surface area hydrogen: Topics by Science.gov

Sample records for surface area hydrogen

Effect of hydrogen on void initiation in tensile test of carbon steel JIS-S25C

NASA Astrophysics Data System (ADS)

Sugawa, S.; Tsutsumi, N.; Oda, K.

2018-06-01

In order to investigate the effect of hydrogen on tensile fracture mechanism of a carbon steel, tensile tests were conducted. Pre-strain specimens (0%, 5% and 10%) were used to study the effect of hydrogen content, since saturated hydrogen content in specimens increases in increasing dislocation density. The tensile strength and the yield stress of hydrogen specimens were almost the same as uncharged. In contrast, the reduction of area of hydrogen charged specimens was smaller than that of uncharged. To reveal the reasons of decrease of the reduction of area, the fracture surface and longitudinal cross section near the fracture surface were observed. On the fracture surface of uncharged specimens, only dimples were observed. On the other hand, dimples and flat fracture surface were observed on the fracture surface of hydrogen charged. On the longitudinal cross section of hydrogen charged specimens, many voids were observed compared to uncharged. From these observations, it is showed that hydrogen gives a rise to the increase of voids and the hydrogen charged specimens break without sufficient necking, thus hydrogen makes the reduction of area smaller.
Molecular effective coverage surface area of optical clearing agents for predicting optical clearing potential

NASA Astrophysics Data System (ADS)

Feng, Wei; Ma, Ning; Zhu, Dan

2015-03-01

The improvement of methods for optical clearing agent prediction exerts an important impact on tissue optical clearing technique. The molecular dynamic simulation is one of the most convincing and simplest approaches to predict the optical clearing potential of agents by analyzing the hydrogen bonds, hydrogen bridges and hydrogen bridges type forming between agents and collagen. However, the above analysis methods still suffer from some problem such as analysis of cyclic molecule by reason of molecular conformation. In this study, a molecular effective coverage surface area based on the molecular dynamic simulation was proposed to predict the potential of optical clearing agents. Several typical cyclic molecules, fructose, glucose and chain molecules, sorbitol, xylitol were analyzed by calculating their molecular effective coverage surface area, hydrogen bonds, hydrogen bridges and hydrogen bridges type, respectively. In order to verify this analysis methods, in vitro skin samples optical clearing efficacy were measured after 25 min immersing in the solutions, fructose, glucose, sorbitol and xylitol at concentration of 3.5 M using 1951 USAF resolution test target. The experimental results show accordance with prediction of molecular effective coverage surface area. Further to compare molecular effective coverage surface area with other parameters, it can show that molecular effective coverage surface area has a better performance in predicting OCP of agents.
Influence of liquid surface area on hydrogen sulfide oxidation during micro-aeration in dairy manure digesters

USDA-ARS?s Scientific Manuscript database

The specific objectives of this study were to evaluate headspace aeration for reducing hydrogen sulfide levels in low cost plug flow digesters, and to characterize the relationship between the liquid surface area and hydrogen sulfide oxidation rates. Experiments with replicate field scale plug flow ...
Nanoporous Ni with High Surface Area for Potential Hydrogen Storage Application.

PubMed

Zhou, Xiaocao; Zhao, Haibo; Fu, Zhibing; Qu, Jing; Zhong, Minglong; Yang, Xi; Yi, Yong; Wang, Chaoyang

2018-06-01

Nanoporous metals with considerable specific surface areas and hierarchical pore structures exhibit promising applications in the field of hydrogen storage, electrocatalysis, and fuel cells. In this manuscript, a facile method is demonstrated for fabricating nanoporous Ni with a high surface area by using SiO₂ aerogel as a template, i.e., electroless plating of Ni into an SiO₂ aerogel template followed by removal of the template at moderate conditions. The effects of the prepared conditions, including the electroless plating time, temperature of the structure, and the magnetism of nanoporous Ni are investigated in detail. The resultant optimum nanoporous Ni with a special 3D flower-like structure exhibited a high specific surface area of about 120.5 m²/g. The special nanoporous Ni exhibited a promising prospect in the field of hydrogen storage, with a hydrogen capacity of 0.45 wt % on 4.5 MPa at room temperature.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hongcai J

In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storagemore » goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the accomplishments of this DOE supported research will greatly benefit the future pursuit of hydrogen storage materials. The ultimate goal to increase the gravimetric and volumetric hydrogen storage capacity to meet DOE targets for Light-Duty Vehicles is achievable.« less
Ion and laser microprobes applied to the measurement of corrosion produced hydrogen on a microscopic scale.

NASA Technical Reports Server (NTRS)

Gray, H. R.

1972-01-01

Use of an ion microprobe and a laser microprobe to measure concentrations of corrosion-produced hydrogen on a microscopic scale. Hydrogen concentrations of several thousand ppm were measured by both analytical techniques below corroded and fracture surfaces of hot salt stress corroded titanium alloy specimens. This extremely high concentration compares with only about 100 ppm hydrogen determined by standard vacuum fusion chemical analyses of bulk samples. Both the ion and laser microprobes were used to measure hydrogen concentration profiles in stepped intervals to substantial depths below the original corroded and fracture surfaces. For the ion microprobe, the area of local analysis was 22 microns in diameter and for the laser microprobe, the area of local analysis was about 300 microns in diameter. The segregation of hydrogen below fracture surfaces supports a previously proposed theory that corrosion-produced hydrogen is responsible for hot salt stress corrosion embrittlement and cracking of titanium alloys. These advanced analytical techniques suggest great potential for many areas of stress corrosion and hydrogen embrittlement research, quality control, and field inspection of corrosion problems. For example, it appears possible that a contour map of hydrogen distribution at notch roots and crack tips could be quantitatively determined. Such information would be useful in substantiating current theories of stress corrosion and hydrogen embrittlement.
New Pathways and Metrics for Enhanced, Reversible Hydrogen Storage in Boron-Doped Carbon Nanospaces

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

Pfeifer, Peter; Wexler, Carlos; Hawthorne, M. Frederick

This project, since its start in 2007—entitled “Networks of boron-doped carbon nanopores for low-pressure reversible hydrogen storage” (2007-10) and “New pathways and metrics for enhanced, reversible hydrogen storage in boron-doped carbon nanospaces” (2010-13)—is in support of the DOE's National Hydrogen Storage Project, as part of the DOE Hydrogen and Fuel Cells Program’s comprehensive efforts to enable the widespread commercialization of hydrogen and fuel cell technologies in diverse sectors of the economy. Hydrogen storage is widely recognized as a critical enabling technology for the successful commercialization and market acceptance of hydrogen powered vehicles. Storing sufficient hydrogen on board a wide rangemore » of vehicle platforms, at energy densities comparable to gasoline, without compromising passenger or cargo space, remains an outstanding technical challenge. Of the main three thrust areas in 2007—metal hydrides, chemical hydrogen storage, and sorption-based hydrogen storage—sorption-based storage, i.e., storage of molecular hydrogen by adsorption on high-surface-area materials (carbons, metal-organic frameworks, and other porous organic networks), has emerged as the most promising path toward achieving the 2017 DOE storage targets of 0.055 kg H2/kg system (“5.5 wt%”) and 0.040 kg H2/liter system. The objective of the project is to develop high-surface-area carbon materials that are boron-doped by incorporation of boron into the carbon lattice at the outset, i.e., during the synthesis of the material. The rationale for boron-doping is the prediction that boron atoms in carbon will raise the binding energy of hydro- gen from 4-5 kJ/mol on the undoped surface to 10-14 kJ/mol on a doped surface, and accordingly the hydro- gen storage capacity of the material. The mechanism for the increase in binding energy is electron donation from H2 to electron-deficient B atoms, in the form of sp2 boron-carbon bonds. Our team is proud to have demonstrated the predicted increase in binding energy experimentally, currently at ~10 kJ/mol. The synthetic route for incorporation of boron at the outset is to create appropriately designed copoly- mers, with a boron-free and a boron-carrying monomer, followed by pyrolysis of the polymer, yielding a bo- ron-substituted carbon scaffold in which boron atoms are bonded to carbon atoms by synthesis. This is in contrast to a second route (funded by DE-FG36-08GO18142) in which first high-surface area carbon is cre- ated and doped by surface vapor deposition of boron, with incorporation of the boron into the lattice the final step of the fabrication. The challenge in the first route is to create high surface areas without compromising sp2 boron-carbon bonds. The challenge in the second route is to create sp2 boron-carbon bonds without com- promising high surface areas.« less
Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage

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

Pfeifer, Peter; Gillespie, Andrew; Stalla, David

The purpose of the project “Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage” is the development of materials that store hydrogen (H 2) by adsorption in quantities and at conditions that outperform current compressed-gas H 2 storage systems for electric power generation from hydrogen fuel cells (HFCs). Prominent areas of interest for HFCs are light-duty vehicles (“hydrogen cars”) and replacement of batteries with HFC systems in a wide spectrum of applications, ranging from forklifts to unmanned areal vehicles to portable power sources. State-of-the-art compressed H 2 tanks operate at pressures between 350 and 700 bar at ambient temperature and storemore » 3-4 percent of H 2 by weight (wt%) and less than 25 grams of H 2 per liter (g/L) of tank volume. Thus, the purpose of the project is to engineer adsorbents that achieve storage capacities better than compressed H 2 at pressures less than 350 bar. Adsorption holds H 2 molecules as a high-density film on the surface of a solid at low pressure, by virtue of attractive surface-gas interactions. At a given pressure, the density of the adsorbed film is the higher the stronger the binding of the molecules to the surface is (high binding energies). Thus, critical for high storage capacities are high surface areas, high binding energies, and low void fractions (high void fractions, such as in interstitial space between adsorbent particles, “waste” storage volume by holding hydrogen as non-adsorbed gas). Coexistence of high surface area and low void fraction makes the ideal adsorbent a nanoporous monolith, with pores wide enough to hold high-density hydrogen films, narrow enough to minimize storage as non-adsorbed gas, and thin walls between pores to minimize the volume occupied by solid instead of hydrogen. A monolith can be machined to fit into a rectangular tank (low pressure, conformable tank), cylindrical tank (high pressure), or other tank shape without any waste of volume.« less
Modified Ni-Cu catalysts for ethanol steam reforming

NASA Astrophysics Data System (ADS)

Dan, M.; Mihet, M.; Almasan, V.; Borodi, G.; Katona, G.; Muresan, L.; Lazar, M. D.

2013-11-01

Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N2 adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.
Molecular hydrogen sorption capacity of D-shwarzites

NASA Astrophysics Data System (ADS)

Krasnov, Pavel O.; Shkaberina, Guzel S.; Kuzubov, Alexander A.; Kovaleva, Evgenia A.

2017-09-01

Schwarzites are one of the most well-known forms of nanoporous carbon. High porosity and large surface area of these materials make them promising candidates for molecular hydrogen storage. Quantum-chemical modeling showed that hydrogen weight fraction inside D-schwarzite structure depends on the number of atoms per unit cell that determines its size and morphology. D480 schwarzite has demonstrated the largest value of hydrogen sorption capacity amongst the structures considered in this work. It reaches 7.65% at the technologically acceptable values of temperature and pressure (300 K and 10 MPa). Though being lower than that required by DOE (9%), this amount can be increased by using schwarzites with larger unit cell corresponding to the larger surface area.
A Large-Surface-Area Boracite-Network-Topology Porous MOF Constructed from a Conjugated Ligand Exhibiting a High Hydrogen Uptake Capacity

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

Wang, Xi-Sen; Ma, Shengqian; Yuan, Daqiang

2009-01-01

A new porous metal-organic framework, PCN-20 with a twisted boracite net topology, was constructed based on a highly conjugated planar tricarboxylate ligand; PCN-20 possesses a large Langmuir surface area of over 4200 m(2)/g as well as demonstrates a high hydrogen uptake capacity of 6.2 wt % at 77 K and 50 bar.
Carbide-Derived Carbons with Tunable Porosity Optimized for Hydrogen Storage

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

Fisher, John E.; Gogotsi, Yury; Yildirim, Taner

2010-01-07

On-board hydrogen storage is a key requirement for fuel cell-powered cars and trucks. Porous carbon-based materials can in principle adsorb more hydrogen per unit weight at room temperature than liquid hydrogen at -176 oC. Achieving this goal requires interconnected pores with very high internal surface area, and binding energies between hydrogen and carbon significantly enhanced relative to H2 on graphite. In this project a systematic study of carbide-derived carbons, a novel form of porous carbon, was carried out to discover a high-performance hydrogen sorption material to meet the goal. In the event we were unable to improve on the statemore » of the art in terms of stored hydrogen per unit weight, having encountered the same fundamental limit of all porous carbons: the very weak interaction between H2 and the carbon surface. On the other hand we did discover several strategies to improve storage capacity on a volume basis, which should be applicable to other forms of porous carbon. Further discoveries with potentially broader impacts include • Proof that storage performance is not directly related to pore surface area, as had been previously claimed. Small pores (< 1.5 nm) are much more effective in storing hydrogen than larger ones, such that many materials with large total surface areas are sub-par performers. • Established that the distribution of pore sizes can be controlled during CDC synthesis, which opens the possibility of developing high performance materials within a common family while targeting widely disparate applications. Examples being actively pursued with other funding sources include methane storage, electrode materials for batteries and supercapacitors with record high specific capacitance, and perm-selective membranes which bind cytokines for control of infections and possibly hemodialysis filters.« less
LANL Virtual Center for Chemical Hydrogen Storage: Chemical Hydrogen Storage Using Ultra-high Surface Area Main Group Materials

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

Susan M. Kauzlarich; Phillip P. Power; Doinita Neiner

The focus of the project was to design and synthesize light element compounds and nanomaterials that will reversibly store molecular hydrogen for hydrogen storage materials. The primary targets investigated during the last year were amine and hydrogen terminated silicon (Si) nanoparticles, Si alloyed with lighter elements (carbon (C) and boron (B)) and boron nanoparticles. The large surface area of nanoparticles should facilitate a favorable weight to volume ratio, while the low molecular weight elements such as B, nitrogen (N), and Si exist in a variety of inexpensive and readily available precursors. Furthermore, small NPs of Si are nontoxic and non-corrosive.more » Insights gained from these studies will be applied toward the design and synthesis of hydrogen storage materials that meet the DOE 2010 hydrogen storage targets: cost, hydrogen capacity and reversibility. Two primary routes were explored for the production of nanoparticles smaller than 10 nm in diameter. The first was the reduction of the elemental halides to achieve nanomaterials with chloride surface termination that could subsequently be replaced with amine or hydrogen. The second was the reaction of alkali metal Si or Si alloys with ammonium halides to produce hydrogen capped nanomaterials. These materials were characterized via X-ray powder diffraction, TEM, FTIR, TG/DSC, and NMR spectroscopy.« less
Mesoporous carbon-supported Pd nanoparticles with high specific surface area for cyclohexene hydrogenation: Outstanding catalytic activity of NaOH-treated catalysts

NASA Astrophysics Data System (ADS)

Puskás, R.; Varga, T.; Grósz, A.; Sápi, A.; Oszkó, A.; Kukovecz, Á.; Kónya, Z.

2016-06-01

Extremely high specific surface area mesoporous carbon-supported Pd nanoparticle catalysts were prepared with both impregnation and polyol-based sol methods. The silica template used for the synthesis of mesoporous carbon was removed by both NaOH and HF etching. Pd/mesoporous carbon catalysts synthesized with the impregnation method has as high specific surface area as 2250 m2/g. In case of NaOH-etched impregnated samples, the turnover frequency of cyclohexene hydrogenation to cyclohexane at 313 K was obtained 14 molecules • site- 1 • s- 1. The specific surface area of HF-etched samples was higher compared to NaOH-etched samples. However, catalytic activity was 3-6 times higher on NaOH-etched samples compared to HF-etched samples, which can be attributed to the presence of sodium and surface hydroxylgroups of the catalysts etched with NaOH solution.
Remarkably Enhanced Room-Temperature Hydrogen Sensing of SnO₂ Nanoflowers via Vacuum Annealing Treatment.

PubMed

Liu, Gao; Wang, Zhao; Chen, Zihui; Yang, Shulin; Fu, Xingxing; Huang, Rui; Li, Xiaokang; Xiong, Juan; Hu, Yongming; Gu, Haoshuang

2018-03-23

In this work, SnO₂ nanoflowers synthesized by a hydrothermal method were employed as hydrogen sensing materials. The as-synthesized SnO₂ nanoflowers consisted of cuboid-like SnO₂ nanorods with tetragonal structures. A great increase in the relative content of surface-adsorbed oxygen was observed after the vacuum annealing treatment, and this increase could have been due to the increase in surface oxygen vacancies serving as preferential adsorption sites for oxygen species. Annealing treatment resulted in an 8% increase in the specific surface area of the samples. Moreover, the conductivity of the sensors decreased after the annealing treatment, which should be attributed to the increase in electron scattering around the defects and the compensated donor behavior of the oxygen vacancies due to the surface oxygen adsorption. The hydrogen sensors of the annealed samples, compared to those of the unannealed samples, exhibited a much higher sensitivity and faster response rate. The sensor response factor and response rate increased from 27.1% to 80.2% and 0.34%/s to 1.15%/s, respectively. This remarkable enhancement in sensing performance induced by the annealing treatment could be attributed to the larger specific surface areas and higher amount of surface-adsorbed oxygen, which provides a greater reaction space for hydrogen. Moreover, the sensors with annealed SnO₂ nanoflowers also exhibited high selectivity towards hydrogen against CH₄, CO, and ethanol.
Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

PubMed

Viditha, V; Srilatha, K; Himabindu, V

2016-05-01

Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.
Cross-cutting High Surface Area Graphene-based Frameworks with Controlled Pore Structure/Dopants

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

Gaillard, J.

The goal of this project is to enhance the performance of graphene-based materials by manufacturing specific 3D architectures. The materials have global applications regarding fuel cell catalysts, gas adsorbents, supercapacitor/battery electrodes, ion (e.g., actinide) capture, gas separation, oil adsorption, and catalysis. This research focuses on hydrogen storage for hydrogen fuel cell vehicles with a potential transformational impact on hydrogen adsorbents that exhibit high gravimetric and volumetric density, a clean energy application sought by the Department of Energy. The development of an adsorbent material would enable broad commercial opportunities in hydrogen-fueled vehicles, promote new advanced nanomanufacturing scale-up, and open other opportunitiesmore » at Savannah River National Laboratory to utilize a high surface area material that is robust, chemically stable, and radiation resistant.« less
Hydrogenated amorphous silicon coatings may modulate gingival cell response

NASA Astrophysics Data System (ADS)

Mussano, F.; Genova, T.; Laurenti, M.; Munaron, L.; Pirri, C. F.; Rivolo, P.; Carossa, S.; Mandracci, P.

2018-04-01

Silicon-based materials present a high potential for dental implant applications, since silicon has been proven necessary for the correct bone formation in animals and humans. Notably, the addition of silicon is effective to enhance the bioactivity of hydroxyapatite and other biomaterials. The present work aims to expand the knowledge of the role exerted by hydrogen in the biological interaction of silicon-based materials, comparing two hydrogenated amorphous silicon coatings, with different hydrogen content, as means to enhance soft tissue cell adhesion. To accomplish this task, the films were produced by plasma enhanced chemical vapor deposition (PECVD) on titanium substrates and their surface composition and hydrogen content were analyzed by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectrophotometry (FTIR) respectively. The surface energy and roughness were measured through optical contact angle analysis (OCA) and high-resolution mechanical profilometry respectively. Coated surfaces showed a slightly lower roughness, compared to bare titanium samples, regardless of the hydrogen content. The early cell responses of human keratinocytes and fibroblasts were tested on the above mentioned surface modifications, in terms of cell adhesion, viability and morphometrical assessment. Films with lower hydrogen content were endowed with a surface energy comparable to the titanium surfaces. Films with higher hydrogen incorporation displayed a lower surface oxidation and a considerably lower surface energy, compared to the less hydrogenated samples. As regards mean cell area and focal adhesion density, both a-Si coatings influenced fibroblasts, but had no significant effects on keratinocytes. On the contrary, hydrogen-rich films increased manifolds the adhesion and viability of keratinocytes, but not of fibroblasts, suggesting a selective biological effect on these cells.
Onboard hydrogen generation for automobiles

NASA Technical Reports Server (NTRS)

Houseman, J.; Cerini, D. J.

1976-01-01

Problems concerning the use of hydrogen as a fuel for motor vehicles are related to the storage of the hydrogen onboard a vehicle. The feasibility is investigated to use an approach based on onboard hydrogen generation as a means to avoid these storage difficulties. Two major chemical processes can be used to produce hydrogen from liquid hydrocarbons and methanol. In steam reforming, the fuel reacts with water on a catalytic surface to produce a mixture of hydrogen and carbon monoxide. In partial oxidation, the fuel reacts with air, either on a catalytic surface or in a flame front, to yield a mixture of hydrogen and carbon monoxide. There are many trade-offs in onboard hydrogen generation, both in the choice of fuels as well as in the choice of a chemical process. Attention is given to these alternatives, the results of some experimental work in this area, and the combustion of various hydrogen-rich gases in an internal combustion engine.
Quantification of peroxide ion passage in dentin, enamel, and cementum after internal bleaching with hydrogen peroxide.

PubMed

Palo, R M; Bonetti-Filho, I; Valera, M C; Camargo, C H R; Camargo, Sea; Moura-Netto, C; Pameijer, C

2012-01-01

The aim of this study was to evaluate the amount of peroxide passage from the pulp chamber to the external enamel surface during the internal bleaching technique. Fifty bovine teeth were sectioned transversally 5 mm below the cemento-enamel junction (CEJ), and the remaining part of the root was sealed with a 2-mm layer of glass ionomer cement. The external surface of the samples was coated with nail varnish, with the exception of standardized circular areas (6-mm diameter) located on the enamel, exposed dentin, or cementum surface of the tooth. The teeth were divided into three experimental groups according to exposed areas close to the CEJ and into two control groups (n=10/group), as follows: GE, enamel exposure area; GC, cementum exposed area; GD, dentin exposed area; Negative control, no presence of internal bleaching agent and uncoated surface; and Positive control, pulp chamber filled with bleaching agent and external surface totally coated with nail varnish. The pulp chamber was filled with 35% hydrogen peroxide (Opalescence Endo, Ultradent). Each sample was placed inside of individual flasks with 1000 μL of acetate buffer solution, 2 M (pH 4.5). After seven days, the buffer solution was transferred to a glass tube, in which 100 μL of leuco-crystal violet and 50 μL of horseradish peroxidase were added, producing a blue solution. The optical density of the blue solution was determined by spectrophotometer and converted into microgram equivalents of hydrogen peroxide. Data were submitted to Kruskal-Wallis and Dunn-Bonferroni tests (α=0.05). All experimental groups presented passage of peroxide to the external surface that was statistically different from that observed in the control groups. It was verified that the passage of peroxide was higher in GD than in GE (p<0.01). The GC group presented a significantly lower peroxide passage than did GD and GE (p<0.01). It can be concluded that the hydrogen peroxide placed into the pulp chamber passed through the dental hard tissues, reaching the external surface and the periodontal tissue. The cementum surface was less permeable than were the dentin and enamel surfaces.

Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

NASA Astrophysics Data System (ADS)

Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh

2015-12-01

Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.
Conformational changes of a calix[8]arene derivative at the air-water interface.

PubMed

de Miguel, Gustavo; Pedrosa, José M; Martín-Romero, María T; Muñoz, Eulogia; Richardson, Tim H; Camacho, Luis

2005-03-10

The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules.
Cryo-Milling and the Hydrogen Storage Properties of NaAlH4

NASA Astrophysics Data System (ADS)

Feller, Kevin; Dobbins, Tabbetha

2013-03-01

High energy ball milling of metal hydrides is a common way to both introduce catalysts (e.g. TiCl3) and to simultaneously increase the surface area. Both catalysis and increased surface area improve hydrogen storage capacity of the material. Nanostructuring of hydrides by depositing them into mesoporous templates (such as anodized alumina, MOFs, and SBA-15) has become a common way to increase surface area. However, the mesoporous template does not add hydrogen storage capacity--and thus, tends to decreased overall storage weight percent for the nanostructured hydride material. As with most materials, hydrides become brittle at low temperatures and will tend to fracture more readily. We will process Sodium Aluminum Hydride (NaAlH4) using cryogenic high energy ball milling using an in-house modified chamber SPEX Certiprep M8000 mixer/mill in order to gain a nanostructured hydride without mesoporous template material. Details of the modified mixer mill design will be presented. Ultimately, our planned future work is to study the resultant material using x-ray diffraction (Scherrer method for crystallite size), absorption/desorption temperature programmed desorption (TPD), and ultrasmall-angle x-ray scattering (USAXS) microstructural quantification to understand the role of cryomilling on enhancing the material's ability to store (and release) hydrogen.
Highly sensitive hydrogen detection of catalyst-free ZnO nanorod networks suspended by lithography-assisted growth.

PubMed

Huh, Junghwan; Park, Jonghyurk; Kim, Gyu Tae; Park, Jeong Young

2011-02-25

We have successfully demonstrated a ZnO nanorod-based 3D nanostructure to show a high sensitivity and very fast response/recovery to hydrogen gas. ZnO nanorods have been synthesized selectively over the pre-defined area at relatively low temperature using a simple self-catalytic solution process assisted by a lithographic method. The conductance of the ZnO nanorod device varies significantly as the concentration of the hydrogen is changed without any additive metal catalyst, revealing a high sensitivity to hydrogen gas. Its superior performance can be explained by the porous structure of its three-dimensional network and the enhanced surface reaction of the hydrogen molecules with the oxygen defects resulting from a high surface-to-volume ratio. It was found that the change of conductance follows a power law depending on the hydrogen concentration. A Langmuir isotherm following an ideal power law and a cross-over behavior of the activation energy with respect to hydrogen concentration were observed. This is a very novel and intriguing phenomenon on nanostructured materials, which suggests competitive surface reactions in ZnO nanorod gas sensors.
Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

PubMed

Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

2014-11-10

A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2) g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.
Electrocatalytically Active Nickel-Based Electrode Coatings Formed by Atmospheric and Suspension Plasma Spraying

NASA Astrophysics Data System (ADS)

Aghasibeig, M.; Mousavi, M.; Ben Ettouill, F.; Moreau, C.; Wuthrich, R.; Dolatabadi, A.

2014-01-01

Ni-based electrode coatings with enhanced surface areas, for hydrogen production, were developed using atmospheric plasma spray (APS) and suspension plasma spray (SPS) processes. The results revealed a larger electrochemical active surface area for the coatings produced by SPS compared to those produced by APS process. SEM micrographs showed that the surface microstructure of the sample with the largest surface area was composed of a large number of small cauliflower-like aggregates with an average diameter of 10 μm.
Hydrogen Adsorption on Activated Carbon an Carbon Nanotubes Using Volumetric Differential Pressure Technique

NASA Astrophysics Data System (ADS)

Sanip, S. M.; Saidin, M. A. R.; Aziz, M.; Ismail, A. F.

2010-03-01

A simple hydrogen adsorption measurement system utilizing the volumetri differential pressure technique has been designed, fabricated and calibrated. Hydroge adsorption measurements have been carried out at temperatures 298 K and 77 K on activate carbon and carbon nanotubes with different surface areas. The adsorption data obtained will b helpful in understanding the adsorption property of the studied carbon materials using th fundamentals of adsorption theory. The principle of the system follows the Sievert-type metho The system measures a change in pressure between the reference cell, R1 and the sample cell S1, S2, S3 over a certain temperature range. R1, S1, S2, and S3 having known fixed volume The sample temperatures will be monitored by thermocouple TC while the pressures in R1 an S1, S2, S3 will be measured using a digital pressure transducer. The maximum operatin pressure of the pressure transducer is 20 bar and calibrated with an accuracy of ±0.01 bar. Hig purity hydrogen is being used in the system and the amount of samples for the study is betwee 1.0-2.0 grams. The system was calibrated using helium gas without any samples in S1, S2 an S3. This will provide a correction factor during the adsorption process providing an adsorption free reference point when using hydrogen gas resulting in a more accurate reading of th adsorption process by eliminating the errors caused by temperature expansion effects and oth non-adsorption related phenomena. The ideal gas equation of state is applied to calculate th hydrogen adsorption capacity based on the differential pressure measurements. Activated carbo with a surface area of 644.87 m2/g showed a larger amount of adsorption as compared to multiwalled nanotubes (commercial) with a surface area of 119.68 m2/g. This study als indicated that there is a direct correlation between the amounts of hydrogen adsorbed an surface area of the carbon materials under the conditions studied and that the adsorption significant at 77 K.
Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull.

PubMed

Shang, Guofeng; Liu, Liang; Chen, Ping; Shen, Guoqing; Li, Qiwu

2016-05-01

The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H2S. At the different pyrolysis temperature, the H2S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g(-1), 2.65 mg·g(-1), 16.30 mg·g(-1), 20.80 mg·g(-1), and 382.70 mg·g(-1), which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar. The paper focuses on the biochar derived from rice hull-removed hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H2S. At the different pyrolysis temperatures, the H2S removal efficiency of rice hull-derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g(-1), and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.
Hydrogen storage in engineered carbon nanospaces.

PubMed

Burress, Jacob; Kraus, Michael; Beckner, Matt; Cepel, Raina; Suppes, Galen; Wexler, Carlos; Pfeifer, Peter

2009-05-20

It is shown how appropriately engineered nanoporous carbons provide materials for reversible hydrogen storage, based on physisorption, with exceptional storage capacities (approximately 80 g H2/kg carbon, approximately 50 g H2/liter carbon, at 50 bar and 77 K). Nanopores generate high storage capacities (a) by having high surface area to volume ratios, and (b) by hosting deep potential wells through overlapping substrate potentials from opposite pore walls, giving rise to a binding energy nearly twice the binding energy in wide pores. Experimental case studies are presented with surface areas as high as 3100 m(2) g(-1), in which 40% of all surface sites reside in pores of width approximately 0.7 nm and binding energy approximately 9 kJ mol(-1), and 60% of sites in pores of width>1.0 nm and binding energy approximately 5 kJ mol(-1). The findings, including the prevalence of just two distinct binding energies, are in excellent agreement with results from molecular dynamics simulations. It is also shown, from statistical mechanical models, that one can experimentally distinguish between the situation in which molecules do (mobile adsorption) and do not (localized adsorption) move parallel to the surface, how such lateral dynamics affects the hydrogen storage capacity, and how the two situations are controlled by the vibrational frequencies of adsorbed hydrogen molecules parallel and perpendicular to the surface: in the samples presented, adsorption is mobile at 293 K, and localized at 77 K. These findings make a strong case for it being possible to significantly increase hydrogen storage capacities in nanoporous carbons by suitable engineering of the nanopore space.
Influence of surface treatments on micropore structure and hydrogen adsorption behavior of nanoporous carbons.

PubMed

Kim, Byung-Joo; Park, Soo-Jin

2007-07-15

The scope of this work was to control the pore sizes of porous carbons by various surface treatments and to investigate the relation between pore structures and hydrogen adsorption capacity. The effects of various surface treatments (i.e., gas-phase ozone, anodic oxidation, fluorination, and oxygen plasma) on the micropore structures of porous carbons were investigated by N(2)/77 K isothermal adsorption. The hydrogen adsorption capacity was measured by H(2) isothermal adsorption at 77 K. In the result, the specific surface area and micropore volume of all of the treated samples were slightly decreased due to the micropore filling or pore collapsing behaviors. It was also found that in F(2)-treated carbons the center of the pore size distribution was shifted to left side, meaning that the average size of the micropores decreased. The F(2)- and plasma-treated samples showed higher hydrogen storage capacities than did the other samples, the F(2)-treated one being the best, indicating that the micropore size of the porous carbons played a key role in the hydrogen adsorption at 77 K.
Hydrogen production with coal using a pulverization device

DOEpatents

Paulson, Leland E.

1989-01-01

A method for producing hydrogen from coal is described wherein high temperature steam is brought into contact with coal in a pulverizer or fluid energy mill for effecting a steam-carbon reaction to provide for the generation of gaseous hydrogen. The high temperature steam is utilized to drive the coal particles into violent particle-to-particle contact for comminuting the particulates and thereby increasing the surface area of the coal particles for enhancing the productivity of the hydrogen.
Hydrogen adsorption in metal-decorated silicon carbide nanotubes

NASA Astrophysics Data System (ADS)

Singh, Ram Sevak; Solanki, Ankit

2016-09-01

Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.
Hydrogen Storage in Metal Hydrides

DTIC Science & Technology

1990-08-01

TitlePage 1. Properties of Reticulated Carbon Foam 26 2. Hydrogen Storage Capacity of Various Metal Hydrides 27 iv INTRODUCTION This is the final technical...pores, and results in coating of only the surface. The substrate for the fabrication of the magnesium foam was a reticulated carbon foam. This...material is an open-pore foam composed solely of vitreous carbon . It has an exceptionally high void volume (97%) and a high surface area, combined with self
Measurements of the electrical resistance and the hydrogen depth distribution for Ni 60Nb 20Zr 20 amorphous alloy before and after hydrogen charging

NASA Astrophysics Data System (ADS)

Nakano, Sumiaki; Ohtsu, Naofumi; Nagata, Shinji; Yamaura, Shin-ichi; Uchinashi, Sakae; Kimura, Hisamichi; Shikama, Tatsuo; Inoue, Akihisa

2005-02-01

A Ni 60Nb 20Zr 20 amorphous alloy was prepared by the single-roller melt-spinning technique. The change in the electrical resistance of the alloy after electrochemical hydrogen charging in 6 N KOH solution was investigated. The change in the hydrogen depth distribution in the alloy was also investigated by elastic recoil detection. As a result, we found that the electrical resistance of the alloy increases with increasing the hydrogen content in the alloy and that a large number of hydrogen atoms are remained in the surface area of the hydrogen-charged alloy.
Surfactant-assisted coal liquefaction

NASA Technical Reports Server (NTRS)

Hsu, G. C.

1977-01-01

Improved process of coal liquefaction utilizing nonaqueous surfactant has increased oil yield from 50 to about 80%. Asphaltene molecule formation of colloid particles is prevented by surfactant. Separated molecules present more surface area for hydrogenation reaction. Lower requirements for temperature, pressure, and hydrogen lead to reduction in capital and operation costs.
Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

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

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less
Mercury Underpotential Deposition to Determine Iridium and Iridium Oxide Electrochemical Surface Areas

DOE PAGES

Alia, Shaun M.; Hurst, Katherine E.; Kocha, Shyam S.; ...

2016-06-02

Determining the surface areas of electrocatalysts is critical for separating the key properties of area-specific activity and electrochemical surface area from mass activity. Hydrogen underpotential deposition and carbon monoxide oxidation are typically used to evaluate iridium (Ir) surface areas, but are ineffective on oxides and can be sensitive to surface oxides formed on Ir metals. Mercury underpotential deposition is presented in this study as an alternative, able to produce reasonable surface areas on Ir and Ir oxide nanoparticles, and able to produce similar surface areas prior to and following characterization in oxygen evolution. Reliable electrochemical surface areas allow for comparativemore » studies of different catalyst types and the characterization of advanced oxygen evolution catalysts. Lastly, they also enable the study of catalyst degradation in durability testing, both areas of increasing importance within electrolysis and electrocatalysis.« less
Adsorption of bovine serum albumin on nano and bulk oxide particles in deionized water.

PubMed

Song, Lei; Yang, Kun; Jiang, Wei; Du, Peng; Xing, Baoshan

2012-06-01

In this work, the influence of particle size and surface functional groups on the adsorption behavior of bovine serum albumin (BSA) by three types of oxide nanoparticles (NPs), TiO(2) (50±5 nm), SiO(2) (30±5 nm), and Al(2)O(3) (150±5 nm for α type and 60±5 nm for γ type) was investigated in deionized water, in order to explore their interaction mechanisms without competitive influence of other ions. Bulkparticles (BPs) were also used for comparison with NPs. BSA adsorption maxima on oxide particles were controlled by the surface area and hydrogen content, while adsorption process was primarily induced by electrostatic interaction, hydrophobic interaction and ligand exchange between BSA and oxide surfaces. With the increase of hydrogen content, the BSA adsorption mechanism switched from mainly hydrophobic interaction to hydrogen bonding and ligand exchange. Calculations, based on surface area and BSA size, suggested that a multilayer of BSA covered on α-Al(2)O(3), and single layer on the other oxide particle surfaces. BPs led to greater conformational change of BSA molecules after the adsorption on the surfaces of oxide particles though NPs adsorbed more BSA than BPs. Copyright © 2012 Elsevier B.V. All rights reserved.
Advanced hydrogen electrode for hydrogen-bromide battery

NASA Technical Reports Server (NTRS)

Kosek, Jack A.; Laconti, Anthony B.

1987-01-01

Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

Electrochemical Hydrogen Evolution at Ordered Mo 7 Ni 7

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

Csernica, Peter M.; McKone, James R.; Mulzer, Catherine R.

2017-04-11

Ni–Mo alloys containing up to ~15 mol % Mo are excellent non-noble electrocatalysts for the hydrogen evolution reaction (HER) in alkaline aqueous electrolytes. To date, studies have not addressed the details of HER activity of ordered Ni–Mo intermetallic compounds, which can contain a significantly larger fraction of Mo (up to 50 mol %) than can be accessed through high-temperature alloying. Here, we present a straightforward and facile synthesis of three phase-pure electrocatalyst powders using a precipitation–reduction approach: ordered Mo7Ni7, disordered Ni0.92Mo0.08, and pure Ni. The Ni0.92Mo0.08 alloy exhibited a nearly 10-fold higher mass-specific HER activity than either pure Ni ormore » Mo7Ni7, where much of the difference could be attributed to relative surface area. Therefore, we attempted to quantify and account for differences in surface areas using electron microscopy, impedance spectroscopy, and gas adsorption measurements. These data suggest that Ni–Mo alloys and intermetallic compounds exhibit substantial pseudocapacitance at potentials near the onset of hydrogen evolution, which can cause impedance spectroscopy to overestimate the interfacial capacitance, and thus the electrochemically active surface area, of these materials. From these observations, we postulate Mo redox activity as the chemical basis for the observed pseudocapacitance of Ni–Mo composites. Furthermore, using gas adsorption measurements, rather than capacitance, to estimate active surface area, we find that ordered Mo7Ni7 is more intrinsically active than the Ni0.92Mo0.08 alloy, implying that Mo7Ni7 intermetallics with high surface area will also give higher mass-specific activities than alloys with comparable roughness.« less
Hydrogen Storage in metal-modified single-walled carbon nanotubes

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

Dr. Ahn

2004-04-30

It has been known for over thirty years that potassium-intercalated graphites can readily adsorb and desorb hydrogen at {approx}1 wt% at 77 K. These levels are much higher than can be attained in pure graphite, owing to a larger thermodynamic enthalpy of adsorption. This increased enthalpy may allow hydrogen sorption at higher temperatures. Potassium has other beneficial effects that enable the design of a new material: (a) Increased adsorption enthalpy in potassium-intercalated graphite compared to pure graphite reduces the pressure and increases the temperature required for a given fractional coverage of hydrogen adsorption. We expect the same effects in potassium-intercalatedmore » SWNTs. (b) As an intercalant, potassium separates c-axis planes in graphite. Potassium also separates the individual tubes of SWNTs ropes producing swelling and increased surface area. Increased surface area provides more adsorption sites, giving a proportionately higher capacity. The temperature of adsorption depends on the enthalpy of adsorption. The characteristic temperature is roughly the adsorption enthalpy divided by Boltzmann's constant, k{sub B}. For the high hydrogen storage capacity of SWNTs to be achieved at room temperature, it is necessary to increase the enthalpy of adsorption. Our goal for this project was to use metal modifications to the carbon surface of SWNTs in order to address both enhanced adsorption and surface area. For instance, the enthalpy of sorption of hydrogen on KC8 is 450 meV/H{sub 2}, whereas it is 38 meV/H{sub 2} for unmodified SWNTs. By adsorption thermodynamics we expect approximately that the same performance of SWNTs at 77 K will be achieved at a temperature of [450/38] 77 K = 900 K. This is a high temperature, so we expect that adsorption on nearly all the available sites for hydrogen will occur at room temperature under a much lower pressure. This pressure can be estimated conveniently, since the chemical potential of hydrogen is approximately proportional to the logarithm of the pressure. Using 300 K for room temperature, the 100 bar pressure requirement is reduced to exp(-900/300) 100 bar = 5 bar at room temperature. This is in the pressure range used for prior experimental work such as that of Colin and Herold in the late 1960's and early 1970's.« less
Analysis Sharpens Mars Hydrogen Map, Hinting Equatorial Water Ice

NASA Image and Video Library

2017-09-28

Re-analysis of 2002-2009 data from a hydrogen-finding instrument on NASA's Mars Odyssey orbiter increased the resolution of maps of hydrogen abundance. The reprocessed data (lower map) shows more "water-equivalent hydrogen" (darker blue) in some parts of this equatorial region of Mars. Puzzingly, this suggests the possible presence of water ice just beneath the surface near the equator, though it would not be thermodynamically stable there. The upper map uses raw data from Odyssey's neutron spectrometer instrument, which senses the energy state of neutrons coming from Mars, providing an indication of how much hydrogen is present in the top 3 feet (1 meter) of the surface. Hydrogen detected by Odyssey at high latitudes of Mars in 2002 was confirmed to be in the form of water ice by the follow-up NASA Phoenix Mars Lander mission in 2008. A 2017 reprocessing of the older data applied image-reconstruction techniques often used to reduce blurring from medical imaging data. The results are shown here for an area straddling the equator for about one-fourth the circumference of the planet, centered at 175 degrees west longitude. The white contours outline lobes of a formation called Medusae Fossae, coinciding with some areas of higher hydrogen abundance in the enhanced-resolution analysis. The black line indicates the limit of a relatively young lava plain, coinciding with areas of lower hydrogen abundance in the enhanced-resolution analysis. The color-coding key for hydrogen abundance in both maps is indicated by the horizontal bar, in units expressed as how much water would be present in the ground if the hydrogen is all in the form of water. Units of the equivalent water weight, as a percentage of the material in the ground, are correlated with counts recorded by the spectrometer, ranging from less than 1 weight-percent water equivalent (red) to more than 30 percent (dark blue). https://photojournal.jpl.nasa.gov/catalog/PIA21848
Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

DOE PAGES

Alia, Shaun M.; Yan, Yushan

2015-05-09

The palladium (Pd) nanotubes we synthesized by the spontaneous galvanic displacement of copper (Cu) nanowires, are forming extended surface nanostructures highly active for the hydrogen oxidation reaction (HOR) in base. The synthesized catalysts produce specific activities in rotating disk electrode half-cells 20 times greater than Pd nanoparticles and about 80% higher than polycrystalline Pd. Although the surface area of the Pd nanotubes was low compared to conventional catalysts, partial galvanic displacement thrifted the noble metal layer and increased the Pd surface area. Moreover, the use of Pd coated Cu nanowires resulted in a HOR mass exchange current density 7 timesmore » greater than the Pd nanoparticles. The activity of the Pd coated Cu nanowires further nears Pt/C, producing 95% of the mass activity.« less
Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

NASA Astrophysics Data System (ADS)

Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

2018-01-01

Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.
Interaction of Hydrogen with MOF-5.

PubMed

Bordiga, Silvia; Vitillo, Jenny G; Ricchiardi, Gabriele; Regli, Laura; Cocina, Donato; Zecchina, Adriano; Arstad, Bjørnar; Bjørgen, Morten; Hafizovic, Jasmina; Lillerud, Karl Petter

2005-10-06

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water.

PubMed

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-22

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m(2) g(-1) were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

NASA Astrophysics Data System (ADS)

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g-1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.
Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

PubMed Central

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-01-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834
Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char.

PubMed

Norouzi, Omid; Jafarian, Sajedeh; Safari, Farid; Tavasoli, Ahmad; Nejati, Behnam

2016-11-01

Conversion of Cladophora glomerata (C. glomerata) as a Caspian Sea's green macroalgae into gaseous, liquid and solid products was carried out via pyrolysis at different temperatures to determine its potential for bio-oil and hydrogen-rich gas production for further industrial utilization. Non-catalytic tests were performed to determine the optimum condition for bio-oil production. The highest portion of bio-oil was retrieved at 500°C. The catalytic test was performed using the bio-char derived at 500°C as a catalyst. Effect of the addition of the algal bio-char on the composition of the bio-oil and also gaseous products was investigated. Pyrolysis derived bio-char was characterized by BET, FESEM and ICP method to show its surface area, porosity, and presence of inorganic metals on its surface, respectively. Phenols were increased from 8.5 to 20.76area% by the addition of bio-char. Moreover, the hydrogen concentration and hydrogen selectivity were also enhanced by the factors of 1.37, 1.59 respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.
Interaction of hydrogen chloride and water with oxide surfaces. III - Titanium dioxide

NASA Technical Reports Server (NTRS)

Siriwardane, R. V.; Wightman, J. P.

