alkali conditioning leads also to the formation of cyclic imidedioxime, which is suspected to bind uranium, vanadium, iron, copper, and other metals. 5. Uptake of V, Fe, and Cu follows the same trend as that of uranium. Uptake of Ca, Mg, and Zn ions increases with increasing KOH conditioning time due to formation of carboxylate groups. 6. SEM showed that long conditioning times may also lead to adsorbent degradation. 7. The optimal conditioning parameters are: 0.44 M KOH, 70 C, for 1 hour. The results of this study are useful in the selection of optimal values of the parameters involved in preparing amidoxime-based adsorbent for uranium uptake from seawater. Additional work is still ongoing to provide a complete understanding of the chemistry of base conditioning and its role on the functioning of the adsorbent.« less

Vibrational Studies of Adsorbate-Induced Reconstruction on Molybdenum Surfaces.

NASA Astrophysics Data System (ADS)

Lopinski, Gregory Peter

Adsorbate-induced rearrangement of the substrate structure strongly modifies the adsorbate-substrate and adsorbate-adsorbate interactions, leading to the complex behavior observed in many chemisorption systems. In this thesis the H/Mo(211), O/Mo(211) and Na/Mo(100) systems have been studied using high resolution electron energy loss spectroscopy (HREELS) to observe vibrations of the adsorbed atoms. The vibrational data is correlated with observations of the long-range order probed by LEED as well as the work function changes induced by adsorption. Adsorbate -induced substrate reconstruction plays an important role in all three of these systems. Studies of the coadsorption systems O+H/Mo(211) and Na+O/Mo(100) indicate how these effects can influence interactions between adsorbates. For H/Mo(211), above 1ML a (1 x 1) to (1 x 2) transition is observed and attributed to modification of the substrate periodicity. Below 1ML, H atoms are bridge bonded and induce local distortions of the substrate. The transition to the (1 x 2) phase involves the ordering of these displacements and occupation of three-fold sites partially populated by conversion of the bridge bonded species. This conversion accounts for the sawtooth-like coverage dependence of the work function. The structural model proposed for this system is also supported by the desorption parameters and partial molar entropy extracted from adsorption isobars. Oxygen adsorption on Mo(211) involves the occupation of multiple binding sites, with both the long-range order and the local geometry of the adsorbate phases strongly temperature dependent. Coadsorption of low coverages of oxygen and hydrogen leads to segregation of the two adsorbates which can be understood in terms of a substrate-mediated repulsive interaction between O and H. For Na/Mo(100), the frequency of the Na-Mo symmetric stretch mode does not shift with coverage although the mode intensity is strongly coverage dependent. The absence of a frequency shift as well as the form of the observed coverage dependence differ from the predictions of the traditional charge transfer model of alkali adsorption. The relevance of the vibrational results to the Na-induced structural changes observed on this surface are also discussed. Na adsorption has been found to dramatically alter the interaction of oxygen with this surface, due to the presence of a strong attractive interaction between Na and O that forces O atoms to occupy a different binding site than on a clean surface.

Simulation of high-energy radiation belt electron fluxes using NARMAX-VERB coupled codes

PubMed Central

Pakhotin, I P; Drozdov, A Y; Shprits, Y Y; Boynton, R J; Subbotin, D A; Balikhin, M A

2014-01-01

This study presents a fusion of data-driven and physics-driven methodologies of energetic electron flux forecasting in the outer radiation belt. Data-driven NARMAX (Nonlinear AutoRegressive Moving Averages with eXogenous inputs) model predictions for geosynchronous orbit fluxes have been used as an outer boundary condition to drive the physics-based Versatile Electron Radiation Belt (VERB) code, to simulate energetic electron fluxes in the outer radiation belt environment. The coupled system has been tested for three extended time periods totalling several weeks of observations. The time periods involved periods of quiet, moderate, and strong geomagnetic activity and captured a range of dynamics typical of the radiation belts. The model has successfully simulated energetic electron fluxes for various magnetospheric conditions. Physical mechanisms that may be responsible for the discrepancies between the model results and observations are discussed. PMID:26167432

Laser-driven electron beam and radiation sources for basic, medical and industrial sciences

PubMed Central

NAKAJIMA, Kazuhisa

2015-01-01

To date active research on laser-driven plasma-based accelerators have achieved great progress on production of high-energy, high-quality electron and photon beams in a compact scale. Such laser plasma accelerators have been envisaged bringing a wide range of applications in basic, medical and industrial sciences. Here inheriting the groundbreaker’s review article on “Laser Acceleration and its future” [Toshiki Tajima, (2010)],1) we would like to review recent progress of producing such electron beams due to relativistic laser-plasma interactions followed by laser wakefield acceleration and lead to the scaling formulas that are useful to design laser plasma accelerators with controllability of beam energy and charge. Lastly specific examples of such laser-driven electron/photon beam sources are illustrated. PMID:26062737

Atrazine Adsorption Potential of Leonardite from Mae Moh Power Plant

NASA Astrophysics Data System (ADS)

Rittirat, A.; Chokejaroenrat, C.; Watcharenwong, A.

2018-01-01

Leonardite is an immature coal from the power plant, which we obtained from Lampang province, Thailand. It is known to contain relatively high humic substance making it suitable as the soil conditioner in agricultural aspect and as an adsorbent. Our objectives were: [1] to determine the leonardite physical and chemical properties (e.g., cation exchange capacity, organic matter content, and electron microscope imaging), and (2) to quantify the adsorption efficiency of atrazine from the soil. We used varied amount of leonardite ranging from 0.05 to 1.60 g to adsorb 8 mg L-1 of atrazine from aqueous solution in a batch experiment. This experiment was achieved within 48 hours so that the equilibrium time and isotherm parameters can be determined. The uncarbonized leonardite characteristic revealed that it could adsorb atrazine as its surface possesses mesopore type, relatively high cation exchange capacity (59.89 cmol Kg-1), and high organic matter of 21.62 %. The isotherm study showed the equilibrium time of 24 hours and adsorption isotherm was Langmuir with qmax of 3.9683 mg g-1. This study provides proof that leonardite used in the agricultural field can also be useful to adsorb atrazine and simultaneously slow the percolating process of atrazine before contaminating groundwater.

Highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste with amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent.

PubMed

Bao, Shuangyou; Tang, Lihong; Li, Kai; Ning, Ping; Peng, Jinhui; Guo, Huibin; Zhu, Tingting; Liu, Ye

2016-01-15

Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent was used as a novel sorbent to highly selective removal of Zn(II) ion from hot-dip galvanizing pickling waste in the presence of Fe(II). These hot-dip galvanizing pickling waste mainly contain ZnCl2 and FeCl2 in aqueous HCl media. The properties of this magnetic adsorbent were examined by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), infrared spectrometer (FT-IR) and BET surface area measurements. Various factors influencing the adsorption of Zn(II) ion such as initial concentration of metal ions, the amount of adsorbent, pH value of the solutions, the concentration of coexisting iron ion were investigated by batch experiments. The results indicated that the adsorption equilibrium data obeyed the Freundlich model with maximum adsorption capacities for Zn(II) to 169.5mg/g. The maximum adsorption occurred at pH 5±0.1 and Fe(II) interferences had no obvious influence. This work provides a potential and unique technique for zinc ion removal from hot-dip galvanizing pickling waste. Copyright © 2015 Elsevier Inc. All rights reserved.