1983-01-01

The adsorption of hydrogen chloride and water vapors on five TiO2 powders in both the anatase and rutile crystalline forms was studied as a function of temperature, pressure, and outgas conditions. The adsorbents were characterized utilizing X-ray powder diffraction, scanning electron microscopy, surface area analysis, indicator method, microelectrophoresis, XPS, and infrared spectroscopy. It was found that both outgas temperature and adsorption temperature influenced the adsorption of water vapor on TiO2, while water vapor adsorption on TiO2 was completely reversible. It is argued that the number of hydroxyl groups present on the surface determines the adsorption capacity of water on the different titanium dioxides. It was found that heats of immersion in water were affected significantly by outgas temperature. Hydrogen chloride adsorption isotherms at 30 C measured on TiO2 after outgassing at 100-400 C showed that a part of the total HCl adsorbed was irreversibly adsorbed. The highest HCl adsorption capacity per unit area was exhibited by anatase, while pure rutile exhibited the lowest adsorption capacity.
Nanomaterials for Hydrogen Storage Applications: A Review

DOE PAGES

Niemann, Michael U.; Srinivasan, Sesha S.; Phani, Ayala R.; ...

2008-01-01

Nmore » anomaterials have attracted great interest in recent years because of the unusual mechanical, electrical, electronic, optical, magnetic and surface properties. The high surface/volume ratio of these materials has significant implications with respect to energy storage. Both the high surface area and the opportunity for nanomaterial consolidation are key attributes of this new class of materials for hydrogen storage devices. anostructured systems including carbon nanotubes, nano-magnesium based hydrides, complex hydride/carbon nanocomposites, boron nitride nanotubes, TiS 2 / MoS 2 nanotubes, alanates, polymer nanocomposites, and metal organic frameworks are considered to be potential candidates for storing large quantities of hydrogen. Recent investigations have shown that nanoscale materials may offer advantages if certain physical and chemical effects related to the nanoscale can be used efficiently. The present review focuses the application of nanostructured materials for storing atomic or molecular hydrogen. The synergistic effects of nanocrystalinity and nanocatalyst doping on the metal or complex hydrides for improving the thermodynamics and hydrogen reaction kinetics are discussed. In addition, various carbonaceous nanomaterials and novel sorbent systems (e.g. carbon nanotubes, fullerenes, nanofibers, polyaniline nanospheres and metal organic frameworks etc.) and their hydrogen storage characteristics are outlined.« less
Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.
The use of the ion probe mass spectrometer in the measurement of hydrogen concentration gradients in Monel K 500

NASA Technical Reports Server (NTRS)

Truhan, J. J., Jr.; Hehemann, R. F.

1974-01-01

The ion probe mass spectrometer was used to measure hydrogen concentration gradients in cathodically charged Monel K 500. Initial work with the ion probe involved the calibration of the instrument and the establishment of a suitable experimental procedure for this application. Samples of Monel K 500 were cathodically charged in a weak sulfuric acid solution. By varying the current density, different levels of hydrogen were introduced into the samples. Hydrogen concentration gradients were taken by ion sputtering on the surface of these samples and monitoring the behavior of the hydrogen mass peak as a function of time. An attempt was made to determine the relative amounts of hydrogen in the bulk and grain boundaries by analyzing a fresh fracture surface with a higher proportion of grain boundary area. It was found that substantially more hydrogen was detected in the grain boundaries than in the bulk, confirming the predictions of previous workers. A sputter rate determination was made in order to establish the rate of erosion.
A passive microfluidic hydrogen-air fuel cell with exceptional stability and high performance.

PubMed

Mitrovski, Svetlana M; Nuzzo, Ralph G

2006-03-01

We describe an advanced microfluidic hydrogen-air fuel cell (FC) that exhibits exceptional durability and high performance, most notably yielding stable output power (>100 days) without the use of an anode-cathode separator membrane. This FC embraces an entirely passive device architecture and, unlike conventional microfluidic designs that exploit laminar hydrodynamics, no external pumps are used to sustain or localize the reagent flow fields. The devices incorporate high surface area/porous metal and metal alloy electrodes that are embedded and fully immersed in liquid electrolyte confined in the channels of a poly(dimethylsiloxane) (PDMS)-based microfluidic network. The polymeric network also serves as a self-supporting membrane through which oxygen and hydrogen are supplied to the cathode and alloy anode, respectively, by permeation. The operational stability of the device and its performance is strongly dependent on the nature of the electrolyte used (5 M H2SO4 or 2.5 M NaOH) and composition of the anode material. The latter choice is optimized to decrease the sensitivity of the system to oxygen cross-over while still maintaining high activity towards the hydrogen oxidation reaction (HOR). Three types of high surface area anodes were tested in this work. These include: high-surface area electrodeposited Pt (Pt); high-surface area electrodeposited Pd (Pd); and thin palladium adlayers supported on a "porous" Pt electrode (Pd/Pt). The FCs display their best performance in 5 M H2SO4 using the Pd/Pt anode. This exceptional stability and performance was ascribed to several factors, namely: the high permeabilities of O2, H2, and CO2 in PDMS; the inhibition of the formation of insoluble carbonate species due to the presence of a highly acidic electrolyte; and the selectivity of the Pd/Pt anode toward the HOR. The stability of the device for long-term operation was modeled using a stack of three FCs as a power supply for a portable display that otherwise uses a 3 V battery.
Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping [Hoffman Estates, IL; Liu, Di-Jia [Naperville, IL; Yuan, Shengwen [Chicago, IL; Yang, Junbing [Westmont, IL

2011-12-13

Porous polymers, tribenzohexazatriphenylene, poly-9,9'-spirobifluorene, poly-tetraphenyl methane and their derivatives for storage of H.sub.2 prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.
Porous polymeric materials for hydrogen storage

DOEpatents

Yu, Luping; Liu, Di-Jia; Yuan, Shengwen; Yang, Junbing

2013-04-02

A porous polymer, poly-9,9'-spirobifluorene and its derivatives for storage of H.sub.2 are prepared through a chemical synthesis method. The porous polymers have high specific surface area and narrow pore size distribution. Hydrogen uptake measurements conducted for these polymers determined a higher hydrogen storage capacity at the ambient temperature over that of the benchmark materials. The method of preparing such polymers, includes oxidatively activating solids by CO.sub.2/steam oxidation and supercritical water treatment.
Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

NASA Astrophysics Data System (ADS)

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-02-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.
Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

PubMed Central

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994
Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

PubMed

Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

Effect of Organic Capping Layers over Monodisperse Platinum Nanoparticles upon Activity for Ethylene Hydrogenation and Carbon Monoxide Oxidation

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

Kuhn, John N.; Tsung, Chia-Kuang; Huang, Wenyu

2009-03-24

The influence of oleylamine (OA), trimethyl tetradecyl ammonium bromide (TTAB), and polyvinlypyrrolidone (PVP) capping agents upon the catalytic properties of Pt/silica catalysts was evaluated. Pt nanoparticles that were 1.5 nm in size were synthesized by the same procedure (ethylene glycol reduction under basic conditions) with the various capping agents added afterward for stabilization. Before examining catalytic properties for ethylene hydrogenation and CO oxidation, the Pt NPs were deposited onto mesoporous silica (SBA-15) supports and characterized by transmission electron microscopy (TEM), H{sub 2} chemisorption, and elemental analysis (ICP-MS). PVP- and TTAB-capped Pt yielded mass-normalized reaction rates that decreased with increasing pretreatmentmore » temperature, and this trend was attributed to the partial coverage of the Pt surface with decomposition products from the organic capping agent. Once normalized to the Pt surface area, similar intrinsic activities were obtained regardless of the pretreatment temperature, which indicated no influence on the nature of the active sites. Consequently, a chemical probe technique using intrinsic activity for ethylene hydrogenation was demonstrated as an acceptable method for estimating the metallic surface areas of Pt. Amine (OA) capping exhibited a detrimental influence on the catalytic properties as severe deactivation and low activity were observed for ethylene hydrogenation and CO oxidation, respectively. These results were consistent with amine groups being strong poisons for Pt surfaces, and revealed the need to consider the effects of capping agents on the catalytic properties.« less
Hydrogen generation from caustic aluminum reaction

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

REYNOLDS, D.A.

2001-10-23

A ''crawler'' is to enter the AY farm annulus to clean the metal surface for corrosion measurements. The ''crawler'' weighs about 190 pounds of which 150 pounds are aluminum. (These values are supplied by the vender of the ''crawler''.) There is a potential that cleaning the surface of the metal may cause a leak to occur in the primary tank wall and the waste may contact the aluminum. The hydroxide in the waste may react with the aluminum and form hydrogen gas. The purpose of this analysis is to estimate the rate of hydrogen gas generation and the time tomore » reach the lower flammable limit (LFL) in the annulus. Surface area of the aluminum piece is estimated to be 2 sq.ft. (This value was given by the vender.) SA:= 2 {center_dot} ft{sup 2}.« less
Design and fabrication of miniaturized PEM fuel cell combined microreactor with self-regulated hydrogen mechanism

NASA Astrophysics Data System (ADS)

Balakrishnan, A.; Frei, M.; Kerzenmacher, S.; Reinecke, H.; Mueller, C.

2015-12-01

In this work we present the design and fabrication of the miniaturized PEM fuel cell combined microreactor system with hydrogen regulation mechanism and testing of prototype microreactor. The system consists of two components (i) fuel cell component and (ii) microreactor component. The fuel cell component represents the miniaturized PEM fuel cell system (combination of screen printed fuel cell assembly and an on-board hydrogen storage medium). Hydrogen production based on catalytic hydrolysis of chemical hydride takes place in the microreactor component. The self-regulated hydrogen mechanism based on the gaseous hydrogen produced from the catalytic hydrolysis of sodium borohydride (NaBH4) gets accumulated as bubbles at the vicinity of the hydrophobic coated hydrogen exhaust holes. When the built up hydrogen bubbles pressure exceeds the burst pressure at the hydrogen exhaust holes the bubble collapses. This collapse causes a surge of fresh NaBH4 solution onto the catalyst surface leading to the removal of the reaction by-products formed at the active sites of the catalyst. The catalyst used in the system is platinum deposited on a base substrate. Nickel foam, carbon porous medium (CPM) and ceramic plate were selected as candidates for base substrate for developing a robust catalyst surface. For the first time the platinum layer fabricated by pulsed electrodeposition and dealloying (EPDD) technique is used for hydrolysis of NaBH4. The major advantages of such platinum catalyst layers are its high surface area and their mechanical stability. Prototype microreactor system with self-regulated hydrogen mechanism is demonstrated.
Detailed Structural Analyses of KOH Activated Carbon from Waste Coffee Beans

NASA Astrophysics Data System (ADS)

Takahata, Tomokazu; Toda, Ikumi; Ono, Hiroki; Ohshio, Shigeo; Akasaka, Hiroki; Himeno, Syuji; Kokubu, Toshinori; Saitoh, Hidetoshi

2009-11-01

The relationship of the detailed structural change of KOH activated carbon and hydrogen storage ability was investigated in activated carbon materials fabricated from waste coffee beans. The specific surface area of porous carbon materials calculated from N2 adsorption isotherms stood at 2070 m2/g when the weight ratio of KOH to carbon materials was 5:1, and pore size was in the range of approximately 0.6 to 1.1 nm as micropores. In the structural analysis, X-ray diffraction analysis and Raman spectroscopy indicated structural change in these carbon materials through KOH activation. The order of the graphite structure changed to a smaller scale with this activation. It is theorized that specific surface area increased using micropores provided by carbon materials developed from the descent of the graphite structure. Hydrogen storage ability improved with these structural changes, and reached 0.6 wt % at 2070 m2/g. These results suggest that hydrogen storage ability is conferred by the chemical effect on graphite of carbon materials.
The potential of organic polymer-based hydrogen storage materials.

PubMed

Budd, Peter M; Butler, Anna; Selbie, James; Mahmood, Khalid; McKeown, Neil B; Ghanem, Bader; Msayib, Kadhum; Book, David; Walton, Allan

2007-04-21

The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H(2) by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H(2) storage materials, particularly at pressures >10 bar. The N(2) and H(2) adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H(2) adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H(2) uptake. The micropore distribution influences the form of the H(2) isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.
Kinetics and mechanisms of iron sulfide reductions in hydrogen and in carbon monoxide

USGS Publications Warehouse

Wiltowski, T.; Hinckley, C.C.; Smith, Gerard V.; Nishizawa, T.; Saporoschenko, Mykola; Shiley, R.H.; Webster, J.R.

1987-01-01

The reduction of iron sulfides by hydrogen and by carbon monoxide has been studied using plug flow and thermogravimetric methods. The reactions were studied in the 523-723??K temperature range and were found to be first-order processes. Plug flow studies were used to correlate reaction rates between pyrite and the gases as a function of the surface area of the pyrite. The rate of H2S formation increases with the surface area of the pyrite sample. The results of thermogravimetric experiments indicate that the reactions consist of several steps. Rate constants for the pyrite reduction by H2 and by CO were obtained. The activation energies increased with degree of reduction. Values of Ea were 113.2 (step I) and 122.5 kJ/mole (step II) for pyrite reduction with CO and 99.4 (step I), 122.4 (step II), 125.2 (step III), and 142.6 kJ/mole (step IV) for pyrite reduction with hydrogen. ?? 1987.
A Flexible Platform Containing Graphene Mesoporous Structure and Carbon Nanotube for Hydrogen Evolution

PubMed Central

Zhang, Rujing; Li, Xiao; Zhang, Li; Lin, Shuyuan

2016-01-01

It is of great significance to design a platform with large surface area and high electrical conductivity for poorly conductive catalyst for hydrogen evolution reaction (HER), such as molybdenum sulfide (MoSx), a promising and cost‐effective nonprecious material. Here, the design and preparation of a free‐standing and tunable graphene mesoporous structure/single‐walled carbon nanotube (GMS/SWCNT) hybrid membrane is reported. Amorphous MoSx is electrodeposited on this platform through a wet chemical process under mild temperature. For MoSx@GMS/SWCNT hybrid electrode with a low catalyst loading of 32 μg cm−2, the onset potential is near 113 mV versus reversible hydrogen electrode (RHE) and a high current density of ≈71 mA cm−2 is achieved at 250 mV versus RHE. The excellent HER performance can be attributed to the large surface area for MoSx deposition, as well as the efficient electron transport and abundant active sites on the amorphous MoSx surface. This novel catalyst is found to outperform most previously reported MoSx‐based HER catalysts. Moreover, the flexibility of the electrode facilitates its stable catalytic performance even in extremely distorted states. PMID:27980998
Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

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

Not Available

1990-03-01

Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)
Powder properties of hydrogenated ball-milled graphite

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

Zhang, Y., E-mail: y.zhang062012@gmail.com; Wedderburn, J.; Harris, R.

2014-12-15

Ball milling is an effective way of producing defective and nanostructured graphite. In this work, the hydrogen storage properties of graphite, ball-milled in a tungsten carbide milling pot under 3 bar hydrogen for various times (0–40 h), were investigated by TGA-Mass Spectrometry, XRD, SEM and laser diffraction particle size analysis. For the conditions used in this study, 10 h is the optimum milling time resulting in desorption of 5.5 wt% hydrogen upon heating under argon to 990 °C. After milling for 40 h, the graphite became significantly more disordered, and the amount of desorbed hydrogen decreased. After milling up tomore » 10 h, the BET surface area increased while particle size decreased; however, there is no apparent correlation between these parameters, and the hydrogen storage properties of the hydrogenated ball-milled graphite.« less
Photocatalytic production of hydrogen from fixed titanium dioxide thin film

NASA Astrophysics Data System (ADS)

Okoye, Njideka Helen

This thesis is focused on further developing of an efficient method for the photocatalytic hydrogen production. The research aimed to use thin films deposited with TiO2 and doped with Pt in order to substitute slurry solutions that are currently being used. A new depositing experimental approach to manufacture the thin films was proposed and tested for both physical properties and chemical reactivity. Therefore, the experiment was designed into two parts: The first part was on the manufacturing and the physical characterization of titanium dioxide deposited on glass surfaces and the second part was focused on the ability of the thin film to produce hydrogen. For the second part, a photochemical reactor vessel was used to properly place the glass slides to UV-irradiation. This was yielded by a mercury lamp located at the centre of the reactor. The thesis is organized into five different chapters including introduction, literature review, characterization of TiO2 coated surface, experimental design and hydrogen production, finally conclusive observations and future work. Hydrogen production by photodecomposition of water into H2 and O2 has a very low efficiency due to rapid reverse reaction and, as mentioned above, it usually requires a slurry type of solution. This needs additional processing steps such as filtration and recycling of particles. Therefore, it is important to develop an efficient process for hydrogen production. TiO2 coated surfaces could be an excellent technological alternative. In this study, a sol-gel method was used to produce a transparent TiO 2 thin film which was deposited on a glass substrate by using a new coating technique introduced in this work for H2 production. The TiO2 deposited film on a glass substrate by using the spraying method of coating was characterized for physical analysis (surface characteristics, size of nanoparticles and distribution, etc.) by using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and UV-Visible optical fiber spectrophotometer. Platinum was deposited on the coated thin film by adsorption from aqueous solutions containing Na 2PtCl4 followed by calcination at 500o C. The chemical reactivity of the new coated thin film for H2 production was tested by examining the effect of different ethanol concentrations and surface area available to hydrogen production rate by using a mercury lamp in a bench scale photo reactor with ethanol and water as the reactants. It was observed over a period of two hr interval that increase in ethanol concentration investigated in this work showed substantial increase in the hydrogen production rate as well as when increasing the surface area.
A study of water electrolysis using ionic polymer-metal composite for solar energy storage

NASA Astrophysics Data System (ADS)

Keow, Alicia; Chen, Zheng

2017-04-01

Hydrogen gas can be harvested via the electrolysis of water. The gas is then fed into a proton exchange membrane fuel cell (PEMFC) to produce electricity with clean emission. Ionic polymer-metal composite (IPMC), which is made from electroplating a proton-conductive polymer film called Nafion encourages ion migration and dissociation of water under application of external voltage. This property has been proven to be able to act as catalyst for the electrolysis of pure water. This renewable energy system is inspired by photosynthesis. By using solar panels to gather sunlight as the source of energy, the generation of electricity required to activate the IPMC electrolyser is acquired. The hydrogen gas is collected as storable fuel and can be converted back into energy using a commercial fuel cell. The goal of this research is to create a round-trip energy efficient system which can harvest solar energy, store them in the form of hydrogen gas and convert the stored hydrogen back to electricity through the use of fuel cell with minimal overall losses. The effect of increasing the surface area of contact is explored through etching of the polymer electrolyte membrane (PEM) with argon plasma or manually sanding the surface and how it affects the increase of energy conversion efficiency of the electrolyser. In addition, the relationship between temperature and the IPMC is studied. Experimental results demonstrated that increases in temperature of water and changes in surface area contact correlate with gas generation.
Mechanical Behavior and Fractography of 304 Stainless Steel with High Hydrogen Concentration

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

Au, M.

2003-02-05

Hydrogen embrittlement of 304 stainless steel with different hydrogen concentrations has been investigated. An electrochemical technique was used to effectively charge the high level of hydrogen into 304 stainless steel in a short period of time. At 25 ppm of hydrogen, 304 stainless steel loses 10 percent of its original mechanical strength and 20 percent plasticity. Although the ductile feature dominates the fractography, the brittle crown area near the outer surface shows the intergranular rupture effected by hydrogen. At 60 ppm of hydrogen, 304 stainless steel loses 23 percent of its strength and 38 percent plasticity, where the brittle modemore » dominates the fracture of the materials. Experimental results show that hydrogen damage to the performance of 304 stainless steel is significant even at very low levels. The fractograph analysis indicates the high penetration ability of hydrogen in 304 stainless steel. This work also demonstrates the advantages of the electrochemical charging technique in the study of hydrogen embrittlement.« less
Surface characterization and chemical analysis of bamboo substrates pretreated by alkali hydrogen peroxide.

PubMed

Song, Xueping; Jiang, Yan; Rong, Xianjian; Wei, Wei; Wang, Shuangfei; Nie, Shuangxi

2016-09-01

The surface characterization and chemical analysis of bamboo substrates by alkali hydrogen peroxide pretreatment (AHPP) were investigated in this study. The results tended to manifest that AHPP prior to enzymatic and chemical treatment was potential for improving accessibility and reactivity of bamboo substrates. The inorganic components, organic solvent extractives and acid-soluble lignin were effectively removed by AHPP. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface of bamboo chips had less lignin but more carbohydrate after pre-treatment. Fiber surfaces became etched and collapsed, and more pores and debris on the substrate surface were observed with Scanning Electron Microscopy (SEM). Brenauer-Emmett-Teller (BET) results showed that both of pore volume and surface area were increased after AHPP. Although XRD analysis showed that AHPP led to relatively higher crystallinity, pre-extraction could overall enhance the accessibility of enzymes and chemicals into the bamboo structure. Copyright © 2016. Published by Elsevier Ltd.
Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.
Reversible transient hydrogen storage in a fuel cell-supercapacitor hybrid device.

PubMed

Unda, Jesus E Zerpa; Roduner, Emil

2012-03-21

A new concept is investigated for hydrogen storage in a supercapacitor based on large-surface-area carbon material (Black Pearls 2000). Protons and electrons of hydrogen are separated on a fuel cell-type electrode and then stored separately in the electrical double layer, the electrons on the carbon and the protons in the aqueous electrolyte of the supercapacitor electrode. The merit of this concept is that it works spontaneously and reversibly near ambient pressure and temperature. This is in pronounced contrast to what has been known as electrochemical hydrogen storage, which does not involve hydrogen gas and where electrical work has to be spent in the loading process. With the present hybrid device, a H(2) storage capacity of 0.13 wt% was obtained, one order of magnitude more than what can be stored by conventional physisorption on large-surface-area carbons at the same pressure and temperature. Raising the pressure from 1.5 to 3.5 bar increased the capacity by less than 20%, indicating saturation. A capacitance of 11 μF cm(-2), comparable with that of a commercial double layer supercapacitor, was found using H(2)SO(4) as electrolyte. The chemical energy of the stored H(2) is almost a factor of 3 larger than the electrical energy stored in the supercapacitor. Further developments of this concept relate to a hydrogen buffer integrated inside a proton exchange membrane fuel cell to be used in case of peak power demand. This serial setup takes advantage of the suggested novel concept of hydrogen storage. It is fundamentally different from previous ways of operating a conventional supercapacitor hooked up in parallel to a fuel cell.
Surveillance of Site A and Plot M, Report for 2009.

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

Golchert, N. W.

2010-04-21

The results of the environmental surveillance program conducted at Site A/Plot M in the Palos Forest Preserve area for Calendar Year 2009 are presented. Based on the results of the 1976-1978 radiological characterization of the site, a determination was made that a surveillance program be established. The characterization study determined that very low levels of hydrogen-3 (as tritiated water) had migrated from the burial ground and were present in two nearby hand-pumped picnic wells. The current surveillance program began in 1980 and consists of sample collection and analysis of surface and subsurface water. The results of the analyses are usedmore » to monitor the migration pathway of hydrogen-3 contaminated water from the burial ground (Plot M) to the hand-pumped picnic wells and monitor for the presence of radioactive materials in the environment of the area. Hydrogen-3 in the Red Gate Woods picnic wells was still detected this year, but the average and maximum concentrations were significantly less than found earlier. Hydrogen-3 continues to be detected in a number of wells, boreholes, dolomite holes, and a surface stream. Analyses since 1984 have indicated the presence of low levels of strontium-90 in water from a number of boreholes next to Plot M. The results of the surveillance program continue to indicate that the radioactivity remaining at Site A/Plot M does not endanger the health or safety of the public visiting the site, using the picnic area, or living in the vicinity.« less
Surveillance of Site A and Plot M report for 2010.

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

Golchert, N. W.

2011-05-31

The results of the environmental surveillance program conducted at Site A/Plot M in the Palos Forest Preserve area for Calendar Year 2010 are presented. Based on the results of the 1976-1978 radiological characterization of the site, a determination was made that a surveillance program be established. The characterization study determined that very low levels of hydrogen-3 (as tritiated water) had migrated from the burial ground and were present in two nearby hand-pumped picnic wells. The current surveillance program began in 1980 and consists of sample collection and analysis of surface and subsurface water. The results of the analyses are usedmore » to monitor the migration pathway of hydrogen-3 contaminated water from the burial ground (Plot M) to the hand-pumped picnic wells and monitor for the presence of radioactive materials in the environment of the area. Hydrogen-3 in the Red Gate Woods picnic wells was still detected this year, but the average and maximum concentrations were significantly less than found earlier. Hydrogen-3 continues to be detected in a number of wells, boreholes, dolomite holes, and a surface stream. Analyses since 1984 have indicated the presence of low levels of strontium-90 in water from a number of boreholes next to Plot M. The results of the surveillance program continue to indicate that the radioactivity remaining at Site A/Plot M does not endanger the health or safety of the public visiting the site, using the picnic area, or living in the vicinity.« less
Facile synthesis high nitrogen-doped porous carbon nanosheet from pomelo peel and as catalyst support for nitrobenzene hydrogenation

NASA Astrophysics Data System (ADS)

Zuo, Pingping; Duan, Jiaqi; Fan, Huailin; Qu, Shijie; Shen, Wenzhong

2018-03-01

Nitrogen-doping porous carbon-based nanosheets were fabricated from pemole peel and melamine through hydrothermal route and carbonization. The pomelo peel with sponge-like natural structure was employed as carbon source, and melamine was used both as nitrogen precursors and as nanosheet structure directing. The morphology and chemical composition of the obtained porous carbon nanosheet carbon materials were characterized by scanning electron microscopy, thermogravimetric analyzer, Fourier transform infrared spectra, transmission electron microscopy, BET surface area measurement, X-ray photoelectron spectroscopy and X-ray powder diffraction. The result indicated that the nanosheet thickness, nitrogen-doped amount and surface area were determined by the ratio of pomelo peel to melamine and carbonization temperature. The catalytic nitrobenzene hydrogenation was evaluated after Pd was loaded on nitrogen-doping porous carbon-based nanosheet. The results showed Pd@PCN had almost 100% conversion and good cycling performance towards the hydrogenation of nitrobenzene due to the developed pore structure, high nitrogen-doping and well dispersed less Pd particle; it was superior to other nanomaterial supports and demonstrated great potential application.
Electrochemical model of local corrosion at the tip of a loaded crack

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

Andreikiv, O.E.; Tym`yak, N.I.

1994-07-01

A model of electrochemical processes near a crack tip in a stressed metal subjected to corrosion with hydrogen depolarization is suggested. It is shown that, in order to describe the kinetics of hydrogenation of the prefracture area, it is necessary to take into account the type of passivation layer on the newly formed metal surface near the crack tip and the mechanism of its formation.
Genetic selection reveals the role of a buried, conserved polar residue

PubMed Central

Johnson, R. Jeremy; Lin, Shawn R.; Raines, Ronald T.

2007-01-01

The burial of nonpolar surface area is known to enhance markedly the conformational stability of proteins. The contribution from the burial of polar surface area is less clear. Here, we report on the tolerance to substitution of Ser75 of bovine pancreatic ribonuclease (RNase A), a residue that has the unusual attributes of being buried, conserved, and polar. To identify variants that retain biological function, we used a genetic selection based on the intrinsic cytotoxicity of ribonucleolytic activity. Cell growth at 30°C, 37°C, and 44°C correlated with residue size, indicating that the primary attribute of Ser75 is its small size. The side-chain hydroxyl group of Ser75 forms a hydrogen bond with a main-chain nitrogen. The conformational stability of the S75A variant, which lacks this hydrogen bond, was diminished by ΔΔG = 2.5 kcal/mol. Threonine, which can reinstate this hydrogen bond, provided a catalytically active RNase A variant at higher temperatures than did some smaller residues (including aspartate), indicating that a secondary attribute of Ser75 is the ability of its uncharged side chain to accept a hydrogen bond. These results provide insight on the imperatives for the conservation of a buried polar residue. PMID:17656580

A novel nano-Ni/SiO2 catalyst for hydrogen production from steam reforming of ethanol.

PubMed

Wu, Chunfei; Williams, Paul T

2010-08-01

Catalytic steam reforming of ethanol has been regarded as a promising way to produce hydrogen. However, catalytic deactivation is a key problem in the process. In this paper, a novel nano-Ni/SiO2 catalyst was prepared by a simple sol-gel method and compared to catalysts prepared by an impregnation method in relation to the steam reforming ethanol process. Good Ni dispersion and high BET surface areas (>700 m2 g(-1)) were obtained for sol-gel catalysts, whereas only 1 m2 g(-1) surface area was obtained for the Ni/SiO2 impregnation catalyst. The results of catalytic steam reforming of ethanol showed that about twice of the hydrogen production was produced with the Ni/SiO2 catalyst prepared by sol-gel (around 0.2 g h(-1)) compared with that prepared by impregnation (around 0.1 g h(-1)). The analysis of the used catalysts showed that 10Ni/SiO2-B and 20Ni/SiO2-B presented the highest stability, while other catalysts were fragmented into small pieces after the reforming process, especially the catalysts prepared by impregnation. A novel catalyst has been produced that has been shown to be effective in the production of hydrogen from the steam reforming of ethanol.
Hydrogen peroxide sensor based on carbon nanowalls grown by plasma-enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Tomatsu, Masakazu; Hiramatsu, Mineo; Foord, John S.; Kondo, Hiroki; Ishikawa, Kenji; Sekine, Makoto; Takeda, Keigo; Hori, Masaru

2017-06-01

Fabrication of an electrochemical sensor for hydrogen peroxide (H2O2) detection was demonstrated. H2O2 is a major messenger molecule in various redox-dependent cellular signaling transductions. Therefore, sensitive detection of H2O2 is greatly important in health inspection and environmental protection. Carbon nanowalls (CNWs) are composed of few-layer graphenes standing almost vertically on a substrate forming a three-dimensional structure. In this work, CNWs were used as a platform for H2O2 sensing, which is based on the large surface area of conducting carbon and surface decoration with platinum (Pt) nanoparticles (NPs). CNWs were grown on carbon fiber paper (CFP) by inductively coupled plasma-enhanced chemical vapor deposition to increase the surface area. Then, the CNW surface was decorated with Pt-NPs by the reduction of H2PtCl6. Cyclic voltammetry results indicate that the Pt-decorated CNW/CFP electrode possesses excellent electrocatalytic activity for the reduction of H2O2. Amperometric responses indicate the high-sensitivity detection capability of the Pt-decorated CNW/CFP electrode for H2O2.
Doped phosphorene for hydrogen capture: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Hong-ping; Hu, Wei; Du, Aijun; Lu, Xiong; Zhang, Ya-ping; Zhou, Jian; Lin, Xiaoyan; Tang, Youhong

2018-03-01

Hydrogen capture and storage is the core of hydrogen energy application. With its high specific surface area, direct bandgap, and variety of potential applications, phosphorene has attracted much research interest. In this study, density functional theory (DFT) is utilized to study the interactions between doped phosphorenes and hydrogen molecules. The effects of different dopants and metallic or nonmetallic atoms on phosphorene/hydrogen interactions is systematically studied by adsorption energy, electron density difference, partial density of states analysis, and Hirshfeld population. Our results indicate that the metallic dopants Pt, Co, and Ni can help to improve the hydrogen capture ability of phosphorene, whereas the nonmetallic dopants have no effect on it. Among the various metallic dopants, Pt performs very differently, such that it can help to dissociate H2 on phosphorene. Specified doped phosphorene could be a promising candidate for hydrogen storage, with behaviors superior to those of intrinsic graphene sheet.
Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

DOE PAGES

Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; ...

2015-01-11

Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C 60H 60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C 60 and increased isosteric heats of adsorption for the lithium doped fullerene Li 12C 60. However, despite these improvements the low amount of physisorbedmore » hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.« less
Interaction of hydrogen chloride with alumina. [atmospheric effluent concentrations and interaction of solid rocket propellants used in space shuttle

NASA Technical Reports Server (NTRS)

Bailey, R. R.; Wightman, J. P.

1978-01-01

The influence of temperature, pressure, and outgas conditions on the absorption of hydrogen chloride and water vapor on both alpha and gamma alumina was studied. Characterization of the adsorbents was performed using X-ray powder diffraction, scanning electron microscopy (SEM), low temperature nitrogen adsorption desorption measurements, BET nitrogen surface area measurements and electron spectroscopy for chemical analysis (ESCA). Water vapor adsorption isotherms at 30, 40, and 50 C were measured on alpha and gamma alumina after outgassing at 80, 200, and 400 C. Both outgas temperature and adsorption temperature influenced the adsorption of water vapor on the aluminas. The water vapor adsorption was completely reversible. Alpha alumina absorbed more water per unit area than gamma alumina. Differences in the adsorption capacity for water vapor of the two aluminas were explained on the basis of ideal surface models of alpha and gamma alumina. Isosteric heats of adsorption for water vapor on the aluminas were determined over a limited range of surface coverage.
The Enhancement of Water Ice Content in the Local Area Northeast of Arcadia Planitia: Evidence from Neutron Data from HEND (Mars Odyssey) and Elevation from MOLA (MGS)

NASA Technical Reports Server (NTRS)

Sanin, A. B.; Mitrofanov, I. G.; Kozyrev, A. S.; Litvak, M. L.; Tretyakov, V.; Smith, D. E.; Zuber, M. T.; Boynton, W.; Saunders, R. S.

2003-01-01

The first year of neutron mapping measurements from the Mars Odyssey spacecraft revealed enormous hydrogen-rich regions in the southern and northern hemispheres of the Martian crust that imply significant amounts of near surface water ice. The hydrogen-rich areas of the southern and northern regions appear generally comparable in spatial extent and water ice content. This observation is interesting in light of topography measured by the Mars Orbiter Laser Altimeter (MOLA) on the Mars Global Surveyor (MGS) spacecraft, which shows a significant difference in elevation between northern lowlands and southern highlands that could imply a difference in seasonal CO2 condensation. In this study we correlate the high energy neutron flux observed by HEND (Mars Odyssey) and surface elevation measured by MOLA in order to interpret the seasonal change in epithermal neutron flux in terms near-surface water ice content.
Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less
Effect of oxygen vacancies and phases on catalytic properties of hydrogen-treated nanoceria particles

NASA Astrophysics Data System (ADS)

Lan, Yuan-Pei; Sohn, Hong Yong

2018-03-01

Nanoceria powder was treated by hydrogen or air at different temperatures and atmospheres, and the phases, oxygen vacancies, catalytic properties of the treated samples were investigated. After treating, the crystallites on the ceria surface were fused, and the SEM and TEM images indicated that the particle size increased with treatment temperature. Both Raman and XPS spectra showed the oxygen vacancies in nanoceria increased with treatment temperature in hydrogen, and at the same temperature CeO2 treated in hydrogen had a higher Ce3+ fraction than that treated in air. The nanoceria after being treated in hydrogen at 900 °C contained the Ce2O3 phase together with CeO2 which was revealed by XRD and TEM results. Oxygen vacancies were found to enhance CO conversion, but the high temperature needed to generate the oxygen vacancies caused the fusion of the crystallites on the ceria surface and thus its area decreased, which resulted in lower catalytic activity. The catalytic activity of nanoceria treated in hydrogen at 900 °C measured higher than that of the ceria powders treated at 700 °C in hydrogen or 900 °C in air, which indicated that the Ce2O3 phase present in the treated nanoceria particles enhanced the catalytic activity.
Nickel-silver alloy electrocatalysts for hydrogen evolution and oxidation in an alkaline electrolyte.

PubMed

Tang, Maureen H; Hahn, Christopher; Klobuchar, Aidan J; Ng, Jia Wei Desmond; Wellendorff, Jess; Bligaard, Thomas; Jaramillo, Thomas F

2014-09-28

The development of improved catalysts for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) in basic electrolytes remains a major technical obstacle to improved fuel cells, water electrolyzers, and other devices for electrochemical energy storage and conversion. Based on the free energy of adsorbed hydrogen intermediates, theory predicts that alloys of nickel and silver are active for these reactions. In this work, we synthesize binary nickel-silver bulk alloys across a range of compositions and show that nickel-silver alloys are indeed more active than pure nickel for hydrogen evolution and, possibly, hydrogen oxidation. To overcome the mutual insolubility of silver and nickel, we employ electron-beam physical vapor codeposition, a low-temperature synthetic route to metastable alloys. This method also produces flat and uniform films that facilitate the measurement of intrinsic catalytic activity with minimal variations in the surface area, ohmic contact, and pore transport. Rotating-disk-electrode measurements demonstrate that the hydrogen evolution activity per geometric area of the most active catalyst in this study, Ni0.75Ag0.25, is approximately twice that of pure nickel and has comparable stability and hydrogen oxidation activity. Our experimental results are supported by density functional theory calculations, which show that bulk alloying of Ni and Ag creates a variety of adsorption sites, some of which have near-optimal hydrogen binding energy.
Interaction of acetonitrile with the surfaces of amorphous and crystalline ice

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

Schaff, J.E.; Roberts, J.T.

1999-10-12

The adsorption of acetonitrile (CH{sub 3}CN) on ultrathin films of ice under ultrahigh vacuum was investigated with temperature-programmed desorption ass spectrometry (TPD) and Fourier transform infrared reflection absorption spectroscopy (FTIRAS). Two types of film were studied, amorphous and crystalline. On the amorphous films, two sates of adsorbed acetonitrile were observed by TPD and FTIRAS. One of the states is attributed to acetonitrile that is hydrogen bonded to agree OH group at the ice surface; the other state is assigned to acetonitrile that is purely physiorbed. Evidence for the hydrogen-bonded state is two-fold. First, there is a large kinetic isotope effectmore » for desorption from H{sub 2}O-and D{sub 2}O-ice: the desorption temperatures from ice-h{sub 2} and ice-d{sub 2} are {approximately}161 and {approximately}176 K, respectively. Second, the C{triple{underscore}bond}N stretching frequency (2,265 cm{sup {minus}1}) is 16 cm{sup {minus}1} is greater than that of physisorbed acetonitrile, and it is roughly equal to that of acetonitrile which is hydrogen bonded to an OH group at the air-liquid water interface. On the crystalline films, there is no evidence for a hydrogen-bonded state in the TPD spectra. The FTIRAS spectra do show that some hydrogen-bonded acetonitrile is present but at a maximum coverage that is roughly one-sixth of that on the amorphous surface. The difference between the amorphous and crystalline surfaces cannot be attributed to a difference n surface areas. Rather, this work provides additional evidence that the surface chemical properties of amorphous ice are different from those of crystalline ice.« less
Heteroatom-doped nanoporous carbon derived from MOF-5 for CO2 capture

NASA Astrophysics Data System (ADS)

Ma, Xiancheng; Li, Liqing; Chen, Ruofei; Wang, Chunhao; Li, Hailong; Wang, Shaobin

2018-03-01

Four nanoporous carbons (MUCT) were prepared from metal-organic framework (MOF-5) template and additional carbon source (i.e. urea) by carbonization at different temperatures (600-900 °C). The results showed that specific surface area of four samples was obtained in the range from 1030 to 2307 m2 g-1. By changing the carbonization temperature it can finely tune the pore volume of the MUCT, which having a uniform pore size of around 4.0 nm. With an increasing carbonization temperature, the micropore surface area of MUCT samples varied slightly, but mesopore surface area increased obviously, which had little influence on carbon dioxide (CO2) adsorption capacity. The as-obtained sample MUC900 exhibited the superior CO2 capture capacity of 3.7 mmol g-1 at 0 °C (1 atm). First principle calculations were conducted on carbon models with various functional groups to distinguish heterogeneity and understand carbon surface chemistry for CO2 adsorption. The interaction between CO2 and N-containing functional groups is mainly weak Lewis acid-base interaction. On the other hand, the pyrrole and amine groups show exceptional hydrogen-bonding interaction. The hydroxyls promote the interaction between carbon dioxide and functional groups through hydrogen-bonding interactions and electrostatic potentials, thereby increasing CO2 capture of MUCT.
Integrated lunar materials manufacturing process

NASA Technical Reports Server (NTRS)

Gibson, Michael A. (Inventor); Knudsen, Christian W. (Inventor)

1990-01-01

A manufacturing plant and process for production of oxygen on the moon uses lunar minerals as feed and a minimum of earth-imported, process materials. Lunar feed stocks are hydrogen-reducible minerals, ilmenite and lunar agglutinates occurring in numerous, explored locations mixed with other minerals in the pulverized surface layer of lunar soil known as regolith. Ilmenite (FeTiO.sub.3) and agglutinates contain ferrous (Fe.sup.+2) iron reducible by hydrogen to yield H.sub.2 O and metallic Fe at about 700.degree.-1,200.degree. C. The H.sub.2 O is electrolyzed in gas phase to yield H.sub.2 for recycle and O.sub.2 for storage and use. Hydrogen losses to lunar vacuum are minimized, with no net hydrogen (or any other earth-derived reagent) consumption except for small leaks. Feed minerals are surface-mined by front shovels and transported in trucks to the processing area. The machines are manned or robotic. Ilmenite and agglutinates occur mixed with silicate minerals which are not hydrogen-reducible at 700.degree.-1,200.degree. C. and consequently are separated and concentrated before feeding to the oxygen generation process. Solids rejected from the separation step and reduced solids from the oxygen process are returned to the mine area. The plant is powered by nuclear or solar power generators. Vapor-phase water electrolysis, a staged, countercurrent, fluidized bed reduction reactor and a radio-frequency-driven ceramic gas heater are used to improve thermal efficiency.
The effects of hydrogen embrittlement by cathodic protection on the CTOD of buried natural gas pipeline

NASA Astrophysics Data System (ADS)

Kim, Cheol-man; Kim, Woo-sik; Kho, Young-tai

2002-04-01

For the corrosion protection of natural gas transmission pipelines, two methods are used, cathodic protection and a coating technique. In the case of cathodic protection, defects are embrittled by hydrogen occurring at crack tips or surfaces of materials. It is, however, very important to evaluate whether cracks in the embrittled area can grow or not, especially in weld metal. In this work, on the basis of elastic plastic fracture mechanics, we performed CTOD testing under various test conditions, such as potential and current density. The CTOD of the base steel and weld metal showed a strong dependence on the test conditions. The CTOD decreased with increasing cathodic potential and current density. The morphology of the fracture surface showed quasi-cleavage. Cathodic overprotection results in hydrogen embrittlement at the crack tip.
Attachment chemistry of aromatic compounds on a Silicon(100) surface

NASA Astrophysics Data System (ADS)

Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

2018-03-01

A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.
Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

DOE PAGES

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.; ...

2016-12-13

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less
Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

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

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less
Numerical Prediction of the Influence of Process Parameters on Large Area Diamond Deposition by DC Arcjet with ARC Roots Rotating and Operating at Gas Recycling Mode

NASA Astrophysics Data System (ADS)

Lu, F. X.; Huang, T. B.; Tang, W. Z.; Song, J. H.; Tong, Y. M.

A computer model have been set up for simulation of the flow and temperature field, and the radial distribution of atomic hydrogen and active carbonaceous species over a large area substrate surface for a new type dc arc plasma torch with rotating arc roots and operating at gas recycling mode A gas recycling radio of 90% was assumed. In numerical calculation of plasma chemistry, the Thermal-Calc program and a powerful thermodynamic database were employed. Numerical calculations to the computer model were performed using boundary conditions close to the experimental setup for large area diamond films deposition. The results showed that the flow and temperature field over substrate surface of Φ60-100mm were smooth and uniform. Calculations were also made with plasma of the same geometry but no arc roots rotation. It was clearly demonstrated that the design of rotating arc roots was advantageous for high quality uniform deposition of large area diamond films. Theoretical predictions on growth rate and film quality as well as their radial uniformity, and the influence of process parameters on large area diamond deposition were discussed in detail based on the spatial distribution of atomic hydrogen and the carbonaceous species in the plasma over the substrate surface obtained from thermodynamic calculations of plasma chemistry, and were compared with experimental observations.
Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-03-01

The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. A large number of gaps between 'cauliflower' like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.
Effects of reducing temperatures on the hydrogen storage capacity of double-walled carbon nanotubes with Pd loading.