Surface sodium lignosulphonate-immobilized sawdust particle as an efficient adsorbent for capturing Hg2+ from aqueous solution.

PubMed

Gao, Shan; Luo, Tiantian; Zhou, Qi; Luo, Wenjun; Li, Haifeng; Jing, Luru

2018-05-01

In this work, the soluble sodium lignosulphonate (LS Na ) molecules were successfully grafted onto the surface of pine sawdust (PSD) particles to obtain an efficient adsorbent (PSD-LS) for removing Hg 2+ from wastewater. In advance, the surface of sawdust particles were carboxymethylated by chloroacetic acid, the LS Na would be anchored on the surface by a heterogeneous esterification reaction occurred between the hydroxyl of LS Na and carboxyl on PSD surface. The resultant product (PSD-LS) exhibited a good adsorption performance for Hg 2+ with adsorption capacity up to 164.77 mg/g and it was characterized by scanning electron microscope (SEM), energy dispersive X-ray diffraction (EDX), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The effects of pH, contact time, adsorption temperature and initial concentration on the adsorption of Hg 2+ were investigated. Results showed that the pseudo-second-order kinetics and Langmuir isotherm model could describe the adsorption process better. In addition, the composite adsorbent has outstanding reusability with high and stable desorption rates under several continuous cycle. These findings suggested that PSD-LS was a potential adsorbent to remove hazardous metal ions from wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.

Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

NASA Technical Reports Server (NTRS)

Tseng, S.-S.; Chang, S.

1975-01-01

Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

Carbon coated magnetic nanoparticles as a novel magnetic solid phase extraction adsorbent for simultaneous extraction of methamphetamine and ephedrine from urine samples.

PubMed

Taghvimi, Arezou; Hamishehkar, Hamed

2017-01-15

This paper develops a highly selective, specific and efficient method for simultaneous determination of ephedrine and methamphetamine by a new carbon coated magnetic nanoparticles (C/MNPs) as a magnetic solid phase extraction (MSPE) adsorbent in biological urine medium. The characterization of synthesized magnetic nano adsorbent was completely carried out by various characterization techniques like Fourier transform infrared (FT-IR) spectroscopy, powder x-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). Nine important parameters influencing extraction efficiency including amount of adsorbent, amounts of sample volume, pH, type and amount of extraction organic solvent, time of extraction and desorption, agitation rate and ionic strength of extraction medium, were studied and optimized. Under optimized extraction conditions, a good linearity was observed in the concentration range of 100-2000ng/mL for ephedrine and 100-2500ng/mL for methamphetamine. Analysis of positive urine samples was carried out by proposed method with the recovery of 98.71 and 97.87% for ephedrine and methamphetamine, respectively. The results indicated that carbon coated magnetic nanoparticles could be applied in clinical and forensic laboratories for simultaneous determination of abused drugs in urine media. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of the carbonaceous materials obtained from different agro-industrial wastes.

PubMed

Ensuncho-Muñoz, A E; Carriazo, J G

2015-01-01

This paper reports the preparation and characterization of carbonaceous materials obtained from three types of vegetable wastes provided by agricultural industries. Soft carbonization (280°C) and H3PO4-activation procedures were used to convert the agricultural wastes to carbon powders with high adsorbent capacities. This process is excellent for eliminating and exploiting the huge masses (many tons) of vegetable residues remaining after each harvest every year in several Colombian agro-industries. The powders were characterized by X-ray diffraction (XRD), IR spectroscopy, scanning electron microscopy (SEM), and N2-adsorption isotherms. XRD and IR verified the formation of carbons, and SEM showed small particles (20-500 µm) with characteristic morphology for each type of residue used and abundant cavities of different sizes. The N2-adsorption analyses showed that the carbons had high adsorption capacities with important surface area values and large pore volumes. The use of the activated carbonaceous materials as adsorbent of azo dyes (allura red and sunset yellow) from aqueous solutions was evaluated. The results showed a good adsorption capacity indicating the potentiality of these materials as pollutant adsorbents in food industry wastewaters. These results indicate that these powders can be used as potential adsorbents for different gaseous or liquid pollutants.

Preparation of lysine-decorated polymer-brush-grafted magnetic nanocomposite for the efficient and selective adsorption of organic dye

NASA Astrophysics Data System (ADS)

Jing, Shiyao; Wang, Xin; Tan, Yebang

2018-05-01

A novel magnetic nanocomposite (Lys-PGMA@Fe3O4) containing amphoteric polymer brushes was synthesized by combining surface-initiated atom-transfer radical polymerization and lysine modification. The chemical structure of Lys-PGMA@Fe3O4 was confirmed by multiple methods, such as FT-IR, TGA, elemental analysis. The core-brush morphology was clearly observed by transmission electron microscopy. Lys-PGMA@Fe3O4 was then used to selectively and efficiently adsorb hazardous dyes. Adsorption results showed that Lys-PGMA@Fe3O4 had considerable adsorption capacity (0.54 and 0.85 mmol·g-1 for LY and MEB, respectively) and rapid adsorption rate (within 10 min), which can be attributed to the nanosize and abundant adsorptive polymer brushes. The selective adsorption of a mixture of lemon yellow (pH = 4.0) and methylene blue (pH = 10.0) was achieved through the amphoteric polymer brushes. Similar to traditional adsorbent materials, Lys-PGMA@Fe3O4 also showed easy magnet-assisted separation property. Lys-PGMA@Fe3O4 adsorbent can also be regenerated to reduce application cost. Overall, results demonstrated that Lys-PGMA@Fe3O4 nanocomposite was an excellent adsorbent material for removing dye pollutants from wastewater.

Eragrostis plana Nees as a novel eco-friendly adsorbent for removal of crystal violet from aqueous solutions.

PubMed

Filho, Augusto Cezar D; Mazzocato, Ana C; Dotto, Guilherme L; Thue, Pascal S; Pavan, Flávio A

2017-08-01

Eragrostis plana Nees (EPN) was used as new and eco-friendly adsorbent for the removal of crystal violet dye (CV) from aqueous solution. Specific surface area (BET), scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), point of zero charge (pH PZC ), and modified Boehm titration method were used to characterize the EPN material. The effects of initial pH of solution, adsorbent mass, contact time and initial dye concentration, and temperature were studied in batch adsorption mode. Kinetic data were evaluated by pseudo-first-order and pseudo-second-order models. The result exhibited that pseudo-second-order model well described the adsorption kinetics of CV onto EPN. Langmuir, Freundlich, and Sips isotherm models were used for analysis of the isothermal data. The equilibrium data of adsorption of CV onto EPN was better fitted with the Sips isotherm. Based on the Sips isotherm model, the maximum adsorption capacity was 76.20 ± 1.20 mg g -1 at 333 K. A high desorption of CV from EPN was obtained using 1.00 mol L -1 of CH 3 COOH as eluent. The thermodynamic data indicated that the adsorption was spontaneous, endothermic, and physical process. EPN can be used as alternative adsorbent to remove CV from aqueous solution.

Liquid phase adsorptions of Rhodamine B dye onto raw and chitosan supported mesoporous adsorbents: isotherms and kinetics studies

NASA Astrophysics Data System (ADS)

Inyinbor, A. A.; Adekola, F. A.; Olatunji, G. A.