PubMed

Sheng, Qu; Wu, Huimin; Wexler, David; Liu, Huakun

2014-06-01

The effects of different temperatures on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) with palladium loading have been investigated. When we use different temperatures, the particle sizes and specific surface areas of the samples are different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the amount of hydrogen storage capacity was determined (by AMC Gas Reactor Controller) to be 1.70, 1.85, 2.00, and 1.93 wt% for pristine DWCNTS and for 2%Pd/DWCNTs-300 degrees C, 2%Pd/DWCNTs-400 degrees C, and 2%Pd/DWCNTs-500 degrees C, respectively. We found that the hydrogen storage capacity can be enhanced by loading with 2% Pd nanoparticles and selecting a suitable temperature. Furthermore, the sorption can be attributed to the chemical reaction between atomic hydrogen and the dangling bonds of the DWCNTs.
Nanoconfinement in activated mesoporous carbon of calcium borohydride for improved reversible hydrogen storage.

PubMed

Comănescu, Cezar; Capurso, Giovanni; Maddalena, Amedeo

2012-09-28

Mesoporous carbon frameworks were synthesized using the soft-template method. Ca(BH(4))(2) was incorporated into activated mesoporous carbon by the incipient wetness method. The activation of mesoporous carbon was necessary to optimize the surface area and pore size. Thermal programmed absorption measurements showed that the confinement of this borohydride into carbon nanoscaffolds improved its reversible capacity (relative to the reactive portion) and performance of hydrogen storage compared to unsupported borohydride. Hydrogen release from the supported hydride started at a temperature as low as 100 °C and the dehydrogenation rate was fast compared to the bulk borohydride. In addition, the hydrogen pressure necessary to regenerate the borohydride from the dehydrogenation products was reduced.

Catalytic hydrogen sensing using microheated platinum nanoparticle-loaded graphene aerogel

DOE PAGES

Harley-Trochimczyk, Anna; Chang, Jiyoung; Zhou, Qin; ...

2014-10-02

We present that low power catalytic hydrogen sensors are fabricated by functionalizing low power polysilicon microheaters with platinum nanoparticle catalyst loaded in a high surface area graphene aerogel support. Fabrication and characterization of the polysilicon microheaters are described. The platinum nanoparticle-loaded graphene aerogel is characterized by transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Finally, the catalytic hydrogen sensors consume as little as 2.2 mW of power, have sensitivity of 1.6%/10,000 ppm hydrogen, a t90 response and recovery time of 0.97 s and 0.72 s, respectively, a lower detection limit of approximately 65 ppm, and negligible crossmore » sensitivity to methane, n-pentane, and diethylether.« less
Improvement of efficiency in graphene/gallium nitride nanowire on Silicon photoelectrode for overall water splitting

NASA Astrophysics Data System (ADS)

Bae, Hyojung; Rho, Hokyun; Min, Jung-Wook; Lee, Yong-Tak; Lee, Sang Hyun; Fujii, Katsushi; Lee, Hyo-Jong; Ha, Jun-Seok

2017-11-01

Gallium nitride (GaN) nanowires are one of the most promising photoelectrode materials due to their high stability in acidic and basic electrolytes, and tunable band edge potentials. In this study, GaN nanowire arrays (GaN NWs) were prepared by molecular beam epitaxy (MBE); their large surface area enhanced the solar to hydrogen conversion efficiency. More significantly, graphene was grown by chemical vapor deposition (CVD), which enhanced the electron transfer between NWs for water splitting and protected the GaN NW surface. Structural characterizations of the prepared composite were performed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photocurrent density of Gr/GaN NWs exhibited a two-fold increase over pristine GaN NWs and sustained water splitting up to 70 min. These improvements may accelerate possible applications for hydrogen generation with high solar to hydrogen conversion efficiency.
Multisample conversion of water to hydrogen by zinc for stable isotope determination

USGS Publications Warehouse

Kendall, C.; Coplen, T.B.

1985-01-01

Two techniques for the conversion of water to hydrogen for stable isotope ratio determination have been developed that are especially suited for automated multisample analysis. Both procedures involve reaction of zinc shot with a water sample at 450 ??C. in one method designed for water samples in bottles, the water is put in capillaries and is reduced by zinc in reaction vessels; overall savings in sample preparation labor of 75% have been realized over the standard uranium reduction technique. The second technique is for waters evolved under vacuum and is a sealed-tube method employing 9 mm o.d. quartz tubing. Problems inherent with zinc reduction include surface inhomogeneity of the zinc and exchange of hydrogen both with the zinc and with the glass walls of the vessels. For best results, water/zinc and water/glass surface area ratios of vessels should be kept as large as possible.
Study of structural, surface and hydrogen storage properties of boric acid mediated metal (sodium)-organic frameworks

NASA Astrophysics Data System (ADS)

Ozer, Demet; Köse, Dursun A.; Sahin, Onur; Oztas, Nursen A.

2018-04-01

Three boric acid mediated metal organic frameworks were synthesized by solution method with using succinic acid, fumaric acid and acetylene dicarboxylic acid as a ligand source and sodium as a metal source. The complexes were characterized by FT-IR, powder XRD, elemental analyses and single crystal measurements. The complexes with the formula, C4H18B2Na2O14, C4H16B2Na2O14 and C4H14B2Na2O14 were successfully obtained. BET surface area of complexes were calculated and found as 13.474 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-succinato)-di-sodium boric acid solvate), 1.692 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-fumarato)-di-sodium boric acid solvate) and 5.600 m2/g for catena-(tetrakis(μ2-hydroxo)-(μ2-trihydrogen borate)-(μ2-acetylenedicarboxylato)-di-sodium boric acid solvate). Hydrogen storage capacities of the complexes were also studied at 77 K 1 bar pressure and found as 0.108%, 0.033%, 0.021% by mass. When different ligands were used, the pore volume, pore width and surface area of the obtained complexes were changed. As a consequence, hydrogen storage capacities also changed.
Driving force for hydrophobic interaction at different length scales.

PubMed

Zangi, Ronen

2011-03-17

We study by molecular dynamics simulations the driving force for the hydrophobic interaction between graphene sheets of different sizes down to the atomic scale. Similar to the prediction by Lum, Chandler, and Weeks for hard-sphere solvation [J. Phys. Chem. B 1999, 103, 4570-4577], we find the driving force to be length-scale dependent, despite the fact that our model systems do not exhibit dewetting. For small hydrophobic solutes, the association is purely entropic, while enthalpy favors dissociation. The latter is demonstrated to arise from the enhancement of hydrogen bonding between the water molecules around small hydrophobes. On the other hand, the attraction between large graphene sheets is dominated by enthalpy which mainly originates from direct solute-solute interactions. The crossover length is found to be inside the range of 0.3-1.5 nm(2) of the surface area of the hydrophobe that is eliminated in the association process. In the large-scale regime, different thermodynamic properties are scalable with this change of surface area. In particular, upon dimerization, a total and a water-induced stabilization of approximately 65 and 12 kJ/mol/nm(2) are obtained, respectively, and on average around one hydrogen bond is gained per 1 nm(2) of graphene sheet association. Furthermore, the potential of mean force between the sheets is also scalable except for interplate distances smaller than 0.64 nm which corresponds to the region around the barrier for removing the last layer of water. It turns out that, as the surface area increases, the relative height of the barrier for association decreases and the range of attraction increases. It is also shown that, around small hydrophobic solutes, the lifetime of the hydrogen bonds is longer than in the bulk, while around large hydrophobes it is the same. Nevertheless, the rearrangement of the hydrogen-bond network for both length-scale regimes is slower than in bulk water. © 2011 American Chemical Society
Identification of Clostridium difficile Reservoirs in The Patient Environment and Efficacy of Aerial Hydrogen Peroxide Decontamination.

PubMed

Yui, Samuel; Ali, Shanom; Muzslay, Monika; Jeanes, Annette; Wilson, A Peter R

2017-12-01

OBJECTIVE To identify, using a novel enhanced method of recovery, environmental sites where spores of Clostridium difficile persist despite cleaning and hydrogen peroxide aerial decontamination. DESIGN Cohort study. SETTING Tertiary referral center teaching hospital. METHODS In total, 16 sites representing high-frequency contact or difficult-to-clean surfaces in a single-isolation room or bed area in patient bed bays were sampled before and after terminal or hydrogen peroxide disinfection using a sponge swab. In some rooms, individual sites were not present (eg, there were no en-suite rooms in the ICU). Swab contents were homogenized, concentrated by membrane-filtration, and plated onto selective media. Results of C. difficile sampling were used to focus cleaning. RESULTS Over 1 year, 2,529 sites from 146 rooms and 44 bays were sampled. Clostridium difficile was found on 131 of 572 surfaces (22.9%) before terminal cleaning, on 105 of 959 surfaces (10.6%) after terminal cleaning, and on 43 of 967 surfaces (4.4%) after hydrogen peroxide disinfection. Clostridium difficile persisted most frequently on floor corners (97 of 334; 29.0%) after disinfection. Between the first and third quarters, we observed a significant decrease in the number of positive sites (25 of 390 vs 6 of 256). However, no similar change in the number of isolates before terminal cleaning was observed. CONCLUSION Persistence of C. difficile in the clinical environment was widespread. Although feedback of results did not improve the efficacy of manual disinfection, numbers of C. difficile following hydrogen peroxide gradually declined. Infect Control Hosp Epidemiol 2017;38:1487-1492.
DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Carter, Richard J.

The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C).more » The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.« less
Activated carbon derived from waste coffee grounds for stable methane storage.

PubMed

Kemp, K Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M; Kim, Kwang S

2015-09-25

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m(2) g(-1) and a micropore volume of 0.574 cm(3) g(-1) and exhibits a stable CH4 adsorption capacity of ∼4.2 mmol g(-1) at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.
Activated carbon derived from waste coffee grounds for stable methane storage

NASA Astrophysics Data System (ADS)

Kemp, K. Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M.; Kim, Kwang S.

2015-09-01

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m2 g-1 and a micropore volume of 0.574 cm3 g-1 and exhibits a stable CH4 adsorption capacity of ˜4.2 mmol g-1 at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.
Characterization of recycled rubber media for hydrogen sulphide (H2S) control.

PubMed

Wang, Ning; Park, Jaeyoung; Evans, Eric A; Ellis, Timothy G

2014-01-01

Hydrogen sulphide (H2S) adsorption capacities on recycled rubber media, tyre-derived rubber particle (TDRP), and other rubber material (ORM) have been evaluated. As part of the research, densities, moisture contents, and surface properties of TDRP and ORM have been determined. The research team findings show that TDRP and ORM are more particulate in nature and not highly porous-like activated carbon. The characteristics of surface area, pore size, and moisture content support chemisorption on the macrosurface rather than physical adsorption in micropores. For example, moisture content is essential for H2S adsorption on ORM, and an increase in moisture content results in an increase in adsorption capacity.
Polyvinylpyrrolidone/Multiwall Carbon Nanotube Composite Based 36° YX LiTaO3 Surface Acoustic Wave For Hydrogen Gas Sensing Applications

NASA Astrophysics Data System (ADS)

Chee, Pei Song; Arsat, Rashidah; He, Xiuli; Kalantar-zadeh, Kourosh; Arsat, Mahyuddin; Wlodarski, Wojtek

2011-05-01

Poly-vinyl-pyrrolidone (PVP) /Multiwall Carbon Nanotubes (MWNTs) based Surface Acoustic Wave (SAW) sensors are fabricated and characterized, and their performances towards hydrogen gas are investigated. The PVP/MWNTs fibers composite are prepared by electrospinning of the composite aqueous solution deposited directly onto the active area of SAW transducers. Via scanning electron microscopy (SEM), the morphology of the deposited nanostructure material is observed. From the dynamic response, frequency shifts of 530 Hz (1% H2) and 11.322 kHz (0.25% H2) are recorded for the sensors contain of 1.525 g and 1.025 g PVP concentrations, respectively.
Changes in surface morphology and mineralization level of human enamel following in-office bleaching with 35% hydrogen peroxide and light irradiation.

PubMed

Berger, Sandrine Bittencourt; Cavalli, Vanessa; Ambrosano, Glaucia Maria Bovi; Giannini, Marcelo

2010-01-01

The objective of this study was to evaluate the alterations on surface morphology and mineral loss of human enamel following in-office bleaching with 35% hydrogen peroxide and light irradiation. Dental enamel samples were obtained from human third molars and randomly divided into 10 groups (n = 10). The control group remained untreated. Bleached groups were treated with one of three whitening products. Bleaching was performed in a single session, during which bleaching gel was applied to the enamel surface three times for 10 minutes each time. During treatment, the bleaching agents were either irradiated by a halogen light or an LED/diode laser or were not irradiated at all. Microhardness testing was performed with a Knoop indentor and the surface morphologic observations were carried out by scanning electron microscopy (SEM). Cross-sectional microhardness (CSMH) and polarized light microscopy (PLM) were used to measure the depth of demineralization. The results revealed a significant decrease in surface microhardness values and changes to the enamel morphology after bleaching. CSMH and PLM showed that bleached enamel presented lower volume percentage of mineral up to 40 micrometers from the enamel surface and demineralization areas located in the subsuperficial region of enamel, respectively. It was concluded that 35% hydrogen peroxide can alter the surface morphology and the mineralization level of the dental enamel surface and sub-surface regardless of what type of bleaching light is used.
Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

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

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N., E-mail: gnp@ncsu.edu

2016-01-15

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less
Diagnostics of hydrogen plasma with in situ optical emission and silicon probes

NASA Astrophysics Data System (ADS)

Lee, Szetsen; Chung, Yi-Jie

2005-11-01

In this work, an approach has been adopted to explore plasma properties by combining an in situ optical emission technique with a contact angle measurement. Hydrogen plasma was generated with a radio-frequency power source. The plasma parameters such as number densities and temperatures were derived from the optical emission spectroscopic data. Small silicon chips were placed at various positions inside a discharge tube as probes for the plasma conditions. The hydrogen-plasma-treated silicon chip surfaces were characterized with the contact angle measurement method. The change of wettability on the silicon surface was observed with various plasma treatment times. The spectroscopic information about the plasma is correlated with the results of the surface characterization. It is found that the rate of the increasing hydrophilicity is sensitive to the amount of helium added and the location in the discharge tube. A simple model describing the relation between the surface coverage area of water droplet and the variation of contact angle has been established. We have proposed plasma excitation and reaction mechanisms for the observed correlation between plasma temperatures and the wettability of the silicon surface. It shows that small silicon chips can serve as "litmus tests" for the plasma conditions without introducing too much perturbation.
Atomic and molecular hydrogen gas temperatures in a low-pressure helicon plasma

NASA Astrophysics Data System (ADS)

Samuell, Cameron M.; Corr, Cormac S.

2015-08-01

Neutral gas temperatures in hydrogen plasmas are important for experimental and modelling efforts in fusion technology, plasma processing, and surface modification applications. To provide values relevant to these application areas, neutral gas temperatures were measured in a low pressure (< 10 mTorr) radiofrequency helicon discharge using spectroscopic techniques. The atomic and molecular species were not found to be in thermal equilibrium with the atomic temperature being mostly larger then the molecular temperature. In low power operation (< 1 kW), the molecular hydrogen temperature was observed to be linearly proportional to the pressure while the atomic hydrogen temperature was inversely proportional. Both temperatures were observed to rise linearly with input power. For high power operation (5-20 kW), the molecular temperature was found to rise with both power and pressure up to a maximum of approximately 1200 K. Spatially resolved measurements near a graphite target demonstrated localised cooling near the sample surface. The temporal evolution of the molecular gas temperature during a high power 1.1 ms plasma pulse was also investigated and found to vary considerably as a function of pressure.
Synthesis of high surface area nanomaterials and their application in catalysis

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

Chaudhary, Umesh

2016-05-01

The dissertation is organized in 4 chapters. Chapter 1 highlights the motivations behind our research along with a general introduction on ceria and carbon catalysts. Chapter 2 reports the investigations on Copper-Ceria catalysts for the selective hydrogenation of fatty acids into fatty alcohols. Chapter 3 discusses the development of nitrogen containing mesoporous carbon. The chapter also reports the catalytic investigations for aldol condensation and nitrobenzene hydrogenation reactions. Finally, Chapter 4 is a general conclusion summarizing this dissertation.
Cometary science. The organic-rich surface of comet 67P/Churyumov-Gerasimenko as seen by VIRTIS/Rosetta.

PubMed

Capaccioni, F; Coradini, A; Filacchione, G; Erard, S; Arnold, G; Drossart, P; De Sanctis, M C; Bockelee-Morvan, D; Capria, M T; Tosi, F; Leyrat, C; Schmitt, B; Quirico, E; Cerroni, P; Mennella, V; Raponi, A; Ciarniello, M; McCord, T; Moroz, L; Palomba, E; Ammannito, E; Barucci, M A; Bellucci, G; Benkhoff, J; Bibring, J P; Blanco, A; Blecka, M; Carlson, R; Carsenty, U; Colangeli, L; Combes, M; Combi, M; Crovisier, J; Encrenaz, T; Federico, C; Fink, U; Fonti, S; Ip, W H; Irwin, P; Jaumann, R; Kuehrt, E; Langevin, Y; Magni, G; Mottola, S; Orofino, V; Palumbo, P; Piccioni, G; Schade, U; Taylor, F; Tiphene, D; Tozzi, G P; Beck, P; Biver, N; Bonal, L; Combe, J-Ph; Despan, D; Flamini, E; Fornasier, S; Frigeri, A; Grassi, D; Gudipati, M; Longobardo, A; Markus, K; Merlin, F; Orosei, R; Rinaldi, G; Stephan, K; Cartacci, M; Cicchetti, A; Giuppi, S; Hello, Y; Henry, F; Jacquinod, S; Noschese, R; Peter, G; Politi, R; Reess, J M; Semery, A

2015-01-23

The VIRTIS (Visible, Infrared and Thermal Imaging Spectrometer) instrument on board the Rosetta spacecraft has provided evidence of carbon-bearing compounds on the nucleus of the comet 67P/Churyumov-Gerasimenko. The very low reflectance of the nucleus (normal albedo of 0.060 ± 0.003 at 0.55 micrometers), the spectral slopes in visible and infrared ranges (5 to 25 and 1.5 to 5% kÅ(-1)), and the broad absorption feature in the 2.9-to-3.6-micrometer range present across the entire illuminated surface are compatible with opaque minerals associated with nonvolatile organic macromolecular materials: a complex mixture of various types of carbon-hydrogen and/or oxygen-hydrogen chemical groups, with little contribution of nitrogen-hydrogen groups. In active areas, the changes in spectral slope and absorption feature width may suggest small amounts of water-ice. However, no ice-rich patches are observed, indicating a generally dehydrated nature for the surface currently illuminated by the Sun. Copyright © 2015, American Association for the Advancement of Science.
Nanocomposites of AgInZnS and graphene nanosheets as efficient photocatalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Tang, Xiaosheng; Chen, Weiwei; Zu, Zhiqiang; Zang, Zhigang; Deng, Ming; Zhu, Tao; Sun, Kuan; Sun, Lidong; Xue, Junmin

2015-11-01

In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field.In this study, AgInZnS-reduced graphene (AIZS-rGO) nanocomposites with tunable band gap absorption and large specific surface area were synthesized by a simple hydrothermal route, which showed highly efficient photocatalytic hydrogen evolution under visible-light irradiation. The relationships between their crystal structures, morphology, surface chemical states and photocatalytic activity have been explored in detail. Importantly, the AIZS-rGO nanocomposites with 0.02 wt% of graphene exhibited the highest hydrogen production rate of 1.871 mmol h-1 g-1, which was nearly 2 times the hydrogen production rate when using pure AIZS nanoparticles as the photocatalyst. This high photocatalytic H2-production activity was attributed predominantly to the incorporation of graphene sheets, which demonstrated an obvious influence on the structure and optical properties of the AIZS nanoparticles. In the AIZS-rGO nanocomposites, graphene could not only serve as an effective supporting layer but also is a recombination center for conduction band electrons and valence band holes. It is believed that this kind of graphene-based material would attract much attention as a promising photocatalyst with a high efficiency and a low cost for photocatalytic H2 evolution and facilitates their application in the environmental protection field. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05145b
Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

DTIC Science & Technology

2013-01-01

guest solvent molecules were removed via supercritical CO2 (see the Supporting Information for activation details),30,31 the samples were further...unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms...NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms were measured over a broad range of
Using Aerogel-Based Insulation Material To Prevent Foam Loss on the Liquid-Hydrogen Intertank

NASA Technical Reports Server (NTRS)

2008-01-01

Uninsulated areas on cryogenic propellant tanks and feedlines cause moisture in the air to condense or ice to form. Flange joints, bracket supports, expansion bellows, and other cavities are uninsulated by design. These areas cannot be sealed because conventional thermal insulation materials would restrict mechanical articulations. Aerogel-based thermal insulation systems are able to seal critical locations such as the liquid-oxygen (LO2) feedline bellows. A new thermal insulation system was also necessary between the intertank wall, flange, and the liquid-hydrogen (LH2) tank dome, where there is a cavity (or crevice) with an exposed 20-K surface. When nitrogen gas is used for purging within the intertank volume, it condenses on this cold surface. Some solid nitrogen may also form on the colder side of the crevice. Voids or discontinuities within the foam can pressurize and cause areas of foam to weaken and break off, reducing thermal efficiency and creating potentially dangerous debris. To prevent this foam loss, we developed a thermal insulation system using bulk-fill aerogel material and demonstrated it with a one-tenth-scale model of the LH2 intertank flange area

STM observation of the chemical reaction of atomic hydrogen on the N-adsorbed Cu(001) surface

NASA Astrophysics Data System (ADS)

Hattori, Takuma; Yamada, Masamichi; Komori, Fumio

2017-01-01

Chemical reaction of atomic hydrogen with the N-adsorbed Cu(001) surfaces was investigated at room temperature by scanning tunnel microscopy. At the low exposure of atomic hydrogen, it reacted with the N atoms and turned to be the NH species on the surface. The reaction rate is proportional to the amount of the unreacted N atoms. By increasing the exposure of atomic hydrogen from this condition, the amount of nitrogen species on the surface decreased. This is attributed to the formation of ammonia and its desorption from the surface. The NH species on the surface turn to NH3 through the surface NH2 species by atomic hydrogen. Coexistence of the clean Cu surface enhances the rate of ammonia formation owing to atomic hydrogen migrating on the clean surface.
Use of low energy hydrogen ion implants in high efficiency crystalline silicon solar cells

NASA Technical Reports Server (NTRS)

Fonash, S. J.; Singh, R.

1985-01-01

This program is a study of the use of low energy hydrogen ion implantation for high efficiency crystalline silicon solar cells. The first quarterly report focuses on two tasks of this program: (1) an examination of the effects of low energy hydrogen implants on surface recombination speed; and (2) an examination of the effects of hydrogen on silicon regrowth and diffusion in silicon. The first part of the project focussed on the measurement of surface properties of hydrogen implanted silicon. Low energy hydrogen ions when bombarded on the silicon surface will create structural damage at the surface, deactivate dopants and introduce recombination centers. At the same time the electrically active centers such as dangling bonds will be passivated by these hydrogen ions. Thus hydrogen is expected to alter properties such as the surface recombination velocity, dopant profiles on the emitter, etc. In this report the surface recombination velocity of a hydrogen emplanted emitter was measured.
Performance Improvement of V-Fe-Cr-Ti Solid State Hydrogen Storage Materials in Impure Hydrogen Gas.

PubMed

Ulmer, Ulrich; Oertel, Daria; Diemant, Thomas; Bonatto Minella, Christian; Bergfeldt, Thomas; Dittmeyer, Roland; Behm, R Jürgen; Fichtner, Maximilian

2018-01-17

Two approaches of engineering surface structures of V-Ti-based solid solution hydrogen storage alloys are presented, which enable improved tolerance toward gaseous oxygen (O 2 ) impurities in hydrogen (H 2 ) gas. Surface modification is achieved through engineering lanthanum (La)- or nickel (Ni)-rich surface layers with enhanced cyclic stability in an H 2 /O 2 mixture. The formation of a Ni-rich surface layer does not improve the cycling stability in H 2 /O 2 mixtures. Mischmetal (Mm, a mixture of La and Ce) agglomerates are observed within the bulk and surface of the alloy when small amounts of this material are added during arc melting synthesis. These agglomerates provide hydrogen-transparent diffusion pathways into the bulk of the V-Ti-Cr-Fe hydrogen storage alloy when the remaining oxidized surface is already nontransparent for hydrogen. Thus, the cycling stability of the alloy is improved in an O 2 -containing hydrogen environment as compared to the same alloy without addition of Mm. The obtained surface-engineered storage material still absorbs hydrogen after 20 cycles in a hydrogen-oxygen mixture, while the original material is already deactivated after 4 cycles.
The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

NASA Astrophysics Data System (ADS)

Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

2018-05-01

Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.
Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings

NASA Astrophysics Data System (ADS)

Segalman, Rachel

Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.
DOE Office of Scientific and Technical Information (OSTI.GOV)

García, Abraham; Cotto, María; Duconge, José

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less
How wood adhesives work and where are the areas for improvement

Treesearch

Charles R. Frihart

2013-01-01

Invoking normal adhesion theory, bonding of wood would seem to be easy in that the surface has plenty of roughness for mechanical interlocking with high enough surface energy, there is an abundance of hydroxyl groups on the wood for hydrogen bonding to the adhesives, and the aqueous solvent in the adhesive can readily soak into the wood. In fact most adhesives will...
New Photocatalysts for Hydrogen Production; Nuevos Fotocatalizadores para la Producción de Hidrógeno

DOE PAGES

García, Abraham; Cotto, María; Duconge, José; ...

2014-06-10

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less
Nanoparticulate gellants for metallized gelled liquid hydrogen with aluminum

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan; Starkovich, John; Adams, Scott

1996-01-01

Gelled liquid hydrogen was experimentally formulated using sol-gel technology. As a follow-on to work with cryogenic simulants, hydrogen was gelled with an alkoxide material: BTMSE. Initial results demonstrated that gellants with a specific surface area of 1000 m(exp 2)/g could be repeatably fabricated. Gelled hexane and metallized gelled hexane (with 13.8-wt% Al) were produced. Propellant settling testing was conducted for acceleration levels of 2 to 10 times normal gravity and a minimum gellant percentage was determined for stable gelled hexane and metalized gelled hexane. A cryogenic capillary rheometer was also designed, constructed, and used to determine the viscosity of gelled hydrogen. Small volumes of liquid hydrogen were gelled with a 7- to 8-wt% gellant level. The gelled H2 viscosity was 1.5 to 3.7 times that of liquid hydrogen: 0.048 to 0.116 mPa-s versus 0.03 mPa-s for liquid H2 (at 16 K and approximately 1 atm pressure).
Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

DOE PAGES

Celik, Fuat E.; Mavrikakis, Manos

2015-01-12

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less
Stability of Surface and Subsurface Hydrogen on and in Au/Ni Near-Surface Alloys

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

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less
Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

NASA Astrophysics Data System (ADS)

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While the metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.
Towards graphane field emitters

PubMed Central

Ding, Shuyi; Li, Chi; Zhou, Yanhuai; Collins, Clare M.; Kang, Moon H.; Parmee, Richard J.; Zhang, Xiaobing; Milne, William I.; Wang, Baoping

2015-01-01

We report on the improved field emission performance of graphene foam (GF) following transient exposure to hydrogen plasma. The enhanced field emission mechanism associated with hydrogenation has been investigated using Fourier transform infrared spectroscopy, plasma spectrophotometry, Raman spectroscopy, and scanning electron microscopy. The observed enhanced electron emissionhas been attributed to an increase in the areal density of lattice defects and the formation of a partially hydrogenated, graphane-like material. The treated GF emitter demonstrated a much reduced macroscopic turn-on field (2.5 V μm–1), with an increased maximum current density from 0.21 mA cm–2 (pristine) to 8.27 mA cm–2 (treated). The treated GFs vertically orientated protrusions, after plasma etching, effectively increased the local electric field resulting in a 2.2-fold reduction in the turn-on electric field. The observed enhancement is further attributed to hydrogenation and the subsequent formation of a partially hydrogenated structured 2D material, which advantageously shifts the emitter work function. Alongside augmentation of the nominal crystallite size of the graphitic superstructure, surface bound species are believed to play a key role in the enhanced emission. The hydrogen plasma treatment was also noted to increase the emission spatial uniformity, with an approximate four times reduction in the per unit area variation in emission current density. Our findings suggest that plasma treatments, and particularly hydrogen and hydrogen-containing precursors, may provide an efficient, simple, and low cost means of realizing enhanced nanocarbon-based field emission devices via the engineered degradation of the nascent lattice, and adjustment of the surface work function. PMID:28066543
Charge induced enhancement of adsorption for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Sun, Xiang

2009-12-01

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy. Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.
Improved efficiency of a large-area Cu(In,Ga)Se₂ solar cell by a nontoxic hydrogen-assisted solid Se vapor selenization process.

PubMed

Wu, Tsung-Ta; Hu, Fan; Huang, Jyun-Hong; Chang, Chia-ho; Lai, Chih-chung; Yen, Yu-Ting; Huang, Hou-Ying; Hong, Hwen-Fen; Wang, Zhiming M; Shen, Chang-Hong; Shieh, Jia-Min; Chueh, Yu-Lun

2014-04-09

A nontoxic hydrogen-assisted solid Se vapor selenization process (HASVS) technique to achieve a large-area (40 × 30 cm(2)) Cu(In,Ga)Se2 (CIGS) solar panel with enhanced efficiencies from 7.1 to 10.8% (12.0% for active area) was demonstrated. The remarkable improvement of efficiency and fill factor comes from improved open circuit voltage (Voc) and reduced dark current due to (1) decreased interface recombination raised from the formation of a widened buried homojunction with n-type Cd(Cu) participation and (2) enhanced separation of electron and hole carriers resulting from the accumulation of Na atoms on the surface of the CIGS film. The effects of microstructural, compositional, and electrical characteristics with hydrogen-assisted Se vapor selenization, including interdiffusion of atoms and formation of buried homojunction, were examined in detail. This methodology can be also applied to CIS (CuInSe2) thin film solar cells with enhanced efficiencies from 5.3% to 8.5% (9.4% for active area) and provides a facile approach to improve quality of CIGS and stimulate the nontoxic progress in the large scale CIGS PV industry.
Long-term hydrogen oxidation catalysts in alkaline fuel cells

NASA Astrophysics Data System (ADS)

Kiros, Y.; Schwartz, S.

Pt/Pd bimetallic combination and Raney Ni catalysts were employed in long-term electrochemical assessment of the hydrogen oxidation reaction (HOR) in 6 M KOH. Steady-state current vs. potential measurements of the gas diffusion electrodes have shown high activity for these types of catalysts. Durability tests of the electrodes have shown increased stability for the Pt/Pd-based catalysts than the Raney Ni at a constant load of 100 mA/cm 2 and at temperatures of 55°C and 60°C, respectively. Surface, structural and chemical analyses by BET surface area, transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were used to characterize the composite electrode/catalyst both before and after the electrochemical testing.
Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

PubMed

Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

2012-01-21

Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.
Vaporous Decontamination Methods: Potential Uses and Research Priorities for Chemical and Biological Contamination Control

DTIC Science & Technology

2006-06-01

Decontamination assessment of Bacillus anthracis, Bacillus subtilis, and Geobacillus stearothermophilus spores on indoor surfaces using a hydrogen...resistant to commonly used disinfectants and require the use of chemical sterilants † to effectively decontaminate exposed areas. Since anthrax...spores can aerosolise the use of vaporous sterilants in the remediation of contaminated areas is desirable. A number of vaporous sterilants exist which
Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

NASA Astrophysics Data System (ADS)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.
Biochar: sustainable and versatile

USDA-ARS?s Scientific Manuscript database

Biochar is a term that describes any charcoal that comes from biomass. It is a renewable, microporous carbon-rich product that also contains nitrogen, hydrogen, oxygen, and ash. Several varieties of biochar are very porous with irregular surface area. The pore size and distribution of a given biocha...

Relating Nanoscale Accessibility within Plant Cell Walls to Improved Enzyme Hydrolysis Yields in Corn Stover Subjected to Diverse Pretreatments.

PubMed

Crowe, Jacob D; Zarger, Rachael A; Hodge, David B

2017-10-04

Simultaneous chemical modification and physical reorganization of plant cell walls via alkaline hydrogen peroxide or liquid hot water pretreatment can alter cell wall structural properties impacting nanoscale porosity. Nanoscale porosity was characterized using solute exclusion to assess accessible pore volumes, water retention value as a proxy for accessible water-cell walls surface area, and solute-induced cell wall swelling to measure cell wall rigidity. Key findings concluded that delignification by alkaline hydrogen peroxide pretreatment decreased cell wall rigidity and that the subsequent cell wall swelling resulted increased nanoscale porosity and improved enzyme binding and hydrolysis compared to limited swelling and increased accessible surface areas observed in liquid hot water pretreated biomass. The volume accessible to a 90 Å dextran probe within the cell wall was found to be correlated to both enzyme binding and glucose hydrolysis yields, indicating cell wall porosity is a key contributor to effective hydrolysis yields.
Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

NASA Astrophysics Data System (ADS)

Boucher, Matthew B.

Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (<1 atomic %) supported on zinc oxide nanoparticles with controlled crystal structures. The performance of these catalysts was studied in a fixed-bed micro-reactor system at ambient pressures, and their structure was characterized by high-resolution microscopic and spectroscopic techniques. Pre-existing oxygen defects in zinc oxide {0001} surfaces, and those created by a perturbation of the defect equilibrium by addition of gold, provide an anchoring site for highly dispersed gold species. By utilizing shape control of zinc oxide supports, it is found that highly dispersed gold, capable of low-temperature redox behavior is most prominent on zinc oxide {0001} surfaces and leads to high SRM activity and selectivity to carbon dioxide. Like other Group IB metal catalysts the SRM over gold-zinc oxide proceeds through the formation and weak binding of formaldehyde, and subsequent coupling with methoxy to produce methyl formate. Mechanistic clarification of this point was achieved by studying the interaction methanol-water mixtures with model catalyst surfaces. Model catalysts were studied in a UHV chamber where the base pressure was maintained at 10-10 mbar. High resolutions surface science techniques show that hydrogen-bonded networks of water are capable of deprotonating methanol to methoxy on low index surfaces in the absence of atomic oxygen. These UHV studies show that adsorbates, other than oxygen, are capable of activating methanol on Group IB metal surfaces. The second reaction involves the selective hydrogenation of alkynes to alkenes. Selective hydrogenations of carbon-carbon multiple bonds are important for a wide range of industrial processes. The governing hypothesis for this reaction system is that cooperation between a minority metal with a low barrier for hydrogen dissociation, and a less-reactive host metal capable of hydrogen uptake via spillover will lead to high alkene selectivity. A strategy for the preparation of such a catalyst is developed using model catalyst studied in a UHV chamber. The model catalyst features isolated palladium atoms in a copper(111) surface, termed single atom alloy (SAA). Individual, isolated palladium atoms act as sites for hydrogen uptake, dissociation, and spillover onto an otherwise inert copper(111) host. Weak binding offered by copper provides a surface where selective hydrogenation reactions can take place. Palladium-copper SAA model catalysts are highly selective to the partial hydrogenation of acetylene, whereas surfaces containing larger palladium ensembles facilitate complete hydrogenation and decomposition. Nanoparticle analogs of palladium-copper SAAs were prepared to investigate the feasibility of this strategy for practical application. Very small amounts of palladium (<0.2 atomic %) on the surface of copper nanoparticles are highly active and selective catalysts for the partial hydrogenation of phenylacetylene to styrene. The performance of these catalysts was studied in a liquid-phase, stirred-tank batch reactor under a hydrogen head pressure of approximately 7 bar. Palladium alloyed into the surface of otherwise inactive copper nanoparticles shows a marked improvement in selectivity when compared to monometallic palladium catalysts with the same metal loading. This effect is attributed hydrogen spillover onto the copper surface. In summary, the development of new, highly active and selective catalysts for the methanol steam reforming reaction and for the partial hydrogenation of alkynes to alkenes was accomplished by the use of state-of-the-art techniques in both surface science and heterogeneous catalysis. The implications of this work can be extended to a wide variety of catalytic systems.
Hydrogen-dominated plasma, due to silane depletion, for microcrystalline silicon deposition

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

Howling, A. A.; Sobbia, R.; Hollenstein, Ch.

2010-07-15

Plasma conditions for microcrystalline silicon deposition generally require a high flux of atomic hydrogen, relative to SiH{sub {alpha}=0{yields}3} radicals, on the growing film. The necessary dominant partial pressure of hydrogen in the plasma is conventionally obtained by hydrogen dilution of silane in the inlet flow. However, a hydrogen-dominated plasma environment can also be obtained due to plasma depletion of the silane in the gas mixture, even up to the limit of pure silane inlet flow, provided that the silane depletion is strong enough. At first sight, it may seem surprising that the composition of a strongly depleted pure silane plasmamore » consists principally of molecular hydrogen, without significant contribution from the partial pressure of silane radicals. The aim here is to bring some physical insight by means of a zero-dimensional, analytical plasma chemistry model. The model is appropriate for uniform large-area showerhead reactors, as shown by comparison with a three-dimensional numerical simulations. The SiH{sub {alpha}} densities remain very low because of their rapid diffusion and surface reactivity, contributing to film growth which is the desired scenario for efficient silane utilization. Significant SiH{sub {alpha}} densities due to poor design of reactor and gas flow, on the other hand, would result in powder formation wasting silane. Conversely, hydrogen atoms are not deposited, but recombine on the film surface and reappear as molecular hydrogen in the plasma. Therefore, in the limit of extremely high silane depletion fraction (>99.9%), the silane density falls below the low SiH{sub {alpha}} densities, but only the H radical can eventually reach significant concentrations in the hydrogen-dominated plasma.« less
Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers

NASA Astrophysics Data System (ADS)

Purewal, J. J.; Kabbour, H.; Vajo, J. J.; Ahn, C. C.; Fultz, B.

2009-05-01

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.
Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers.

PubMed

Purewal, J J; Kabbour, H; Vajo, J J; Ahn, C C; Fultz, B

2009-05-20

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.
Surface Modification of Plastic Substrates Using Atomic Hydrogen

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

The surface properties of a plastic substrate were changed by a novel surface treatment called atomic hydrogen annealing (AHA). In this method, a plastic substrate was exposed to atomic hydrogen generated by cracking of hydrogen molecules on heated tungsten wire. Surface roughness was increased and halogen elements (F and Cl) were selectively etched by AHA. In addition, plastic surface was reduced by AHA. The surface can be modified by the recombination reaction of atomic hydrogen, the reduction reaction and selective etching of halogen atom. It is concluded that this method is a promising technique for improvement of adhesion between inorganic films and plastic substrates at low temperatures.
Enhanced Hydrogen Evolution Reactions on Nanostructured Cu2ZnSnS4 (CZTS) Electrocatalyst

NASA Astrophysics Data System (ADS)

Digraskar, Renuka V.; Mulik, Balaji B.; Walke, Pravin S.; Ghule, Anil V.; Sathe, Bhaskar R.

2017-08-01

A novel and facile one-step sonochemical method is used to synthesize Cu2ZnSnS4 (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer-Emmett-Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density -130 mA/cm2, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm2, excellent stability (> 500 cycles) and lower charge transfer resistance. This sonochemically fabricated CZTSs nanoparticles are leading to significantly reduce cell cost and simplification of preparation process over existing high efficiency Pt and other nobel metal-free cathode electrocatalyst.
Comparison of the structural basis for thermal stability between archaeal and bacterial proteins.

PubMed

Ding, Yanrui; Cai, Yujie; Han, Yonggang; Zhao, Bingqiang

2012-01-01

In this study, the structural basis for thermal stability in archaeal and bacterial proteins was investigated. There were many common factors that confer resistance to high temperature in both archaeal and bacterial proteins. These factors include increases in the Lys content, the bends and blanks of secondary structure, the Glu content of salt bridge; decreases in the number of main-side chain hydrogen bond and exposed surface area, and changes in the bends and blanks of amino acids. Certainly, the utilization of charged amino acids to form salt bridges is a primary factor. In both heat-resistant archaeal and bacterial proteins, most Glu and Asp participate in the formation of salt bridges. Other factors may influence either archaeal or bacterial protein thermostability, which includes the more frequent occurrence of shorter 3(10)-helices and increased hydrophobicity in heat-resistant archaeal proteins. However, there were increases in average helix length, the Glu content in salt bridges, temperature factors and decreases in the number of main-side chain hydrogen bonds, uncharged-uncharged hydrogen bonds, hydrophobicity, and buried and exposed polar surface area in heat-resistant bacterial proteins. Evidently, there are few similarities and many disparities between the heat-resistant mechanisms of archaeal and bacterial proteins.
Nanostructured materials for hydrogen storage

DOEpatents

Williamson, Andrew J.; Reboredo, Fernando A.

2007-12-04

A system for hydrogen storage comprising a porous nano-structured material with hydrogen absorbed on the surfaces of the porous nano-structured material. The system of hydrogen storage comprises absorbing hydrogen on the surfaces of a porous nano-structured semiconductor material.
Photocatalytic activity and reusability of ZnO layer synthesised by electrolysis, hydrogen peroxide and heat treatment.

PubMed

Akhmal Saadon, Syaiful; Sathishkumar, Palanivel; Mohd Yusoff, Abdull Rahim; Hakim Wirzal, Mohd Dzul; Rahmalan, Muhammad Taufiq; Nur, Hadi

2016-08-01

In this study, the zinc oxide (ZnO) layer was synthesised on the surface of Zn plates by three different techniques, i.e. electrolysis, hydrogen peroxide and heat treatment. The synthesised ZnO layers were characterised using scanning electron microscopy, X-ray diffraction, UV-visible diffuse reflectance and photoluminescence spectroscopy. The photocatalytic activity of the ZnO layer was further assessed against methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB was achieved up to 84%, 79% and 65% within 1 h for ZnO layers synthesised by electrolysis, heat and hydrogen peroxide treatment, respectively. The reusability results show that electrolysis and heat-treated ZnO layers have considerable photocatalytic stability. Furthermore, the results confirmed that the photocatalytic efficiency of ZnO was directly associated with the thickness and enlarged surface area of the layer. Finally, this study proved that the ZnO layers synthesised by electrolysis and heat treatment had shown better operational stability and reusability.
Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Cho, Kyung Min; Park, Sunyoung; Song, In Kyu

Mesoporous alumina xerogel (A-SG) is prepared by a sol-gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.
Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

NASA Astrophysics Data System (ADS)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.
Argillization by descending acid at Steamboat Springs, Nevada

USGS Publications Warehouse

Schoen, Robert; White, Donald E.; Hemley, J.J.

1974-01-01

Steamboat Springs, Nevada, an area of present-day hot springs, clearly illustrates the genetic dependence of some kaolin deposits on hot-spring activity. Andesite, granodiorite and arkosic sediments are locally altered at the land surface to siliceous residues consisting of primary quartz and anatase, plus opal from primary silicates. These siliceous residues commonly exhibit the textural and structural features of their unaltered equivalents. Beneath the siliceous residues, kaolin and alunite replace primary silicates and fill open spaces, forming a blanketlike deposit. Beneath the kaolin-alunite zone, montmorillonite, commonly accompanied by pyrite, replaces the primary silicates. On the ground surface, the same alteration mineral zones can be traced outward from the siliceous residue; however, hematite rather than pyrite accompanies montmorillonite.Chemical analysis indicates that sulfuric acid is the active altering agent. The acid forms from hydrogen sulfide that exsolves from deep thermal water, rises above the water table and is oxidized by sulfur-oxidizing bacteria living near the ground surface. This acid dissolves in precipitation or condensed water vapor and percolates downward destroying most of the primary minerals producing a siliceous residue. Coincidence of the water table with the downward transition from siliceous residue to kaolin-alunite signifies decreasing hydrogen metasomatism because of dilution of descending acid by ground water.In hot-spring areas, beds of siliceous sinter deposited at the surface by hypogene thermal water look, superficially, like areas of surficial acid alteration. Features diagnostic of a surficial alteration are the relict rock structures of a siliceous residue and a kaolin-alunite zone immediately beneath.
Ammonia adsorption capacity of biomass and animal-manure derived biochars

USDA-ARS?s Scientific Manuscript database

The objective of this research was to characterize and investigate ammonia and hydrogen sulfide gas adsorption capacities of low- and high-temperature biochars made from wood shavings and chicken litter. The biochar samples were activated with steam or phosphoric acid. The specific surface areas and...
Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage.

PubMed

Jin, Jiao; Ouyang, Jing; Yang, Huaming

2017-12-01

Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.
Pd Nanoparticles and MOFs Synergistically Hybridized Halloysite Nanotubes for Hydrogen Storage

NASA Astrophysics Data System (ADS)

Jin, Jiao; Ouyang, Jing; Yang, Huaming

2017-03-01

Natural halloysite nanotubes (HNTs) were hybridized with metal-organic frameworks (MOFs) to prepare novel composites. MOFs were transformed into carbon by carbonization calcination, and palladium (Pd) nanoparticles were introduced to build an emerging ternary compound system for hydrogen adsorption. The hydrogen adsorption capacities of HNT-MOF composites were 0.23 and 0.24 wt%, while those of carbonized products were 0.24 and 0.27 wt% at 25 °C and 2.65 MPa, respectively. Al-based samples showed higher hydrogen adsorption capacities than Zn-based samples on account of different selectivity between metal and hydrogen and approximate porous characteristics. More pore structures are generated by the carbonization reaction from metal-organic frameworks into carbon; high specific surface area, uniform pore size, and large pore volume benefited the hydrogen adsorption ability of composites. Moreover, it was also possible to promote hydrogen adsorption capacity by incorporating Pd. The hydrogen adsorption capacity of ternary compound, Pd-C-H3-MOFs(Al), reached 0.32 wt% at 25 °C and 2.65 MPa. Dissociation was assumed to take place on the Pd particles, then atomic and molecule hydrogen spilled over to the structure of carboxylated HNTs, MOFs, and the carbon products for enhancing the hydrogen adsorption capacity.
An amperometric hydrogen peroxide biosensor based on Co3O4 nanoparticles and multiwalled carbon nanotube modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Kaçar, Ceren; Dalkiran, Berna; Erden, Pınar Esra; Kiliç, Esma

2014-08-01

In this work a new type of hydrogen peroxide biosensor was fabricated based on the immobilization of horseradish peroxidase (HRP) by cross-linking on a glassy carbon electrode (GCE) modified with Co3O4 nanoparticles, multiwall carbon nanotubes (MWCNTs) and gelatin. The introduction of MWCNTs and Co3O4 nanoparticles not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate, resulting in a high sensitivity of the biosensor. The fabrication process of the sensing surface was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Amperometric detection of hydrogen peroxide was investigated by holding the modified electrode at -0.30 V (vs. Ag/AgCl). The biosensor showed optimum response within 5 s at pH 7.0. The optimized biosensor showed linear response range of 7.4 × 10-7-1.9 × 10-5 M with a detection limit of 7.4 × 10-7. The applicability of the purposed biosensor was tested by detecting hydrogen peroxide in disinfector samples. The average recovery was calculated as 100.78 ± 0.89.
Hydrogen sulphide removal from corroding concrete: comparison between surface removal rates and biomass activity.

PubMed

Jensen, H S; Nielsen, A H; Lens, P N L; Hvitved-Jacobsen, T; Vollertsen, J

2009-11-01

Corrosion of concrete sewer pipes caused by hydrogen sulphide is a problem in many sewer networks. The mechanisms of production and fate of hydrogen sulphide in the sewer biofilms and wastewater as well as its release to the sewer atmosphere are largely understood. In contrast, the mechanisms of the uptake of hydrogen sulphide on the concrete surfaces and subsequent concrete corrosion are basically unknown. To shed light on these mechanisms, the uptake of hydrogen sulphide from a sewer gas phase was compared to the biological hydrogen sulphide removal potential of the concrete corrosion products. The results showed that both microbial degradation at and sorption to the concrete surfaces were important for the uptake of hydrogen sulphide on the concrete surfaces.
Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

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

Gill, Lance; Beste, Ariana; Chen, Banghao

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less
Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE PAGES

Gill, Lance; Beste, Ariana; Chen, Banghao; ...

2017-03-22

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less

Multi-scale theoretical investigation of hydrogen storage in covalent organic frameworks.

PubMed

Tylianakis, Emmanuel; Klontzas, Emmanouel; Froudakis, George E

2011-03-01

The quest for efficient hydrogen storage materials has been the limiting step towards the commercialization of hydrogen as an energy carrier and has attracted a lot of attention from the scientific community. Sophisticated multi-scale theoretical techniques have been considered as a valuable tool for the prediction of materials storage properties. Such techniques have also been used for the investigation of hydrogen storage in a novel category of porous materials known as Covalent Organic Frameworks (COFs). These framework materials are consisted of light elements and are characterized by exceptional physicochemical properties such as large surface areas and pore volumes. Combinations of ab initio, Molecular Dynamics (MD) and Grand Canonical Monte-Carlo (GCMC) calculations have been performed to investigate the hydrogen adsorption in these ultra-light materials. The purpose of the present review is to summarize the theoretical hydrogen storage studies that have been published after the discovery of COFs. Experimental and theoretical studies have proven that COFs have comparable or better hydrogen storage abilities than other competitive materials such as MOF. The key factors that can lead to the improvement of the hydrogen storage properties of COFs are highlighted, accompanied with some recently presented theoretical multi-scale studies concerning these factors.
Hydrogen Storage in Diamond Powder Utilizing Plasma NaF Surface Treatment for Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Leal, David A.; Velez, Angel; Prelas, Mark A.; Gosh, Tushar; Leal-Quiros, E.

2006-12-01

Hydrogen Fuel Cells offer the vital solution to the world's socio-political dependence on oil. Due to existing difficulty in safe and efficient hydrogen storage for fuel cells, storing the hydrogen in hydrocarbon compounds such as artificial diamond is a realistic solution. By treating the surface of the diamond powder with a Sodium Fluoride plasma exposure, the surface of the diamond is cleaned of unwanted molecules. Due to fluorine's electro negativity, the diamond powder is activated and ready for hydrogen absorption. These diamond powder pellets are then placed on a graphite platform that is heated by conduction in a high voltage circuit made of tungsten wire. Then, the injection of hydrogen gas into chamber allows the storage of the Hydrogen on the surface of the diamond powder. By neutron bombardment in the nuclear reactor, or Prompt Gamma Neutron Activation Analysis, the samples are examined for parts per million amounts of hydrogen in the sample. Sodium Fluoride surface treatment allows for higher mass percentage of stored hydrogen in a reliable, resistant structure, such as diamond for fuel cells and permanently alters the diamonds terminal bonds for re-use in the effective storage of hydrogen. The highest stored amount utilizing the NaF plasma surface treatment was 22229 parts per million of hydrogen in the diamond powder which amounts to 2.2229% mass increase.
Biomolecular Chemistry of Isopropyl Fibrates

PubMed Central

Rath, Niharika; Kotheimer, Amenda; Miller, Chad; Zeller, Matthias; Rath, Nigam P.

2012-01-01

Isopropyl 2-[4-(4-chlorobenzoyl)-phenoxy]-2-methylpropanoic acid and isopropyl 2-(4-chlorophenoxy)-2-methylpropanoate, also known as fenofibrate and isopropyl clofibrate, are hypolipidemic agents of the fibrate family. In a previously reported triclinic structure of fenofibrate (polymorph I) the methyl groups of the isopropyl moiety (iPr) are located symmetrically about the carboxylate group. We report a new monoclinic form (polymorph II) of fenofibrate and a first structural description of isopropyl clofibrate, and in these the methyl groups are placed asymmetrically about the carboxylate group. In particular the dihedral (torsion) angle between the hydrogen atom on the secondary C and the C atom of the carboxyl group makes a 2.74° angle about the ester O-C bond in the symmetric fenofibrate structure of polymorph I, whereas the same dihedral angle is 45.94° in polymorph II and -30.9° in the crystal structure of isopropyl clofibrate. Gas phase DFT geometry minimizations of fenofibrate and isopropyl clofibrate result in lowest energy conformations for both molecules with a value of about ± 30° for this same angle between the O=C-O-C plane and the C-H bond of the iPr group. A survey of crystal structures containing an iPr ester group reveals that the asymmetric conformation is predominant. Although the hydrogen atom on the secondary C atom of the isopropyl group is located at a comparable distance from the carbonyl oxygen in the symmetric and asymmetric fenofibrate (2.52 and 2.28 Å) and the isopropyl clofibrate (2.36 Å) structures, this hydrogen atom participates in a puckered five membered ring arrangement in the latter two that is unlike the planar arrangement found in symmetric fenofibrate (polymorph I). Polar molecular surface area (PSA) values indicate fenofibrate and isopropyl clofibrate are less able to act as acceptors of hydrogen bonds than their corresponding acid derivatives. Surface area calculations show dynamic polar molecular surface area (PSAd) values of the iPr esters of the fibrates are lower than those of their acids, implying that the fibrates have better membrane permeability and a higher absorbability and hence are better prodrugs when these agents need to be orally administered. PMID:22246648
Cryogenic Fluid Storage Technology Development: Recent and Planned Efforts at NASA

NASA Technical Reports Server (NTRS)

Moran, Matthew E.

2009-01-01

Recent technology development work conducted at NASA in the area of Cryogenic Fluid Management (CFM) storage is highlighted, including summary results, key impacts, and ongoing efforts. Thermodynamic vent system (TVS) ground test results are shown for hydrogen, methane, and oxygen. Joule-Thomson (J-T) device tests related to clogging in hydrogen are summarized, along with the absence of clogging in oxygen and methane tests. Confirmation of analytical relations and bonding techniques for broad area cooling (BAC) concepts based on tube-to-tank tests are presented. Results of two-phase lumped-parameter computational fluid dynamic (CFD) models are highlighted, including validation of the model with hydrogen self pressurization test data. These models were used to simulate Altair representative methane and oxygen tanks subjected to 210 days of lunar surface storage. Engineering analysis tools being developed to support system level trades and vehicle propulsion system designs are also cited. Finally, prioritized technology development risks identified for Constellation cryogenic propulsion systems are presented, and future efforts to address those risks are discussed.
Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.
Fugitive gas adsorption capacity of biomass and animal-manure derived biochars

USDA-ARS?s Scientific Manuscript database

This research characterized and investigated ammonia and hydrogen sulfide gas adsorption capacities of low- and high-temperature biochars made from wood shavings and chicken litter. The biochar samples were activated with steam or phosphoric acid. The specific surface areas and pore volumes of the a...
Some surface characteristics and gas interactions of Apollo 14 fines and rock fragments.

NASA Technical Reports Server (NTRS)

Cadenhead, D. A.; Wagner, N. J.; Jones, B. R.; Stetter, J. R.

1972-01-01

Comprehensive survey of the physical surface characteristics of Apollo 14 fines, two fragments of a breccia (14321), and a crystalline rock (14310). The survey was carried out with optical and both scanning and transmission electron microscopy and by studying the adsorption of a variety of gases including nitrogen, hydrogen, and water vapor. Our objective in the optical microscope study was to relate the visible geological and petrological features to the surface properties. Electron microscopy particularly helped relate surface roughness and particle fusion to gas adsorption and pore structure. The fine sample (14163,111) had a surface area of 0.210 sq m/g and a helium density of 2.9 g/cc. Similar values have been observed with breccia fragments. Other observations include physical adsorption of molecular hydrogen at low temperatures and of water vapor at ambient temperatures. It is concluded that these particular lunar materials, while capable of adsorbing water vapor, do not retain it for any significant time at low pressures, nor, under lunar conditions, is there any indication of absorption or penetration.
The effect of PECVD plasma decomposition on the wettability and dielectric constant changes in silicon modified DLC films for potential MEMS and low stiction applications

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

Ogwu, A. A.; Okpalugo, T. I. T.; Nanotechnology Institute, School of Electrical and Mechanical Engineering, University of Ulster, Northern Ireland

We have carried out investigations aimed at understanding the mechanism responsible for a water contact angle increase of up to ten degrees and a decrease in dielectric constant in silicon modified hydrogenated amorphous carbon films compared to unmodified hydrogenated amorphous carbon films. Our investigations based on surface chemical constituent analysis using Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), SIMS, FTIR, contact angle / surface energy measurements and spectroscopic ellipsometry suggests the presence of hydrophobic chemical entities on the surface of the films. This observation is consistent with earlier theoretical plasma chemistry predictions and observed Raman peak shifts in the films. Thesemore » surface hydrophobic entities also have a lower polarizability than the bonds in the un-modified films thereby reducing the dielectric constant of the silicon modified films measured by spectroscopic ellipsometry. Ellipsometric dielectric constant measurement is directly related to the surface energy through Hamaker's constant. Our current finding is expected to be of benefit to understanding stiction, friction and lubrication in areas that range from nano-tribology to microfluidics.« less
The effect of PECVD plasma decomposition on the wettability and dielectric constant changes in silicon modified DLC films for potential MEMS and low stiction applications

NASA Astrophysics Data System (ADS)

Ogwu, A. A.; Okpalugo, T. I. T.; McLaughlin, J. A. D.

2012-09-01

We have carried out investigations aimed at understanding the mechanism responsible for a water contact angle increase of up to ten degrees and a decrease in dielectric constant in silicon modified hydrogenated amorphous carbon films compared to unmodified hydrogenated amorphous carbon films. Our investigations based on surface chemical constituent analysis using Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), SIMS, FTIR, contact angle / surface energy measurements and spectroscopic ellipsometry suggests the presence of hydrophobic chemical entities on the surface of the films. This observation is consistent with earlier theoretical plasma chemistry predictions and observed Raman peak shifts in the films. These surface hydrophobic entities also have a lower polarizability than the bonds in the un-modified films thereby reducing the dielectric constant of the silicon modified films measured by spectroscopic ellipsometry. Ellipsometric dielectric constant measurement is directly related to the surface energy through Hamaker's constant. Our current finding is expected to be of benefit to understanding stiction, friction and lubrication in areas that range from nano-tribology to microfluidics.
Polyacrylonitrile Fibers Anchored Cobalt/Graphene Sheet Nanocomposite: A Low-Cost, High-Performance and Reusable Catalyst for Hydrogen Generation.

PubMed

Zhang, Fei; Huang, Guoji; Hou, Chengyi; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

2016-06-01

Cobalt and its composites are known to be active and inexpensive catalysts in sodium borohydride (NaBH4) hydrolysis to generate clean and renewable hydrogen energy. A novel fiber catalyst, cobalt/graphene sheet nanocomposite anchored on polyacrylonitrile fibers (Co/GRs-PANFs), which can be easily recycled and used in any reactor with different shapes, were synthesized by anchoring cobalt/graphene (Co/GRs) on polyacrylonitrile fibers coated with graphene (GRs-PANFs) at low temperature. The unique structure design effectively prevents the inter-sheet restacking of Co/GRs and fully exploits the large surface area of novel hybrid material for generate hydrogen. And the extra electron transfer path supplied by GRs on the surface of GRs-PANFs can also enhance their catalysis performances. The catalytic activity of the catalyst was investigated by the hydrolysis of NaBH4 in aqueous solution with GRs-PANFs. GRs powders and Co powders were used as control groups. It was found that both GRs and fiber contributed to the hydrogen generation rate of Co/GRs-PANFs (3222 mL x min(-1) x g(-1)), which is much higher than that of cobalt powders (915 mL x min(-1) x g(-1)) and Co/GRs (995 mL x min(-1) x g(-1)). The improved hydrogen generation rate, low cost and uncomplicated recycling make the Co/GRs-PANFs promising candidate as catalysts for hydrogen generation.
Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.; Marsik, S. J.

1974-01-01

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.
Optimization studies of bio-hydrogen production in a coupled microbial electrolysis-dye sensitized solar cell system.

PubMed

Ajayi, Folusho Francis; Kim, Kyoung-Yeol; Chae, Kyu-Jung; Choi, Mi-Jin; Chang, In Seop; Kim, In S

2010-03-01

Bio-hydrogen production in light-assisted microbial electrolysis cell (MEC) with a dye sensitized solar cell (DSSC) was optimized by connecting multiple MECs to a single dye (N719) sensitized solar cell (V(OC) approx. 0.7 V). Hydrogen production occurred simultaneously in all the connected MECs when the solar cell was irradiated with light. The amount of hydrogen produced in each MEC depends on the activity of the microbial catalyst on their anode. Substrate (acetate) to hydrogen conversion efficiencies ranging from 42% to 65% were obtained from the reactors during the experiment. A moderate light intensity of 430 W m(-2) was sufficient for hydrogen production in the coupled MEC-DSSC. A higher light intensity of 915 W m(-2), as well as an increase in substrate concentration, did not show any improvement in the current density due to limitation caused by the rate of microbial oxidation on the anode. A significant reduction in the surface area of the connected DSSC only showed a slight effect on current density in the coupled MEC-DSSC system when irradiated with light.
Hydrogen storage behaviors of Ni-doped graphene Oxide/MIL-101 hybrid composites.

PubMed

Lee, Seul-Yi; Park, Soo-Jin

2013-01-01

In this work, Ni-doped graphene oxide/MIL-101 hybrid composites (Ni--GO/MIL) were prepared to investigate their hydrogen storage behaviors. Ni--GO/MIL was synthesized by adding Ni--GO in situ during the synthesis of MIL-101 using a hydrothermal process, which was conducted by conventional convection heating with Cr(III) ion as a metal center and telephthalic acid as organic ligands. The crystalline structures and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The specific surface area and micropore volume were investigated by N2/77 K adsorption isotherms using the Brunauer-Emmett-Teller (BET) method and Dubinin-Radushkevic (D-R) equation, respectively. The hydrogen storage capacity was investigated by BEL-HP at 77 K and 1 bar. The obtained results show that Ni--GO/MIL presents new directions for achieving novel hybrid materials with higher hydrogen storage capacity.
Development of a Micro-Fiber Nickel Electrode for Nickel-Hydrogen Cell

NASA Technical Reports Server (NTRS)

Britton, Doris L.

1996-01-01

The development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (NiH2) program at the NASA Lewis Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a more efficient and lighter weight electrode for the nickel-hydrogen fuel cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active materials. Initial tests include activation and capacity measurements at different discharge levels followed by half-cell cycle testing at 80 percent depth-of-discharge in a low Earth orbit regime. The electrodes that pass the initial tests are life cycle tested in a boiler plate nickel-hydrogen cell before flightweight designs are built and tested.
Hydrogen sensing properties of nanocomposite graphene oxide/Co-based metal organic frameworks (Co-MOFs@GO)

NASA Astrophysics Data System (ADS)

Fardindoost, Somayeh; Hatamie, Shadie; Iraji Zad, Azam; Razi Astaraei, Fatemeh

2018-01-01

This paper reports on hydrogen sensing based graphene oxide hybrid with Co-based metal organic frameworks (Co-MOFs@GO) prepared by the hydrothermal process. The texture and morphology of the hybrid were characterized by powder x-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller analysis. Porous flower like structures assembled from Co-MOFs and GO flakes with sufficient specific surface area are obtained, which are ideal for gas molecules diffusion and interactions. Sensing performance of Co-MOFs@GO were tested and also improved by sputtering platinum (Pt) as a catalyst. The Pt-sputtered Co-MOFs@GO show outstanding hydrogen resistive-sensing with response and recovery times below 12 s at 15 °C. Also, they show stable, repeatable and selective responses to the target gas which make it suitable for the development of a high performance hydrogen sensor.
Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

NASA Astrophysics Data System (ADS)

Murillo, Luis E.

Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.
Surface engineering on CeO2 nanorods by chemical redox etching and their enhanced catalytic activity for CO oxidation

NASA Astrophysics Data System (ADS)

Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

2015-07-01

Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c
Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

PubMed

Varadhan, Purushothaman; Fu, Hui-Chun; Priante, Davide; Retamal, Jose Ramon Duran; Zhao, Chao; Ebaid, Mohamed; Ng, Tien Khee; Ajia, Idirs; Mitra, Somak; Roqan, Iman S; Ooi, Boon S; He, Jr-Hau

2017-03-08

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm 2 at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.
Fundamental Pathways for the Adsorption and Transport of Hydrogen on TiO2 Surfaces: Origin for Effective Sensing at about Room Temperature.

PubMed

Wang, Zhuo; Xia, Xiaohong; Guo, Meilan; Shao, Guosheng

2016-12-28

Effective detection of hydrogen at lowered temperature is highly desirable in promoting safety in using this abundant gas as a clean energy source. Through first-principle calculations in the framework of density functional theory, we find that the high-energy (002) surface for rutile TiO 2 is significantly more effective in adsorbing hydrogen atoms through dissociating hydrogen molecules. The pathways for the dissociation of hydrogen molecules and sequential migration of hydrogen atoms are identified through searching along various transitional states. Pathways of low potential barriers indicate promise for hydrogen sensing, even close to room temperature. This has been proven through sensors made of thin films of well-aligned rutile nanorods, wherein the high-energy (002) surface dictates the top surface of the active layer of the sensors.
A finite element model of a MEMS-based surface acoustic wave hydrogen sensor.

PubMed

El Gowini, Mohamed M; Moussa, Walied A

2010-01-01

Hydrogen plays a significant role in various industrial applications, but careful handling and continuous monitoring are crucial since it is explosive when mixed with air. Surface Acoustic Wave (SAW) sensors provide desirable characteristics for hydrogen detection due to their small size, low fabrication cost, ease of integration and high sensitivity. In this paper a finite element model of a Surface Acoustic Wave sensor is developed using ANSYS12© and tested for hydrogen detection. The sensor consists of a YZ-lithium niobate substrate with interdigital electrodes (IDT) patterned on the surface. A thin palladium (Pd) film is added on the surface of the sensor due to its high affinity for hydrogen. With increased hydrogen absorption the palladium hydride structure undergoes a phase change due to the formation of the β-phase, which deteriorates the crystal structure. Therefore with increasing hydrogen concentration the stiffness and the density are significantly reduced. The values of the modulus of elasticity and the density at different hydrogen concentrations in palladium are utilized in the finite element model to determine the corresponding SAW sensor response. Results indicate that with increasing the hydrogen concentration the wave velocity decreases and the attenuation of the wave is reduced.

Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto

2017-02-01

Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.
Surface morphology and grain analysis of successively industrially grown amorphous hydrogenated carbon films (a-C:H) on silicon

NASA Astrophysics Data System (ADS)

Catena, Alberto; McJunkin, Thomas; Agnello, Simonpietro; Gelardi, Franco M.; Wehner, Stefan; Fischer, Christian B.

2015-08-01

Silicon (1 0 0) has been gradually covered by amorphous hydrogenated carbon (a-C:H) films via an industrial process. Two types of these diamond-like carbon (DLC) coatings, one more flexible (f-DLC) and one more robust (r-DLC), have been investigated. Both types have been grown by a radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. Surface morphologies have been studied in detail by atomic force microscopy (AFM) and Raman spectroscopy has been used to investigate the DLC structure. Both types appeared to have very similar morphology and sp2 carbon arrangement. The average height and area for single grains have been analyzed for all depositions. A random distribution of grain heights was found for both types. The individual grain structures between the f- and r-type revealed differences: the shape for the f-DLC grains is steeper than for the r-DLC grains. By correlating the average grain heights to the average grain areas for all depositions a limited region is identified, suggesting a certain regularity during the DLC deposition mechanisms that confines both values. A growth of the sp2 carbon entities for high r-DLC depositions is revealed and connected to a structural rearrangement of carbon atom hybridizations and hydrogen content in the DLC structure.
Ionic liquid-assisted synthesis of Br-modified g-C3N4 semiconductors with high surface area and highly porous structure for photoredox water splitting

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Wang, Yanyun; Zhou, Yuming; Qiu, Kaibo; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-12-01

Coping with the gradually increasing worldwide energy and environmental issues, it is urgent to develop efficient, cheap and visible-light-driven photocatalysts for hydrogen production. Here, we present a facile way to synthesize bromine doped graphitic carbon nitride (CN-BrX) with highly porous structure by using ionic liquid (1-butyl-3-vinylimidazolium bromide) as the Br source and soft-template for the first time, which applied in hydrogen evolution under visible light irradiation. A systematic study is conducted on the optimization in the doping amount. The results find that the as-fabricated CN-BrX photocatalysts possess a uniform porous network with thin walls due to the release of volatile domains and decomposition of ionic liquids. The highly porous structure with the large surface area (≤150 m2/g) benefits the exposure of active sites. Moreover, the bromine modification and porous structure can narrow the band gap, enhance the transportation capability of photogenerated electrons, improve the optical and conductive properties of CN, thus contribute to an outstanding H2 evolution rate under visible light irradiation (120 μmol h-1), which is about 3.6 times higher than pure CN. This work provides a new insight for designing the novel g-C3N4 based photocatalysts for hydrogen production, CO2 conversion and environmental remediation.
Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals

NASA Astrophysics Data System (ADS)

Kuo, Yenting; Klabunde, Kenneth J.

2012-07-01

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO3 structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh3 + ; however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area. An increase in the rhodium doping level also led to an increase in absorption at 370 nm however, the higher amounts of dopant lowered the photocatalytic activity. The modified aerogel synthesis allows greatly enhanced H2 production performance from an aqueous methanol solution under visible light irradiation compared with lower surface area conventional materials. We believe that this enhanced activity is due to the higher surface areas while high quality nanocrystalline materials are still obtained. Furthermore, the surface properties of these nanocrystalline aerogel materials are different, as exhibited by the higher activities in alkaline solutions, while conventional materials (obtained via high temperature solid-state synthesis methods) only exhibit reasonable hydrogen production in acidic solutions. Moreover, an aerogel synthesis approach gives the possibility of thin-film formation and ease of incorporation into practical solar devices.
Secondary Electron Emission Spectroscopy of Diamond Surfaces

NASA Technical Reports Server (NTRS)

Krainsky, Isay L.; Asnin, Vladimir M.; Petukhov, Andre G.

1999-01-01

This report presents the results of the secondary electron emission spectroscopy study of hydrogenated diamond surfaces for single crystals and chemical vapor-deposited polycrystalline films. One-electron calculations of Auger spectra of diamond surfaces having various hydrogen coverages are presented, the major features of the experimental spectra are explained, and a theoretical model for Auger spectra of hydrogenated diamond surfaces is proposed. An energy shift and a change in the line shape of the carbon core-valence-valence (KVV) Auger spectra were observed for diamond surfaces after exposure to an electron beam or by annealing at temperatures higher than 950 C. This change is related to the redistribution of the valence-band local density of states caused by hydrogen desorption from the surface. A strong negative electron affinity (NEA) effect, which appeared as a large, narrow peak in the low-energy portion of the spectrum of the secondary electron energy distribution, was also observed on the diamond surfaces. A fine structure in this peak, which was found for the first time, reflected the energy structure of the bottom of the conduction band. Further, the breakup of the bulk excitons at the surface during secondary electron emission was attributed to one of the features of this structure. The study demonstrated that the NEA type depends on the extent of hydrogen coverage of the diamond surface, changing from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surface.
Determination of hydrogen abundance in selected lunar soils

NASA Technical Reports Server (NTRS)

Bustin, Roberta

1987-01-01

Hydrogen was implanted in lunar soil through solar wind activity. In order to determine the feasibility of utilizing this solar wind hydrogen, it is necessary to know not only hydrogen abundances in bulk soils from a variety of locations but also the distribution of hydrogen within a given soil. Hydrogen distribution in bulk soils, grain size separates, mineral types, and core samples was investigated. Hydrogen was found in all samples studied. The amount varied considerably, depending on soil maturity, mineral types present, grain size distribution, and depth. Hydrogen implantation is definitely a surface phenomenon. However, as constructional particles are formed, previously exposed surfaces become embedded within particles, causing an enrichment of hydrogen in these species. In view of possibly extracting the hydrogen for use on the lunar surface, it is encouraging to know that hydrogen is present to a considerable depth and not only in the upper few millimeters. Based on these preliminary studies, extraction of solar wind hydrogen from lunar soil appears feasible, particulary if some kind of grain size separation is possible.
The control of Pt and Ru nanoparticle size on high surface area supports.

PubMed

Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

2014-12-28

Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.
Repeatable hydrogen generation of 3D microporous nickel membrane using chemical milling

NASA Astrophysics Data System (ADS)

Seo, Keumyoung; Lim, Taekyung; Ju, Sanghyun

2018-05-01

In this study, we investigated a novel method of hydrogen generation through a chemical milling process. In the process of generating hydrogen with a thermochemical water-splitting method using a 3D microporous nickel membrane, the nickel surface is oxidized, leading to a decreased generation of hydrogen gas with time. To regenerate hydrogen from the oxidized catalysts, the oxidized metal surface was easily removed at room temperature, re-exposing a metal surface with abundant oxygen vacancies for continuous hydrogen generation. With this method, ~110 µmol · g‑1 of hydrogen gas was continuously produced per cycle. Since this method enabled us to create a fit state for hydrogen generation without extra heat, light, or electrical energy, it can solve the biggest commercialization challenge: inefficiency because the energy required for hydrogen generation is higher than the energy of the generated hydrogen.
Palladium Supported on Titanium Carbide: A Highly Efficient, Durable, and Recyclable Bifunctional Catalyst for the Transformation of 4-Chlorophenol and 4-Nitrophenol

PubMed Central

Fan, Guangyin; Li, Xiaojing; Xu, Caili; Jiang, Weidong; Zhang, Yun; Gao, Daojiang; Bi, Jian; Wang, Yi

2018-01-01

Developing highly efficient and recyclable catalysts for the transformation of toxic organic contaminates still remains a challenge. Herein, Titanium Carbide (Ti3C2) MXene modified by alkali treatment process was selected as a support (designated as alk-Ti3C2X2, where X represents the surface terminations) for the synthesis of Pd/alk-Ti3C2X2. Results show that the alkali treatment leads to the increase of surface area and surface oxygen-containing groups of Ti3C2X2, thereby facilitating the dispersion and stabilization of Pd species on the surface of alk-Ti3C2X2. The Pd/alk-Ti3C2X2 catalyst shows excellent catalytic activity for the hydrodechlorination of 4-chlorophenol and the hydrogenation of 4-nitrophenol in aqueous solution at 25 °C and hydrogen balloon pressure. High initial reaction rates of 216.6 and 126.3 min−1·gpd−1 are observed for the hydrodechlorination of 4-chlorophenol and hydrogenation of 4-nitrophenol, respectively. Most importantly, Pd/alk-Ti3C2X2 exhibits excellent stability and recyclability in both reactions without any promoters. The superior property of Pd/alk-Ti3C2X2 makes it as a potential material for practical applications. PMID:29498652
Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

PubMed

DeGregorio, Nicole; Iyengar, Srinivasan S

2018-01-09

We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen-bonded systems is demonstrated here.
Characterization of narrow micropores in almond shell biochars by nitrogen, carbon dioxide, and hydrogen adsorption

USDA-ARS?s Scientific Manuscript database

Characterization of biochars usually includes surface area and pore volume determination by nitrogen adsorption. In this study, we show that there is a substantial pore volume in biochars created via slow pyrolysis from low- and high-ash almond shells that cannot be characterized in this fashion due...
Decontamination Efficacy of Three Commercial Off-the-Shelf Sporicidal Agents on Medium-Sized Panels Contaminated with Surrogates of Bacillus anthracis

DTIC Science & Technology

2012-04-01

chlorine dioxide (CD) or vapor hydrogen peroxide ( VHP ). A wide-area release and contamination of building exteriors and the outdoors would likely...from the panels. Depending on the surface composition and the decontamination technology tested, viable spore recovery from the panels varied after
New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer-A Density Functional Theory Approach.

PubMed

Landeros-Martinez, Linda-Lucila; Glossman-Mitnik, Daniel; Orrantia-Borunda, Erasmo; Flores-Holguín, Norma

2017-10-19

The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR) spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski's rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6-31G (d); for the esterified nanodiamond-Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.
Adsorption and chemical reaction of gaseous mixtures of hydrogen chloride and water on aluminum oxide and application to solid-propellant rocket exhaust clouds

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Pellett, G. L.

1978-01-01

Hydrogen chloride (HCl) and aluminum oxide (Al2O3) are major exhaust products of solid rocket motors (SRM). Samples of calcination-produced alumina were exposed to continuously flowing mixtures of gaseous HCl/H2O in nitrogen. Transient sorption rates, as well as maximum sorptive capacities, were found to be largely controlled by specific surface area for samples of alpha, theta, and gamma alumina. Sorption rates for small samples were characterized linearly with an empirical relationship that accounted for specific area and logarithmic time. Chemisorption occurred on all aluminas studied and appeared to form from the sorption of about a 2/5 HCl-to-H2O mole ratio. The chemisorbed phase was predominantly water soluble, yielding chloride/aluminum III ion mole ratios of about 3.3/1 suggestive of dissolved surface chlorides and/or oxychlorides. Isopiestic experiments in hydrochloric acid indicated that dissolution of alumina led to an increase in water-vapor pressure. Dissolution in aqueous SRM acid aerosol droplets, therefore, might be expected to promote evaporation.
Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, Gary L.

1988-08-16

A method for preparing highly hydrogen-reactive surfaces on metals which normally require substantial heating, high pressures, or an extended induction period, which involves pretreatment of said surfaces with either a non-oxidizing acid or hydrogen gas to form a hydrogen-bearing coating on said surfaces, and subsequently heating said coated metal in the absence of moisture and oxygen for a period sufficient to decompose said coating and cooling said metal to room temperature. Surfaces so treated will react almost instantaneously with hydrogen gas at room temperature and low pressure. The method is particularly applicable to uranium, thorium, and lanthanide metals.
Sustainable resource recovery and energy conversion processes using microbial electrochemical technologies

NASA Astrophysics Data System (ADS)

Yates, Matthew D.

Microbial Electrochemical Technologies (METs) are emerging technological platforms for the conversion of waste into usable products. METs utilize naturally occurring bacteria, called exoelectrogens, capable of transferring electrons to insoluble terminal electron acceptors. Electron transfer processes in the exoelectrogen Geobacter sulfurreducens were exploited here to develop sustainable processes for synthesis of industrially and socially relevant end products. The first process examined was the removal of soluble metals from solution to form catalytic nanoparticles and nanoporous structures. The second process examined was the biocatalytic conversion of electrons into hydrogen gas using electrons supplied directly to an electrode. Nanoparticle formation is desirable because materials on the nanoscale possess different physical, optical, electronic, and mechanical properties compared to bulk materials. In the first process, soluble palladium was used to form catalytic palladium nanoparticles using extracellular electron transfer (EET) processes of G. sulfurreducens, typically the dominant member of mixedculture METs. Geobacter cells reduced the palladium extracellularly using naturally produced pili, which provided extracellular adsorption and reduction sites to help delay the diffusion of soluble metals into the cell. The extracellular reduction prevented cell inactivation due to formation of intracellular particles, and therefore the cells could be reused in multiple palladium reduction cycles. A G. sulfurreducens biofilm was next investigated as a biotemplate for the formation of a nanoporous catalytic palladium structure. G. sulfurreducens biofilms have a dense network of pili and extracellular cytochromes capable of high rates of electron transfer directly to an electrode surface. These pili and cytochromes provide a dense number of reduction sites for nanoparticle formation without the need for any synthetic components. The cells within the biofilm also can act as natural agents for preventing agglomeration of nanoparticles, and subsequent decrease of active surface area, on the electrode surface. The cell template was carbonized and removed via thermal treatments, leaving a catalytically active mesoporous palladium structure. The biotemplated mesoporous structure had a high surface area composed of nanoparticles, and a high pore volume and surface area. The biotemplated porous structure also exhibited an increased catalytic activity compared to an electroplated palladium electrode and an electrode coated with synthetically produced palladium nanoparticles attached to the surface with a Nafion binder. The biotemplated mesoporous structure was found to be an alternative process to form a porous structure directly on an electrode using only materials and processes that naturally occur in G. sulfurreducens biofilms. Biotemplated catalytic structures are an alternative method to form a porous structure with high catalytic activity without using any synthetic compounds. However, their uses in large scale processes require that the catalyst layer be durable. The electrochemical and mechanical stability of biotemplated mesoporous structures was tested on different support materials (polished graphite, carbon paper, carbon cloth, and stainless steel) subjected to electrochemical and/or mechanical stress. Carbon paper was found to withstand the most electrochemical and mechanical stress of the four different support materials tested. Polished graphite was able to withstand electrochemical stress, but deteriorated under a combination of electrochemical and mechanical stress. Different readily available and inexpensive polymers (polyaniline and polydimethylsiloxane) were also tested against a widely used polymer (NafionRTM) to stabilize the palladium catalyst on the polished graphite surface. The polyaniline was the most effective binder because it enhanced the catalytic activity and could be electropolymerized around the catalyst, giving the greatest amount of control over the thickness of the polymer layer. The second process studied used exoelectrogenic bacteria in METs for the conversion of electrons to hydrogen via water electrolysis in a biocathodic system. Naturally occurring biocatalytic cell material on the cathode surface was used to lower the cathode overpotential. Different cell cultures ( G. sulfurreducens, Methanosarcina barkeri, and Escherichia coli) were tested for their effect on hydrogen formation using electrons supplied to an insoluble electrode. The mode of hydrogen production was investigated by monitoring hydrogen production over three to five months using G. sulfurreducens biofilms (pregrown under anodic conditions with acetate) that were: (1) not supplied with an organic carbon source for cell growth and maintenance, (2) killed with ethanol, or (3) supplied with lactate, an organic carbon source and electron donor for G. sulfurreducens. Hydrogen was produced at a rate 10--20 times higher over five months in reactors that were either not given organic carbon or killed with ethanol, compared to reactors with lactate added. The methanogen, M. barkeri, was also tested as a biocatalyst because it is able to grow autotrophically. However, M. barkeri cells did not grow in the reactor with the electrode potential poised, based on the lack of evidence for methane production. Despite the lack of cell activity, the rate of hydrogen production with M. barkeri was similar to the rate observed in killed G. sulfurreducens reactors. The addition of E. coli, a non-exoelectrogenic bacteria, resulted in an initial elevated hydrogen gas production, but hydrogen production rates similar to background levels after three months. No cells were detected on the electrode surfaces after five months using scanning electron microscopy and unique metals, such as iron, nickel, cobalt, and zinc, were detected on the electrode surfaces exposed to cells. The identifiable peptides extracted from the electrodes were found to be derived primarily from metalloproteins produced by G. sulfurreducens and M. barkeri cells. These findings show that hydrogen can be produced in a biocathodic system by abiotic cell material attached to a graphite electrode surface and that it does not require electron uptake by living cells.
Hydrogen sorption characteristics of nanostructured Pd–10Rh processed by cryomilling

DOE PAGES

Yang, Nancy; Yee, Joshua K.; Zhang, Zhihui; ...

2014-10-03

Palladium and its alloys are model systems for studying solid-state storage of hydrogen. Mechanical milling is commonly used to process complex powder systems for solid-state hydrogen storage; however, milling can also be used to evolve nanostructured powder to modify hydrogen sorption characteristics. In the present study, cryomilling (mechanical attrition milling in a cryogenic liquid) is used to produce nanostructured palladium-rhodium alloy powder. Characterization of the cryomilled Pd-10Rh using electron microscopy, X-ray diffraction, and surface area analysis reveals that (i) particle morphology evolves from spherical to flattened disk-like particles; while the (ii) crystallite size decreases from several microns to less thanmore » 100 nm and (iii) dislocation density increases with increased cryomilling time. Hydrogen absorption and desorption isotherms as well as the time scales for absorption were measured for cryomilled Pd-10Rh, and correlated with observed microstructural changes induced by the cryomilling process. In short, as the microstructure of the Pd-10Rh alloy is refined by cryomilling: (i) the maximum hydrogen concentration in the α-phase increases, (ii) the pressure plateau becomes flatter, and (iii) the equilibrium hydrogen capacity at 760 Torr increases. In addition, the rate of hydrogen absorption was reduced by an order of magnitude compared to non-cryomilled (atomized) powder.« less
Silicon based multilayer photoelectrodes for photoelectrolysis of water to produce hydrogen from the sun

NASA Astrophysics Data System (ADS)

Faruque, Faisal

The main objective of this work is to study different materials for the direct photosynthesis of hydrogen from water. A variety of photocatalysts such as titanium dioxide, titanium oxy-nitride, silicon carbide, and gallium nitride are being investigated by others for the clean production of hydrogen for fuel cells and hydrogen economy. Our approach was to deposit suitable metallic regions on photocatalyst nanoparticles to direct the efficient synthesis of hydrogen to a particular site for convenient collection. We studied different electrode metals such as gold, platinum, titanium, palladium, and tungsten. We also studied different solar cell materials such as silicon (p- and n-types), silicon carbide and titanium dioxide semiconductors in order to efficiently generate electrons under illumination. We introduced a novel silicon-based multilayer photosynthesis device to take advantage of suitable properties of silicon and tungsten to efficiently produce hydrogen. The device consisted of a silicon (0.5mm) substrate, a deposited atomic layer of Al2O 3 (1nm), a doped polysilicon (0.1microm), and finally a tungsten nanoporous (5-10nm) layer acting as an interface electrode with water. The Al2O 3 layer was introduced to reduce leakage current and to prevent the spreading of the diffused p-n junction layer between the silicon and doped polysilicon layers. The surface of the photoelectrode was coated with nanotextured tungsten nanopores (TNP), which increased the surface area of the electrodes to the electrolyte, assisting in electron-hole mobility, and acting as a photocatalyst. The reported device exhibited a fill factor (%FF) of 27.22% and solar-to-hydrogen conversion efficiency of 0.03174%. This thesis describes the structures of the device, and offers a characterization and comparison between different photoelectrodes.
Hydrogen peroxide on the surface of Europa

USGS Publications Warehouse

Carlson, R.W.; Anderson, M.S.; Johnson, R.E.; Smythe, W.D.; Hendrix, A.R.; Barth, C.A.; Soderblom, L.A.; Hansen, G.B.; McCord, T.B.; Dalton, J.B.; Clark, R.N.; Shirley, J.H.; Ocampo, A.C.; Matson, D.L.

1999-01-01

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.
Hydrogen peroxide on the surface of Europa.

PubMed

Carlson, R W; Anderson, M S; Johnson, R E; Smythe, W D; Hendrix, A R; Barth, C A; Soderblom, L A; Hansen, G B; McCord, T B; Dalton, J B; Clark, R N; Shirley, J H; Ocampo, A C; Matson, D L

1999-03-26

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

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

Johnson, Justin C; Braunecker, Wade A; Hurst, Katherine E

A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer-Emmet-Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ~37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (~1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features inmore » FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.« less
Hydrogenation of artemisinin to dihydroartemisinin over heterogeneous metal catalysts

NASA Astrophysics Data System (ADS)

Kristiani, Anis; Pertiwi, Ralentri; Adilina, Indri Badria

2017-01-01

A series of heterogeneous metal catalysts of Ni, Pd, and Pt, both of synthesized and commercial catalysts were used for hydrogenation of artemisinin to dihydroartemisinin. Their catalytic properties were determsined by Surface Area Analyzer and Thermogravimetry Analyzer. The catalytic properties in various reaction conditions in terms of temperature, pressure, reaction time and reactant/catalyst ratio were also studied. The results catalytic activity tests showed that synthesized catalysts of Ni/zeolite, Ni-Sn/zeolite, Ni/bentonite and Ni-Sn/bentonite were not able to produced dihydroartemisinin and deoxyartemisinin was mainly formed. Meanwhile, commercial catalysts of Ni skeletal, Pd/activated charcoal and Pt/activated charcoal yielded the desired dihydroartemisinin product. Ni skeletal commercial catalyst gave the best performance of hydrogenation artemisinin to dihydroartemisinin in room temperature and low H2 pressure.
Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

The highest performance fuel cell cathode electrocatalyst combination ever observed gives 755 mV vs hydrogen at 100 ASF on air at 180 C and shows a potential improvement to 775 mV vs hydrogen for better electrode structures. A pressurized fuel cell (UTC at 5 atm) would then give 805 mV at 320 ASF and 180 C. Another activity diagnostic is the performance of this electrocatalyst on oxygen at 900 mV vs hydrogen. The value for electrocatalyst is 44 mA per milligram of platinum and is projected to reach 60 mA per milligram of platinum with improved electrode structures. Since the electrocatalyst surface area and the electrode structure are not yet optimized there is considerable room for performance enhancement beyond these values, especially at higher temperatures.
Design of a Helium Vapor Shroud for Liquid Hydrogen Fueling of an Unmanned Aerial Vehicle (UAV)

NASA Astrophysics Data System (ADS)

Cavender, K.; Evans, C.; Haney, J.; Leachman, J.