2017-09-01

Irvingia gabonensis endocarp waste was charred (DNc) and subsequently coated with chitosan (CCDNc). Physicochemical characteristics of the two adsorbents were established, while Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area methods were further employed for characterization. Efficiencies of the prepared adsorbents in the uptake of Rhodamine B (RhB) from aqueous effluent were investigated and adsorption data were tested using four isotherms and four kinetics models. The BET surface areas of the prepared adsorbent were 0.0092 and 4.99 m2/g for DNc and CCDNc, respectively, and maximum adsorption was recorded at pH between 3 and 4, respectively. While monolayer adsorption dominates the uptake of RhB onto DNc, uptake of RhB onto CCDNc was onto heterogeneous surface. The maximum monolayer adsorption capacities ( q max) obtained from the Langmuir equation are 52.90 and 217.39 mg/g for DNc and CCDNc, respectively. Pseudo second order and Elovich kinetic models well described the kinetics of the two adsorption processes. The mean sorption energy ( E) calculated from the D-R model and desorption efficiencies suggests that while the uptake of RhB onto DNc was physical in nature, for RhB-CCDNc system chemisorption dominates.

Study of space charge layer in silver bromide microcrystals by means of ultraviolet photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Inami, Yoshiyasu

2000-09-01

Ultraviolet photoelectron spectroscopy has been successfully used to measure the heights of the tops of the valence bands of the surfaces of AgBr layers on Ag substrates for the verification of the space charge layer model. According to this model, the positive space charge layer (composed of negative charges with excess negative kink sites on the surface and corresponding positive charges with interstitial silver ions in the interior) is formed in silver halides, causing the difference in the electronic energy levels between their surface and interior. The depression of the positive space charge layer of AgBr caused by such adsorbates as photographic stabilizers and antifoggants was estimated from the decrease in the ionic conductivity of cubic AgBr microcrystals by the adsorbates. It was confirmed by the decrease in the heights of the tops of the valence bands of the surfaces of AgBr layers caused by the adsorbates in the presence of thin gelatin membranes on their surfaces. This result provided the explanation for the fact that the adsorbates increased the number of the microcrystals which formed latent image centers on the surface and decreased the number of the microcrystals, which formed latent image centers in the interior.

Adaptive Neuro-Fuzzy Inference system analysis on adsorption studies of Reactive Red 198 from aqueous solution by SBA-15/CTAB composite

NASA Astrophysics Data System (ADS)

Aghajani, Khadijeh; Tayebi, Habib-Allah

2017-01-01

In this study, the Mesoporous material SBA-15 were synthesized and then, the surface was modified by the surfactant Cetyltrimethylammoniumbromide (CTAB). Finally, the obtained adsorbent was used in order to remove Reactive Red 198 (RR 198) from aqueous solution. Transmission electron microscope (TEM), Fourier transform infra-red spectroscopy (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD), and BET were utilized for the purpose of examining the structural characteristics of obtained adsorbent. Parameters affecting the removal of RR 198 such as pH, the amount of adsorbent, and contact time were investigated at various temperatures and were also optimized. The obtained optimized condition is as follows: pH = 2, time = 60 min and adsorbent dose = 1 g/l. Moreover, a predictive model based on ANFIS for predicting the adsorption amount according to the input variables is presented. The presented model can be used for predicting the adsorption rate based on the input variables include temperature, pH, time, dosage, concentration. The error between actual and approximated output confirm the high accuracy of the proposed model in the prediction process. This fact results in cost reduction because prediction can be done without resorting to costly experimental efforts. SBA-15, CTAB, Reactive Red 198, adsorption study, Adaptive Neuro-Fuzzy Inference systems (ANFIS).

Adsorption capacity of Curcuma longa for the removal of basic green 1 dye--equilibrium, kinetics and thermodynamic study.

PubMed

Roopavathi, K V; Shanthakumar, S

2016-09-01

In the present study, Curcuma longa (turmeric plant) was used as an adsorbent to remove Basic Green 1 (BG) dye. Batch study was carried out to evaluate the adsorption potential of C. longa and influencing factors such as pH (4-10), adsorbent dose (0.2-5 g l-1), initial dye concentration (50-250 mg l-1) and temperature (30-50°C) on dye removal were analysed. The characterisation of adsorbent was carried out using fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Brunauer, Emmett and Teller (BET) method. Isotherm models that included Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich, and kinetic models such as pseudo first order, pseudo second-order, Elovich and intraparticle diffusion models were studied. A maximum removal percentage (82.76%) of BG dye from aqueous solution was obtained with optimum conditions of pH 7, 1g l-1 adsorbent dose and 30°C temperature, for 100 mg l-1 initial dye concentration. The equilibrium and kinetic study revealed that the experimental data fitted suitably the Freundlich isotherm and Pseudo second order kinetic model. Thermodynamic analysis proved that adsorption system in this study was spontaneous, feasible and endothermic in nature.

Ultrafast Surface-Enhanced Raman Probing of the Role of Hot Electrons in Plasmon-Driven Chemistry.

PubMed

Brandt, Nathaniel C; Keller, Emily L; Frontiera, Renee R

2016-08-18

Hot electrons generated through plasmonic excitations in metal nanostructures show great promise for efficiently driving chemical reactions with light. However, the lifetime, yield, and mechanism of action of plasmon-generated hot electrons involved in a given photocatalytic process are not well understood. Here, we develop ultrafast surface-enhanced Raman scattering (SERS) as a direct probe of plasmon-molecule interactions in the plasmon-catalyzed dimerization of 4-nitrobenzenethiol to p,p'-dimercaptoazobenzene. Ultrafast SERS probing of these molecular reporters in plasmonic hot spots reveals transient Fano resonances, which we attribute to near-field coupling of Stokes-shifted photons to hot electron-driven metal photoluminescence. Surprisingly, we find that hot spots that yield more photoluminescence are much more likely to drive the reaction, which indirectly proves that plasmon-generated hot electrons induce the photochemistry. These ultrafast SERS results provide insight into the relative reactivity of different plasmonic hot spot environments and quantify the ultrafast lifetime of hot electrons involved in plasmon-driven chemistry.

Evolution of magnetism of Cr nanoclusters on a Au(111) surface

NASA Astrophysics Data System (ADS)

Gotsis, Harry; Kioussis, Nicholas; Papaconstantopoulos, Dimitri

2004-03-01

Advances in low-temperature scanning tunneling microscopy under ultrahigh vacuum have provided new opportunities for investigating the magnetic structures of nanoclusters adsorbed on surfaces. Recent STM studies of Cr trimers on the Au(111) surface suggest a switching between two distinct electronic states. We have carried out ab initio electronic structure calculations to investigate the structural, electronic and magnetic properties of isolated Cr atoms, Cr dimers and trimers in different geometry. We will present results for the evolution of magnetic behavior including noncollinear magnetism and provide insight in the connection between magnetism and geometry.

Quantum theoretical study of electron solvation dynamics in ice layers on a Cu(111) surface.

PubMed

Andrianov, I; Klamroth, T; Saalfrank, P; Bovensiepen, U; Gahl, C; Wolf, M

2005-06-15

Recent experiments using time- and angle-resolved two-photon photoemission (2PPE) spectroscopy at metal/polar adsorbate interfaces succeeded in time-dependent analysis of the process of electron solvation. A fully quantum mechanical, two-dimensional simulation of this process, which explicitly includes laser excitation, is presented here, confirming the origin of characteristic features, such as the experimental observation of an apparently negative dispersion. The inference of the spatial extent of the localized electron states from the angular dependence of the 2PPE spectra has been found to be non-trivial and system-dependent.

Electron tunnelling through single azurin molecules can be on/off switched by voltage pulses

NASA Astrophysics Data System (ADS)

Baldacchini, Chiara; Kumar, Vivek; Bizzarri, Anna Rita; Cannistraro, Salvatore

2015-05-01

Redox metalloproteins are emerging as promising candidates for future bio-optoelectronic and nano-biomemory devices, and the control of their electron transfer properties through external signals is still a crucial task. Here, we show that a reversible on/off switching of the electron current tunnelling through a single protein can be achieved in azurin protein molecules adsorbed on gold surfaces, by applying appropriate voltage pulses through a scanning tunnelling microscope tip. The observed changes in the hybrid system tunnelling properties are discussed in terms of long-sustained charging of the protein milieu.

Plasmon-driven sequential chemical reactions in an aqueous environment.

PubMed

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-06-24

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

Plasmon-driven sequential chemical reactions in an aqueous environment

PubMed Central

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-01-01

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight. PMID:24958029

Thermally Driven Electronic Topological Transition in FeTi

NASA Astrophysics Data System (ADS)

Yang, F. C.; Muñoz, J. A.; Hellman, O.; Mauger, L.; Lucas, M. S.; Tracy, S. J.; Stone, M. B.; Abernathy, D. L.; Xiao, Yuming; Fultz, B.

2016-08-01

Ab initio molecular dynamics, supported by inelastic neutron scattering and nuclear resonant inelastic x-ray scattering, showed an anomalous thermal softening of the M5- phonon mode in B 2 -ordered FeTi that could not be explained by phonon-phonon interactions or electron-phonon interactions calculated at low temperatures. A computational investigation showed that the Fermi surface undergoes a novel thermally driven electronic topological transition, in which new features of the Fermi surface arise at elevated temperatures. The thermally induced electronic topological transition causes an increased electronic screening for the atom displacements in the M5- phonon mode and an adiabatic electron-phonon interaction with an unusual temperature dependence.

Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

NASA Astrophysics Data System (ADS)

Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

2017-12-01

As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

First staging of two laser accelerators.

PubMed

Kimura, W D; van Steenbergen, A; Babzien, M; Ben-Zvi, I; Campbell, L P; Cline, D B; Dilley, C E; Gallardo, J C; Gottschalk, S C; He, P; Kusche, K P; Liu, Y; Pantell, R H; Pogorelsky, I V; Quimby, D C; Skaritka, J; Steinhauer, L C; Yakimenko, V

2001-04-30

Staging of two laser-driven, relativistic electron accelerators has been demonstrated for the first time in a proof-of-principle experiment, whereby two distinct and serial laser accelerators acted on an electron beam in a coherently cumulative manner. Output from a CO2 laser was split into two beams to drive two inverse free electron lasers (IFEL) separated by 2.3 m. The first IFEL served to bunch the electrons into approximately 3 fs microbunches, which were rephased with the laser wave in the second IFEL. This represents a crucial step towards the development of practical laser-driven electron accelerators.

Enhanced adsorption of Co atoms on grain boundary of boron nitride

NASA Astrophysics Data System (ADS)

Zhang, Tingting; Chen, Guibin; Zhu, Liyan

2017-11-01

Structural, energetic, electronic, and magnetic properties of Co monomer, dimer, and trimer adsorbed on a single-layer boron nitride (BN) with a grain boundary (GB) consisting of tetragons and octagons ( 4|8) are theoretically explored via density functional calculations. Due to the presence of 4|8 GB, the adsorption energies (EAs) of small Co clusters are generally enhanced by 10% as compared with those adsorbed on pristine BN, e.g., the EA of Co monomer, and dimer increase by 0.1 eV on a global amount of 0.87 eV, and 0.2 eV for the case of Co trimer. Most interestingly, the increase in adsorption energy exhibits a strong correlation to the number of atoms directly bonded to the substrate. The enhanced binding of Co adatom on the BN with 4|8 GBs ( BN 48 ) is due to the strong hybridization of d orbitals of Co adatom and the localized defect states at the 4|8 GBs. However, the GBs have negligible influence on the electronic and magnetic properties of adsorbates. Hence, the two-dimensional (2D) nanosheets with linear GBs might be a better candidate for anchoring the transition metal atoms than pristine BN. Such a strategy may also be applied to other 2D materials, e.g., MoS2 and phosphorene, to enhance the binding of adatom on them, or to utilize them as 1D templates to assemble transition metal atoms into nanowires.

Carbon Nanotubes as an Ultrafast Emitter with a Narrow Energy Spread at Optical Frequency.

PubMed

Li, Chi; Zhou, Xu; Zhai, Feng; Li, Zhenjun; Yao, Fengrui; Qiao, Ruixi; Chen, Ke; Cole, Matthew Thomas; Yu, Dapeng; Sun, Zhipei; Liu, Kaihui; Dai, Qing

2017-08-01

Ultrafast electron pulses, combined with laser-pump and electron-probe technologies, allow ultrafast dynamics to be characterized in materials. However, the pursuit of simultaneous ultimate spatial and temporal resolution of microscopy and spectroscopy is largely subdued by the low monochromaticity of the electron pulses and their poor phase synchronization to the optical excitation pulses. Field-driven photoemission from metal tips provides high light-phase synchronization, but suffers large electron energy spreads (3-100 eV) as driven by a long wavelength laser (>800 nm). Here, ultrafast electron emission from carbon nanotubes (≈1 nm radius) excited by a 410 nm femtosecond laser is realized in the field-driven regime. In addition, the emitted electrons have great monochromaticity with energy spread as low as 0.25 eV. This great performance benefits from the extraordinarily high field enhancement and great stability of carbon nanotubes, superior to metal tips. The new nanotube-based ultrafast electron source opens exciting prospects for extending current characterization to sub-femtosecond temporal resolution as well as sub-nanometer spatial resolution. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Observation of Individual Charges and Their Dynamics on Graphene by Low-Energy Electron Holography.

PubMed

Latychevskaia, Tatiana; Wicki, Flavio; Longchamp, Jean-Nicolas; Escher, Conrad; Fink, Hans-Werner

2016-09-14

Visualizing individual charges confined to molecules and observing their dynamics with high spatial resolution is a challenge for advancing various fields in science, ranging from mesoscopic physics to electron transfer events in biological molecules. We show here that the high sensitivity of low-energy electrons to local electric fields can be employed to directly visualize individual charged adsorbates and to study their behavior in a quantitative way. This makes electron holography a unique probing tool for directly visualizing charge distributions with a sensitivity of a fraction of an elementary charge. Moreover, spatial resolution in the nanometer range and fast data acquisition inherent to lens-less low-energy electron holography allows for direct visual inspection of charge transfer processes.

Effects of coconut granular activated carbon pretreatment on membrane filtration in a gravitational driven process to improve drinking water quality.