2017-12-01

Filling a vehicular liquid hydrogen fuel tank presents the potential for flammable mixtures due to oxygen concentration from liquid air condensation. Current liquid hydrogen tank designs utilize insulating paradigms such as aerogel/fiberglass materials, vacuum jackets, or inert gas purge systems to keep the outer surface from reaching the condensation temperature of air. This work examines the heat transfer at the refuelling connection of the tank to identify potential areas of condensation, as well as the surface temperature gradient. A shrouded inert gas purge was designed to minimize vehicle weight and refuelling time. The design of a shrouded inert gas purge system is presented to displace air preventing air condensation. The design investigates 3D printed materials for an inert gas shroud, as well as low-temperature sealing designs. Shroud designs and temperature profiles were measured and tested by running liquid nitrogen through the filling manifold. Materials for the inert gas shroud are discussed and experimental results are compared to analytical model predictions. Suggestions for future design improvements are made.
Effect of alkaline earth metals on the liquid-phase hydrogenation of hydroquinone over Ru-based catalysts

NASA Astrophysics Data System (ADS)

Li, Hongwei; Ji, Dong; Li, Yu; Liang, Yalan; Li, Gui Xian

2015-12-01

A series of Ru-based catalysts modified by alkaline earth metals were prepared by the impregnation-precipitation method and characterized using transmission electron microscopy, X-ray diffraction, ICP optical emission spectroscopy, Infrared Spectroscopy of adsorbed pyridine analysis and surface area analysis. The performance of the catalysts was measured via liquid-phase hydroquinone hydrogenation reaction. Results show that the Ru-Sr/NaY catalyst has the best activity and selectivity among those Ru-based catalysts. The conversion of hydroquinone and the selectivity to 1,4-cyclohexanediol reached up to 99.6% and 89.6% at optimum reaction condition (700 r/min, 423 K and 5 MPa pressure of H2 in 3 h). This may be attributed to the fact that the right amount of Strontium is beneficial to the good dispersion of the ruthenium nanoclusters on the surface of NaY and modify the acidic properties of the catalyst. Moreover, IR of adsorbed pyridine analysis suggested the proper ratio of L/B acid of the catalysts played an important role in the performance of the hydroquinone hydrogenation reaction.
Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

DOE PAGES

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...

2016-08-30

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less
Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

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

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less
Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.
Effect of high surface area activated carbon on thermal degradation of jet fuel

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

Gergova, K.; Eser, S.; Arumugam, R.

1995-05-01

Different solid carbons added to jet fuel during thermal stressing cause substantial changes in pyrolytic degradation reactions. Activated carbons, especially high surface area activated carbons were found to be very effective in suppressing solid deposition on metal reactor walls during stressing at high temperatures (425 and 450{degrees}C). The high surface area activated carbon PX-21 prevented solid deposition on reactor walls even after 5h at 450{degrees}C. The differences seen in the liquid product composition when activated carbon is added indicated that the carbon surfaces affect the degradation reactions. Thermal stressing experiments were carried out on commercial petroleum-derived JPTS jet fuel. Wemore » also used n-octane and n-dodecane as model compounds in order to simplify the study of the chemical changes which take place upon activated carbon addition. In separate experiments, the presence of a hydrogen donor, decalin, together with PX-21 was also studied.« less
Evaluation on the Nanoscale Zero Valent Iron Based Microbial Denitrification for Nitrate Removal from Groundwater

NASA Astrophysics Data System (ADS)

Peng, Lai; Liu, Yiwen; Gao, Shu-Hong; Chen, Xueming; Xin, Pei; Dai, Xiaohu; Ni, Bing-Jie

2015-07-01

Nanoscale zero valent iron (NZVI) based microbial denitrification has been demonstrated to be a promising technology for nitrate removal from groundwater. In this work, a mathematical model is developed to evaluate the performance of this new technology and to provide insights into the chemical and microbial interactions in the system in terms of nitrate reduction, ammonium accumulation and hydrogen turnover. The developed model integrates NZVI-based abiotic reduction of nitrate, NZVI corrosion for hydrogen production and hydrogen-based microbial denitrification and satisfactorily describes all of the nitrate and ammonium dynamics from two systems with highly different conditions. The high NZVI corrosion rate revealed by the model indicates the high reaction rate of NZVI with water due to their large specific surface area and high surface reactivity, leading to an effective microbial nitrate reduction by utilizing the produced hydrogen. The simulation results further suggest a NZVI dosing strategy (3-6 mmol/L in temperature range of 30-40 °C, 6-10 mmol/L in temperature range of 15-30 °C and 10-14 mmol/L in temperature range of 5-15 °C) during groundwater remediation to make sure a low ammonium yield and a high nitrogen removal efficiency.
Evaluation on the Nanoscale Zero Valent Iron Based Microbial Denitrification for Nitrate Removal from Groundwater

PubMed Central

Peng, Lai; Liu, Yiwen; Gao, Shu-Hong; Chen, Xueming; Xin, Pei; Dai, Xiaohu; Ni, Bing-Jie

2015-01-01

Nanoscale zero valent iron (NZVI) based microbial denitrification has been demonstrated to be a promising technology for nitrate removal from groundwater. In this work, a mathematical model is developed to evaluate the performance of this new technology and to provide insights into the chemical and microbial interactions in the system in terms of nitrate reduction, ammonium accumulation and hydrogen turnover. The developed model integrates NZVI-based abiotic reduction of nitrate, NZVI corrosion for hydrogen production and hydrogen-based microbial denitrification and satisfactorily describes all of the nitrate and ammonium dynamics from two systems with highly different conditions. The high NZVI corrosion rate revealed by the model indicates the high reaction rate of NZVI with water due to their large specific surface area and high surface reactivity, leading to an effective microbial nitrate reduction by utilizing the produced hydrogen. The simulation results further suggest a NZVI dosing strategy (3–6 mmol/L in temperature range of 30–40 °C, 6–10 mmol/L in temperature range of 15–30 °C and 10–14 mmol/L in temperature range of 5–15 °C) during groundwater remediation to make sure a low ammonium yield and a high nitrogen removal efficiency. PMID:26199053
Ultrathin MoS2-coated Ag@Si nanosphere arrays as an efficient and stable photocathode for solar-driven hydrogen production

NASA Astrophysics Data System (ADS)

Zhou, Qingwei; Su, Shaoqiang; Hu, Die; Lin, Lin; Yan, Zhibo; Gao, Xingsen; Zhang, Zhang; Liu, Jun-Ming

2018-03-01

Solar-driven photoelectrochemical (PEC) water splitting has attracted a great deal of attention recently. Silicon (Si) is an ideal light absorber for solar energy conversion. However, the poor stability and inefficient surface catalysis of Si photocathodes for the hydrogen evolution reaction (HER) have remained key challenges. Alternatively, MoS2 has been reported to exhibit excellent catalysis performance if sufficient active sites for the HER are available. Here, ultrathin MoS2 nanoflakes are directly synthesized to coat arrays of Ag-core Si-shell nanospheres (Ag@Si NSs) by using chemical vapor deposition. Due to the high surface area ratio and large curvature of these NSs, the as-grown MoS2 nanoflakes can accommodate more active sites. In addition, the high-quality coating of MoS2 nanoflakes on the Ag@Si NSs protects the photocathode from damage during the PEC reaction. An photocurrent density of 33.3 mA cm-2 at a voltage of -0.4 V is obtained versus the reversible hydrogen electrode. The as-prepared nanostructure as a hydrogen photocathode is evidenced to have high stability over 12 h PEC performance. This work opens up opportunities for composite photocathodes with high activity and stability using cheap and stable co-catalysts.
Ultrathin MoS2-coated Ag@Si nanosphere arrays as an efficient and stable photocathode for solar-driven hydrogen production.

PubMed

Zhou, Qingwei; Su, Shaoqiang; Hu, Die; Lin, Lin; Yan, Zhibo; Gao, Xingsen; Zhang, Zhang; Liu, Jun-Ming

2018-01-30

Solar-driven photoelectrochemical (PEC) water splitting has attracted a great deal of attention recently. Silicon (Si) is an ideal light absorber for solar energy conversion. However, the poor stability and inefficient surface catalysis of Si photocathodes for the hydrogen evolution reaction (HER) have remained key challenges. Alternatively, MoS 2 has been reported to exhibit excellent catalysis performance if sufficient active sites for the HER are available. Here, ultrathin MoS 2 nanoflakes are directly synthesized to coat arrays of Ag-core Si-shell nanospheres (Ag@Si NSs) by using chemical vapor deposition. Due to the high surface area ratio and large curvature of these NSs, the as-grown MoS 2 nanoflakes can accommodate more active sites. In addition, the high-quality coating of MoS 2 nanoflakes on the Ag@Si NSs protects the photocathode from damage during the PEC reaction. An photocurrent density of 33.3 mA cm -2 at a voltage of -0.4 V is obtained versus the reversible hydrogen electrode. The as-prepared nanostructure as a hydrogen photocathode is evidenced to have high stability over 12 h PEC performance. This work opens up opportunities for composite photocathodes with high activity and stability using cheap and stable co-catalysts.
A facile and green approach for the controlled synthesis of porous SnO₂ nanospheres: application as an efficient photocatalyst and an excellent gas sensing material.

PubMed

Manjula, P; Boppella, Ramireddy; Manorama, Sunkara V

2012-11-01

A facile and elegant methodology invoking the principles of Green Chemistry for the synthesis of porous tin dioxide nanospheres has been described. The low-temperature (∼50 °C) synthesis of SnO₂ nanoparticles and their self-assembly into organized, uniform, and monodispersed porous nanospheres with high surface area is facilitated by controlling the concentration of glucose, which acts as a stabilizing as well as structure-directing agent. A systematic control on the stannate to glucose molar concentration ratio determines the exact conditions to obtain monodispersed nanospheres, preferentially over random aggregation. Detailed characterization of the structure, morphology, and chemical composition reveals that the synthesized material, 50 nm SnO₂ porous nanospheres possess BET surface area of about 160 m²/g. Each porous nanosphere consists of a few hundred nanoparticles ∼2-3 nm in diameter with tetragonal cassiterite crystal structure. The SnO₂ nanospheres exhibit elevated photocatalytic activity toward methyl orange with good recyclability. Because of the high activity and stability of this photocatalyst, the material is ideal for applications in environmental remediation. Moreover, SnO₂ nanospheres display excellent gas sensing capabilities toward hydrogen. Surface modification of the nanospheres with Pd transforms this sensing material into a highly sensitive and selective room-temperature hydrogen sensor.
Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: An efficient electrocatalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei

2018-02-01

The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.
Porosity control in nanoporous carbide-derived carbon by oxidation in air and carbon dioxide

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

Osswald, S.; Portet, C.; Gogotsi, Y., E-mail: gogotsi@drexel.ed

2009-07-15

Carbide-derived carbons (CDC) allow a precise control over the pore size through the selection of the carbide precursor and varying of the synthesis conditions. However, their pore volume is limited by the carbide stoichiometry. While activation of carbons derived from various organic precursors has been widely studied, this process may similarly be able to increase the pore volume and specific surface area of CDC. Oxidation of carbide-derived carbon in air and CO{sub 2} at different temperatures and times allows for significant increase in pore volume and specific surface area as well as control over average pore size with subnanometer accuracy.more » The effect of activation and associated changes in the pore volume and surface area on the hydrogen uptake are also discussed. - Graphical abstract: Carbide-derived carbons (CDC) provide great potential for sorption of toxicants and gas storage applications. Activation of CDC in air and CO{sub 2} at different temperatures and times is applied in order to maximize pore volume and specific surface area, and control the average pore size with subnanometer accuracy.« less
Periodic density functional theory study of ethylene hydrogenation over Co3O4 (1 1 1) surface: The critical role of oxygen vacancies

NASA Astrophysics Data System (ADS)

Lu, Jinhui; Song, JiaJia; Niu, Hongling; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2016-05-01

Recently, metal oxides are attracting increasing interests as hydrogenation catalyst. Herein we studied the hydrogenation of ethylene on perfect and oxygen defective Co3O4 (1 1 1) using periodic density functional theory. The energetics and pathways of ethylene hydrogenation to ethane were determined. We have demonstrated that (i) H2 dissociation on Co3O4 is a complicated two-step process through a heterolytic cleavage, followed by the migration of H atom and finally yields the homolytic product on both perfect and oxygen defective Co3O4 (1 1 1) surfaces easily. (ii) After introducing the surface oxygen vacancy, the stepwise hydrogenation of ethylene by atomic hydrogen is much easier than that on perfect surface due to the weaker bond strength of OH group. The strength of Osbnd H bond is a crucial factor for the hydrogenation reaction which involves the breakage of Osbnd H bond. The formation of oxygen vacancy increases the electronic charges at the adjacent surface O, which reduces its capability of further gaining electrons from adsorbed atomic hydrogen and then weakens the strength of Osbnd H bond. These results emphasize the importance of the oxygen vacancies for hydrogenation on metal oxides.
Chemistry of acetylene on platinum (111) and (100) surfaces

PubMed Central

Muetterties, E. L.; Tasi, M.-C.; Kelemen, S. R.

1981-01-01

An ultra-high vacuum experimental study of acetylene chemisorption on Pt(111) and Pt(100) and of the reaction of hydrogen with the acetylene adsorbate has established distinguishing features of carbon-hydrogen bond breaking and making processes as a function of pressure, temperature, and surface crystallography. The rates for both processes are substantially higher on the Pt(100) surface. Net acetylene-hydrogen processes, in the temperature range of 20°C to ≈130°C, are distinctly different on the two surfaces: on Pt(100) the net reaction is hydrogen exchange (1H-2H exchange) and on Pt(111) the only detectable reaction is hydrogenation. Stereochemical differences in the acetylene adsorbate structure are considered to be a contributing factor to the differences in acetylene chemistry on these two surfaces. Images PMID:16593110
An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

NASA Technical Reports Server (NTRS)

Shanabarger, Mickey R.

1993-01-01

The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.
Activation characteristics of multiphase Zr-based hydrogen storage alloys for Ni/MH rechargeable batteries

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

Lee, H.; Lee, S.M.; Lee, J.Y.

1999-10-01

AB{sub 2} type Zr-based Laves phase alloys have been studied for possible use as negative electrodes of Ni/MH batteries with high hydrogen storage capacity. However, these alloys have the serious problem of slow activation owing to the formation of surface oxide films. To overcome this problem, alloys with multiphase microstructures have been developed. These alloys become electrochemically active via the creation of micropores by the dissolution of soluble oxide components such as vanadium oxide. However, this phenomenon has been described based only on changes in the chemical composition of the oxide layer. In the present study, this phenomenon is approachedmore » with respect to interactions between the constituent phases. An electrochemical analysis of constituent phases showed that the second phase, resulting in localized Ni-rich pits on the alloy surface. The presence of microcracks at the periphery of the Ni-rich pits after 30 h exposure to KOH electrolyte implies that hydrogen is absorbed preferentially at Ni-rich pits, thereby forming a large active surface area. However, such multiphase alloys have poor cycle durability due to the persistent dissolution of components in the second phase. Through Cr substitution, the authors have developed a family of durable alloys to prevent this unwanted dissolution from the second phase.« less

Ab Initio Surface Phase Diagrams for Coadsorption of Aromatics and Hydrogen on the Pt(111) Surface

DOE PAGES

Ferguson, Glen Allen; Vorotnikov, Vassili; Wunder, Nicholas; ...

2016-11-02

Supported metal catalysts are commonly used for the hydrogenation and deoxygenation of biomass-derived aromatic compounds in catalytic fast pyrolysis. To date, the substrate-adsorbate interactions under reaction conditions crucial to these processes remain poorly understood, yet understanding this is critical to constructing detailed mechanistic models of the reactions important to catalytic fast pyrolysis. Density functional theory (DFT) has been used in identifying mechanistic details, but many of these works assume surface models that are not representative of realistic conditions, for example, under which the surface is covered with some concentration of hydrogen and aromatic compounds. In this study, we investigate hydrogen-guaiacolmore » coadsorption on Pt(111) using van der Waals-corrected DFT and ab initio thermodynamics over a range of temperatures and pressures relevant to bio-oil upgrading. We find that relative coverage of hydrogen and guaiacol is strongly dependent on the temperature and pressure of the system. Under conditions relevant to ex situ catalytic fast pyrolysis (CFP; 620-730 K, 1-10 bar), guaiacol and hydrogen chemisorb to the surface with a submonolayer hydrogen (~0.44 ML H), while under conditions relevant to hydrotreating (470-580 K, 10-200 bar), the surface exhibits a full-monolayer hydrogen coverage with guaiacol physisorbed to the surface. These results correlate with experimentally observed selectivities, which show ring saturation to methoxycyclohexanol at hydrotreating conditions and deoxygenation to phenol at CFP-relevant conditions. Additionally, the vibrational energy of the adsorbates on the surface significantly contributes to surface energy at higher coverage. Ignoring this contribution results in not only quantitatively, but also qualitatively incorrect interpretation of coadsorption, shifting the phase boundaries by more than 200 K and ~10-20 bar and predicting no guaiacol adsorption under CFP and hydrotreating conditions. We discuss the implications of this work in the context of modeling hydrogenation and deoxygenation reactions on Pt(111), and we find that only the models representative of equilibrium surface coverage can capture the hydrogenation kinetics correctly. Lastly, as a major outcome of this work, we introduce a freely available web-based tool, dubbed the Surface Phase Explorer (SPE), which allows researchers to conveniently determine surface composition for any one- or two-component system at thermodynamic equilibrium over a wide range of temperatures and pressures on any crystalline surface using standard DFT output.« less
Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

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

Kuila, Debasish; Ilias, Shamsuddin

2013-02-13

In steam reforming reactions (SRRs) of alkanes and alcohols to produce H 2, noble metals such as platinum (Pt) and palladium (Pd) are extensively used as catalyst. These metals are expensive; so, to reduce noble-metal loading, bi-metallic nanocatalysts containing non-noble metals in MCM-41 (Mobil Composition of Material No. 41, a mesoporous material) as a support material with high-surface area were synthesized using one-pot hydrothermal procedure with a surfactant such as cetyltrimethylammonium bromide (CTAB) as a template. Bi-metallic nanocatalysts of Pd-Ni and Pd-Co with varying metal loadings in MCM-41 were characterized by x-ray diffraction (XRD), N 2 adsorption, and Transmission electronmore » microscopy (TEM) techniques. The BET surface area of MCM-41 (~1000 m 2/g) containing metal nanoparticles decreases with the increase in metal loading. The FTIR studies confirm strong interaction between Si-O-M (M = Pd, Ni, Co) units and successful inclusion of metal into the mesoporous silica matrix. The catalyst activities were examined in steam reforming of methanol (SRM) reactions to produce hydrogen. Reference tests using catalysts containing individual metals (Pd, Ni and Co) were also performed to investigate the effect of the bimetallic system on the catalytic behavior in the SRM reactions. The bimetallic system remarkably improves the hydrogen selectivity, methanol conversion and stability of the catalyst. The results are consistent with a synergistic behavior for the Pd-Ni-bimetallic system. The performance, durability and thermal stability of the Pd-Ni/MCM-41 and Pd-Co/MCM-41 suggest that these materials may be promising catalysts for hydrogen production from biofuels. A part of this work for synthesis and characterization of Pd-Ni-MCM-41 and its activity for SRM reactions has been published (“Development of Mesoporous Silica Encapsulated Pd-Ni Nanocatalyst for Hydrogen Production” in “Production and Purification of Ultraclean Transportation Fuels”; Hu, Y., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2011.)« less
Titanium hydride and hydrogen concentration in acid-etched commercially pure titanium and titanium alloy implants: a comparative analysis of five implant systems.

PubMed

Szmukler-Moncler, S; Bischof, M; Nedir, R; Ermrich, M

2010-09-01

Acid etching is a popular method to texture the surface of dental implants. During etching, the titanium oxide protective layer is dissolved and small native hydrogen ions diffuse into the unprotected implant surface. They enrich the implant surface with hydrogen and precipitate into titanium hydride (TiH). The aim of this study was to measure the concentration of TiH at the implant surface and the total concentration of Hydrogen at five commercially available implant systems, made of either commercially pure (cp) titanium or titanium alloy. X-Ray diffraction (XRD) was conducted on each implant system to determine the compounds present at the implant surface. Following a TiH(2)/Ti calibration curve, the concentration of TiH was determined. Concentration of hydrogen in the implants was measured by the inert gas fusion thermal conductivity/infrared detection method. XRD data showed that TiH was present on all cp titanium implants but not on the alloyed implants. TiH concentration varied between 5% and 37%. Hydrogen concentration varied between 43 and 108 ppm, no difference in uptake was found between the cp titanium and alloyed implants. Low solubility of hydrogen in alpha-titanium is responsible for precipitation into TiH. Stronger etching conditions led to higher concentration of TiH2-x. High solubility of hydrogen in the beta-phase of the alloy is preventing hydrogen from precipitating into TiH. All implants, even those lacking TiH at the surface, were enriched with hydrogen. In all implants, hydrogen concentration was within the normative limit of 130 ppm.
Surface characterization of hydrogen charged and uncharged alpha-2 and gamma titanium aluminide alloys using AES and REELS

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1990-01-01

The surfaces of selected uncharged and hydrogen charged alpha-2 and gamma titanium aluminide alloys with Nb additions were characterized by Auger electron (AES) and reflected electron energy loss (REELS) spectroscopy. The alloy surfaces were cleaned before analysis at room temperature by ion sputtering. The low energy (500 eV) ion sputtering process preferentially sputtered the surface concentration. The surface concentrations were determined by comparing AES data from the alloys with corresponding data from elemental references. No differences were observed in the Ti or Nb Auger spectra for the uncharged and hydrogen charged alloys, even though the alpha-2 alloy had 33.4 atomic percent dissolved hydrogen. Also, no differences were observed in the AES spectra when hydrogen was adsorbed from the gas phase. Bulk plasmon energy shifts were observed in all alloys. The energy shifts were induced either by dissolved hydrogen (alpha-2 alloy) or hydrogen adsorbed from the gas phase (alpha-2 and gamma alloys). The adsorption induced plasmon energy shifts were greatest for the gamma alloy and cp-Ti metal.
Surface Treatment of Plastic Substrates using Atomic Hydrogen Generated on Heated Tungsten Wire at Low Temperatures

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2007-06-01

The surface properties of a plastic substrate were changed by a novel surface treatment called atomic hydrogen annealing (AHA). In this method, a plastic substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. For the substrate, surface roughness was increased and halogen elements (F and Cl) were selectively etched by AHA. AHA was useful for pretreatment before film deposition on a plastic substrate because the changes in surface state relate to adhesion improvement. It is concluded that this method is a promising technique for preparing high-performance plastic substrates at low temperatures.
Copper-Exchanged Zeolite L Traps Oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Seshan, Panchalam K.

1991-01-01

Brief series of simple chemical treatments found to enhance ability of zeolite to remove oxygen from mixture of gases. Thermally stable up to 700 degrees C and has high specific surface area which provides high capacity for adsorption of gases. To increase ability to adsorb oxygen selectively, copper added by ion exchange, and copper-exchanged zeolite reduced with hydrogen. As result, copper dispersed atomically on inner surfaces of zeolite, making it highly reactive to oxygen, even at room temperature. Reactivity to oxygen even greater at higher temperatures.
Surface chemistry of a hydrogenated mesoporous p-type silicon

NASA Astrophysics Data System (ADS)

Media, El-Mahdi; Outemzabet, Ratiba

2017-02-01

The finality of this work is devoted to the grafting of organic molecules on hydrogen passivated mesoporous silicon surfaces. The study would aid in the development for the formation of organic monolayers on silicon surface to be exploited for different applications such as the realisation of biosensors and medical devices. The basic material is silicon which has been first investigated by FTIR at atomistic plane during the anodic forward and backward polarization (i.e. "go" and "return"). For this study, we applied a numerical program based on least squares method to infrared absorbance spectra obtained by an in situ attenuated total reflection on p-type silicon in diluted HF electrolyte. Our numerical treatment is based on the fitting of the different bands of IR absorbance into Gaussians corresponding to the different modes of vibration of molecular groups such as siloxanes and hydrides. An adjustment of these absorbance bands is done systematically. The areas under the fitted bands permit one to follow the intensity of the different modes of vibration that exist during the anodic forward and backward polarization in order to compare the reversibility of the phenomenon of the anodic dissolution of silicon. It permits also to follow the evolution between the hydrogen silicon termination at forward and backward scanning applied potential. Finally a comparison between the states of the initial and final surface was carried out. We confirm the presence of clearly four and three distinct vibration modes of siloxanes/hydroxide, SiOx, and hydrides, SiHx, respectively. The results show clearly that the adsorbed species found in the final stage after an electrochemical treatment consist of surface hydrogen and they show also that the surface morphology is different compared to the starting one, which is considered as reference. It is clear that the H-terminated of porous silicon surface is hydrophobic in nature. The hydrophobic character of this surface makes difficult the grafting of a probe which serves to get other molecules; where from the necessity of the presence of a hydrophilic surface on the porous silicon surface. This will facilitate the penetration and the grafting of the molecules probes. So to improve the penetration and the grafting of the organic molecules or the immobilization of the probes on the hydrogenated mesoporous silicon surfaces under wet chemical conditions an intermediate step is required. In this second study, we use the following procedure. After the porosification of the silicon by electrochemical anodisation, the porous SiH layer returns a hydrophobic surface. This stage is a starting point of multistep scheme for the surface modification. The next step is the thermal hydrosilylation in order to have an acidic surface. The acidic surface was then modified by the chains of Poly(ethylene glycol) (PEG) which is a highly investigated polymer for the covalent modification of biological macromolecules and surfaces. The grafting of PEG returns a hydrophilic surface confirmed by the IR results.
Porous graphitic carbon nitride synthesized via direct polymerization of urea for efficient sunlight-driven photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Zhang, Yuewei; Liu, Jinghai; Wu, Guan; Chen, Wei

2012-08-01

Energy captured directly from sunlight provides an attractive approach towards fulfilling the need for green energy resources on the terawatt scale with minimal environmental impact. Collecting and storing solar energy into fuel through photocatalyzed water splitting to generate hydrogen in a cost-effective way is desirable. To achieve this goal, low cost and environmentally benign urea was used to synthesize the metal-free photocatalyst graphitic carbon nitride (g-C3N4). A porous structure is achieved via one-step polymerization of the single precursor. The porous structure with increased BET surface area and pore volume shows a much higher hydrogen production rate under simulated sunlight irradiation than thiourea-derived and dicyanamide-derived g-C3N4. The presence of an oxygen atom is presumed to play a key role in adjusting the textural properties. Further improvement of the photocatalytic function can be expected with after-treatment due to its rich chemistry in functionalization.Energy captured directly from sunlight provides an attractive approach towards fulfilling the need for green energy resources on the terawatt scale with minimal environmental impact. Collecting and storing solar energy into fuel through photocatalyzed water splitting to generate hydrogen in a cost-effective way is desirable. To achieve this goal, low cost and environmentally benign urea was used to synthesize the metal-free photocatalyst graphitic carbon nitride (g-C3N4). A porous structure is achieved via one-step polymerization of the single precursor. The porous structure with increased BET surface area and pore volume shows a much higher hydrogen production rate under simulated sunlight irradiation than thiourea-derived and dicyanamide-derived g-C3N4. The presence of an oxygen atom is presumed to play a key role in adjusting the textural properties. Further improvement of the photocatalytic function can be expected with after-treatment due to its rich chemistry in functionalization. Electronic supplementary information (ESI) available: Methods for preparing and characterizing UCN, TCN and DCN samples. Methods for examining the photocatalytic hydrogen production. FTIR, XPS, and digital photos of three products are shown in Fig. S1-6. See DOI: 10.1039/c2nr30948c
Advanced nanoporous TiO2 photocatalysts by hydrogen plasma for efficient solar-light photocatalytic application

NASA Astrophysics Data System (ADS)

An, Ha-Rim; Park, So Young; Kim, Hyeran; Lee, Che Yoon; Choi, Saehae; Lee, Soon Chang; Seo, Soonjoo; Park, Edmond Changkyun; Oh, You-Kwan; Song, Chan-Geun; Won, Jonghan; Kim, Youn Jung; Lee, Jouhahn; Lee, Hyun Uk; Lee, Young-Chul

2016-07-01

We report an effect involving hydrogen (H2)-plasma-treated nanoporous TiO2(H-TiO2) photocatalysts that improve photocatalytic performance under solar-light illumination. H-TiO2 photocatalysts were prepared by application of hydrogen plasma of assynthesized TiO2(a-TiO2) without annealing process. Compared with the a-TiO2, the H-TiO2 exhibited high anatase/brookite bicrystallinity and a porous structure. Our study demonstrated that H2 plasma is a simple strategy to fabricate H-TiO2 covering a large surface area that offers many active sites for the extension of the adsorption spectra from ultraviolet (UV) to visible range. Notably, the H-TiO2 showed strong ·OH free-radical generation on the TiO2 surface under both UV- and visible-light irradiation with a large responsive surface area, which enhanced photocatalytic efficiency. Under solar-light irradiation, the optimized H-TiO2 120(H2-plasma treatment time: 120 min) photocatalysts showed unprecedentedly excellent removal capability for phenol (Ph), reactive black 5(RB 5), rhodamine B (Rho B) and methylene blue (MB) — approximately four-times higher than those of the other photocatalysts (a-TiO2 and P25) — resulting in complete purification of the water. Such well-purified water (>90%) can utilize culturing of cervical cancer cells (HeLa), breast cancer cells (MCF-7), and keratinocyte cells (HaCaT) while showing minimal cytotoxicity. Significantly, H-TiO2 photocatalysts can be mass-produced and easily processed at room temperature. We believe this novel method can find important environmental and biomedical applications.
Advanced nanoporous TiO2 photocatalysts by hydrogen plasma for efficient solar-light photocatalytic application

PubMed Central

An, Ha-Rim; Park, So Young; Kim, Hyeran; Lee, Che Yoon; Choi, Saehae; Lee, Soon Chang; Seo, Soonjoo; Park, Edmond Changkyun; Oh, You-Kwan; Song, Chan-Geun; Won, Jonghan; Kim, Youn Jung; Lee, Jouhahn; Lee, Hyun Uk; Lee, Young-Chul

2016-01-01

We report an effect involving hydrogen (H2)-plasma-treated nanoporous TiO2(H-TiO2) photocatalysts that improve photocatalytic performance under solar-light illumination. H-TiO2 photocatalysts were prepared by application of hydrogen plasma of assynthesized TiO2(a-TiO2) without annealing process. Compared with the a-TiO2, the H-TiO2 exhibited high anatase/brookite bicrystallinity and a porous structure. Our study demonstrated that H2 plasma is a simple strategy to fabricate H-TiO2 covering a large surface area that offers many active sites for the extension of the adsorption spectra from ultraviolet (UV) to visible range. Notably, the H-TiO2 showed strong ·OH free-radical generation on the TiO2 surface under both UV- and visible-light irradiation with a large responsive surface area, which enhanced photocatalytic efficiency. Under solar-light irradiation, the optimized H-TiO2 120(H2-plasma treatment time: 120 min) photocatalysts showed unprecedentedly excellent removal capability for phenol (Ph), reactive black 5(RB 5), rhodamine B (Rho B) and methylene blue (MB) — approximately four-times higher than those of the other photocatalysts (a-TiO2 and P25) — resulting in complete purification of the water. Such well-purified water (>90%) can utilize culturing of cervical cancer cells (HeLa), breast cancer cells (MCF-7), and keratinocyte cells (HaCaT) while showing minimal cytotoxicity. Significantly, H-TiO2 photocatalysts can be mass-produced and easily processed at room temperature. We believe this novel method can find important environmental and biomedical applications. PMID:27406992
Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

NASA Astrophysics Data System (ADS)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.
CO2 hydrogenation on a metal hydride surface.

PubMed

Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012
Generation of hierarchical pore systems in the titanosilicate ETS-10 by hydrogen peroxide treatment under microwave irradiation.

PubMed

Pavel, Claudiu C; Schmidt, Wolfgang

2006-02-28

Supermicropores and well-defined mesopores with an average size of 10 nm were created in ETS-10 structure by post-synthesis treatment with H2O2 under microwave irradiation. Macropores were also formed and the external surface area of the material was increased during the treatment.
3D-Printable Silicone Materials with Hydrogen Getter Capability

DOE PAGES

Ortiz-Acosta, Denisse; Moore, Tanya; Safarik, Douglas Joseph; ...

2018-03-01

Organic getters are used to reduce the amount of reactive hydrogen in applications such as nuclear plants and transuranic waste. Here, the present study examines the performance of getter loaded silicone elastomers in reducing reactive hydrogen gas from the gas phase and their capability of being 3D printed using direct ink writing techniques. The samples are placed in closed vessels and exposed to hydrogen atmosphere at pressures of 580 torr and 750 mtorr and at a temperature of 25 °C. The hydrogen consumption is measured as a function of time and normalized to getter concentration in the polymer. The performancemore » of the getter-loaded silicone elastomer containing 1,4-bis[phenylethynyl]benzene (DEB) as the organic getter and Pd/C catalyst (ratio of 3:1 DEB to catalyst) decreases with increasing the resin's curing temperature. Chemical analysis suggests that DEB reacts with the silicone resin at high temperatures. In addition, it is demonstrated that the increased surface area of 3D printed composites results in improved getter performance.« less
3D-Printable Silicone Materials with Hydrogen Getter Capability

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

Ortiz-Acosta, Denisse; Moore, Tanya; Safarik, Douglas Joseph

Organic getters are used to reduce the amount of reactive hydrogen in applications such as nuclear plants and transuranic waste. Here, the present study examines the performance of getter loaded silicone elastomers in reducing reactive hydrogen gas from the gas phase and their capability of being 3D printed using direct ink writing techniques. The samples are placed in closed vessels and exposed to hydrogen atmosphere at pressures of 580 torr and 750 mtorr and at a temperature of 25 °C. The hydrogen consumption is measured as a function of time and normalized to getter concentration in the polymer. The performancemore » of the getter-loaded silicone elastomer containing 1,4-bis[phenylethynyl]benzene (DEB) as the organic getter and Pd/C catalyst (ratio of 3:1 DEB to catalyst) decreases with increasing the resin's curing temperature. Chemical analysis suggests that DEB reacts with the silicone resin at high temperatures. In addition, it is demonstrated that the increased surface area of 3D printed composites results in improved getter performance.« less
Immersed finger-type indium tin oxide ohmic contacts on p-GaN photoelectrodes for photoelectrochemical hydrogen generation.

PubMed

Liu, Shu-Yen; Sheu, J K; Lee, M L; Lin, Yu-Chuan; Tu, S J; Huang, F W; Lai, W C

2012-03-12

In this study, we demonstrated photoelectrochemical (PEC) hydrogen generation using p-GaN photoelectrodes associated with immersed finger-type indium tin oxide (IF-ITO) ohmic contacts. The IF-ITO/p-GaN photoelectrode scheme exhibits higher photocurrent and gas generation rate compared with p-GaN photoelectrodes without IF-ITO ohmic contacts. In addition, the critical external bias for detectable hydrogen generation can be effectively reduced by the use of IF-ITO ohmic contacts. This finding can be attributed to the greatly uniform distribution of the IF-ITO/p-GaN photoelectrode applied fields over the whole working area. As a result, the collection efficiency of photo-generated holes by electrode contacts is higher than that of p-GaN photoelectrodes without IF-ITO contacts. Microscopy revealed a tiny change on the p-GaN surfaces before and after hydrogen generation. In contrast, photoelectrodes composed of n-GaN have a short lifetime due to n-GaN corrosion during hydrogen generation. Findings of this study indicate that the ITO finger contacts on p-GaN layer is a potential candidate as photoelectrodes for PEC hydrogen generation.
Mixed ionic and electronic conducting membranes for hydrogen generation and separation

NASA Astrophysics Data System (ADS)

Cui, Hengdong

Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process conditions of interest. Over 10 mumol·cm-2·s-1 (micromoles per square cm per second) of area specific hydrogen flux has been achieved employing a membrane of this material with thickness of 0.2 mm. This flux is several orders of magnitude higher than the hydrogen generation rates reported using other MIEC materials under similar operating conditions.
Surface Modification of Poly(ethylene naphthalate) Substrate and Its Effect on SiNx Film Deposition by Atomic Hydrogen Annealing

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2007-07-01

The surface modification of a plastic substrate by atomic hydrogen annealing (AHA) was investigated for flexible displays. In this method, the plastic substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. Both surface roughness and contact angle of water droplet on poly(ethylene naphthalate) (PEN) substrates were increased by AHA. The surface of a PEN substrate was reduced by atomic hydrogen without optical transmittance degradation. In addition, the properties of a silicon nitride (SiNx) film deposited on a PEN substrate were changed by AHA, and the adhesion between the SiNx film and the PEN substrate was excellent for application to flexible displays.
Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.
Modeling of hydrogen evolution reaction on the surface of GaInP2

NASA Astrophysics Data System (ADS)

Choi, Woon Ih; Wood, Brandon; Schwegler, Eric; Ogitsu, Tadashi

2012-02-01

GaInP2 is promising candidate material for hydrogen production using sunlight. It reduces solvated proton into hydrogen molecule using light-induced excited electrons in the photoelectrochemical cell. However, it is challenging to model hydrogen evolution reaction (HER) using first-principles molecular dynamics. Instead, we use Anderson-Newns model and generalized solvent coordinate in Marcus-Hush theory to describe adiabatic free energy surface of HER. Model parameters are fitted from the DFT calculations. We model Volmer-Heyrovsky reaction path on the surfaces of CuPt phase of GaInP2. We also discuss effects of surface oxide and catalyst atoms that exist on top of bare surfaces in experimental circumstances.

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

NASA Astrophysics Data System (ADS)

Riba, Olga; Barnes, Robert J.; Scott, Thomas B.; Gardner, Murray N.; Jackman, Simon A.; Thompson, Ian P.

2011-10-01

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m2/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity 30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H2 on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m2/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.
American Recovery & Reinvestment Act: Fuel Cell Hybrid Power Packs and Hydrogen Refueling for Lift Trucks

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

Block, Gus

2011-07-31

HEB Grocery Company, Inc. (H-E-B) is a privately-held supermarket chain with 310 stores throughout Texas and northern Mexico. H-E-B converted 14 of its lift reach trucks to fuel cell power using Nuvera Fuel Cells’ PowerEdge™ units to verify the value proposition and environmental benefits associated with the technology. Issues associated with the increasing power requirements of the distribution center operation, along with high ambient temperature in the summer and other operating conditions (such as air quality and floor surface condition), surfaced opportunities for improving Nuvera’s PowerEdge fuel cell system design in high-throughput forklift environments. The project included on-site generation ofmore » hydrogen from a steam methane reformer, called PowerTap™ manufactured by Nuvera. The hydrogen was generated, compressed and stored in equipment located outside H-E-B’s facility, and provided to the forklifts by hydrogen dispensers located in high forklift traffic areas. The PowerEdge fuel cell units logged over 25,300 operating hours over the course of the two-year project period. The PowerTap hydrogen generator produced more than 11,100 kg of hydrogen over the same period. Hydrogen availability at the pump was 99.9%. H-E-B management has determined that fuel cell forklifts help alleviate several issues in its distribution centers, including truck operator downtime associated with battery changing, truck and battery maintenance costs, and reduction of grid electricity usage. Data collected from this initial installation demonstrated a 10% productivity improvement, which enabled H-E-B to make economic decisions on expanding the fleet of PowerEdge and PowerTap units in the fleet, which it plans to undertake upon successful demonstration of the new PowerEdge reach truck product. H-E-B has also expressed interst in other uses of hydrogen produced on site in the future, such as for APUs used in tractor trailers and refrigerated transport trucks in its fleet.« less
Investigating the Counteracting Effect of Trehalose on Urea-Induced Protein Denaturation Using Molecular Dynamics Simulation.

PubMed

Paul, Subrata; Paul, Sandip

2015-08-27

Molecular dynamics simulations are performed to investigate the counteracting effect of trehalose against urea-induced denaturation of S-peptide analogue. The calculations of Cα root-mean-square deviation, radius of gyration, and solvent-accessible surface area reveal that the peptide loses its native structure in aqueous 8 M urea solution at 310 K and that this unfolding process is prevented in the presence of trehalose. Interestingly, the native structure of the peptide in ternary mixed urea/trehalose solution is similar to that in the pure water system. The estimation of helical percentage of peptide residues as well as peptide-peptide intramolecular hydrogen bond number for different systems also support the above findings. Decomposition of protein-urea total interaction energy into electrostatic and van der Waals contributions shows that the presence of trehalose molecules makes the latter contribution unfavorable without affecting the former. These observations are further supported by preferential interaction calculations. Furthermore, the hydrogen bond analyses show that with the addition of urea molecules to the peptide-water system, the formation of peptide-urea hydrogen bonds takes place at the expense of peptide-water hydrogen bonds. In ternary mixed osmolytes system, because of formation of a considerable amount of peptide-trehalose hydrogen bonds, some urea molecules are excluded from the peptide surface. This essentially reduces the interaction between peptide and urea molecules, and because of this, we notice a reduction in the number of peptide-urea hydrogen bonds. Interestingly, the total number of peptide-solution species hydrogen bonds in the pure water system is very similar to that for the mixed osmolytes system. From these observations we infer that in the ternary solution, peptide-solution species hydrogen bonds are shared by water, urea, and trehalose molecules. The presence of trehalose in the mixed osmolyte system causes a significant reduction in the translational dynamics of water molecules. We discuss these results to understand the molecular explanation of trehalose's counteracting ability on urea-induced protein denaturation.
Adsorption and desorption of hydrogen at nonpolar GaN (1 1 ¯ 00 ) surfaces: Kinetics and impact on surface vibrational and electronic properties

NASA Astrophysics Data System (ADS)

Lymperakis, L.; Neugebauer, J.; Himmerlich, M.; Krischok, S.; Rink, M.; Kröger, J.; Polyakov, V. M.

2017-05-01

The adsorption of hydrogen at nonpolar GaN (1 1 ¯00 ) surfaces and its impact on the electronic and vibrational properties is investigated using surface electron spectroscopy in combination with density functional theory (DFT) calculations. For the surface mediated dissociation of H2 and the subsequent adsorption of H, an energy barrier of 0.55 eV has to be overcome. The calculated kinetic surface phase diagram indicates that the reaction is kinetically hindered at low pressures and low temperatures. At higher temperatures ab initio thermodynamics show, that the H-free surface is energetically favored. To validate these theoretical predictions experiments at room temperature and under ultrahigh vacuum conditions were performed. They reveal that molecular hydrogen does not dissociatively adsorb at the GaN (1 1 ¯00 ) surface. Only activated atomic hydrogen atoms attach to the surface. At temperatures above 820 K, the attached hydrogen gets desorbed. The adsorbed hydrogen atoms saturate the dangling bonds of the gallium and nitrogen surface atoms and result in an inversion of the Ga-N surface dimer buckling. The signatures of the Ga-H and N-H vibrational modes on the H-covered surface have experimentally been identified and are in good agreement with the DFT calculations of the surface phonon modes. Both theory and experiment show that H adsorption results in a removal of occupied and unoccupied intragap electron states of the clean GaN (1 1 ¯00 ) surface and a reduction of the surface upward band bending by 0.4 eV. The latter mechanism largely reduces surface electron depletion.
The role of surface oxides on hydrogen sorption kinetics in titanium thin films

NASA Astrophysics Data System (ADS)

Hadjixenophontos, Efi; Michalek, Lukas; Roussel, Manuel; Hirscher, Michael; Schmitz, Guido

2018-05-01

Titanium is presently discussed as a catalyst to accelerate the hydrogenation kinetics of hydrogen storage materials. It is however known that H absorption in Ti decisively depends on the surface conditions (presence or absence of the natural surface oxide). In this work, we use Ti thin films of controlled thickness (50-800 nm) as a convenient tool for quantifying the atomic transport. XRD and TEM investigations allow us to follow the hydrogenation progress inside the film. Hydrogenation of TiO2/Ti bi-layers is studied at 300 °C, for different durations (10 s to 600 min) and at varying pressures of pure H2 atmosphere. Under these conditions, the hydrogenation is found to be linear in time. By comparing films with and without TiO2, as well as by studying the pressure dependence of hydrogenation, it is demonstrated that hydrogen transport across the oxide represents the decisive kinetic barrier rather than the splitting of H2 molecules at the surface. Hydrogenation appears by a layer-like reaction initiated by heterogeneous nucleation at the backside interface to the substrate. The linear growth constant and the H diffusion coefficient inside the oxide are quantified, as well as a reliable lower bound to the hydrogen diffusion coefficient in Ti is derived. The pressure dependence of hydrogen absorption is quantitatively modelled.
Progress in the Development of Lightweight Nickel Electrode for Nickel-Hydrogen Cell

NASA Technical Reports Server (NTRS)

Britton, Doris L.