PubMed

da Silva, Flávia Vieira; Yamaguchi, Natália Ueda; Lovato, Gilselaine Afonso; da Silva, Fernando Alves; Reis, Miria Hespanhol Miranda; de Amorim, Maria Teresa Pessoa Sousa; Tavares, Célia Regina Granhen; Bergamasco, Rosângela

2012-01-01

This study evaluates the performance of a polymeric microfiltration membrane, as well as its combination with a coconut granular activated carbon (GAC) pretreatment, in a gravitational filtration module, to improve the quality of water destined to human consumption. The proposed membrane and adsorbent were thoroughly characterized using instrumental techniques, such as contact angle, Brunauer-Emmett-Teller) and Fourier transform infrared spectroscopy analyses. The applied processes (membrane and GAC + membrane) were evaluated regarding permeate flux, fouling percentage, pH and removal of Escherichia coli, colour, turbidity and free chlorine. The obtained results for filtrations with and without GAC pretreatment were similar in terms of water quality. GAC pretreatment ensured higher chlorine removals, as well as higher initial permeate fluxes. This system, applying GAC as a pretreatment and a gravitational driven membrane filtration, could be considered as an alternative point-of-use treatment for water destined for human consumption.

Adaptive neuro-fuzzy inference system model for adsorption of 1,3,4-thiadiazole-2,5-dithiol onto gold nanoparticales-activated carbon.

PubMed

Ghaedi, M; Hosaininia, R; Ghaedi, A M; Vafaei, A; Taghizadeh, F

2014-10-15

In this research, a novel adsorbent gold nanoparticle loaded on activated carbon (Au-NP-AC) was synthesized by ultrasound energy as a low cost routing protocol. Subsequently, this novel material characterization and identification followed by different techniques such as scanning electron microscope(SEM), Brunauer-Emmett-Teller(BET) and transmission electron microscopy (TEM) analysis. Unique properties such as high BET surface area (>1229.55m(2)/g) and low pore size (<22.46Å) and average particle size lower than 48.8Å in addition to high reactive atoms and the presence of various functional groups make it possible for efficient removal of 1,3,4-thiadiazole-2,5-dithiol (TDDT). Generally, the influence of variables, including the amount of adsorbent, initial pollutant concentration, contact time on pollutants removal percentage has great effect on the removal percentage that their influence was optimized. The optimum parameters for adsorption of 1,3,4-thiadiazole-2, 5-dithiol onto gold nanoparticales-activated carbon were 0.02g adsorbent mass, 10mgL(-1) initial 1,3,4-thiadiazole-2,5-dithiol concentration, 30min contact time and pH 7. The Adaptive neuro-fuzzy inference system (ANFIS), and multiple linear regression (MLR) models, have been applied for prediction of removal of 1,3,4-thiadiazole-2,5-dithiol using gold nanoparticales-activated carbon (Au-NP-AC) in a batch study. The input data are included adsorbent dosage (g), contact time (min) and pollutant concentration (mg/l). The coefficient of determination (R(2)) and mean squared error (MSE) for the training data set of optimal ANFIS model were achieved to be 0.9951 and 0.00017, respectively. These results show that ANFIS model is capable of predicting adsorption of 1,3,4-thiadiazole-2,5-dithiol using Au-NP-AC with high accuracy in an easy, rapid and cost effective way. Copyright © 2014 Elsevier B.V. All rights reserved.

Adaptive neuro-fuzzy inference system model for adsorption of 1,3,4-thiadiazole-2,5-dithiol onto gold nanoparticales-activated carbon

NASA Astrophysics Data System (ADS)

Ghaedi, M.; Hosaininia, R.; Ghaedi, A. M.; Vafaei, A.; Taghizadeh, F.

2014-10-01

In this research, a novel adsorbent gold nanoparticle loaded on activated carbon (Au-NP-AC) was synthesized by ultrasound energy as a low cost routing protocol. Subsequently, this novel material characterization and identification followed by different techniques such as scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and transmission electron microscopy (TEM) analysis. Unique properties such as high BET surface area (>1229.55 m2/g) and low pore size (<22.46 Å) and average particle size lower than 48.8 Å in addition to high reactive atoms and the presence of various functional groups make it possible for efficient removal of 1,3,4-thiadiazole-2,5-dithiol (TDDT). Generally, the influence of variables, including the amount of adsorbent, initial pollutant concentration, contact time on pollutants removal percentage has great effect on the removal percentage that their influence was optimized. The optimum parameters for adsorption of 1,3,4-thiadiazole-2, 5-dithiol onto gold nanoparticales-activated carbon were 0.02 g adsorbent mass, 10 mg L-1 initial 1,3,4-thiadiazole-2,5-dithiol concentration, 30 min contact time and pH 7. The Adaptive neuro-fuzzy inference system (ANFIS), and multiple linear regression (MLR) models, have been applied for prediction of removal of 1,3,4-thiadiazole-2,5-dithiol using gold nanoparticales-activated carbon (Au-NP-AC) in a batch study. The input data are included adsorbent dosage (g), contact time (min) and pollutant concentration (mg/l). The coefficient of determination (R2) and mean squared error (MSE) for the training data set of optimal ANFIS model were achieved to be 0.9951 and 0.00017, respectively. These results show that ANFIS model is capable of predicting adsorption of 1,3,4-thiadiazole-2,5-dithiol using Au-NP-AC with high accuracy in an easy, rapid and cost effective way.

Observation of 690 MV m -1 Electron Accelerating Gradient with a Laser-Driven Dielectric Microstructure

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

Wootton, K. P.; Wu, Z.; Cowan, B. M.

Acceleration of electrons using laser-driven dielectric microstructures is a promising technology for the miniaturization of particle accelerators. In this work, experimental results are presented of relativistic electron acceleration with 690±100 MVm -1 gradient. This is a record-high accelerating gradient for a dielectric microstructure accelerator, nearly doubling the previous record gradient. To reach higher acceleration gradients the present experiment employs 90 fs duration laser pulses.

Effect of Organic Cations on Hydrogen Oxidation Reaction of Carbon Supported Platinum

DOE PAGES

Chung, Hoon Taek; Choe, Yong-Kee; Martinez, Ulises; ...

2016-11-02

Effect of organic cations on hydrogen oxidation reaction (HOR) of carbon supported platinum (Pt/C) is investigated using three 0.1 M alkaline electrolytes, tetramethylammonium hydroxide (TMAOH), tetrabutylammonium hydroxide (TBAOH) and tetrabutylphosphonium hydroxide (TBPOH). Rotating disk electrode experiments indicate that the HOR of Pt/C is adversely impacted by time-dependent and potential-driven chemisorption of organic cations. In-situ infrared reflection adsorption spectroscopy experiments indicated that the specific chemisorption of organic cations drives the hydroxide co-adsorption on Pt surface. The co-adsorption of TMA + and hydroxide at 0.1 V vs. reversible hydrogen electrode is the strongest; consequently, complete removal of the co-adsorbed layer from Ptmore » surface is difficult even after exposure the Pt surface to 1.2 V. Conversely, the chemisorption of TBP+ is the weakest, yet notable decrease of HOR current density is still observed. The adsorption energies, ΔE, for TMA +, TBA +, and TBP + on Pt (111) surface from density functional theory are computed to be -2.79, -2.42 and -2.00 eV, respectively. The relatively low adsorption energy of TBP + is explained by the steric hindrance and electronic effect. This study emphasizes the importance of cationic group on HOR activity of alkaline anion exchange membrane fuel cells.« less

Modeling laser-driven electron acceleration using WARP with Fourier decomposition

DOE PAGES

Lee, P.; Audet, T. L.; Lehe, R.; ...

2015-12-31

WARP is used with the recent implementation of the Fourier decomposition algorithm to model laser-driven electron acceleration in plasmas. Simulations were carried out to analyze the experimental results obtained on ionization-induced injection in a gas cell. The simulated results are in good agreement with the experimental ones, confirming the ability of the code to take into account the physics of electron injection and reduce calculation time. We present a detailed analysis of the laser propagation, the plasma wave generation and the electron beam dynamics.

Modeling laser-driven electron acceleration using WARP with Fourier decomposition

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

Lee, P.; Audet, T. L.; Lehe, R.

WARP is used with the recent implementation of the Fourier decomposition algorithm to model laser-driven electron acceleration in plasmas. Simulations were carried out to analyze the experimental results obtained on ionization-induced injection in a gas cell. The simulated results are in good agreement with the experimental ones, confirming the ability of the code to take into account the physics of electron injection and reduce calculation time. We present a detailed analysis of the laser propagation, the plasma wave generation and the electron beam dynamics.

Hard x-ray (>100 keV) imager to measure hot electron preheat for indirectly driven capsule implosions on the NIF.

PubMed

Döppner, T; Dewald, E L; Divol, L; Thomas, C A; Burns, S; Celliers, P M; Izumi, N; Kline, J L; LaCaille, G; McNaney, J M; Prasad, R R; Robey, H F; Glenzer, S H; Landen, O L

2012-10-01

We have fielded a hard x-ray (>100 keV) imager with high aspect ratio pinholes to measure the spatially resolved bremsstrahlung emission from energetic electrons slowing in a plastic ablator shell during indirectly driven implosions at the National Ignition Facility. These electrons are generated in laser plasma interactions and are a source of preheat to the deuterium-tritium fuel. First measurements show that hot electron preheat does not limit obtaining the fuel areal densities required for ignition and burn.

Self-injection of electrons in a laser-wakefield accelerator by using longitudinal density ripple

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

Dahiya, Deepak; Sharma, A. K.; Sajal, Vivek

By introducing a longitudinal density ripple (periodic modulation in background plasma density), we demonstrate self-injection of electrons in a laser-wakefield accelerator. The wakefield driven plasma wave, in presence of density ripple excites two side band waves of same frequency but different wave numbers. One of these side bands, having smaller phase velocity compared to wakefield driven plasma wave, preaccelerates the background plasma electrons. Significant number of these preaccelerated electrons get trapped in the laser-wakefield and further accelerated to higher energies.

DFT investigation on the electronic structure of Faujasite

NASA Astrophysics Data System (ADS)

Popeneciu, Horea; Calborean, Adrian; Tudoran, Cristian; Buimaga-Iarinca, Luiza

2013-11-01

We report here first-principle pseudopotential DFT calculations to investigate relevant aspects of the electronic structure of zeolites based FAU. Fundamental molecular issues of the band-gap and electronic population analysis were reviewed under GGA/RPBE level of theory, corroborated with a DZP basis set and Troullier-Martins norm conserving pseudo-potentials. The atom-projected density of states and the analysis of HOMO-LUMO frontier orbitals at Gamma point were performed. Their electronic transfers are discussed through the alignment and relative positions of orbitals in order to determine the way that the molecule interacts with adsorbed molecules and other practical applications. Mulliken population analysis was employed for describing atomic charge distribution in the chosen systems.

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

Zhou, Wenqiang; School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003; Liu, Minmin

We present the synthesis and multifunctional utilization of core-satellite carbon-Fe{sub 3}O{sub 4} nanoparticles to serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The synergistic combination of Fe{sub 3}O{sub 4} and N-doped carbon endows the nanocomposite with high electrochemical activity in ORR and mainly four electrons transferred in reaction process. Furthermore, carbon-Fe{sub 3}O{sub 4} nanoparticles used as magnetic adsorbent exhibit the efficient removal of Rhodamine B frommore » an aqueous solution. The recovery and reuse of the adsorbent is demonstrated 5 times without any detectible loss in activity. - Graphical abstract: Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The nanocomposites serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. - Highlights: • Carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. • Polydopamine and Fe(NO{sub 3}){sub 3} are precursors for N-doped carbon source and Fe{sub 3}O{sub 4} nanoparticles, respectively. • The nanocomposites exhibit high electrochemical activity in ORR. • The nanocomposites effectively adsorb organic dyes with magnetic recovery and good recycle property.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

NASA Astrophysics Data System (ADS)

Hong, Sung-Young; Xu, Pan; Camillone, Nina R.; White, Michael G.; Camillone, Nicholas

2016-07-01

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

Schwertmannite stability in anoxic Fe(II)-rich aqueous solution

NASA Astrophysics Data System (ADS)

Paikaray, Susanta; Schröder, Christian; Peiffer, Stefan

2017-11-01

Schwertmannite (SHM) is a powerful scavenger for As(III) leading to As(III)-enriched precipitates around acid mine drainage environments that may become exposed to aqueous Fe(II). In this study we have investigated the stability of pure SHM and SHM containing 0.92 wt% As(III) under Fe(II)aq-rich (0.4-1.0 mM) anoxic conditions using XRD, SEM, Mössbauer and FTIR spectroscopic techniques. Schwertmannite transformation proceeded through an alkalinity-driven pathway releasing sulfate and a Fe(II)-catalyzed pathway that generated lepidocrocite and goethite at pH 6 and 6.9 in the presence of 1 mM Fe(II)aq. Lepidocrocite was found to be needle shaped if the SHM contained As(III) and platy for pure SHM. Goethite had a poor degree of crystallinity in As(III) containing SHM. Pre-adsorption of As(III) inhibited the extent of SHM transformation. Fe(II) sorption onto SHM was pH dependent and reflected a sorption edge with complete consumption at pH 6.9, while only ∼20% were adsorbed at pH 5. Surface coverage with Fe(II) appears to be the key parameter controlling extent and products of the transformation process. As(III) concentrations in solution are controlled by two mechanisms: (1) exchange of As(III) for sulfate upon alkalinity-driven transformation of schwertmannite and (2) re-adsorption to new phases formed upon Fe(II)-catalyzed transformation. The adsorbed As(III) has inhibited the extent of transformation and was partly released with the maximum release at pH 5 (0.5%) in the absence of Fe(II)aq.

Role of quinones in electron transfer of PQQ–glucose dehydrogenase anodes—mediation or orientation effect

DOE PAGES

Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow; ...

2015-06-16

In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-sGDH anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2- and 1,4-benzoquinones introducedmore » in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Electron-stimulated reactions in nanoscale water films adsorbed on (alpha)-Al2O3(0001)

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

Petrik, Nikolay G.; Kimmel, Gregory A.

2018-05-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.