1999-01-01

Development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (Ni-H2) program at the NASA Glenn Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a lighter weight electrode for the nickel-hydrogen cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active material. Initial tests include activation and capacity measurements at five different discharge levels, C/2, 1.0 C, 1.37 C, 2.0 C, and 2.74 C. The electrodes are life cycle tested using a half-cell configuration at 40 and 80% depths-of-discharge (DOD) in a low-Earth-orbit regime. The electrodes that pass the initial tests are life cycle-tested in a boiler plate nickel-hydrogen cell before flight weight design are built and tested.
Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

PubMed

Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

2014-06-01

A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2) g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cryogenic Gellant and Fuel Formulation for Metallized Gelled Propellants: Hydrocarbons and Hydrogen with Aluminum

NASA Technical Reports Server (NTRS)

Wong, Wing; Starkovich, John; Adams, Scott; Palaszewski, Bryan; Davison, William; Burt, William; Thridandam, Hareesh; Hu-Peng, Hsiao; Santy, Myrrl J.

1994-01-01

An experimental program to determine the viability of nanoparticulate gellant materials for gelled hydrocarbons and gelled liquid hydrogen was conducted. The gellants included alkoxides (BTMSE and BTMSH) and silica-based materials. Hexane, ethane, propane and hydrogen were gelled with the newly-formulated materials and their rheological properties were determined: shear stress versus shear rate and their attendant viscosities. Metallized hexane with aluminum particles was also rheologically characterized. The propellant and gellant formulations were selected for the very high surface area and relatively-high energy content of the gellants. These new gellants can therefore improve rocket engine specific impulse over that obtained with traditional cryogenic-fuel gellant materials silicon dioxide, frozen methane, or frozen ethane particles. Significant reductions in the total mass of the gellant were enabled in the fuels. In gelled liquid hydrogen, the total mass of gellant was reduced from 10-40 wt percent of frozen hydrocarbon particles to less that 8 wt percent with the alkoxide.
Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less
Effect of nanoparticle nature on hydrogen concentration profiles and improved switching characteristics in Gd switchable mirrors.

PubMed

Aruna, I; Mehta, B R; Malhotra, L K; Khan, S A; Avasthi, D K

2005-10-01

A detailed elastic recoil detection analysis using 40 MeV 28Si5+ ions has been carried out to study the changes in the H concentration and concentration profiles during the hydrogenation/dehydrogenation process in polycrystalline and nanoparticle Gd layers formed using vacuum evaporation and inert gas evaporation techniques, respectively. Nanoparticle sample exhibits a larger difference in the [H]/[Gd] values (2.9 and 1.7) in comparison to polycrystalline sample (2.4 and 2.0) in the loaded and deloaded states. Hydrogenation/dehydrogenation activity is restricted to the top portion in case of polycrystalline sample. In contrast to this, size induced structural transformation; enhanced surface area and the presence of large number of inter particle boundaries due to nanoparticle character result in the complete Gd layer becoming active during switching.
Double-side illuminated titania nanotubes for high volume hydrogen generation by water splitting

NASA Astrophysics Data System (ADS)

Mohapatra, Susanta K.; Mahajan, Vishal K.; Misra, Mano

2007-11-01

A sonoelectrochemical anodization method is proposed to synthesize TiO2 nanotubular arrays on both sides of a titanium foil (TiO2/Ti/TiO2). Highly ordered TiO2 nanotubular arrays of 16 cm2 area with uniform surface distribution can be obtained using this anodization procedure. These double-sided TiO2/Ti/TiO2 materials are used as both photoanode (carbon-doped titania nanotubes) and cathode (Pt nanoparticles dispersed on TiO2 nanotubes; PtTiO2/Ti/PtTiO2) in a specially designed photoelectrochemical cell to generate hydrogen by water splitting at a rate of 38 ml h-1. The nanomaterials are characterized by FESEM, HRTEM, STEM, EDS, FFT, SAED and XPS techniques. The present approach can be used for large-scale hydrogen generation using renewable energy sources.
Development of a para-orthohydrogen catalytic converter for a solid hydrogen cooler

NASA Technical Reports Server (NTRS)

Nast, T. C.; Hsu, I. C.

1984-01-01

Design features of a tested catalytic converter for altering vented cryogenic parahydrogen used as a coolant on spacecraft into a para-ortho equilibrium for channeling to other cooling functions are described. The hydrogen is expected to be stored in either liquid or solid form. A high surface area Ni-on-Si catalyst was selected for tests at an operating pressure of 2 torr at a ratio of 1000 gr catalyst for a gr/sec hydrogen flow. Cylindrical and radial flow geometries were tried and measurements centered on the converter efficiencies at different operating temperatures when the converter was placed in the vent line of the H2 cooler. Efficiencies ranging from 10-100 percent were obtained for varying flow rates. Further testing is necessary to characterize the converter performance under a wider range of operating temperatures and environments.
Copper Oxide Nanograss for Efficient and Stable Photoelectrochemical Hydrogen Production by Water Splitting

NASA Astrophysics Data System (ADS)

Borkar, Rajnikant; Dahake, Rashmi; Rayalu, Sadhana; Bansiwal, Amit

2018-03-01

A biphasic copper oxide thin film of grass-like appendage morphology is synthesized by two-step electro-deposition method and later investigated for photoelectrochemical (PEC) water splitting for hydrogen production. Further, the thin film was characterized by UV-Visible spectroscopy, x-ray diffraction (XRD), Scanning electron microscopy (SEM) and PEC techniques. The XRD analysis confirms formation of biphasic copper oxide phases, and SEM reveals high surface area grass appendage-like morphology. These grass appendage structures exhibit a high cathodic photocurrent of - 1.44 mAcm-2 at an applied bias of - 0.7 (versus Ag/AgCl) resulting in incident to photon current efficiency (IPCE) of ˜ 10% at 400 nm. The improved light harvesting and charge transport properties of grass appendage structured biphasic copper oxides makes it a potential candidate for PEC water splitting for hydrogen production.
Enhanced Photocatalytic Hydrogen Evolution by Loading Cd0.5Zn0.5S QDs onto Ni2P Porous Nanosheets.

PubMed

Xiao, Lingfeng; Su, Tong; Wang, Zhuo; Zhang, Kun; Peng, Xiaoniu; Han, Yibo; Li, Quan; Wang, Xina

2018-02-02

Ni 2 P has been decorated on CdS nanowires or nanorods for efficient photocatalytic H 2 production, whereas the specific surface area remains limited because of the large size. Here, the composites of Cd 0.5 Zn 0.5 S quantum dots (QDs) on thin Ni 2 P porous nanosheets with high specific surface area were constructed for noble metal-free photocatalytic H 2 generation. The porous Ni 2 P nanosheets, which were formed by the interconnection of 15-30 nm-sized Ni 2 P nanoparticles, allowed the uniform loading of 7 nm-sized Cd 0.5 Zn 0.5 S QDs and the loading density being controllable. By tuning the content of Ni 2 P, H 2 generation rates of 43.3 μM h - 1 (1 mg photocatalyst) and 700 μM h - 1 (100 mg photocatalyst) and a solar to hydrogen efficiency of 1.5% were achieved for the Ni 2 P-Cd 0.5 Zn 0.5 S composites. The effect of Ni 2 P content on the light absorption, photoluminescence, and electrochemical property of the composite was systematically studied. Together with the band structure calculation based on density functional theory, the promotion of Ni 2 P in charge transfer and HER activity together with the shading effect on light absorption were revealed. Such a strategy can be applied to other photocatalysts toward efficient solar hydrogen generation.
Enhanced Photocatalytic Hydrogen Evolution by Loading Cd0.5Zn0.5S QDs onto Ni2P Porous Nanosheets

NASA Astrophysics Data System (ADS)

Xiao, Lingfeng; Su, Tong; Wang, Zhuo; Zhang, Kun; Peng, Xiaoniu; Han, Yibo; Li, Quan; Wang, Xina

2018-02-01

Ni2P has been decorated on CdS nanowires or nanorods for efficient photocatalytic H2 production, whereas the specific surface area remains limited because of the large size. Here, the composites of Cd0.5Zn0.5S quantum dots (QDs) on thin Ni2P porous nanosheets with high specific surface area were constructed for noble metal-free photocatalytic H2 generation. The porous Ni2P nanosheets, which were formed by the interconnection of 15-30 nm-sized Ni2P nanoparticles, allowed the uniform loading of 7 nm-sized Cd0.5Zn0.5S QDs and the loading density being controllable. By tuning the content of Ni2P, H2 generation rates of 43.3 μM h- 1 (1 mg photocatalyst) and 700 μM h- 1 (100 mg photocatalyst) and a solar to hydrogen efficiency of 1.5% were achieved for the Ni2P-Cd0.5Zn0.5S composites. The effect of Ni2P content on the light absorption, photoluminescence, and electrochemical property of the composite was systematically studied. Together with the band structure calculation based on density functional theory, the promotion of Ni2P in charge transfer and HER activity together with the shading effect on light absorption were revealed. Such a strategy can be applied to other photocatalysts toward efficient solar hydrogen generation.
High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

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

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermostmore » atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.« less
High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

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

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

Search for active, stable and cost-efficient electrocatalysts for hydrogen production via water splitting could make substantial impact to the energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high surface area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) compared to Rh/C and Pt/C catalysts. The atomic structure of the rhodium phosphide nanocubes was directly observed by annular dark-field scanning transmission electron microscopy (ADF-STEM),more » which revealed phosphorous-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorous plays crucial role in determining the robust catalyst properties.« less
Effect of hydrogen coverage on hydrogenation of o-cresol on Pt(111)

NASA Astrophysics Data System (ADS)

Li, Yaping; Liu, Zhimin; Crossley, Steven P.; Jentoft, Friederike C.; Wang, Sanwu

2018-06-01

The conversion of phenolics over metal catalysts is an important process for upgrading biofuels. With density functional calculations, hydrogenation of o-cresol on the hydrogen-covered Pt(111) surface was investigated. The results show that the coverage of hydrogen plays a significant role in the reaction rate while it does not affect the reaction selectivity. The reaction barriers of the hydrogenation process leading to the formation of both 2-methyl-cyclohexanone (the intermediate product) and 2-methyl-cyclohexanol (the final product) at high H coverages (∼1 ML) are found to be smaller by 0.14-0.69 eV than those at lower H coverages (∼1/25 ML). After both hydrogen and cresol are adsorbed on Pt(111) from their initial gas phase state, the reaction energy of each hydrogenation step on the surface is also dependent on the hydrogen coverage. On the H-covered Pt(111) surface, most steps of hydrogenation involve exothermic reactions when the hydrogen coverage is high while they are endothermic reactions at low hydrogen coverages. The differences in reaction rate and reaction energy between high and low H coverages can be understood with the coverage-dependent bonding strength and configurations.
Decontamination assessment of Bacillus anthracis, Bacillus subtilis, and Geobacillus stearothermophilus spores on indoor surfaces using a hydrogen peroxide gas generator.

PubMed

Rogers, J V; Sabourin, C L K; Choi, Y W; Richter, W R; Rudnicki, D C; Riggs, K B; Taylor, M L; Chang, J

2005-01-01

To evaluate the decontamination of Bacillus anthracis, Bacillus subtilis, and Geobacillus stearothermophilus spores on indoor surface materials using hydrogen peroxide gas. Bacillus anthracis, B. subtilis, and G. stearothermophilus spores were dried on seven types of indoor surfaces and exposed to > or =1000 ppm hydrogen peroxide gas for 20 min. Hydrogen peroxide exposure significantly decreased viable B. anthracis, B. subtilis, and G. stearothermophilus spores on all test materials except G. stearothermophilus on industrial carpet. Significant differences were observed when comparing the reduction in viable spores of B. anthracis with both surrogates. The effectiveness of gaseous hydrogen peroxide on the growth of biological indicators and spore strips was evaluated in parallel as a qualitative assessment of decontamination. At 1 and 7 days postexposure, decontaminated biological indicators and spore strips exhibited no growth, while the nondecontaminated samples displayed growth. Significant differences in decontamination efficacy of hydrogen peroxide gas on porous and nonporous surfaces were observed when comparing the mean log reduction in B. anthracis spores with B. subtilis and G. stearothermophilus spores. These results provide comparative information for the decontamination of B. anthracis spores with surrogates on indoor surfaces using hydrogen peroxide gas.
In-Vitro Comparative Study of In-office and Home Bleaching Agents on Surface Micro-morphology of Enamel.

PubMed

Fatima, Nazish

2016-01-01

To evaluate the effect of home-use bleaching agent containing 16% Carbamide Peroxide (CP) and in-office bleaching agent with 38% Hydrogen Peroxide (HP) on surface micro-morphology of enamel. An experimental study. The discs were prepared at Material Engineering Department of NED University of Engineering and Technology, Karachi, and surface morphology was analyzed at Centralized Science Laboratory of Karachi University, Pakistan. Duration of study was one year from January to December 2012. Forty five sound human third molar crowns, extracted for periodontal reason, were included in the study. Longitudinal sections were made using diamond disks (0.2 mm) under water lubrication to obtain enamel slabs measuring (3 mm x 3 mm). The slabs were embedded in polystyrene resin by using 2.0 cm diameter PVC molds, leaving the outer enamel surface uncovered by the resin. Ninety dental enamel slabs were prepared. The slabs were then randomly divided into 3 groups. Each group contained thirty specimens (n=30). Group 1 was kept in artificial saliva at 37°C in incubator (Memart, Germany) during whole experiment. Group 2 was treated with power whitening gel (White Smile 2011, Germany). Group 3 was treated with tooth whitening pen (White Smile 2011, Germany). The most central region or the region that was most representative of the entire surface area was used. The SEM (Jeol-Japan-JSM6380A, JAPAN) micrographs were examined to determine the type of surface presented. The enamel changes were classified as no or mild alteration, moderate alteration and severe altered surface. Regarding micro-morphology, the enamel surface of control groups showed smooth surface in general with some scattered clear scratches due to the polishing procedure. The specimens bleached in group 2 and group 3, represented areas of mild erosion. Bleaching with 38% Hydrogen Peroxide (HP) and 16% Carbamide Peroxide (CP) resulted in mild changes in surface micro-morphology of enamel.

Hydrogenated TiO2 Branches Coated Mn3O4 Nanorods as an Advanced Anode Material for Lithium Ion Batteries.

PubMed

Wang, Nana; Yue, Jie; Chen, Liang; Qian, Yitai; Yang, Jian

2015-05-20

Rational design and delicate control on the component, structure, and surface of electrodes in lithium ion batteries are highly important to their performances in practical applications. Compared with various components and structures for electrodes, the choices for their surface are quite limited. The most widespread surface for numerous electrodes, a carbon shell, has its own issues, which stimulates the desire to find another alternative surface. Here, hydrogenated TiO2 is exemplified as an appealing surface for advanced anodes by the growth of ultrathin hydrogenated TiO2 branches on Mn3O4 nanorods. High theoretical capacity of Mn3O4 is well matched with low volume variation (∼4%), enhanced electrical conductivity, good cycling stability, and rate capability of hydrogenated TiO2, as demonstrated in their electrochemical performances. The proof-of-concept reveals the promising potential of hydrogenated TiO2 as a next-generation material for the surface in high-performance hybrid electrodes.
Self-assembled air-stable magnesium hydride embedded in 3-D activated carbon for reversible hydrogen storage.

PubMed

Shinde, S S; Kim, Dong-Hyung; Yu, Jin-Young; Lee, Jung-Ho

2017-06-01

The rational design of stable, inexpensive catalysts with excellent hydrogen dynamics and sorption characteristics under realistic environments for reversible hydrogen storage remains a great challenge. Here, we present a simple and scalable strategy to fabricate a monodispersed, air-stable, magnesium hydride embedded in three-dimensional activated carbon with periodic synchronization of transition metals (MHCH). The high surface area, homogeneous distribution of MgH 2 nanoparticles, excellent thermal stability, high energy density, steric confinement by carbon, and robust architecture of the catalyst resulted in a noticeable enhancement of the hydrogen storage performance. The resulting MHCH-5 exhibited outstanding hydrogen storage performance, better than that of most reported Mg-based hydrides, with a high storage density of 6.63 wt% H 2 , a rapid kinetics loading in <5 min at 180 °C, superior reversibility, and excellent long-term cycling stability over ∼435 h. The significant reduction of the enthalpy and activation energy observed in the MHCH-5 demonstrated enhancement of the kinetics of de-/hydrogenation compared to that of commercial MgH 2 . The origin of the intrinsic hydrogen thermodynamics was elucidated via solid state 1 H NMR. This work presents a readily scaled-up strategy towards the design of realistic catalysts with superior functionality and stability for applications in reversible hydrogen storage, lithium ion batteries, and fuel cells.
Electrodeposition of Highly Porous Pt Nanoparticles Studied by Quantitative 3D Electron Tomography: Influence of Growth Mechanisms and Potential Cycling on the Active Surface Area.

PubMed

Ustarroz, Jon; Geboes, Bart; Vanrompay, Hans; Sentosun, Kadir; Bals, Sara; Breugelmans, Tom; Hubin, Annick

2017-05-17

Nanoporous Pt nanoparticles (NPs) are promising fuel cell catalysts due to their large surface area and increased electrocatalytic activity toward the oxygen reduction reaction (ORR). Herein, we report on the influence of the growth mechanisms on the surface properties of electrodeposited Pt dendritic NPs with large surface areas. The electrochemically active surface was studied by hydrogen underpotential deposition (H UPD) and compared for the first time to high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) quantitative 3D electron tomography of individual nanoparticles. Large nucleation overpotential leads to a large surface coverage of roughened spheroids, which provide a large roughness factor (R f ) but low mass-specific electrochemically active surface area (EASA). Lowering the nucleation overpotential leads to highly porous Pt NPs with pores stretching to the center of the structure. At the expense of smaller R f , the obtained EASA values of these structures are in the range of those of large surface area supported fuel cell catalysts. The active surface area of the Pt dendritic NPs was measured by electron tomography, and it was found that the potential cycling in the H adsorption/desorption and Pt oxidation/reduction region, which is generally performed to determine the EASA, leads to a significant reduction of that surface area due to a partial collapse of their dendritic and porous morphology. Interestingly, the extrapolation of the microscopic tomography results in macroscopic electrochemical parameters indicates that the surface properties measured by H UPD are comparable to the values measured on individual NPs by electron tomography after the degradation caused by the H UPD measurement. These results highlight that the combination of electrochemical and quantitative 3D surface analysis techniques is essential to provide insights into the surface properties, the electrochemical stability, and, hence, the applicability of these materials. Moreover, it indicates that care must be taken with widely used electrochemical methods of surface area determination, especially in the case of large surface area and possibly unstable nanostructures, since the measured surface can be strongly affected by the measurement itself.
Microstructure and mechanical properties of 2024-T3 and 7075-T6 aluminum alloys and austenitic stainless steel 304 after being exposed to hydrogen peroxide

NASA Astrophysics Data System (ADS)

Sofyan, Nofrijon Bin Imam

The effect of hydrogen peroxide used as a decontaminant agent on selected aircraft metallic materials has been investigated. The work is divided into three sections; bacterial attachment behavior onto an austenitic stainless steel 304 surface; effect of decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials of two aluminum alloys, i.e. 2024-T3 and 7075-T6, and an austenitic stainless steel 304 as used in galley and lavatory surfaces; and copper dissolution rate into hydrogen peroxide. With respect to bacterial attachment, the results show that surface roughness plays a role in the attachment of bacteria onto metallic surfaces at certain extent. However, when the contact angle of the liquid on a surface increased to a certain degree, detachment of bacteria on that surface became more difficult. In its relation to the decontamination process, the results show that a corrosion site, especially on the austenitic stainless steel 304 weld and its surrounding HAZ area, needs more attention because it could become a source or a harborage of bio-contaminant agent after either incidental or intentional bio-contaminant delivery. On the effect of the decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials, the results show that microstructural effects are both relatively small in magnitude and confined to a region immediately adjacent to the exposed surface. No systematic effect is found on the tensile properties of the three alloys under the conditions examined. The results of this investigation are promising with respect to the application of vapor phase hydrogen peroxide as a decontaminant agent to civilian aircraft, in that even under the most severe circumstances that could occur; only very limited damage was observed. The results from the dissolution of copper by concentrated liquid hydrogen peroxide showed that the rate of copper dissolution increased for the first 15 minutes of the reaction time with an activation energy of 19 kJ/mol, and then the fraction of copper dissolved became constant. This constant dissolution was expected to be due to the formation of copper hydroxide, which was observed to precipitate after the solution settled for some time. However, because the final consumption of hydrogen peroxide was not controlled, the exact reason for this constant dissolution cannot be determined at this time. The value of activation energy is within the range of activation energy found in the literature for other dissolution process. The low activation energy for dissolution of pure copper correlates with the observation of dissolution of copper from intermetallic particles in the aluminum alloys.
Synthesis and energy applications of mesoporous titania thin films

NASA Astrophysics Data System (ADS)

Islam, Syed Z.

The optical and electronic properties of TiO2 thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO2, critical challenges include the innate inability of TiO2 to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, mesoporous TiO2 thin films are modified by doping using hydrogen and nitrogen, and sensitization using graphene quantum dot sensitization. For all of these modifiers, well-ordered mesoporous titania films were synthesized by surfactant templated sol-gel process. Two methods: hydrazine and plasma treatments have been developed for nitrogen and hydrogen doping in the mesoporous titania films for band gap reduction, visible light absorption and enhancement of photocatalytic activity. The hydrazine treatment in mesoporous titania thin films suggests that hydrazine induced doping is a promising approach to enable synergistic incorporation of N and Ti3+ into the lattice of surfactant-templated TiO2 films and enhanced visible light photoactivity, but that the benefits are limited by gradual mesostructure deterioration. The plasma treated nitrogen doped mesoporous titania showed about 240 times higher photoactivity compared to undoped film in hydrogen production from photoelectrochemical water splitting under visible light illumination. Plasma treated hydrogen doped mesoporous titania thin films has also been developed for enhancement of visible light absorption. Hydrogen treatment has been shown to turn titania (normally bright white) black, indicating vastly improved visible light absorption. The cause of the color change and its effectiveness for photocatalysis remain open questions. For the first time, we showed that a significant amount of hydrogen is incorporated in hydrogen plasma treated mesoporous titania films by neutron reflectometry measurements. In addition to the intrinsic modification of titania by doping, graphene quantum dot sensitization in mesoporous titania film was also investigated for visible light photocatalysis. Graphene quantum dot sensitization and nitrogen doping of ordered mesoporous titania films showed synergistic effect in water splitting due to high surface area, band gap reduction, enhanced visible light absorption, and efficient charge separation and transport. This study suggests that plasma based doping and graphene quantum dot sensitization are promising strategies to reduce band gap and enhance visible light absorption of high surface area surfactant templated mesoporous titania films, leading to superior visible-light driven photoelectrochemical hydrogen production. The results demonstrate the importance of designing and manipulating the energy band alignment in composite nanomaterials for fundamentally improving visible light absorption, charge separation and transport, and thereby photoelectrochemical properties.
Effect of attrition milling on the reaction sintering of silicon nitride

NASA Technical Reports Server (NTRS)

Herbell, T. P.; Glasgow, T. K.; Yeh, H. C.

1978-01-01

Silicon powder was ground in a steel attrition mill under nitrogen. Air exposed powder was compacted, prefired in helium, and reaction sintered in nitrogen-4 v/o hydrogen. For longer grinding times, oxygen content, surface area and compactability of the powder increased; and both alpha/beta ratio and degreee of nitridation during sintering increased. Iron content remained constant.
Effect of attrition milling on the reaction sintering of silicon nitride

NASA Technical Reports Server (NTRS)

Herbell, T. P.; Glasgow, T. K.; Yeh, H. C.

1978-01-01

Silicon powder was ground in a steel attrition mill under nitrogen. Air-exposed powder was compacted, prefired in helium, and reaction-sintered in nitrogen-4 v/o hydrogen. For longer grinding times, oxygen content, surface area and compactability of the powder increased; and both alpha/beta ratio and degree of nitridation during sintering increased. Iron content remained constant.
Ultra-thin MoS₂ coated Ag@Si nanosphere arrays as efficient and stable photocathode for solar-driven hydrogen production.

PubMed

Zhou, Qingwei; Su, Shaoqiang; Hu, Die; Lin, Lin; Yan, Zhibo; Gao, Xingsen; Zhang, Zhang; Liu, Junming

2018-01-02

Solar-driven photoelectrochemical (PEC) water splitting has recently attracted much attention. Silicon (Si) is an ideal light absorber for solar energy conversion. However, the poor stability and inefficient surface catalysis of Si photocathode for hydrogen evolution reaction (HER) have been remained as the key challenges. Alternatively, MoS2 has been reported to exhibit the excellent catalysis performance if sufficient active sites for the HER are available. Here, ultra-thin MoS2 nanoflakes are directly synthesized to coat on the arrays of Ag-core Si-shell nanospheres (Ag@Si NSs) using the chemical vapor deposition (CVD). Due to the high surface area ratio and large curvature of these NSs, the as-grown MoS2 nanoflakes can accommodate more active sites. Meanwhile, the high-quality coating of MoS2 nanoflakes on the Ag@Si NSs protects the photocathode from damage during the PEC reaction. A high efficiency with a photocurrent of 33.3 mA cm-2 at a voltage of -0.4 V vs. the reversible hydrogen electrode is obtained. The as-prepared nanostructure as hydrogen photocathode is evidenced to have high stability over 12 hour PEC performance. This work opens opportunities for composite photocathode with high activity and stability using cheap and stable co-catalysts. © 2017 IOP Publishing Ltd.
Charging/discharging stability of a metal hydride battery electrode

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

Geng, M.; Han, J.; Feng, F.

1999-07-01

The metal hydride (MH) alloy powder for the negative electrode of the Ni/MH battery was first pulverized and oxidized by electrochemically charging and discharging for a number of cycles. The plate of the negative electrode of an experimental cell in this study was made from a mixture of a multicomponent AB{sub 5}-based alloy powder, nickel powder, and polytetra fluoroethylene (PTFE). The characteristics of the negative electrode, including discharge capacity, exchange current density, and hydrogen diffusivity, were studied by means of the electrochemical experiments and analysis in an experimental cell. The exchange current density of a Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{submore » 0.35}Al{sub 0.35} alloy electrode increases with increasing number of charge/discharge cycles and then remains almost constant after 20 cycles. A microcracking activation, resulting from an increase in reaction surface area and an improvement in the electrode surface activation, increases the hydrogen exchange current densities. Measurement of hydrogen diffusivities for Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} alloy powder shows that the ratio of D/a{sup 2} (D = hydrogen diffusivity; a = sphere radius) increases with increasing number of cycles but remains constant after 20 cycles.« less
Characterization of the intragranular water regime within subsurface sediments: Pore volume, surface area, and mass transfer limitations

USGS Publications Warehouse

Hay, M.B.; Stoliker, D.L.; Davis, J.A.; Zachara, J.M.

2011-01-01

Although "intragranular" pore space within grain aggregates, grain fractures, and mineral surface coatings may contain a relatively small fraction of the total porosity within a porous medium, it often contains a significant fraction of the reactive surface area, and can thus strongly affect the transport of sorbing solutes. In this work, we demonstrate a batch experiment procedure using tritiated water as a high-resolution diffusive tracer to characterize the intragranular pore space. The method was tested using uranium-contaminated sediments from the vadose and capillary fringe zones beneath the former 300A process ponds at the Hanford site (Washington). Sediments were contacted with tracers in artificial groundwater, followed by a replacement of bulk solution with tracer-free groundwater and the monitoring of tracer release. From these data, intragranular pore volumes were calculated and mass transfer rates were quantified using a multirate first-order mass transfer model. Tritium-hydrogen exchange on surface hydroxyls was accounted for by conducting additional tracer experiments on sediment that was vacuum dried after reaction. The complementary ("wet" and "dry") techniques allowed for the simultaneous determination of intragranular porosity and surface area using tritium. The Hanford 300A samples exhibited intragranular pore volumes of ???1% of the solid volume and intragranular surface areas of ???20%-35% of the total surface area. Analogous experiments using bromide ion as a tracer yielded very different results, suggesting very little penetration of bromide into the intragranular porosity. Copyright 2011 by the American Geophysical Union.
Characterization of the intragranular water regime within subsurface sediments: pore volume, surface area, and mass transfer limitations

USGS Publications Warehouse

Hay, Michael B.; Stoliker, Deborah L.; Davis, James A.; Zachara, John M.

2011-01-01

Although "intragranular" pore space within grain aggregates, grain fractures, and mineral surface coatings may contain a relatively small fraction of the total porosity within a porous medium, it often contains a significant fraction of the reactive surface area, and can thus strongly affect the transport of sorbing solutes. In this work, we demonstrate a batch experiment procedure using tritiated water as a high-resolution diffusive tracer to characterize the intragranular pore space. The method was tested using uranium-contaminated sediments from the vadose and capillary fringe zones beneath the former 300A process ponds at the Hanford site (Washington). Sediments were contacted with tracers in artificial groundwater, followed by a replacement of bulk solution with tracer-free groundwater and the monitoring of tracer release. From these data, intragranular pore volumes were calculated and mass transfer rates were quantified using a multirate first-order mass transfer model. Tritium-hydrogen exchange on surface hydroxyls was accounted for by conducting additional tracer experiments on sediment that was vacuum dried after reaction. The complementary ("wet" and "dry") techniques allowed for the simultaneous determination of intragranular porosity and surface area using tritium. The Hanford 300A samples exhibited intragranular pore volumes of ~1% of the solid volume and intragranular surface areas of ~20%–35% of the total surface area. Analogous experiments using bromide ion as a tracer yielded very different results, suggesting very little penetration of bromide into the intragranular porosity.
Surface Roughness of Various Diamond-Like Carbon Films

NASA Astrophysics Data System (ADS)

Liu, Dongping; Liu, Yanhong; Chen, Baoxiang

2006-11-01

Atomic force microscopy is used to estimate and compare the surface morphology of hydrogenated and hydrogen-free diamond-like carbon (DLC) films. The films were prepared by using DC magnetron sputtering of a graphite target, pulsed cathodic carbon arcs, electron cyclotron resonance (ECR), plasma source ion implantation and dielectric barrier discharge (DBD). The difference in the surface structure is presented for each method of deposition. The influences of various discharge parameters on the film surface properties are discussed based upon the experimental results. The coalescence process via the diffusion of adsorbed carbon species is responsible for the formation of hydrogen-free DLC films with rough surfaces. The films with surface roughness at an atomic level can be deposited by energetic ion impacts in a highly ionized carbon plasma. The dangling bonds created by atomic hydrogen lead to the uniform growth of hydrocarbon species at the a-C:H film surfaces of the ECR or DBD plasmas.
Electron- and photon-stimulated desorption of atomic hydrogen from radiation-modified alkali halide surfaces

NASA Astrophysics Data System (ADS)

Hudson, L. T.; Tolk, N. H.; Bao, C.; Nordlander, P.; Russell, D. P.; Xu, J.

2000-10-01

The desorption yields of excited hydrogen atoms from the surfaces of KCl, KBr, NaCl, NaF, and LiF have been measured as a function of incident photon and electron energy and flux, time of irradiation, dosing pressure of H2 and sample temperature. As these surfaces are exposed to H2 gas during electron or photon bombardment, the fluorescence from excited hydrogen atoms ejected from the surface is monitored. The desorption yields are found to be contingent upon surface damage induced by the incident particle radiation, leading to dissociative adsorption at surface sites containing an excess of alkali metal. A desorption mechanism is presented in which incident electrons or photons induce a valence excitation to a neutral, antibonding state of the surface alkali hydride molecule complex, leading to the desorption of hydrogen atoms possessing several eV of kinetic energy.
An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

NASA Technical Reports Server (NTRS)

Shanabarger, Mickey R.

1994-01-01

The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.
Unique Three-Dimensional InP Nanopore Arrays for Improved Photoelectrochemical Hydrogen Production.

PubMed

Li, Qiang; Zheng, Maojun; Ma, Liguo; Zhong, Miao; Zhu, Changqing; Zhang, Bin; Wang, Faze; Song, Jingnan; Ma, Li; Shen, Wenzhong

2016-08-31

Ordered three-dimensional (3D) nanostructure arrays hold promise for high-performance energy harvesting and storage devices. Here, we report the fabrication of InP nanopore arrays (NPs) in unique 3D architectures with excellent light trapping characteristic and large surface areas for use as highly active photoelectrodes in photoelectrochemical (PEC) hydrogen evolution devices. The ordered 3D NPs were scalably synthesized by a facile two-step etching process of (1) anodic etching of InP in neutral 3 M NaCl electrolytes to realize nanoporous structures and (2) wet chemical etching in HCl/H3PO4 (volume ratio of 1:3) solutions for removing the remaining top irregular layer. Importantly, we demonstrated that the use of neutral electrolyte of NaCl instead of other solutions, such as HCl, in anodic etching of InP can significantly passivate the surface states of 3D NPs. As a result, the maximum photoconversion efficiency obtained with ∼15.7 μm thick 3D NPs was 0.95%, which was 7.3 and 1.4 times higher than that of planar and 2D NPs. Electrochemical impedance spectroscopy and photoluminescence analyses further clarified that the improved PEC performance was attributed to the enhanced charge transfer across 3D NPs/electrolyte interfaces, the improved charge separation at 3D NPs/electrolyte junction, and the increased PEC active surface areas with our unique 3D NP arrays.
Effects of oxidation on surface heterogeneity of carbosils

NASA Astrophysics Data System (ADS)

Charmas, B.; Leboda, R.; Gérard, G.; Villiéras, F.

2002-08-01

Carbon-silica adsorbents (carbosils), prepared by pyrolysis of methylene chloride (CH 2Cl 2) on the surface of a porous silica gel, were subjected to an oxidizing hydrothermal treatment (HTT) at 200 °C, using a hydrogen peroxide water solution as a modification medium. Conventional nitrogen adsorption volumetry and low-pressure argon and nitrogen adsorption techniques were used to analyze and compare textural properties and surface heterogeneity of initial and hydrothermally treated samples. In the presence of carbon, the mesoporous network of silica gel is protected from the massive collapse generally observed after oxidizing HTT. For carbosils, some changes occur during HTT, leading to a slight decrease of specific surface areas accompanied by an increase in mean mesopore size. The argon and nitrogen condensation energy distributions, derived from low-pressure adsorption experiments, indicate that both silica and pyrocarbon materials were modified during HTT. Depolymerization and recondensation processes occur for silica, creating new silica surfaces. These processes are responsible of the decrease in specific surface areas. For pyrocarbon, similar depolymerization and recondensation processes probably occur, creating new and high-energy surface sites.
Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

NASA Technical Reports Server (NTRS)

Skiles, J. A.; Wightman, J. P.

1979-01-01

The characterization of water adsorption on silica is necessary to an understanding of how hydrogen chloride interacts with silica. The adsorption as a function of outgas temperatures of silica and as a function of the isotherm temperature was studied. Characterization of the silica structure by infrared analysis, X-ray diffraction and differential scanning calorimetry, surface area determinations, characterization of the sample surface by electron spectroscopy for chemical analysis (ESCA), and determinations of the heat of immersion in water of silica were investigated. The silica with a scanning electron microscope was examined.
Computational Study of the Adsorption of Dimethyl Methylphosphonate (DMMP) on the (010) Surface of Anatase TiO2 With and Without Faceting

DTIC Science & Technology

2009-12-05

surface area of anatase nanocrystals [6] and to be es- pecially active in photocatalysis [7]. Recent work by Dzwigaj et al. [8] has clearly shown that the...two-fold-coordinated (O2c) sites can also be involved in hydrogen bond (H-bond) formation. The effects, on the structure of the (100) and other...To reduce the computational cost , geometry optimization was done at the restricted Hartree Fock (RHF) level. This has previously been shown [36,37
Highly nitrogen-doped porous carbon derived from zeolitic imidazolate framework-8 for CO2 capture.

PubMed

Ma, Xiancheng; Li, Liqing; Chen, Ruofei; Wang, Chunhao; Li, Haoyang; Li, Hailong

2018-05-18

CO2 adsorption capacity of nitrogen-doped porous carbon depends to a large nitrogen doping levels and high surface area in previous studies. However, it seems difficult to incorporate large amounts of nitrogen while maintaining a high surface area and pore structure. Here we have reported porous carbon having a nitrogen content of up to 25.52% and specific surface area of 948 m2 g-1, which is prepared by pyrolyzing the nitrogen-containing zeolite imidazole framework-8 and urea composite at 650 °C under a nitrogen atmosphere. ZNC650 exhibits a superior CO2 uptake of 3.7 mmol g-1 at 25 ℃ and 1 bar. Experimental and theoretical results indicate that the nitrogen-containing functional groups can enhance CO2 uptake electrostatic interactions, Lewis acid-base interactions and hydrogen-bonding interactions, which are elucidated by density functional theory calculations. As CO2 adsorbent materials, these carbons have excellent adsorption capacity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

SPE (tm) regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications

NASA Technical Reports Server (NTRS)

Mcelroy, J. F.

1990-01-01

Viewgraphs on SPE regenerative hydrogen/oxygen fuel cells for extraterrestrial surface and microgravity applications are presented. Topics covered include: hydrogen-oxygen regenerative fuel cell energy storage system; electrochemical cell reactions; SPE cell voltage stability; passive water removal SPE fuel cell; fuel cell performance; SPE water electrolyzers; hydrophobic oxygen phase separator; hydrophilic/electrochemical hydrogen phase separator; and unitized regenerative fuel cell.
Nonequilibrium 2-Hydroxyoctadecanoic Acid Monolayers: Effect of Electrolytes

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

Lendrum, Conrad D.; Ingham, Bridget; Lin, Binhua

2012-02-06

2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position {alpha} to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of {approx}6. Themore » role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.« less
Developing a Novel Hydrogen Sponge with Ideal Binding Energy and High Surface Area for Practical Hydrogen Storage

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

Chung, T. C. Mike

This Phase I (5 quarters) research project was to examine the validity of a new class of boron-containing polymer (B-polymer) frameworks, serving as the adsorbents for the practical onboard H2 storage applications. Three B-polymer frameworks were synthesized and investigated, which include B-poly(butyenylstyrene) (B-PBS) framework (A), B-poly(phenyldiacetyene) (B-PPDA) framework (B), and B-poly(phenyltriacetylene) (B-PPTA) framework (C). They are 2-D polymer structures with the repeating cyclic units that spontaneously form open morphology and the B-doped (p-type) π-electrons delocalized surfaces. The ideal B-polymer framework shall exhibit open micropores (pore size in the range of 1-1.5nm) with high surface area (>3000 m 2/g), and themore » B-dopants in the conjugated framework shall provide high surface energy for interacting with H 2 molecules (an ideal H 2 binding energy in the range of 15-25 kJ/mol). The pore size distribution and H2 binding energy were investigated at both Penn State and NREL laboratories. So far, the experimental results show the successful synthesis of B-polymer frameworks with the relatively well-defined planar (2-D) structures. The intrinsically formed porous morphology exhibits a broad pore size distribution (in the range of 0.5-10 nm) with specific surface area (~1000 m 2/g). The miss-alignment between 2-D layers may block some micropore channels and limit gas diffusion throughout the entire matrix. In addition, the 2-D planar conjugated structure may also allow free π-electrons delocalization throughout the framework, which significantly reduces the acidity of B-moieties (electron-deficiency).The resulting 2-D B-polymer frameworks only exhibit a small increase of H 2 binding energy in the range of 8-9 KJ/mole (quite constant over the whole sorption range).« less
Computational study of pristine and titanium-doped sodium alanates for hydrogen storage applications

NASA Astrophysics Data System (ADS)

Dathar, Gopi Krishna Phani

The emphasis of this research is to study and elucidate the underlying mechanisms of reversible hydrogen storage in pristine and Ti-doped sodium aluminum hydrides using molecular modeling techniques. An early breakthrough in using complex metal hydrides as hydrogen storage materials is from the research on sodium alanates by Bogdanovic et al., in 1997 reporting reversible hydrogen storage is possible at moderate temperatures and pressures in transition metal doped sodium alanates. Anton reported titanium salts as the best catalysts compared to all other transition metal salts from his further research on transition metal doped sodium alanates. However, a few questions remained unanswered regarding the role of Ti in reversible hydrogen storage of sodium alanates with improved thermodynamics and kinetics of hydrogen desorption. The first question is about the position of transition metal dopants in the sodium aluminum hydride lattice. The position is investigated by identifying the possible sites for titanium dopants in NaAlH4 lattice and studying the structure and dynamics of possible compounds resulting from titanium doping in sodium alanates. The second question is the role of titanium dopants in improved thermodynamics of hydrogen desorption in Ti-doped NaAlH4. Though it is accepted in the literature that formation of TiAl alloys (Ti-Al and TiAl3) is favorable, reaction pathways are not clearly established. Furthermore, the source of aluminum for Ti-Al alloy formation is not clearly understood. The third question in this area is the role of titanium dopants in improved kinetics of hydrogen absorption and desorption in Ti-doped sodium alanates. This study is directed towards addressing the three longstanding questions in this area. Thermodynamic and kinetic pathways for hydrogen desorption in pristine NaAlH4 and formation of Ti-Al alloys in Ti-doped NaAlH 4, are elucidated to understand the underlying mechanisms of hydrogen desorption. Density functional theory formalism as implemented in CASTEP (Cambridge Serial Total Energy Package) is used to study the structure and energetics of pristine and Ti-doped sodium alanates. From investigations of various models of sodium alanates with Ti dopants, it is shown that the difference between the energy required for Ti→SNa (Ti-substituted Na at the lattice site on the surface) and Ti→TI (Ti placed on top of the surface interstitial SI site) is 0.003 eV atom-1, and is minimal compared to other models. Since less energy is required for Ti→S Na and Ti→TI, these two sites (SNa and T I) would be preferred by the Ti dopants. In Ti→SNa model, Ti is coordinated to two aluminum and seven hydrogen atoms resulting in the possible formation of a TiAl2H7 complex. At elevated temperatures (423 and 448 K), the number of aluminum atoms coordinating with titanium in the complex increase from two (at distances in the 2.6-2.7 A range) to five (at distances in the 2.6-2.7 A range). Besides the formation of a Ti-Al-H complex, Al-Al association (with a 2.97 A bond length) is also seen from the DFT-MD results. In the case of Ti→TI, Ti is coordinated to two aluminum and two hydrogen atoms resulting in the possible formation of a TiAl2H2 complex. TiAl2 H2 complex becomes TiAl3H6 and TiAl 3H7 at elevated temperatures of 423 and 448 K, respectively. The investigation of thermodynamics pathways in Ti-doped sodium alanates illustrates a three step reaction pathway to the formation of TiAl3 (Ti and AlH3 after the first reaction, TiAl after the second and finally TiAl3). This investigation also suggests aluminum in its +3 oxidation state present in aluminum hydride species is responsible in the formation of Ti-Al alloys. From kinetics studies, the proposed mechanism is related to transition from AlH4- to AlH6 3-. The rate limiting step is determined to be associated with hydrogen evolution from association of AlH3 species nucleating aluminum phase. This step is 15 kJ/mol higher than the nearest highest barrier in the reaction path related to transition from AlH52- to AlH63-. From the DFT-MD simulations, it is observed that the titanium dopants are present on the surface during the entire simulation time and exhibit the role in catalytic splitting of hydrogen from surrounding AlH4 groups. Besides the catalytic role, Ti dopants also form bonds with Al, and we also see that the AlH4 groups on the surface and that are present in the sub-surface layers are drawn towards the Ti dopants. This association of Al around titanium indicates the initiation of Al nucleation site facilitated by Ti dopants residing on the surface.
Elementary Chemical Reactions in Surface Photocatalysis

NASA Astrophysics Data System (ADS)

Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

2018-04-01

Photocatalytic hydrogen evolution and organic degradation on oxide materials have been extensively investigated in the last two decades. Great efforts have been dedicated to the study of photocatalytic reaction mechanisms of a variety of molecules on TiO2 surfaces by using surface science methods under ultra-high vacuum (UHV) conditions, providing fundamental understanding of surface chemical reactions in photocatalysis. In this review, we summarize the recent progress in the study of photocatalysis of several important species (water, methanol, and aldehydes) on different TiO2 surfaces. The results of these studies have provided us deep insights into the elementary processes of surface photocatalysis and stimulated a new frontier of research in this area. Based on the results of these studies, a new dynamics-based photocatalysis model is also discussed.
Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance.

PubMed

Alia, Shaun M; Pivovar, Bryan S

2018-04-27

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing to 250 °C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 °C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. These techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongfen, E-mail: wanghongfen11@163.com; Wang, Zhiqi; Chen, Shougang

Molybdenum carbides with surfactants as carbon sources were prepared using the carbothermal reduction of the appropriate precursors (molybdenum oxides deposited on surfactant micelles) at 1023 K under hydrogen gas. The carburized products were characterized using scanning electron microscopy (SEM), X-ray diffraction and BET surface area measurements. From the SEM images, hollow microspherical and rod-like molybdenum carbides were observed. X-ray diffraction patterns showed that the annealing time of carburization had a large effect on the conversion of molybdenum oxides to molybdenum carbides. And BET surface area measurements indicated that the difference of carbon sources brought a big difference in specific surfacemore » areas of molybdenum carbides. - Graphical abstract: Molybdenum carbides having hollow microspherical and hollow rod-like morphologies that are different from the conventional monodipersed platelet-like morphologies. Highlights: Black-Right-Pointing-Pointer Molybdenum carbides were prepared using surfactants as carbon sources. Black-Right-Pointing-Pointer The kinds of surfactants affected the morphologies of molybdenum carbides. Black-Right-Pointing-Pointer The time of heat preservation at 1023 K affected the carburization process. Black-Right-Pointing-Pointer Molybdenum carbides with hollow structures had larger specific surface areas.« less
Fully methylated, atomically flat (111) silicon surface

NASA Astrophysics Data System (ADS)

Fidélis, A.; Ozanam, F.; Chazalviel, J.-N.

2000-01-01

The atomically flat hydrogenated (111) silicon surface has been methylated by anodization in a Grignard reagent and the surface obtained characterized by infrared spectroscopy. 100% substitution of the hydrogen atoms by methyl groups is observed. The resulting surface exhibits preserved ordering and superior chemical stability.
Carbon quantum dots coated BiVO{sub 4} inverse opals for enhanced photoelectrochemical hydrogen generation

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

Nan, Feng; Shen, Mingrong; Fang, Liang, E-mail: zhkang@suda.edu.cn, E-mail: lfang@suda.edu.cn

Carbon quantum dots (CQDs) coated BiVO{sub 4} inverse opal (io-BiVO{sub 4}) structure that shows dramatic improvement of photoelectrochemical hydrogen generation has been fabricated using electrodeposition with a template. The io-BiVO{sub 4} maximizes photon trapping through slow light effect, while maintaining adequate surface area for effective redox reactions. CQDs are then incorporated to the io-BiVO{sub 4} to further improve the photoconversion efficiency. Due to the strong visible light absorption property of CQDs and enhanced separation of the photoexcited electrons, the CQDs coated io-BiVO{sub 4} exhibit a maximum photo-to-hydrogen conversion efficiency of 0.35%, which is 6 times higher than that of themore » pure BiVO{sub 4} thin films. This work is a good example of designing composite photoelectrode by combining quantum dots and photonic crystal.« less
Calcium-decorated carbyne networks as hydrogen storage media.

PubMed

Sorokin, Pavel B; Lee, Hoonkyung; Antipina, Lyubov Yu; Singh, Abhishek K; Yakobson, Boris I

2011-07-13

Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of ∼0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed ∼8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.
Development of a micro-fiber nickel electrode for nickel-hydrogen cell

NASA Technical Reports Server (NTRS)

Britton, Doris L.

1995-01-01

Development of a high specific energy nickel electrode is the main goal of the lightweight nickel electrode program at the NASA Lewis Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a more efficient and lighter weight electrode for the nickel-hydrogen cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active material. Initial tests include activation and capacity measurements at different discharge levels followed by half-cell cycle testing at 80 percent depth-of-discharge in a low-Earth-orbit regime. The electrodes that pass the initial tests are life cycle-tested in a boiler plate nickel-hydrogen cell before flightweight designs are built and tested.
Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

PubMed

Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

2014-12-01

Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.
A trimodal porous carbon as an effective catalyst for hydrogen production by methane decomposition.

PubMed

Shen, Yi; Lua, Aik Chong

2016-01-15

A new type of porous carbon with an interconnected trimodal pore system is synthesized by a nanocasting method using nanoparticulated bimodal micro-mesoporous silica particles as the template. The synthesized template and carbon material are characterized using transmission electron microscopy (TEM), field emission electron scanning microscopy (FESEM) and nitrogen adsorption-desorption test. The synthesized carbon material has an extremely high surface area, a large pore volume and an interconnected pore structure, which could provide abundant active sites and space for chemical reactions and minimize the diffusion resistance of the reactants. The resulting carbon is used as the catalyst for hydrogen production by the thermal decomposition of methane. The catalytic results show that the as-synthesized carbon in this study produces much higher methane conversion and hydrogen yield than the commercial carbon materials. Copyright © 2015 Elsevier Inc. All rights reserved.
Pt deposited TiO2 catalyst fabricated by thermal decomposition of titanium complex for solar hydrogen production

NASA Astrophysics Data System (ADS)

Truong, Quang Duc; Le, Thanh Son; Ling, Yong-Chien

2014-12-01

C, N codoped TiO2 catalyst has been synthesized by thermal decomposition of a novel water-soluble titanium complex. The structure, morphology, and optical properties of the synthesized TiO2 catalyst were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Pt deposited TiO2 catalysts synthesized at different temperatures was evaluated by means of hydrogen evolution reaction under both UV-vis and visible light irradiation. The investigation results reveal that the photocatalytic H2 evolution rate strongly depended on the crystalline grain size as well as specific surface area of the synthesized catalyst. Our studies successfully demonstrate a simple method for the synthesis of visible-light responsive Pt deposited TiO2 catalyst for solar hydrogen production.
Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.
Chemical microreactor and method thereof

DOEpatents

Morse, Jeffrey D.; Jankowski, Alan

2005-11-01

A chemical microreactor suitable for generation of hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. One such microreactor employs a packed catalyst capillary microchannel and at least one porous membrane. Another employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2 /cm.sup.3. The packed catalyst capillary microchannels, porous membranes and porous membrane support structures may be formed by a variety of methods.
Catalyst for hydrotreating carbonaceous liquids

DOEpatents

Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.

1982-01-01

A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.
Protein hydrogen exchange: Testing current models

PubMed Central

Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

2012-01-01

To investigate the determinants of protein hydrogen exchange (HX), HX rates of most of the backbone amide hydrogens of Staphylococcal nuclease were measured by NMR methods. A modified analysis was used to improve accuracy for the faster hydrogens. HX rates of both near surface and well buried hydrogens are spread over more than 7 orders of magnitude. These results were compared with previous hypotheses for HX rate determination. Contrary to a common assumption, proximity to the surface of the native protein does not usually produce fast exchange. The slow HX rates for unprotected surface hydrogens are not well explained by local electrostatic field. The ability of buried hydrogens to exchange is not explained by a solvent penetration mechanism. The exchange rates of structurally protected hydrogens are not well predicted by algorithms that depend only on local interactions or only on transient unfolding reactions. These observations identify some of the present difficulties of HX rate prediction and suggest the need for returning to a detailed hydrogen by hydrogen analysis to examine the bases of structure-rate relationships, as described in the companion paper (Skinner et al., Protein Sci 2012;21:996–1005). PMID:22544567
Nanoplasmonic hydrogen sensing

NASA Astrophysics Data System (ADS)

Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

2014-09-01

In this review we discuss the evolution of surface plasmon resonance and localized surface plasmon resonance based hydrogen sensors. We put particular focus on how they are used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and the single nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes. However, nanoplasmonic hydrogen sensors are not only of academic interest but may also find more practical use as all-optical gas detectors in industrial and medical applications, as well in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier.
Effect of laser activated bleaching on the chemical stability and morphology of intracoronal dentin.

PubMed

Lopes, Fabiane Carneiro; Roperto, Renato; Akkus, Anna; Akkus, Ozan; Palma-Dibb, Regina Guenka; de Sousa-Neto, Manoel Damião

2018-02-01

To evaluate the effect of the bleaching with 35% hydrogen peroxide either activated or not by a 970nm diode laser on the chemical stability and dentin surface morphology of intracoronary dentin. Twenty-seven slabs of intracoronary dentin specimens (3×3mm) were distributed into three groups (n=9), according to surface treatment: HP - 35% hydrogen peroxide (1×4'), DL - 970nm diode laser (1×30"/0,8W/10Hz), HP+DL - 35% HP activated with 970nm diode laser (1×30"/0,8W/10Hz leaving the gel in contact to the surface for 4' after activation). Three Raman spectra from each fragment were obtained to calculate the mean intensity of peaks of inorganic component (a.u.), organic collagen content (a.u.), and the ratio of inorganic/organic content, before and after treatment. Analyses of the samples by confocal laser microscopy were performed to evaluate the surface roughness, percentage of tubules, perimeter and area percentage of tubules, before and after treatment. Data were analyzed by Kruskal-Wallis, Dunn's, and Wilcoxon test (P<0.05). Data analysis showed that HP+DL did not change the inorganic content peaks 8.31 [29.78] or the inorganic/organic ratio 3.37 [14.67] (P>0.05). Similarly, DL did not affect the chemical stability of the dentin surface (P>0.05). However, HP significantly increased inorganic content peaks 10.87 [22.62], as well as the inorganic/organic ratio 6.25 [27.78] (P<0.05). Regarding the morphological alterations, all surface treatments increase tubules exposure; HP treatment significantly increases perimeter and area percentage; and HP+DL increases surface roughness. Bleaching HP combined with DL offers an improvement in terms of intracoronal dentin surface protection, yielding better maintenance of dentin chemical stability and morphology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mg2+ Doped into Electro-synthesized HKUST-1 and Their Initial Hydrogen Sorption Properties

NASA Astrophysics Data System (ADS)

Lestari, W. W.; Ni'maturrohmah, D.; Arrozi, U. S. F.; Suwarno, H.

2018-01-01

The hydrogen storage materials are essentially play important roles in supporting the utilization of hydrogen as a promising alternative energy. Several innovative materials have been proposed and intensively investigated in this regard, including Metal-Organic Framework (MOFs). MOFs type HKUST-1 [Cu3(BTC)2] (BTC = benzene-tri-carboxylate) is the most explored materials in hydrogen storage. In this research, HKUST-1 was electro-synthesized under 15 volt for 1.5 h. This material was ex-situ modified with magnesium(II) ion with variation: 3, 5 and 10 wt% to add attractive sites for hydrogen to form Mg2+@HKUST-1. The final materials were characterized by XRD, FTIR, SEM-EDX, and SAA. Hydrogen sorption measurement was conducted using Sievert system at 30 and 80 °C with pressure from 0.2 to 1.5 bar in 10 minutes for each condition. According to XRD analysis, the basic structure of Mg2+@HKUST-1 was remaining stable. In contrary, SEM analysis showed that HKUST-1 morphology was changed after modification with Mg2+. In addition, the surface area of materials significantly increased from 372.112 to 757.617m2/g, based on SAA analysis. The presence of Mg2+ in the HKUST-1 increased the hydrogen sorption capacity up to 0.475 wt% at 1.4 bar at 30 °C and 0.256 wt% at 80 °C (1.4 bar).
Modelling of discrete TDS-spectrum of hydrogen desorption

NASA Astrophysics Data System (ADS)

Rodchenkova, Natalia I.; Zaika, Yury V.

2015-12-01

High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.
Hydrogenation and dehydrogenation of cyclohexene on Pt(1 0 0): A sum frequency generation vibrational spectroscopic and kinetic study

NASA Astrophysics Data System (ADS)

Bratlie, Kaitlin M.; Flores, Lucio D.; Somorjai, Gabor A.

2005-12-01

Sum frequency generation (SFG) vibrational spectroscopy and kinetic measurements were performed during cyclohexene hydrogenation/dehydrogenation over a range of pressures (10 -8-5 Torr) and temperatures (300-500 K) on the Pt(1 0 0) surface. Upon adsorption at pressures below 1.5 Torr and at 300 K, cyclohexene dehydrogenates to form π-allyl c-C 6H 9 and hydrogenates to form cyclohexyl (C 6H 11) surface intermediates. Increasing the pressure to 1.5 Torr produces adsorbed 1,4-cyclohexadiene, π-allyl c-C 6H 9, and cyclohexyl species. These adsorbed molecules are found both in the absence and presence of excess hydrogen on the Pt(1 0 0) surface at high pressures and up to 380 K and 360 K, respectively. π-Allyl c-C 6H 9 and cyclohexyl are adsorbed on the surface up to 440 K in the absence of excess hydrogen and 460 K in the presence of excess hydrogen, at which point they are no longer detectable by SFG. Kinetic studies in the absence of excess hydrogen show that the apparent activation energy for the dehydrogenation pathway (14.3 ± 1.2 kcal/mol) is similar to that of the hydrogenation pathway (12.9 ± 0.6 kcal/mol). Different apparent activation energies are observed for the dehydrogenation pathway (22.4 ± 1.6 kcal/mol) and the hydrogenation pathway (18.8 ± 0.9 kcal/mol) in the presence of excess hydrogen.
Active sites and states in the heterogeneous catalysis of carbon-hydrogen bonds.

PubMed

Somorjai, Gabor A; Marsh, Anderson L

2005-04-15

C-H bond activation for several alkenes (ethylene, propylene, isobutene, cyclohexene and 1-hexene) and alkanes (methane, ethane, n-hexane, 2-methylpentane and 3-methylpentane) has been studied on the (111) crystal face of platinum as a function of temperature at low (10(-6) Torr) and high (>/=1 Torr) pressures in the absence and presence of hydrogen pressures (>/=10 Torr). Sum frequency generation (SFG) vibrational spectroscopy has been used to characterize the adsorbate structures and high pressure scanning tunnelling microscopy (HP-STM) has been used to monitor their surface mobility under reaction conditions during hydrogenation, dehydrogenation and CO poisoning. C-H bond dissociation occurs at low temperatures, approximately 250 K, for all of these molecules, although only at high pressures for the weakly bound alkanes because of their low desorption temperatures. Bond dissociation is known to be surface structure sensitive and we find that it is also accompanied by the restructuring of the metal surface. The presence of hydrogen slows down dehydrogenation and for some of the molecules it influences the molecular rearrangement, thus altering reaction selectivity. Surface mobility of adsorbates is essential to produce catalytic activity. When surface diffusion is inhibited by CO adsorption, ordered surface structures form and the reaction is poisoned. Ethylene hydrogenation is surface structure insensitive, while cyclohexene hydrogenation and dehydrogenation are structure sensitive. n-Hexane and other C6 alkanes form either upright or flat-lying molecules on the platinum surface which react to produce branched isomers or benzene, respectively.
Influence of electric field on the hydrogen bond network of methanol.

PubMed

Suresh, S J; Prabhu, Arun Laxman; Arora, Abhinav

2007-04-07

The understanding of the structure of hydrogen (H) bonding liquids in electric (E) fields is important in the context of several areas of research, such as electrochemistry, surface science, and thermodynamics of electrolyte solutions. We had earlier presented a general thermodynamic framework for this purpose, and had shown that the application of E field enhances H-bond interactions among water molecules. The present investigation with methanol suggests a different result-the H-bond structure, as indicated by the average number of H bonds per molecule, goes through a maxima with increasing field strength. This result is explained based on the symmetry in the location of the H-bonding sites in the two types of molecules.
Properties of Surface-Modification Layer Generated by Atomic Hydrogen Annealing on Poly(ethylene naphthalate) Substrate

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2008-01-01

The surface of a poly(ethylene naphthalate) (PEN) substrate was modified by atomic hydrogen annealing (AHA). In this method, a PEN substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. The properties of the surface-modification layer by AHA were evaluated by spectroscopic ellipsometry. It is found that the thickness of the modified layer was 5 nm and that the modification layer has a low refractive index compared with the PEN substrate. The modification layer relates to the reduction reaction of the PEN substrate by AHA.
Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

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

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less
Influence of Hydrogen Bonding on the Surface Diffusion of Molecular Glasses: Comparison of Three Triazines

DOE PAGES

Chen, Yinshan; Zhu, Men; Laventure, Audrey; ...

2017-06-26

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less
Biofilm growth on polyvinylchloride surface incubated in suboptimal microbial warm water and effect of sanitizers on biofilm removal post biofilm formation.

PubMed

Maharjan, Pramir; Huff, Geraldine; Zhang, Wen; Watkins, Susan

2017-01-01

An in vitro experiment was conducted to understand the nature of biofilm growth on polyvinyl chloride (PVC) surface when exposed to suboptimal-quality microbial water (>4 log 10 cfu/mL) obtained from a poultry drinking water source mimicking water in waterlines during the first week of poultry brooding condition. PVC sections (internal surface area of 15.16 cm 2 ) were utilized in the study to grow biofilm. After a 7-d test period, test coupons with 7-day-old biofilm were transferred into autoclaved municipal water and then treated with either chlorine-based or hydrogen peroxide-based sanitizer at bird drinking water rate, to see the impact on removal of biofilm formed on test coupons. Two trials (T1 and T2) were conducted. Test coupons used in T1 and T2 had the bacterial growth of 3.67 (SEM 0.04) and 3.97 (SEM 0.11) log 10 cfu/cm 2 on d 7. After sanitizer application, chlorine-based sanitizer removed bacteria in biofilm completely (0 cfu/cm 2 ) within 24 h post treatment whereas hydrogen peroxide-based sanitizer reduced the counts to 1.68 log 10 cfu/cm 2 (P < 0.05) by 48 h post sanitizer application. Control remained the same (P > 0.05). Results indicated that biofilm formation can occur quickly under suboptimal water condition on PVC surface, and sanitizer application helped mitigate already formed biofilm, yet chlorine proved to be more effective than hydrogen peroxide. © 2016 Poultry Science Association Inc.
Microstructure and hydrogenation properties of a melt-spun non-stoichiometric Zr-based Laves phase alloy

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

Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Zhang, Yunlong; Li, Jinshan

2016-01-15

Alloy with composition of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} off normal stoichiometric proportion is selected to investigate the effect of defects introduced by non-stoichiometry on hydrogenation kinetics of Zr–Ti–V Laves phase alloys. Microstructure and phase constituent of melt-spun ribbons have been investigated in this work. The activation process, hydrogenation kinetics, thermodynamics characteristics and hydride phase constituent of as-cast alloy and melt-spun ribbons are also compared. Comparing with the as-cast alloy, the dominant Laves phase ZrV{sub 2} is preserved, V-BCC phase is reduced and α-Zr phase is replaced by a small amount of Zr{sub 3}V{sub 3}O phase in melt-spun ribbons. Melt-spun ribbonsmore » exhibit easy activation and fast initial hydrogen absorption on account of the increased specific surface area. However, the decrease in unit cell volume of the dominant phase leads to the decrease in hydrogen absorption capacity. Melt-spinning technique raises the equilibrium pressure and decreases the stability of hydride due to the decrease of unit cell volume and the elimination of α-Zr phase, respectively. Melt-spun ribbons with fine grains show improved hydrogen absorption kinetics comparing with that of the as-cast alloy. Meanwhile, the prevalent micro twins observed within melt-spun ribbons are believed to account for the improved hydrogen absorption kinetics. - Highlights: • Role of defects on hydrogenation kinetics of Zr-based alloys is proposed. • Microstructure and hydrogenation properties of as-cast/melt-spun alloy are compared. • Melt-spinning technique improves the hydrogenation kinetics of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} alloy. • Refined grains and twin defects account for improved hydrogen absorption kinetics.« less
'No touch' technologies for environmental decontamination: focus on ultraviolet devices and hydrogen peroxide systems.

PubMed

Weber, David J; Kanamori, Hajime; Rutala, William A

2016-08-01

This article reviews 'no touch' methods for disinfection of the contaminated surface environment of hospitalized patients' rooms. The focus is on studies that assessed the effectiveness of ultraviolet (UV) light devices, hydrogen peroxide systems, and self-disinfecting surfaces to reduce healthcare-associated infections (HAIs). The contaminated surface environment in hospitals plays an important role in the transmission of several key nosocomial pathogens including methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus spp., Clostridium difficile, Acinetobacter spp., and norovirus. Multiple clinical trials have now demonstrated the effectiveness of UV light devices and hydrogen peroxide systems to reduce HAIs. A limited number of studies have suggested that 'self-disinfecting' surfaces may also decrease HAIs. Many studies have demonstrated that terminal cleaning and disinfection with germicides is often inadequate and leaves environmental surfaces contaminated with important nosocomial pathogens. 'No touch' methods of room decontamination (i.e., UV devices and hydrogen peroxide systems) have been demonstrated to reduce key nosocomial pathogens on inoculated test surfaces and on environmental surfaces in actual patient rooms. Further UV devices and hydrogen peroxide systems have been demonstrated to reduce HAI. A validated 'no touch' device or system should be used for terminal room disinfection following discharge of patients on contact precautions. The use of a 'self-disinfecting' surface to reduce HAI has not been convincingly demonstrated.
Hydrogen-related defects in hydrogenated amorphous semiconductors

NASA Astrophysics Data System (ADS)

Jin, Shu; Ley, Lothar

1991-07-01

One of the key steps in the formation of glow-discharge-deposited (GD) a-Si:H or a-Ge:H films by plasma deposition from the gas phase is the elimination of excess hydrogen from the growth surface which is necessary for the cross linking of the Si or Ge network and the reduction of the defect density associated with the hydrogen-rich surface layer. The high defect density (~1018 cm-3) in a growing surface layer can, depending on preparation conditions, be either reduced (to ~1016 cm-3) or be trapped in the bulk upon subsequent growth, as evidenced by a great deal of data. However, little is known about its origin and implication. We have investigated the change in electronic structure related with this process using UHV-evaporated a-Ge as a model system, subjected to thermal hydrogenation, plasma hydrogenation, and various annealing cycles. The density of occupied states in the pseudogap of the a-Ge(:H) surface (probing depth ~50 Å) was determined with total-yield photoelectron spectroscopy. In this way, effects of thermal annealing, hydrogenation, and ion bombarding on the near-surface defect density could be studied. We identify in room-temperature (RT) hydrogenated a-Ge:H another defect at about Ev+0.45 eV in addition to the dangling-bond defect. This defect exists at the initial stage of hydrogen incorporation, decreases upon ~250 °C annealing, and is restored upon RT rehydrogenation. Therefore we suspect that this defect is hydrogen induced and concomitant with the formation of unexpected bondings [both multiply bonded XHx (X=Si or Ge and x=2 and 3) and polyhydride (XH2)n configurations] favored at RT hydrogenation. As a possible candidate we suggest the Ge-H-Ge three-center bond in which one electron is placed in a nonbonding orbital that gives rise to the paramagnetic state in the gap of a-Ge:H observed here. This defect also accounts for the large defect density at the growing surface in the optimized plasma chemical-vapor-deposition process, where the special bonding configurations mentioned above are the predominant species. The formation and annealing of this defect will be discussed.
Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis

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

Ong, Phuong-Vu; Johnson, Lewis E.; Hosono, Hideo

Structure, thermodynamic stability, and electronic properties of CaH 2 surfaces in (001),(110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (~5.2 eV) is in agree-ment with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ~2.7 eV. Surface VH aremore » predicted to aggregate into dimers and form electron-rich centers (e -)Ca 2+(e -) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH 2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.« less
Ultrasonic assisted synthesis of Bikitaite zeolite: A potential material for hydrogen storage application.

PubMed

Roy, Priyanka; Das, Nandini

2017-05-01

Li containing Bikitaite zeolite has been synthesized by an ultrasound-assisted method and used as a potential material for hydrogen storage application. The Sonication energy was varied from 150W to 250W and irradiation time from 3h to 6h. The Bikitaite nanoparticles were characterized by X-ray diffraction (XRD), infrared (IR) spectral analysis, and field-emission scanning electron microscopy (FESEM) thermo-gravimetrical analysis and differential thermal analysis (TGA, DTA). XRD and IR results showed that phase pure, nano crystalline Bikitaite zeolites were started forming after 3h irradiation and 72h of aging with a sonication energy of 150W and nano crystalline Bikitaite zeolite with prominent peaks were obtained after 6h irradiation of 250W sonic energy. The Brunauer-Emmett-Teller (BET) surface area of the powder by N 2 adsorption-desorption measurements was found to be 209m 2 /g. The TEM micrograph and elemental analysis showed that desired atomic ratio of the zeolite was obtained after 6h irradiation. For comparison, sonochemical method, followed by the hydrothermal method, with same initial sol composition was studied. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, and sonication time phase formation was almost completed. The FESEM images revealed that 50nm zeolite crystals were formed at room temperature. However, agglomerated particles having woollen ball like structure was obtained by sonochemical method followed by hydrothermal treatment at 100°C for 24h. The hydrogen adsorption capacity of Bikitaite zeolite with different Li content, has been investigated. Experimental results indicated that the hydrogen adsorption capacities were dominantly related to their surface areas as well as total pore volume of the zeolite. The hydrogen adsorption capacity of 143.2c.c/g was obtained at 77K and ambient pressure of (0.11MPa) for the Bikitaite zeolite with 100% Li, which was higher than the reported values for other zeolites. To the best of our knowledge, there is no report on the synthesis of a Bikitaite zeolite by sonochemical method for H 2 storage. Copyright © 2016. Published by Elsevier B.V.
Surface Passivation of CdZnTe Detector by Hydrogen Peroxide Solution Etching

NASA Technical Reports Server (NTRS)

Hayes, M.; Chen, H.; Chattopadhyay, K.; Burger, A.; James, R. B.

1998-01-01

The spectral resolution of room temperature nuclear radiation detectors such as CdZnTe is usually limited by the presence of conducting surface species that increase the surface leakage current. Studies have shown that the leakage current can be reduced by proper surface preparation. In this study, we try to optimize the performance of CdZnTe detector by etching the detector with hydrogen peroxide solution as function of concentration and etching time. The passivation effect that hydrogen peroxide introduces have been investigated by current-voltage (I-V) measurement on both parallel strips and metal-semiconductor-metal configurations. The improvements on the spectral response of Fe-55 and 241Am due to hydrogen peroxide treatment are presented and discussed.
Evaluation of hydrogen radical treatment for indium surface oxide removal and analysis of re-oxidation behavior

NASA Astrophysics Data System (ADS)

Furuyama, Kohta; Yamanaka, Kazuyuki; Higurashi, Eiji; Suga, Tadatomo

2018-02-01

Indium is a commonly used metal for sealing, bonding, and soldering due to its good malleability and ductility even at cryogenic temperatures. The effects of hydrogen radical treatment on indium surface oxide removal were evaluated by the spreading ratio test of indium balls (diameter, 300 µm purity, 99.99%). It was found that hydrogen radical treatment longer than 20 s at temperatures higher than 170 °C results in successful surface oxide removal. X-ray photoelectron spectroscopy analysis was carried out to study the re-oxidation behavior after treatment, and it was found that hydrogen radical treatment slows down the re-oxidation of indium compared with surface oxide removal realized by physical bombardment with an argon fast atom beam.
Surface Magnetism of Cobalt Nanoislands Controlled by Atomic Hydrogen

DOE PAGES

Park, Jewook; Park, Changwon; Yoon, Mina; ...

2016-12-01

Controlling the spin states of the surface and interface is key to spintronic applications of magnetic materials. We report the evolution of surface magnetism of Co nanoislands on Cu(111) upon hydrogen adsorption and desorption with the hope of realizing reversible control of spin-dependent tunneling. Spin-polarized scanning tunneling microscopy reveals three types of hydrogen-induced surface superstructures, 1H-(2 × 2), 2H-(2 × 2), and 6H-(3 × 3), with increasing H coverage. The prominent magnetic surface states of Co, while being preserved at low H coverage, become suppressed as the H coverage level increases, which can then be recovered by H desorption. First-principlesmore » calculations reveal the origin of the observed magnetic surface states by capturing the asymmetry between the spin-polarized surface states and identify the role of hydrogen in controlling the magnetic states. This study offers new insights into the chemical control of magnetism in low-dimensional systems.« less
Bubble template synthesis of hollow gold nanoparticles and their applications as theranostic agents

NASA Astrophysics Data System (ADS)

Huang, Chienwen

Hollow gold nanoparticle with a sub-30nm polycrystalline shell and a 50 nm hollow core has been successfully synthesized through the reduction of sodium gold sulfite by electrochemically evolved hydrogen. Such hollow gold nanoparticles exhibit unique plasmonic properties. They strongly scatter and absorb near infrared light. In this thesis we seek to understand the formation mechanism of hollow gold nanoparticles in this new synthesis process and their plasmonic properties. Also, we explore their biomedical applications as theranostic agents (therapeutic and diagnostic imaging). A lithographically patterned electrode consisting of Ag stripes on a glass substrate was used to investigate the formation process of hollow gold nanoparticles. Ag stripes served as working electrode for electrochemically evolution of hydrogen, and adjacent glass areas provided supporting surface for hydrogen nanobubbles nucleation and growth. Hydrogen nanobubbles served as both templates and reducing agents to trigger the autocatalytic disproportionation reaction of sodium gold sulfite. The effects of applied potential and the additives in the electrolyte have been studied. It has been found that the size and size distribution of hollow gold nanoparticle are directly relative to the applied potential, i.e. the hydrogen evolution rate. It has also been found the addition of Ni2+ ions can greatly improve the size distribution of hollow gold nanoparticles that can be contributed to that the newly electrodeposited nickel metal can enhance the hydrogen evolution efficiency. Another additive, ethylenediamine (EDA) can suppress the autocatalytic reaction of gold sulfite to increase the stability of sodium gold sulfite electrolyte. To capture such electrochemically evolved hydrogen nanobubbles, and subsequently to generate hollow gold nanoparticles in large numbers, alumina membranes were placed on the top of the working electrode. Anodic alumina membrane consists of ~200 nm pores, which provides a large surface area for the formation of hydrogen nanobubbles. By this approach, the electroless reaction can be easily separated from the electrodeposition process, and hollow gold nanoparticles can be easily collected. Synthesized hollow gold nanoparticles exhibit unique plasmonic properties; the surface plasmon resonance (SPR) lies in the near infrared region (NIR). This is very different from the solid spherical gold nanoparticles. Three-dimensional finite difference time domain (FDTD) simulation was employed to study the plasmonic properties of hollow gold nanoparticles. It has been found that the red-shifts of SPR peaks are mainly caused by their surface roughness, and the hollow nature of these particles only plays a minor role. The surface roughness of hollow gold nanoparticles can be tuned by adjusting the pH of the electrolyte (from 6.0 to 7.0) by adding sodium sulfite. Different surface roughness (from smooth to very rough) can be readily obtained, and correspondingly, surface plasmon resonance (SPR) peaks red-shift from ~600 nm to ~750 nm. Using hollow gold nanoparticles as multifunctional agents for biomedical applications have been explored. Two kinds of agents have been constructed. It has been demonstrated that pegylated Raman dye encoded hollow gold nanoparticles, terms as Raman nanotags, can serve as both diagnostic imaging agents and photothermal therapy agents. When illuminated by near infrared light, the enhanced Raman signal makes the hollow gold nanoparticles to become optically detectable for biomedical imaging, and absorbed light rapidly heat up the hollow gold nanoparticles which can be used to photothermal ablation therapy. The cytotoxicity evaluation using [3H] thymidine incorporation method has shown non-toxicity of the Raman nanotags. The photothermal effects of hollow gold nanoparticles have been examined by two methods: (1) by embedding hollow gold nanoparticles in tissue-like phantom environment; (2) by recording infrared images as temperature increase. The results show that hollow gold nanoparticles are capable to generate sufficiency heat for photothermal therapy. To fully take advantage of the unique hollow core space of hollow gold nanoparticles, a facile route has been develop to trap Fe3O4 nanoparticles into the hollow gold nanoparticles to form Fe3O4/Au core/shell nanoparticles. Fe3O4/Au core/shell nanoparticles possess the desirable magnetic and plasmonic properties that can be used as magnetic resonance contrast (MRI) agents and photothermal therapy agents.
Laser peening for reducing hydrogen embrittlement

DOEpatents

Hackel, Lloyd A.; Zaleski, Tania M.; Chen, Hao-Lin; Hill, Michael R.; Liu, Kevin K.

2010-05-25

A laser peening process for the densification of metal surfaces and sub-layers and for changing surface chemical activities provides retardation of the up-take and penetration of atoms and molecules, particularly Hydrogen, which improves the lifetime of such laser peened metals. Penetration of hydrogen into metals initiates an embrittlement that leaves the material susceptible to cracking.
Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

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

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those ofmore » the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.« less

Global Map of Epithermal Neutrons

NASA Image and Video Library

2002-05-28

Observations by NASA's 2001 Mars Odyssey spacecraft show a global view of Mars in intermediate-energy, or epithermal, neutrons. Soil enriched by hydrogen is indicated by the deep blue colors on the map, which show a low intensity of epithermal neutrons. Progressively smaller amounts of hydrogen are shown in the colors light blue, green, yellow and red. The deep blue areas in the polar regions are believed to contain up to 50 percent water ice in the upper one meter (three feet) of the soil. Hydrogen in the far north is hidden at this time beneath a layer of carbon dioxide frost (dry ice). Light blue regions near the equator contain slightly enhanced near-surface hydrogen, which is most likely chemically or physically bound because water ice is not stable near the equator. The view shown here is a map of measurements made during the first three months of mapping using the neutron spectrometer instrument, part of the gamma ray spectrometer instrument suite. The central meridian in this projection is zero degrees longitude. Topographic features are superimposed on the map for geographic reference. http://photojournal.jpl.nasa.gov/catalog/PIA03800
First-Principles Study of Electronic Structure and Hydrogen Adsorption of 3d Transition Metal Exposed Paddle Wheel Frameworks

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

Bak, J. H.; Le, V. D.; Kang, J.

2012-04-05

Open-site paddle wheels, comprised of two transition metals bridged with four carboxylate ions, have been widely used for constructing metal-organic frameworks with large surface area and high binding energy sites. Using first-principles density functional theory calculations, we have investigated atomic and electronic structures of various 3d transition metal paddle wheels before and after metal exposure and their hydrogen adsorption properties at open metal sites. Notably, the hydrogen adsorption is impeded by covalent metal-metal bonds in early transition metal paddle wheels from Sc to Cr and by the strong ferromagnetic coupling of diatomic Mn and Fe in the paddle wheel configurations.more » A significantly enhanced H{sub 2} adsorption is predicted in the nonmagnetic Co{sub 2} and Zn{sub 2} paddle wheel with the binding energy of {approx}0.2 eV per H{sub 2}. We also propose the use of two-dimensional Co{sub 2} and Zn{sub 2} paddle wheel frameworks that could have strongly adsorbed dihydrogen up to 1.35 wt % for noncryogenic hydrogen storage applications.« less
Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) α-quartz surface

NASA Astrophysics Data System (ADS)

Abbasi, A.; Nadimi, E.; Plänitz, P.; Radehaus, C.

2009-08-01

In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl-hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.
Low friction wear resistant graphene films

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

Sumant, Anirudha V.; Berman, Diana; Erdemir, Ali

A low friction wear surface with a coefficient of friction in the superlubric regime including graphene and nanoparticles on the wear surface is provided, and methods of producing the low friction wear surface are also provided. A long lifetime wear resistant surface including graphene exposed to hydrogen is provided, including methods of increasing the lifetime of graphene containing wear surfaces by providing hydrogen to the wear surface.
Effects of indium contents on photocatalytic performance of ZnIn{sub 2}S{sub 4} for hydrogen evolution under visible light

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

Song, Kelin; Zhu, Rongshu, E-mail: rszhu@hitsz.edu.cn; Public Platform for Technological Service in Urban Waste Reuse and Energy Regeneration, Shenzhen 518055

2015-12-15

A series of ZnIn{sub x}S{sub 4+y} (x=1.6, 2.0, 2.3, 2.6, 2.9, 3.1) photocatalysts were synthesized via a facile hydrothermal method and characterized by various analytical techniques, such as XRD, EDS, UV–vis DRS, SEM, TEM, BET and PL. The ZnIn{sub x}S{sub 4+y} photocatalysts had a similar crystal structure. With the increase of indium content, the absorption edges of ZnIn{sub x}S{sub 4+y} photocatalysts shifted to longer wavelength, their crystal sizes decreased firstly and then increased and the variation of the specific surface area and total pore volume was exactly opposite. Especially, when x=2.3, ZnIn{sub 2.3}S{sub 4+y} catalyst had smallest crystal size, largestmore » specific surface area and total pore volume. Additionally, the morphology of ZnIn{sub x}S{sub 4+y} greatly depended on the contents of indium. The photocatalytic activity of ZnIn{sub x}S{sub 4+y} was evaluated by photocatalytic hydrogen production from water under visible light. The ZnIn{sub 2.3}S{sub 4+y} sample had the highest photocatalytic activity among these ZnIn{sub x}S{sub 4+y} photocatalysts and its hydrogen production rate was 363 μmol/g h. - Graphical abstract: First, a series of catalysts were synthesized. And then those were characterized by various analytical techniques (such as SEM). finally, The photocatalytic activity of catalyst was evaluated by photocatalytic hydrogen production from water under visible light. - Highlights: • The photocatalytic property was studied upon visible-light irradiation. • ZnIn{sub x}S{sub 4+y} photocatalysts show superior photocatalytic activity. • The catalyst of grain size, morphology and BET are related to indium content. • ZnIn{sub x}S{sub 4+y} photocatalysts were synthesized via a facile hydrothermal method.« less
Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

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

King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F.

2015-09-15

Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorptionmore » (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and Si–O bonding, they may still exhibit significant chemical reactivity due to the creation of surface dangling bonds resulting from H{sub 2} desorption from previously undetected silicon hydride and surface hydroxide species.« less
Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study

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

Ye, Jingyun; Liu, Changjun; Mei, Donghai

2013-06-03

Methanol synthesis from CO2 hydrogenation on the defective In2O3(110) surface with surface oxygen vacancies has been investigated using periodic density functional theory calculations. The relative stabilities of six possible surface oxygen vacancies numbered from Ov1 to Ov6 on the perfect In2O3(110) surface were examined. The calculated oxygen vacancy formation energies show that the D1 surface with the Ov1 defective site is the most thermodynamically favorable while the D4 surface with the Ov4 defective site is the least stable. Two different methanol synthesis routes from CO2 hydrogenation over both D1 and D4 surfaces were studied and the D4 surface was foundmore » to be more favorable for CO2 activation and hydrogenation. On the D4 surface, one of the O atoms of the CO2 molecule fills in the Ov4 site upon adsorption. Hydrogenation of CO2 to HCOO on the D4 surface is both thermodynamically and kinetically favorable. Further hydrogenation of HCOO involves both forming the C-H bond and breaking the C-O bond, resulting in H2CO and hydroxyl. The HCOO hydrogenation is slightly endothermic with an activation barrier of 0.57 eV. A high barrier of 1.14 eV for the hydrogenation of H2CO to H3CO indicates that this step is the rate-limiting step in the methanol synthesis on the defective In2O3(110) surface. We gratefully acknowledge the supports from the National Natural Science Foundation of China (#20990223) and from US Department of Energy, Basic Energy Science program (DE-FG02-05ER46231). D. Mei was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory in Richland, Washington. PNNL is a multiprogram national laboratory operated for DOE by Battelle.« less
Adsorption of 2 Chloroethyl Ethyl Sulfide on Silica: Binding Mechanism and Energy of a Bifunctional Hydrogen-Bond Acceptor at the Gas Surface Interface

DTIC Science & Technology

2014-11-19

C. A. S.; Sumpter, K. B.; Wagner, G. W.; Rice, J. S. Degradation of the Blister Agent Sulfur Mustard, Bis(2-chloroethyl) Sulfide, on Concrete . J...SECURITY CLASSIFICATION OF: This work investigates the fundamental nature of sulfur mustard surface adsorption by characterizing interfacial hydrogen...nature of sulfur mustard surface adsorption by characterizing interfacial hydrogen bonding and other intermolecular forces for the surrogate molecule
Catalysis beyond frontier molecular orbitals: Selectivity in partial hydrogenation of multi-unsaturated hydrocarbons on metal catalysts

PubMed Central

Liu, Wei; Jiang, Yingda; Dostert, Karl-Heinz; O’Brien, Casey P.; Riedel, Wiebke; Savara, Aditya; Schauermann, Swetlana; Tkatchenko, Alexandre

2017-01-01

The mechanistic understanding and control over transformations of multi-unsaturated hydrocarbons on transition metal surfaces remains one of the major challenges of hydrogenation catalysis. To reveal the microscopic origins of hydrogenation chemoselectivity, we performed a comprehensive theoretical investigation on the reactivity of two α,β-unsaturated carbonyls—isophorone and acrolein—on seven (111) metal surfaces: Pd, Pt, Rh, Ir, Cu, Ag, and Au. In doing so, we uncover a general mechanism that goes beyond the celebrated frontier molecular orbital theory, rationalizing the C═C bond activation in isophorone and acrolein as a result of significant surface-induced broadening of high-energy inner molecular orbitals. By extending our calculations to hydrogen-precovered surface and higher adsorbate surface coverage, we further confirm the validity of the “inner orbital broadening mechanism” under realistic catalytic conditions. The proposed mechanism is fully supported by our experimental reaction studies for isophorone and acrolein over Pd nanoparticles terminated with (111) facets. Although the position of the frontier molecular orbitals in these molecules, which are commonly considered to be responsible for chemical interactions, suggests preferential hydrogenation of the C═O double bond, experiments show that hydrogenation occurs at the C═C bond on Pd catalysts. The extent of broadening of inner molecular orbitals might be used as a guiding principle to predict the chemoselectivity for a wide class of catalytic reactions at metal surfaces. PMID:28782033
Ab initio molecular dynamics simulations for the role of hydrogen in catalytic reactions of furfural on Pd(111)

NASA Astrophysics Data System (ADS)

Xue, Wenhua; Dang, Hongli; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2014-03-01

In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of hydrogen has attracted wide attention. We report ab initio molecular dynamics simulations for furfural and hydrogen on the Pd(111) surface at finite temperatures. The simulations demonstrate that the presence of hydrogen is important in promoting furfural conversion. In particular, hydrogen molecules dissociate rapidly on the Pd(111) surface. As a result of such dissociation, atomic hydrogen participates in the reactions with furfural. The simulations also provide detailed information about the possible reactions of hydrogen with furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.
Surface Passivation and Junction Formation Using Low Energy Hydrogen Implants

NASA Technical Reports Server (NTRS)

Fonash, S. J.

1985-01-01

New applications for high current, low energy hydrogen ion implants on single crystal and polycrystal silicon grain boundaries are discussed. The effects of low energy hydrogen ion beams on crystalline Si surfaces are considered. The effect of these beams on bulk defects in crystalline Si is addressed. Specific applications of H+ implants to crystalline Si processing are discussed. In all of the situations reported on, the hydrogen beams were produced using a high current Kaufman ion source.
The interaction of hydrogen with the {010} surfaces of Mg and Fe olivine as models for interstellar dust grains: a density functional theory study

PubMed Central

Downing, C. A.; Ahmady, B.; Catlow, C. R. A.; de Leeuw, N. H.