2018-04-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

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

Petrik, Nikolay G.; Kimmel, Greg A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Role of Quinones in Electron Transfer of PQQ–Glucose Dehydrogenase Anodes—Mediation or Orientation Effect

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

Babanova, Sofia; Matanovic, Ivana; Chavez, Madelaine Seow

2015-06-24

In this study, the influence of two quinones (1,2- and 1,4-benzoquinone) on the operation and mechanism of electron transfer in PQQ-dependent glucose dehydrogenase (PQQ–sGDH) anodes has been determined. Benzoquinones were experimentally explored as mediators present in the electrolyte. The electrochemical performance of the PQQ–sGDH anodes with and without the mediators was examined and for the first time molecular docking simulations were used to gain a fundamental understanding to explain the role of the mediator molecules in the design and operation of the enzymatic electrodes. It was proposed that the higher performance of the PQQ–sGDH anodes in the presence of 1,2-more » and 1,4-benzoquinones introduced in the solution is due to the shorter distance between these molecules and PQQ in the enzymatic molecule. It was also hypothesized that when 1,4-benzoquinone is adsorbed on a carbon support, it would play the dual role of a mediator and an orienting agent. At the same time, when 1,2-benzoquinone and ubiquinone are adsorbed on the electrode surface, the enzyme would transfer the electrons directly to the support, and these molecules would primarily play the role of an orienting agent.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

NASA Astrophysics Data System (ADS)

Morbec, Juliana M.; Kratzer, Peter

2017-01-01

Using first-principles calculations based on density-functional theory (DFT), we investigated the effects of the van der Waals (vdW) interactions on the structural and electronic properties of anthracene and pentacene adsorbed on the Ag(111) surface. We found that the inclusion of vdW corrections strongly affects the binding of both anthracene/Ag(111) and pentacene/Ag(111), yielding adsorption heights and energies more consistent with the experimental results than standard DFT calculations with generalized gradient approximation (GGA). For anthracene/Ag(111) the effect of the vdW interactions is even more dramatic: we found that "pure" DFT-GGA calculations (without including vdW corrections) result in preference for a tilted configuration, in contrast to the experimental observations of flat-lying adsorption; including vdW corrections, on the other hand, alters the binding geometry of anthracene/Ag(111), favoring the flat configuration. The electronic structure obtained using a self-consistent vdW scheme was found to be nearly indistinguishable from the conventional DFT electronic structure once the correct vdW geometry is employed for these physisorbed systems. Moreover, we show that a vdW correction scheme based on a hybrid functional DFT calculation (HSE) results in an improved description of the highest occupied molecular level of the adsorbed molecules.

Multielectron effects in the photoelectron momentum distribution of noble-gas atoms driven by visible-to-infrared-frequency laser pulses: A time-dependent density-functional-theory approach

NASA Astrophysics Data System (ADS)

Murakami, Mitsuko; Zhang, G. P.; Chu, Shih-I.

2017-05-01

We present the photoelectron momentum distributions (PMDs) of helium, neon, and argon atoms driven by a linearly polarized, visible (527-nm) or near-infrared (800-nm) laser pulse (20 optical cycles in duration) based on the time-dependent density-functional theory (TDDFT) under the local-density approximation with a self-interaction correction. A set of time-dependent Kohn-Sham equations for all electrons in an atom is numerically solved using the generalized pseudospectral method. An effect of the electron-electron interaction driven by a visible laser field is not recognizable in the helium and neon PMDs except for a reduction of the overall photoelectron yield, but there is a clear difference between the PMDs of an argon atom calculated with the frozen-core approximation and TDDFT, indicating an interference of its M -shell wave functions during the ionization. Furthermore, we find that the PMDs of degenerate p states are well separated in intensity when driven by a near-infrared laser field, so that the single-active-electron approximation can be adopted safely.

Oxide-organic heterostructures: a case study of charge transfer disturbance at a SnO2-copper phthalocyanine buried interface.

PubMed

Krzywiecki, Maciej; Grządziel, Lucyna; Powroźnik, Paulina; Kwoka, Monika; Rechmann, Julian; Erbe, Andreas

2018-06-13

Reduced tin dioxide/copper phthalocyanine (SnOx/CuPc) heterojunctions recently gained much attention in hybrid electronics due to their defect structure, allowing tuning of the electronic properties at the interface towards particular needs. In this work, we focus on the creation and analysis of the interface between the oxide and organic layer. The inorganic/organic heterojunction was created by depositing CuPc on SnOx layers prepared with the rheotaxial growth and vacuum oxidation (RGVO) method. Exploiting surface sensitive photoelectron spectroscopy techniques, angle dependent X-ray and UV photoelectron spectroscopy (ADXPS and UPS, respectively), supported by semi-empirical simulations, the role of carbon from adventitious organic adsorbates directly at the SnOx/CuPc interface was investigated. The adventitious organic adsorbates were blocking electronic interactions between the environment and surface, hence pinning energy levels. A significant interface dipole of 0.4 eV was detected, compensating for the difference in work functions of the materials in contact, however, without full alignment of the energy levels. From the ADXPS and UPS results, a detailed diagram of the interfacial electronic structure was constructed, giving insight into how to tailor SnOx/CuPc heterojunctions towards specific applications. On the one hand, parasitic surface contamination could be utilized in technology for passivation-like processes. On the other hand, if one needs to keep the oxide's surficial interactions fully accessible, like in the case of stacked electronic systems or gas sensor applications, carbon contamination must be carefully avoided at each processing step.

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2O 3 (0001)

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

Petrik, Nikolay G.; Kimmel, Gregory A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.100 eV electrons are stopped in the H 2O portion of the isotopically-layered nanoscale film on α-Al 2O 3(0001) but D 2is produced at the D 2O/alumina interface by mobile electronic excitations and/or hydronium ions.« less

Thermally Driven Electronic Topological Transition in FeTi

DOE PAGES

Yang, F. C.; Muñoz, J. A.; Hellman, O.; ...

2016-08-08

In this paper, ab initio molecular dynamics, supported by inelastic neutron scattering and nuclear resonant inelastic x-ray scattering, showed an anomalous thermal softening of the M 5 - phonon mode in B2-ordered FeTi that could not be explained by phonon-phonon interactions or electron-phonon interactions calculated at low temperatures. A computational investigation showed that the Fermi surface undergoes a novel thermally driven electronic topological transition, in which new features of the Fermi surface arise at elevated temperatures. Finally, the thermally induced electronic topological transition causes an increased electronic screening for the atom displacements in the M 5 - phonon mode andmore » an adiabatic electron-phonon interaction with an unusual temperature dependence.« less

Nonlinear structure formation in ion-temperature-gradient driven drift waves in pair-ion plasma with nonthermal electron distribution

NASA Astrophysics Data System (ADS)

Razzaq, Javaria; Haque, Q.; Khan, Majid; Bhatti, Adnan Mehmood; Kamran, M.; Mirza, Arshad M.

2018-02-01

Nonlinear structure formation in ion-temperature-gradient (ITG) driven waves is investigated in pair-ion plasma comprising ions and nonthermal electrons (kappa, Cairns). By using the transport equations of the Braginskii model, a new set of nonlinear equations are derived. A linear dispersion relation is obtained and discussed analytically as well as numerically. It is shown that the nonthermal population of electrons affects both the linear and nonlinear characteristics of the ITG mode in pair-ion plasma. This work will be useful in tokamaks and stellarators where non-Maxwellian population of electrons may exist due to resonant frequency heating, electron cyclotron heating, runaway electrons, etc.

Dynamics of electron injection and acceleration driven by laser wakefield in tailored density profiles

DOE PAGES

Lee, Patrick; Maynard, G.; Audet, T. L.; ...

2016-11-16

The dynamics of electron acceleration driven by laser wakefield is studied in detail using the particle-in-cell code WARP with the objective to generate high-quality electron bunches with narrow energy spread and small emittance, relevant for the electron injector of a multistage accelerator. Simulation results, using experimentally achievable parameters, show that electron bunches with an energy spread of ~11% can be obtained by using an ionization-induced injection mechanism in a mm-scale length plasma. By controlling the focusing of a moderate laser power and tailoring the longitudinal plasma density profile, the electron injection beginning and end positions can be adjusted, while themore » electron energy can be finely tuned in the last acceleration section.« less

Split ring resonator based THz-driven electron streak camera featuring femtosecond resolution

PubMed Central

Fabiańska, Justyna; Kassier, Günther; Feurer, Thomas

2014-01-01

Through combined three-dimensional electromagnetic and particle tracking simulations we demonstrate a THz driven electron streak camera featuring a temporal resolution on the order of a femtosecond. The ultrafast streaking field is generated in a resonant THz sub-wavelength antenna which is illuminated by an intense single-cycle THz pulse. Since electron bunches and THz pulses are generated with parts of the same laser system, synchronization between the two is inherently guaranteed. PMID:25010060

Numerical Study of Current Driven Instabilities and Anomalous Electron Transport in Hall-effect Thrusters

NASA Astrophysics Data System (ADS)

Tran, Jonathan

Plasma turbulence and the resulting anomalous electron transport due to azimuthal current driven instabilities in Hall-effect thrusters is a promising candidate for developing predictive models for the observed anomalous transport. A theory for anomalous electron transport and current driven instabilities has been recently studied by [Lafluer et al., 2016a]. Due to the extreme cost of fully resolving the Debye length and plasma frequency, hybrid plasma simulations utilizing kinetic ions and quasi-steady state fluid electrons have long been the principle workhorse methodology for Hall-effect thruster modeling. Using a reduced dimension particle in cell simulation implemented in the Thermophysics Universal Research Framework developed by the Air Force Research Lab, we show collective electron-wave scattering due to large amplitude azimuthal fluctuations of the electric field and the plasma density. These high-frequency and short wavelength fluctuations can lead to an effective cross-field mobility many orders of magnitude larger than what is expected from classical electron-neutral momentum collisions in the low neutral density regime. We further adapt the previous study by [Lampe et al., 1971] and [Stringer, 1964] for related current driven instabilities to electric propulsion relevant mass ratios and conditions. Finally, we conduct a preliminary study of resolving this instability with a modified hybrid simulation with the hope of integration with established hybrid Hall-effect thruster simulations.

Low-energy electron-induced reactions in condensed matter

NASA Astrophysics Data System (ADS)

Arumainayagam, Christopher R.; Lee, Hsiao-Lu; Nelson, Rachel B.; Haines, David R.; Gunawardane, Richard P.

2010-01-01

The goal of this review is to discuss post-irradiation analysis of low-energy (≤50 eV) electron-induced processes in nanoscale thin films. Because electron-induced surface reactions in monolayer adsorbates have been extensively reviewed, we will instead focus on low-energy electron-induced reactions in multilayer adsorbates. The latter studies, involving nanoscale thin films, serve to elucidate the pivotal role that the low-energy electron-induced reactions play in high-energy radiation-induced chemical reactions in condensed matter. Although electron-stimulated desorption (ESD) experiments conducted during irradiation have yielded vital information relevant to primary or initial electron-induced processes, we wish to demonstrate in this review that analyzing the products following low-energy electron irradiation can provide new insights into radiation chemistry. This review presents studies of electron-induced reactions in nanoscale films of molecular species such as oxygen, nitrogen trifluoride, water, alkanes, alcohols, aldehydes, ketones, carboxylic acids, nitriles, halocarbons, alkane and phenyl thiols, thiophenes, ferrocene, amino acids, nucleotides, and DNA using post-irradiation techniques such as temperature-programmed desorption (TPD), reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), gel electrophoresis, and microarray fluorescence. Post-irradiation temperature-programmed desorption, in particular, has been shown to be useful in identifying labile radiolysis products as demonstrated by the first identification of methoxymethanol as a reaction product of methanol radiolysis. Results of post-irradiation studies have been used not only to identify radiolysis products, but also to determine the dynamics of electron-induced reactions. For example, studies of the radiolysis yield as a function of incident electron energy have shown that dissociative electron attachment plays an important role in the electron-induced single strand breaks in DNA leading to mutagenic damage. Studies such as these not only provide insight into the fundamentals of electron-molecule interactions in the condensed phase but also may provide information valuable to (a) furthering cost-efficient destruction of hazardous chemicals, (b) understanding the electron-induced decomposition of feed gases used in the plasma processing of semiconductor devices, (c) clarifying the role, if any, of low-energy electrons, produced by cosmic rays, contributing to the formation of the ozone hole by interacting with halocarbons and producing Cl atoms, (d) illuminating the dynamics of electron-induced oligomerization and/or polymerization, and (e) explicating the astrochemistry of icy grains.

Mobilization of arsenite by dissimilatory reduction of adsorbed arsenate

USGS Publications Warehouse

Zobrist, J.; Dowdle, P.R.; Davis, J.A.; Oremland, R.S.

2000-01-01

Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite, a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.

Rapid detection of trace amounts of surfactants using nanoparticles in fluorometric assays

NASA Astrophysics Data System (ADS)

Härmä, Harri; Laakso, Susana; Pihlasalo, Sari; Hänninen, Pekka; Faure, Bertrand; Rana, Subhasis; Bergström, Lennart

2010-01-01

Rapid microtiter assays that utilize the time-resolved fluorescence resonance energy transfer or quenching of dye-labeled proteins adsorbed onto the surfaces of polystyrene or maghemite nanoparticles have been developed for the detection and quantification of trace amounts of surfactants at concentrations down to 10 nM.Rapid microtiter assays that utilize the time-resolved fluorescence resonance energy transfer or quenching of dye-labeled proteins adsorbed onto the surfaces of polystyrene or maghemite nanoparticles have been developed for the detection and quantification of trace amounts of surfactants at concentrations down to 10 nM. Electronic supplementary information (ESI) available: Experimental details and Fig. S1 and S2. See DOI: 10.1039/b9nr00172g

Magnetic and Electronic Properties of h-BN Nanosheets with Nonmetal Atoms Adsorbed: an Ab Initio Study

NASA Astrophysics Data System (ADS)

Luo, M.; Yin, H. H.; Chu, J. H.

2018-04-01

The magnetic properties of the h-BN monolayer with nonmetal atoms are studied by ab initio methods. Different dopants (C, Cl, F, and O) and doping sites are considered. Magnetic behavior is observed in the two-dimensional (2D) BN system with C, Cl, and O atoms. On the other hand, the O adsorbed system shows a more stable formed structure among above three magnetic materials, we study the ferromagnetic (FM) interaction in 2D-BN system with two O adatoms. Interestingly, as the O-O distance increases, the interaction between two O adatoms prefers to a long-range FM coupling. This phenomenon could be well described by a simple Heisenberg model.