2013-01-01

There is no consensus as yet to account for the significant presence of water on the terrestrial planets, but suggested sources include direct hydrogen adsorption from the parent molecular cloud after the planets’ formation, and delivery of hydrous material via comets or asteroids external to the zone of the terrestrial planets. Alternatively, a more recent idea is that water may have directly adsorbed onto the interstellar dust grains involved in planetary formation. In this work, we use electronic structure calculations based on the density functional theory to investigate and compare the bulk and {010} surface structures of the magnesium and iron end-members of the silicate mineral olivine, namely forsterite and fayalite, respectively. We also report our results on the adsorption of atomic hydrogen at the mineral surfaces, where our calculations show that there is no activation barrier to the adsorption of atomic hydrogen at these surfaces. Furthermore, different surface sites activate the atom to form either adsorbed hydride or proton species in the form of hydroxy groups on the same surface, which indicates that these mineral surfaces may have acted as catalytic sites in the immobilization and reaction of hydrogen atoms to form dihydrogen gas or water molecules. PMID:23734054
DFT study of CO2 conversion on InZr3(110) surface.

PubMed

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2017-11-01

Methanol and methane synthesis from CO 2 hydrogenation on a InZr 3 (110) surface has been studied using density functional theory calculations. The CO 2 can be chemically adsorbed via a polydentated configuration and the H 2 molecule can dissociate to H atoms spontaneously. The methanol is primarily formed via the HCOO route instead of the RWGS route, due to its higher activation barrier of 1.35 eV for HCO hydrogenation. In the HCOO route, the adsorbed CO 2 consecutively hydrogenates to form HCOO, H 2 COO and the H 3 CO species. The H 3 COH is produced via the reaction of H 3 CO with a surface OH group. Furthermore, the C-O bonds of CO, CHO, CH 2 O and CH 3 O species prefer to dissociate to C, CH, CH 2 CH 3 and surface O species. Methane is formed via the hydrogenation of CH x (x = 0-3) monomers with the highest activation barrier of 1.19 eV for CH 3 hydrogenation, which is higher than that of the hydrogenation of H 2 COO in methanol synthesis via the HCOO route. The surface O species formed during CO 2 hydrogenation reacts with the adsorbed H 2 molecule to produce an OH group which reacts with a surface H atom to form H 2 O with an activation barrier of 1.13 eV, which then desorbs to the gas phase. Our calculated results indicate that the InZr 3 alloy is a potential candidate catalyst for CO 2 utilization and conversion.
Advanced capabilities and applications of a sputter-RBS system

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

Brijs, B.; Deleu, J.; Beyer, G.

1999-06-10

In previous experiments, sputter-RBS{sup 1} has proven to be an ideal tool to study the interaction of low energy ions. This contribution employs the same methodology to identify surface contamination induced during sputtering and to the determine absolute sputter yields. In the first experiment ERDA analysis was used to study the evolution of Hydrogen contamination during sputter-RBS experiments. Since the determination of Hydrogen concentration in very thin near surface layers is frequently limited by the presence of a strong surface peak of Hydrogen originating from adsorbed contamination of the residual vacuum, removal of this contamination would increase the sensitivity formore » Hydrogen detection in the near sub surface drastically. Therefore low energy (12 keV) Argon sputtering was used to remove the Hydrogen surface peak. However enhanced Hydrogen adsorption was observed related to the Ar dose. This experiment shows that severe vacuum conditions and the use of high current densities/sputter yields are a prerequisite for an efficient detection of Hydrogen in the near surface layers. In the second experiment, an attempt was made to determine the sputter yield of Cu during low energy (12 keV) Oxygen bombardment. In order to determine the accumulated dose of the low energy ion beam, a separate Faraday cup in combination with a remote controlled current have been added to the existing sputter-RBS set-up. Alternating sputtering and RBS analysis seem to be an adequate tool for the determination of the absolute sputter yield of Cu and this as well in the as under steady state conditions.« less
Growth of Desulfovibrio on the surface of agar media.

PubMed

Iverson, W P

1966-07-01

Growth of Desulfovibrio desulfuricans (API strain) was found to take place in an atmosphere of hydrogen on the agar surface of complex media, including yeast extract (Difco), and Trypticase Soy Agar (BBL) without any added reducing agents. For growth on a 2% yeast extract-agar surface in the absence of hydrogen (nitrogen atmosphere), sodium lactate was required in the medium. Growth on the surface of Trypticase Soy Agar (TSA) under nitrogen took place readily in the absence of an added hydrogen donor. A medium (TSA plus salts) is described based upon the addition of sodium lactate (4 ml per liter), magnesium sulfate (2 g per liter), and ferrous ammonium sulfate (0.05%) to TSA, which appears suitable for the isolation and growth of Desulfovibrio on the surface of agar plates in an atmosphere of hydrogen. Sodium lactate does not appear to be essential in this medium for good growth and sulfate reduction in a hydrogen atmosphere, but is essential in a nitrogen atmosphere. Growth of Desulfovibrio (hydrogen atmosphere) on the agar surface of media commonly used for its cultivation as well as on an inorganic medium containing bicarbonate as a source of carbon is poor and erratic unless inoculated (Desulfovibrio) plates of TSA plus salts are incubated in the same container with plates of these media. This stimulatory effect of incubation with inoculated plates of TSA plus salts medium appears to be due to as yet unidentified volatile material produced by D. desulfuricans when growing on this medium. Another volatile material, or possibly the identical material, appears to act similarly to a hydrogen donor.
An ab initio cluster study of the chemisorption of atomic cesium and hydrogen on reconstructed surfaces of gallium rich gallium arsenide

NASA Astrophysics Data System (ADS)

Schailey, Ronald

1999-11-01

Chemisorption properties of cesium and hydrogen atoms on the Ga-rich GaAs (100) (2 x 1), (2 x 2), and β(4 x 2) surfaces are investigated using ab initio self-consistent restricted open shell Hartree-Fock (ROHF) total energy calculations with Hay- Wadt effective core potentials. The effects of electron correlation have been included using many-body perturbation theory through second order, with the exception of β(4 x 2) symmetry due to computational limitations. The semiconductor surface is modeled by finite sized hydrogen saturated clusters. The effects of surface relaxation and reconstruction have been investigated in detail. Results are given for the energetics of chemisorption, charge population analysis, HOMO-LUMO gaps, and consequent possibilities of metallization for atomic cesium adsorption. For the chemisorption of atomic hydrogen, the experimentally verified mechanism of surface dimer bond breaking is investigated in detail.
Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

PubMed

Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

2016-03-29

Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).
Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis

PubMed Central

Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

2016-01-01

Nuclear reaction analysis (NRA) via the resonant 1H(15N,αγ)12C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a 15N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the 1H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~1013 cm-2 (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~1018 cm-3 (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal 15N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, 1H(15N,αγ)12C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of 15N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100). PMID:27077920
Devolatilization of coal particles in a flat flame -- Experimental and modeling study

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

Therssen, E.; Gourichon, L.; Delfosse, L.

1995-10-01

Pulverized coals have been tested under the conditions of industrial flames, with high heating rate and high temperatures. The chars were collected after different pyrolysis times. For eight coals, the devolatilized fraction of coal has been measured, as well as those of carbon, hydrogen and nitrogen. During pyrolysis, the evolution of the texture of the grains has been studied by measurement of their microporous surface area, which undergoes a large increase, depending on coal rank. The composition of the volatiles, as deduced from the ultimate and proximate analysis of chars, showed high volatile bituminous coals to essentially produce tars withmore » an aromatic structure. Low and medium volatile bituminous coals produced light hydrocarbons on devolatilization and the char`s surface area continued increasing slowly during the whole of devolatilization, according to the slow increase of the fraction of hydrogen devolatilized. The char`s reactivity with oxygen was followed by measurements of Active Surface Area (ASA). It was shown that the ASA continuously decreases during devolatilization. Five models of devolatilization in the literature were tested and compared to the experimental results, assuming first-order reactions with respect to the remaining volatile matter. Badzioch`s model correctly fitted the experimental results and values of the rate constant obtained by computer trial and error adjustment were higher for lower ranks of the four bituminous coals. Anthony`s model also fits the measurements, provided an adjustment of the preexponential factor of activation energy for which it is shown that an infinite number of such pairs is suitable. If the model is run isothermally at the flame`s peak temperature, it also correctly fits the experimental results.« less
Electrodeposition of Rhodium Nanowires Arrays and Their Morphology-Dependent Hydrogen Evolution Activity

PubMed Central

Zhang, Liqiu; Liu, Lichun; Wang, Hongdan; Shen, Hongxia; Cheng, Qiong; Yan, Chao; Park, Sungho

2017-01-01

This work reports on the electrodeposition of rhodium (Rh) nanowires with a controlled surface morphology synthesized using an anodic aluminum oxide (AAO) template. Vertically aligned Rh nanowires with a smooth and coarse morphology were successfully deposited by adjusting the electrode potential and the concentration of precursor ions and by involving a complexing reagent in the electrolyte solution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses were used to follow the morphological evolution of Rh nanowires. As a heterogeneous electrocatalyst for hydrogen evolution reactions (HER), the coarse Rh nanowire array exhibited an enhanced catalytic performance respect to smooth ones due to the larger surface area to mass ratio and the higher density of catalytically active defects, as evidenced by voltammetric measurements and TEM. Results suggest that the morphology of metallic nanomaterials could be readily engineered by electrodeposition. The controlled electrodeposition offers great potential for the development of an effective synthesis tool for heterogeneous catalysts with a superior performance for wide applications. PMID:28467375

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

Ali T-Raissi

The aim of this work was to assess issues of cost, and performance associated with the production and storage of hydrogen via following three feedstocks: sub-quality natural gas (SQNG), ammonia (NH{sub 3}), and water. Three technology areas were considered: (1) Hydrogen production utilizing SQNG resources, (2) Hydrogen storage in ammonia and amine-borane complexes for fuel cell applications, and (3) Hydrogen from solar thermochemical cycles for splitting water. This report summarizes our findings with the following objectives: Technoeconomic analysis of the feasibility of the technology areas 1-3; Evaluation of the hydrogen production cost by technology areas 1; and Feasibility of ammoniamore » and/or amine-borane complexes (technology areas 2) as a means of hydrogen storage on-board fuel cell powered vehicles. For each technology area, we reviewed the open literature with respect to the following criteria: process efficiency, cost, safety, and ease of implementation and impact of the latest materials innovations, if any. We employed various process analysis platforms including FactSage chemical equilibrium software and Aspen Technologies AspenPlus and HYSYS chemical process simulation programs for determining the performance of the prospective hydrogen production processes.« less
Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

NASA Astrophysics Data System (ADS)

Bates, Michael

Understanding the fundamentals of electrochemical interfaces will undoubtedly reveal a path forward towards a society based on clean and renewable energy. In particular, it has been proposed that hydrogen can play a major role as an energy carrier of the future. To fully utilize the clean energy potential of a hydrogen economy, it is vital to produce hydrogen via water electrolysis, thus avoiding co-production of CO2 inherent to reformate hydrogen. While significant research efforts elsewhere are focused on photo-chemical hydrogen production from water, the inherent low efficiency of this method would require a massive land-use footprint to achieve sufficient hydrogen production rates to integrate hydrogen into energy markets. Thus, this research has primarily focused on the water splitting reactions on base-metal catalysts in the alkaline environment. Development of high-performance base-metal catalysts will help move alkaline water electrolysis to the forefront of hydrogen production methods, and when paired with solar and wind energy production, represents a clean and renewable energy economy. In addition to the water electrolysis reactions, research was conducted to understand the de-activation of reversible hydrogen electrodes in the corrosive environment of the hydrogen-bromine redox flow battery. Redox flow batteries represent a promising energy storage option to overcome the intermittency challenge of wind and solar energy production methods. Optimization of modular and scalable energy storage technology will allow higher penetration of renewable wind and solar energy into the grid. In Chapter 1, an overview of renewable energy production methods and energy storage options is presented. In addition, the fundamentals of electrochemical analysis and physical characterization of the catalysts are discussed. Chapter 2 reports the development of a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).
Amine–mixed oxide hybrid materials for carbon dioxide adsorption from CO2/H2 mixture

NASA Astrophysics Data System (ADS)

Ravi, Navin; Aishah Anuar, Siti; Yusuf, Nur Yusra Mt; Isahak, Wan Nor Roslam Wan; Shahbudin Masdar, Mohd

2018-05-01

Bio-hydrogen mainly contains hydrogen and high level of carbon dioxide (CO2). High concentration of CO2 lead to a limitation especially in fuel cell application. In this study, the amine-mixed oxide hybrid materials for CO2 separation from bio-hydrogen model (50% CO2:50% H2) have been studied. Fourier-transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD) characterizations showed that the amine–mixed oxide hybrid materials successfully adsorbed CO2 physically with no chemical adsorption evidence. The dry gas of CO2/H2 mixture adsorbed physically on amine–CuO–MgO hybrid material. No carbonates were detected after several times of adsorption, which indicated the good recyclability of adsorbents. The adsorbent system of diethanolamine (DEA)/15% CuO–75% MgO showed the highest CO2 adsorption capacity of 21.2 wt% due to the presence of polar substance on MgO surface, which can adsorb CO2 at ambient condition. The alcohol group of DEA can enhance the CO2 solubility on the adsorbent surface. In the 20% CuO–50% MgO adsorbent system, DEA as amine type showed a high CO2 adsorption of 19.4 wt%. The 10% amine loading system showed that the DEA adsorption system provided high CO2 adsorption. The BET analysis confirmed that a high amine loading contributed to the decrease in CO2 adsorption due to the low surface area of the adsorbent system.
On the effect of hydrogen on the mechanical behavior of Beta-C titanium in aged condition

NASA Astrophysics Data System (ADS)

Alvarez, Anna-Maria

The effect of hydrogen in solid solution on the mechanical behavior of the metastable beta-titanium alloy Beta-C was studied. The samples were aged at 482°C for 28 h prior to hydrogen charging in order to obtain a microstructure of alpha-precipitates in a beta-phase matrix. The kinetics and thermodynamics of hydrogen uptake in the alloy were studied in order to determine the required parameters to gas charge the samples with hydrogen, without altering the microstructure. The mechanical samples were hydrogen charged at 350°C to hydrogen concentrations between 0.6 and 24 at%. The samples were thereafter tested under tensile and alternating loading in order to study the effect of hydrogen on the tensile properties, fatigue properties and crack propagation rate. The fracture surfaces were then studied by using SEM, TEM and X-ray diffraction techniques. The macroscopic mechanical properties were compared with the micromechanisms of deformation and fracture in order to obtain information about the operating hydrogen-enhanced fracture mechanism. It was found that the tensile behavior was sensitive to hydrogen. A sharp ductile-to-brittle transition (DBT) occurred when hydrogen in solid solution reached a concentration of about 3.5 at%. TEM and X-ray analysis showed that stress-induced hydrides form in areas of low stress intensities at hydrogen concentrations above the DBT, and it is therefore believed that this is the cause of the hydrogen embrittlement in this alloy. However, at higher stress intensities, slip localization and enhanced slip band fracture were observed. Since slip localization and hydrogen-induced slip band fracture have previously been connected with a large decrease in ductility it can not be excluded that these effects of hydrogen affects the DBT. The cyclic stress strain behavior was not affected by hydrogen; the non-linear elastic behavior and the cyclic softening did not change with introduction of hydrogen up to a level of 10.8 at%. The fatigue life was, however, reduced when hydrogen charged samples were tested at low frequency (0.00032 Hz).
Electrochemical Approach for Effective Antifouling and Antimicrobial Surfaces.

PubMed

Gaw, Sheng Long; Sarkar, Sujoy; Nir, Sivan; Schnell, Yafit; Mandler, Daniel; Xu, Zhichuan J; Lee, Pooi See; Reches, Meital

2017-08-09

Biofouling, the adsorption of organisms to a surface, is a major problem today in many areas of our lives. This includes: (i) health, as biofouling on medical device leads to hospital-acquired infections, (ii) water, since the accumulation of organisms on membranes and pipes in desalination systems harms the function of the system, and (iii) energy, due to the heavy load of the organic layer that accumulates on marine vessels and causes a larger consumption of fuel. This paper presents an effective electrochemical approach for generating antifouling and antimicrobial surfaces. Distinct from previously reported antifouling or antimicrobial electrochemical studies, we demonstrate the formation of a hydrogen gas bubble layer through the application of a low-voltage square-waveform pulses to the conductive surface. This electrochemically generated gas bubble layer serves as a separation barrier between the surroundings and the target surface where the adhesion of bacteria can be deterred. Our results indicate that this barrier could effectively reduce the adsorption of bacteria to the surface by 99.5%. We propose that the antimicrobial mechanism correlates with the fundamental of hydrogen evolution reaction (HER). HER leads to an arid environment that does not allow the existence of live bacteria. In addition, we show that this drought condition kills the preadhered bacteria on the surface due to water stress. This work serves as the basis for the exploration of future self-sustainable antifouling techniques such as incorporating it with photocatalytic and photoelectrochemical reactions.
FI-STM study of hydrogen adsorption on Si(100) surface

NASA Astrophysics Data System (ADS)

Hua, Lu; Xiang-dong, Wang; Motai, K.; Hashizume, T.; Sakurai, T.

1992-11-01

Chemisorption of atomic hydrogen on the Si(100)2 × 1 surface has been investigated in detail by using a field ion-scanning tunneling microscope (FI-STM). The results showed that the adsorption geometry changed from the 2 × 1 monohydride phase to the 1 × 1 dihydride phase with increasing exposure of hydrogen. The data of desorption of the hydrogen-saturated Si surface showed that on annealing at 670 K the surface becomes highly disordered: the 1 × 1 dihydride structure is eliminated and the 2 × 1 reconstructed monohydride is also hardly to identify. When the temperature rises to as high as 730 K, the surface is dominated by the 2 × 1 structure with missing dimer rows, and some adatom chains occur on the Si substrate terraces. We attribute the formation of these atomic chains to an epitaxial growth of Si atoms which are formed by the dissociation of SiHx (x = 1, 2, 3 or 4) compounds on the Si surface.
Heat and mass transfer rates during flow of dissociated hydrogen gas over graphite surface

NASA Technical Reports Server (NTRS)

Nema, V. K.; Sharma, O. P.

1986-01-01

To improve upon the performance of chemical rockets, the nuclear reactor has been applied to a rocket propulsion system using hydrogen gas as working fluid and a graphite-composite forming a part of the structure. Under the boundary layer approximation, theoretical predictions of skin friction coefficient, surface heat transfer rate and surface regression rate have been made for laminar/turbulent dissociated hydrogen gas flowing over a flat graphite surface. The external stream is assumed to be frozen. The analysis is restricted to Mach numbers low enough to deal with the situation of only surface-reaction between hydrogen and graphite. Empirical correlations of displacement thickness, local skin friction coefficient, local Nusselt number and local non-dimensional heat transfer rate have been obtained. The magnitude of the surface regression rate is found low enough to ensure the use of graphite as a linear or a component of the system over an extended period without loss of performance.
Carbon-based supercapacitors produced by activation of graphene.

PubMed

Zhu, Yanwu; Murali, Shanthi; Stoller, Meryl D; Ganesh, K J; Cai, Weiwei; Ferreira, Paulo J; Pirkle, Adam; Wallace, Robert M; Cychosz, Katie A; Thommes, Matthias; Su, Dong; Stach, Eric A; Ruoff, Rodney S

2011-06-24

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp(2)-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.
Carbon-Based Supercapacitors Produced by Activation of Graphene

NASA Astrophysics Data System (ADS)

Zhu, Yanwu; Murali, Shanthi; Stoller, Meryl D.; Ganesh, K. J.; Cai, Weiwei; Ferreira, Paulo J.; Pirkle, Adam; Wallace, Robert M.; Cychosz, Katie A.; Thommes, Matthias; Su, Dong; Stach, Eric A.; Ruoff, Rodney S.

2011-06-01

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp2-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.
Method for forming a chemical microreactor

DOEpatents

Morse, Jeffrey D [Martinez, CA; Jankowski, Alan [Livermore, CA

2009-05-19

Disclosed is a chemical microreactor that provides a means to generate hydrogen fuel from liquid sources such as ammonia, methanol, and butane through steam reforming processes when mixed with an appropriate amount of water. The microreactor contains capillary microchannels with integrated resistive heaters to facilitate the occurrence of catalytic steam reforming reactions. Two distinct embodiment styles are discussed. One embodiment style employs a packed catalyst capillary microchannel and at least one porous membrane. Another embodiment style employs a porous membrane with a large surface area or a porous membrane support structure containing a plurality of porous membranes having a large surface area in the aggregate, i.e., greater than about 1 m.sup.2/cm.sup.3. Various methods to form packed catalyst capillary microchannels, porous membranes and porous membrane support structures are also disclosed.
Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

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

Matanovic, Ivana; Garzon, Fernando H.

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less
Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

DOE PAGES

Matanovic, Ivana; Garzon, Fernando H.

2018-04-26

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less
Efficacy of "green" cleaning products with respect to common respiratory viruses and mold growth.

PubMed

Light, Ed

2009-05-01

Some disinfectants have been demonstrated to be effective against surface mold growth and/or viruses responsible for the spread of common respiratory infections. Antimicrobial efficacy of green cleaning products has generally not been established in these areas. In this survey, the author found that out of 27 products approved by Green Seal as hard surface cleaners, 26 do not claim antimicrobial capability. While some contained hydrogen peroxide, a compound with limited spectrum disinfection capabilities, only one was registered with the U.S. Environmental Protection Agency as antimicrobial. The need for additional research and documentation is discussed.
Surface Acidity and Properties of TiO2/SiO2 Catalysts Prepared by Atomic Layer Deposition: UV-visible Diffuse Reflectance, DRIFTS, and Visible Raman Spectroscopy Studies

DTIC Science & Technology

2009-06-15

titanium isopropoxide (TTIP) as metal precursors. The deposition rate of titania films from TiCl4 was found to be stable in the 150-300 °C...tetrachloride (TiCl4) and titanium isopropoxide (TTIP) are widely used as metal precursors and water or hydrogen peroxide are used as oxygen precursors.29-36... titanium dioxide supported on high surface area silica gel have been synthesized by atomic layer deposition (ALD) using titanium tetrachloride (TiCl4) and
The Potential Role Played by the Fullerene-Like Structures of Interstellar Carbon Dust in the Formation of Molecular Hydrogen in Space

NASA Astrophysics Data System (ADS)

Cataldo, Franco; Iglesias-Groth, Susana

After a general introduction to the problem of formation of molecular hydrogen from atomic hydrogen in the interstellar medium and in the dense molecular clouds in particular, and after the explanation of the key role played by the surfaces on this process, it is proposed that the most suitable carbon surface for the formation of molecular hydrogen (from the radiative association process of atomic hydrogen) can be represented by carbon black rather than by graphite. Furthermore, it is proposed that the fullerene-like structures present in the carbon black graphene sheets are the reaction sites where molecular hydrogen may be formed.
Impedance spectroscopy of reduced monoclinic zirconia.

PubMed

Eder, Dominik; Kramer, Reinhard

2006-10-14

Zirconia doped with low-valent cations (e.g. Y3+ or Ca2+) exhibits an exceptionally high ionic conductivity, making them ideal candidates for various electrochemical applications including solid oxide fuel cells (SOFC) and oxygen sensors. It is nevertheless important to study the undoped, monoclinic ZrO2 as a model system to construct a comprehensive picture of the electrical behaviour. In pure zirconia a residual number of anion vacancies remains because of contaminants in the material as well as the thermodynamic disorder equilibrium, but electronic conduction may also contribute to the observed conductivity. Reduction of zirconia in hydrogen leads to the adsorption of hydrogen and to the formation of oxygen vacancies, with their concentration affected by various parameters (e.g. reduction temperature and time, surface area, and water vapour pressure). However, there is still little known about the reactivities of defect species and their effect on the ionic and electronic conduction. Thus, we applied electrochemical impedance spectroscopy to investigate the electric performance of pure monoclinic zirconia with different surface areas in both oxidizing and reducing atmospheres. A novel equivalent circuit model including parallel ionic and electronic conduction has previously been developed for titania and is used herein to decouple the conduction processes. The concentration of defects and their formation energies were measured using volumetric oxygen titration and temperature programmed oxidation/desorption.
Photocatalytic degradation of H2S aqueous media using sulfide nanostructured solid-solution solar-energy-materials to produce hydrogen fuel.

PubMed

Lashgari, Mohsen; Ghanimati, Majid

2018-03-05

H 2 S is a corrosive, flammable and noxious gas, which can be neutralized by dissolving in alkaline media and employed as H 2 -source by utilizing inside semiconductor-assisted/photochemical reactors. Herein, through a facile hydrothermal route, a ternary nanostructured solid-solution of iron, zinc and sulfur was synthesized in the absence and presence of Ag-dopant, and applied as efficient photocatalyst of hydrogen fuel production from H 2 S media. The effect of pH on the photocatalyst performance was scrutinized and the maximum activity was attained at pH=11, where HS - concentration is high. BET, diffuse reflectance and photoluminescence studies indicated that the ternary solid-solution photocatalyst, in comparison to its solid-solvent (ZnS), has a greater surface area, stronger photon absorption and less charge recombination, which justify its superiority. Moreover, the effect of silver-dopant on the photocatalyst performance was examined. The investigations revealed that although silver could boost the absorption of photons and increase the surface area, it could not appreciably enhance the photocatalyst performance due to its weak influence on retarding the charge-recombination process. Finally, the phenomenon was discussed in detail from mechanistic viewpoint. Copyright © 2017 Elsevier B.V. All rights reserved.
Chemical vapor deposition of mesoporous graphene nanoballs for supercapacitor.

PubMed

Lee, Jung-Soo; Kim, Sun-I; Yoon, Jong-Chul; Jang, Ji-Hyun

2013-07-23

A mass-producible mesoporous graphene nanoball (MGB) was fabricated via a precursor-assisted chemical vapor deposition (CVD) technique for supercapacitor application. Polystyrene balls and reduced iron created under high temperature and a hydrogen gas environment provide a solid carbon source and a catalyst for graphene growth during the precursor-assisted CVD process, respectively. Carboxylic acid and sulfonic acid functionalization of the polystyrene ball facilitates homogeneous dispersion of the hydrophobic polymer template in the metal precursor solution, thus, resulting in a MGB with a uniform number of graphene layers. The MGB is shown to have a specific surface area of 508 m(2)/g and is mesoporous with a mean mesopore diameter of 4.27 nm. Mesopores are generated by the removal of agglomerated iron domains, permeating down through the soft polystyrene spheres and providing the surface for subsequent graphene growth during the heating process in a hydrogen environment. This technique requires only drop-casting of the precursor/polystyrene solution, allowing for mass-production of multilayer MGBs. The supercapacitor fabricated by the use of the MGB as an electrode demonstrates a specific capacitance of 206 F/g and more than 96% retention of capacitance after 10,000 cycles. The outstanding characteristics of the MGB as an electrode for supercapacitors verify the strong potential for use in energy-related areas.
Process for producing methane from gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.
Diffusion of hydrogen into and through γ-iron by density functional theory

NASA Astrophysics Data System (ADS)

Chohan, Urslaan K.; Koehler, Sven P. K.; Jimenez-Melero, Enrique

2018-06-01

This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.

Structural changes caused by H 2 adsorption on the Si(111)7 × 7 surface

NASA Astrophysics Data System (ADS)

Wolff, S. H.; Wagner, S.; Gibson, J. M.; Loretto, D.; Robinson, I. K.; Bean, J. C.

1990-12-01

Structural changes caused by the adsorption of molecular hydrogen adsorption onto the Si(111)7 × 7 surface reconstruction are quantified using the first structure parameter refinement on transmission electron diffraction (TED) data. We find that initial adsorption of molecular hydrogen onto the Si(111)7 × 7 surface causes a preferential decrease in the occupancy of the center adatoms. Further adsorption of hydrogen results in the breaking of the dimer bonds and the removal of the corner adatoms.
Intelligent Chemical Sensor Systems for In-space Safety Applications

NASA Technical Reports Server (NTRS)

Hunter, G. W.; Xu, J. C.; Neudeck, P. G.; Makel, D. B.; Ward, B.; Liu, C. C.

2006-01-01

Future in-space and lunar operations will require significantly improved monitoring and Integrated System Health Management (ISHM) throughout the mission. In particular, the monitoring of chemical species is an important component of an overall monitoring system for space vehicles and operations. For example, in leak monitoring of propulsion systems during launch, inspace, and on lunar surfaces, detection of low concentrations of hydrogen and other fuels is important to avoid explosive conditions that could harm personnel and damage the vehicle. Dependable vehicle operation also depends on the timely and accurate measurement of these leaks. Thus, the development of a sensor array to determine the concentration of fuels such as hydrogen, hydrocarbons, or hydrazine as well as oxygen is necessary. Work has been on-going to develop an integrated smart leak detection system based on miniaturized sensors to detect hydrogen, hydrocarbons, or hydrazine, and oxygen. The approach is to implement Microelectromechanical Systems (MEMS) based sensors incorporated with signal conditioning electronics, power, data storage, and telemetry enabling intelligent systems. The final sensor system will be self-contained with a surface area comparable to a postage stamp. This paper discusses the development of this "Lick and Stick" leak detection system and it s application to In-Space Transportation and other Exploration applications.
Baking and helium glow discharge cleaning of SST-1 Tokamak with graphite plasma facing components

NASA Astrophysics Data System (ADS)

Semwal, P.; Khan, Z.; Raval, D. C.; Dhanani, K. R.; George, S.; Paravastu, Y.; Prakash, A.; Thankey, P.; Ramesh, G.; Khan, M. S.; Saikia, P.; Pradhan, S.

2017-04-01

Graphite plasma facing components (PFCs) were installed inside the SST-1 vacuum vessel. Prior to installation, all the graphite tiles were baked at 1000 °C in a vacuum furnace operated below 1.0 × 10-5 mbar. However due to the porous structure of graphite, they absorb a significant amount of water vapour from air during the installation process. Rapid desorption of this water vapour requires high temperature bake-out of the PFCs at ≥ 250 °C. In SST-1 the PFCs were baked at 250 °C using hot nitrogen gas facility to remove the absorbed water vapour. Also device with large graphite surface area has the disadvantage that a large quantity of hydrogen gets trapped inside it during plasma discharges which makes density control difficult. Helium glow discharge cleaning (He-GDC) effectively removes this stored hydrogen as well as other impurities like oxygen and hydrocarbon within few nano-meters from the surface by particle induced desorption. Before plasma operation in SST-1 tokamak, both baking of PFCs and He-GDC were carried out so that these impurities were removed effectively. The mean desorption yield of hydrogen was found to be 0.24. In this paper the results of baking and He-GDC experiments of SST-1 will be presented in detail.
Improving the engine power of a catalytic Janus-sphere micromotor by roughening its surface.

PubMed

Longbottom, Brooke W; Bon, Stefan A F

2018-03-15

Microspheres with catalytic caps have become a popular model system for studying self-propelled colloids. Existing experimental studies involve predominantly "smooth" particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces of polymer microspheres were deformed prior to depositing a layer of platinum which resulted in the formation of nanoscopic pillars of catalyst. Self-propulsion was induced upon exposure of the micromotors to hydrogen peroxide, whilst they were dispersed in water. The topological surface features were shown to boost speed (~2×) when the underlying deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their "smooth" counterparts.
Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

NASA Astrophysics Data System (ADS)

Liu, Zhi-Pan; Hu, P.; Lee, Ming-Hsien

2003-09-01

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N2+3H2→2NH3). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H→NH, NH+H→NH2 and NH2+H→NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H→CH and O+H→OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors.
From Coordination Cages to a Stable Crystalline Porous Hydrogen-Bonded Framework

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

Ju, Zhanfeng; Liu, Guoliang; Chen, Yu-Sheng

2017-03-20

A stable framework has been constructed through multiple charge-assisted H-bonds between cationic coordination cages and chloride ions. The framework maintained its original structure upon desolvation, which has been established by single-crystal structure analysis. This is the first fully characterized stable porous framework based on coordination cages after desolvation, with a moderately high Brunauer–Emmett–Teller (BET) surface area of 1201 m2 g-1. This work will not only give a light to construct stable porous frameworks based on coordination cages and thus broaden their applications, but will also provide a new avenue to the assembly of other porous materials such as porous organicmore » cages and hydrogen-bonded organic frameworks (HOFs) through non covalent bonds.« less
Improvement and analysis of the hydrogen-cerium redox flow cell

NASA Astrophysics Data System (ADS)

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-09-01

The H2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm-2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50 °C. The H2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.
Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

NASA Astrophysics Data System (ADS)

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.
Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

PubMed

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-19

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.
Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

PubMed Central

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-01-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276
A computational study on the adsorption configurations and reactions of SiHx(x = 1-4) on clean and H-covered Si(100) surfaces

NASA Astrophysics Data System (ADS)

Le, Thong N.-M.; Raghunath, P.; Huynh, Lam K.; Lin, M. C.

2016-11-01

Possible adsorption configurations of H and SiHx (x = 1 - 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH3 radicals effectively adsorb on the top sites, while SiH and SiH2 prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiHx species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiHx precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiHx radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiHx, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.
Fabrication method for a room temperature hydrogen sensor

NASA Technical Reports Server (NTRS)

Shukla, Satyajit V. (Inventor); Cho, Hyoung (Inventor); Seal, Sudipta (Inventor); Ludwig, Lawrence (Inventor)

2011-01-01

A sensor for selectively determining the presence and measuring the amount of hydrogen in the vicinity of the sensor. The sensor comprises a MEMS device coated with a nanostructured thin film of indium oxide doped tin oxide with an over layer of nanostructured barium cerate with platinum catalyst nanoparticles. Initial exposure to a UV light source, at room temperature, causes burning of organic residues present on the sensor surface and provides a clean surface for sensing hydrogen at room temperature. A giant room temperature hydrogen sensitivity is observed after making the UV source off. The hydrogen sensor of the invention can be usefully employed for the detection of hydrogen in an environment susceptible to the incursion or generation of hydrogen and may be conveniently used at room temperature.
Realizing controllable graphene nucleation by regulating the competition of hydrogen and oxygen during chemical vapor deposition heating.

PubMed

Zhang, Haoran; Zhang, Yaqian; Zhang, Yanhui; Chen, Zhiying; Sui, Yanping; Ge, Xiaoming; Deng, Rongxuan; Yu, Guanghui; Jin, Zhi; Liu, Xinyu

2016-08-24

Oxygen can passivate Cu surface active sites when graphene nucleates. Thus, the nucleation density is decreased. The CuO/Cu substrate was chosen for graphene domain synthesis in our study. The results indicate that the CuO/Cu substrate is beneficial for large-scale, single-crystal graphene domain synthesis. Graphene grown on the CuO/Cu substrate exhibits fewer nucleation sites than on Cu foils, suggesting that graphene follows an oxygen-dominating growth. Hydrogen treatment via a heating process could weaken the surface oxygen's role in limiting graphene nucleation under the competition of hydrogen and oxygen and could transfer the synthesis of graphene into a hydrogen-dominating growth. However, the competition only exists during the chemical vapor deposition heating process. For non-hydrogen heated samples, oxygen-dominating growth is experienced even though the samples are annealed in hydrogen for a long time after the heating process. With the temperature increases, the role of hydrogen gradually decreases. The balance of hydrogen and oxygen is adjusted by introducing hydrogen gas at a different heating temperatures. The oxygen concentration on the substrate surface is believed to determine the reactions mechanisms based on the secondary ion mass spectrometry test results. This study provides a new method for the controllable synthesis of graphene nucleation during a heating process.
Compensated amorphous silicon solar cell

DOEpatents

Devaud, Genevieve

1983-01-01

An amorphous silicon solar cell including an electrically conductive substrate, a layer of glow discharge deposited hydrogenated amorphous silicon over said substrate and having regions of differing conductivity with at least one region of intrinsic hydrogenated amorphous silicon. The layer of hydrogenated amorphous silicon has opposed first and second major surfaces where the first major surface contacts the electrically conductive substrate and an electrode for electrically contacting the second major surface. The intrinsic hydrogenated amorphous silicon region is deposited in a glow discharge with an atmosphere which includes not less than about 0.02 atom percent mono-atomic boron. An improved N.I.P. solar cell is disclosed using a BF.sub.3 doped intrinsic layer.
Effects of Surface Treatments on Secondary Electron Emission from CVD Diamond Films

NASA Technical Reports Server (NTRS)

Mearini, G. T.; Krainsky, I. L.; Dayton, J. A., Jr.; Zorman, Christian; Wang, Yaxin; Lamouri, A.

1995-01-01

Secondary electron emission (SEE) properties of polycrystalline diamond films grown by chemical vapor deposition (CVD) were measured. The total secondary yield (sigma) from as-grown samples was observed to be as high as 20 at room temperature and 48 while heating at 700 K in vacuum. Electron-beam-activated, alkali-terminated diamond films have shown stable values of sigma as high as 60 when coated with CsI and similarly high values when coated with other alkali halides. Diamond coated with BaF2 had a stable sigma of 6, but no enhancement of the SEE properties was observed with coatings of Ti or Au. Hydrogen was identified to give rise to this effect in as-grown films. However, electron beam exposure led to a reduction in sigma values as low as 2. Exposure to a molecular hydrogen environment restored sigma to its original value after degradation, and enabled stable secondary emission during electron beam exposure. Atomic hydrogen and hydrogen plasma treatments were performed on diamond/Mo samples in an attempt to increase the near-surface hydrogen concentration which might lead to increased stability in the secondary emission. Raman scattering analysis, scanning electron microscopy, and Auger electron spectroscopy (AES) confirmed that hydrogen plasma and atomic hydrogen treatments improved the quality of the CVD diamond significantly. Elastic recoil detection (ERD) showed that heating as-grown diamond targets to 7OO K, which was correlated with an increase in sigma, removed contaminants from the surface but did not drive hydrogen from the diamond bulk. ERD showed that the hydrogen plasma treatment produced an increase in the hydrogen concentration in the near-surface region which did not decrease while heating in vacuum at 700 K, but no improvement in the SEE properties was observed.
Modeling molecular hydrogen emission in M dwarf exoplanetary systems

NASA Astrophysics Data System (ADS)

Evonosky, William; France, Kevin; Kruczek, Nick E.; Youngblood, Allison; Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanet host Stars (MUSCLES)

2017-01-01

Exoplanets orbiting low-mass stars are prime candidates for atmospheric characterization due to their astronomical abundance and short orbital periods. These planets orbit stars that are often more active than main sequence solar-type stars. They are exposed to differing levels of ultraviolet radiation which can cause traditional “biosignature” gases to be generated abiotically, potentially causing false-positive identifications of life. We modeled the recently discovered molecular hydrogen emission in the ultraviolet spectra (1350 - 1650 Å) as arising from the stellar surface, excited by radiation generated in the upper chromosphere. The model was compared with observed hydrogen emission from the “Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanet host Stars” (MUSCLES) survey by conducting a grid search and implementing a chi-squared minimization routine. We considered only progressions from the [1, 4] and [1, 7] first excited electronic levels. Our modeling procedure varied the atomic hydrogen column density (in the chromosphere) as well as the photospheric molecular hydrogen column density and temperature. The model required as an input a reconstructed intrinsic Lyman α profile which served as the pumping radiation for the molecular hydrogen. We found that an atomic hydrogen column density of log10N(H I) = 14.13 ± 0.16 cm-2 represents a breaking point above which there is not enough Lyman α flux available to excite a significant molecular hydrogen population into the [1, 7] state. We also present H2 temperatures which may suggest that star spots on low mass stars persist longer, and encompass more area than star spots on solar-type stars.
Modeling Molecular Hydrogen Emission in M-Dwarf Exoplanetary Systems

NASA Astrophysics Data System (ADS)

Evonosky, W. R.; France, K.; Kruczek, N.; Youngblood, A.

2016-12-01

Exoplanets orbiting low-mass stars are prime candidates for atmospheric characterization due to their astronomical abundance and short orbital periods. These planets orbit stars that are often more active than main sequence solar-type stars. They are exposed to differing levels of ultraviolet radiation which can cause traditional "biosignature" gases to be generated abiotically, potentially causing false-positive identifications of life. We modeled the recently discovered molecular hydrogen emission in the ultraviolet spectra (1350 - 1650 Å) as arising from the stellar surface, excited by radiation generated in the upper chromosphere. The model was compared with observed hydrogen emission from the "Measurements of the Ultraviolet Spectral Characteristics of Low-mass Exoplanet host Stars" (MUSCLES) survey by conducting a grid search and implementing a chi-squared minimization routine. We considered only progressions from the [1, 4] and [1, 7] first excited electronic levels. Our modeling procedure varied the atomic hydrogen column density (in the chromosphere) as well as the photospheric molecular hydrogen column density and temperature. The model required as an input a reconstructed intrinsic Lyman α profile which served as the pumping radiation for the molecular hydrogen. We found that an atomic hydrogen column density of log10N(H I) = 14.13 ± 0.16 cm-2 represents a breaking point above which there is not enough Lyman α flux available to excite a significant molecular hydrogen population into the [1, 7] state. We also present H2 temperatures which may suggest that star spots on low mass stars persist longer, and encompass more area than star spots on solar-type stars.
Evaluating topologically diverse metal–organic frameworks for cryo-adsorbed hydrogen storage

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

Gómez-Gualdrón, Diego A.; Colón, Yamil J.; Zhang, Xu

Metal–organic frameworks (MOFs) are porous materials synthesized by combining inorganic and organic molecular building blocks into crystalline networks of distinct topologies. Due to the combinatorial possibilities, there are millions of possible MOF structures. Aiming to exploit their exceptional tunability, surface areas and pore volumes, researchers have investigated MOFs for storage of gaseous fuels such as hydrogen for over a decade, but a suitable MOF to store hydrogen at ambient conditions has not yet been found. Here, we sought to rapidly determine the viability of using MOFs for hydrogen storage at recently proposed, cryogenic operating conditions. We constructed a large andmore » structurally diverse set of 13 512 potential MOF structures based on 41 different topologies and used molecular simulation to determine MOF hydrogen deliverable capacities between 100 bar/77 K and 5 bar/160 K. The highest volumetric deliverable capacity was 57 g L-1 of MOF, which surpasses the 37 g L-1 of tank of the incumbent technology (compressing hydrogen to 700 bar at ambient temperature). To validate our in silico MOF construction method, we synthesized a new isoreticular family of MOFs (she-MOF-x series) based on the she topology, which is extremely rare among MOFs. To validate our hydrogen storage predictions, we activated and measured hydrogen adsorption on she-MOF-1 and NU-1103. The latter MOF showed outstanding stability and a good combination of volumetric and gravimetric performance, presenting 43.2 g L-1 of MOF and 12.6 wt% volumetric and gravimetric deliverable capacities, respectively.« less
Radiolytic hydrogen generation at silicon carbide-water interfaces

NASA Astrophysics Data System (ADS)

Schofield, Jennifer; Reiff, Sarah C.; Pimblott, Simon M.; LaVerne, Jay A.

2016-02-01

While many of the proposed uses of SiC in the nuclear industry involve systems that are assumed to be dry, almost all materials have dissociated chemisorbed water associated with their surface, which can undergo chemistry in radiation fields. Silicon carbide α-phase and β-phase nanoparticles with water were irradiated with γ-rays and 5 MeV 4He ions followed by the determination of the production of molecular hydrogen, H2, and characterization of changes in the particle surface. The yields of H2 from SiC-water slurries were always greater than expected from a simple mixture rule indicating that the presence of SiC was influencing the production of H2 from water, probably through an energy transfer from the solid to liquid phase. Although the increase in H2 yields was modest, a decrease in the water mass percentage led to an increase in H2 yields, especially for very low amounts of water. Surface analysis techniques included diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), nitrogen absorption with the Brunauer - Emmett - Teller (BET) methodology for surface area determination, X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Little change in the SiC surface was observed following radiolysis except for some conversion of β-phase SiC to the α-phase and the formation of SiO2 with He ion radiolysis.
Heterogeneous enantioselective hydrogenation of beta-keto esters using chirally modified supported Ni nanoparticles

NASA Astrophysics Data System (ADS)

Acharya, Sushma

Enantioselective heterogeneous catalysis is an important and rapidly expanding research area. The two most heavily researched examples of this type of catalysis are the enantioselective hydrogenation of α-keto-esters over Pt-based catalysts and the enantioselective hydrogenation of β-keto-esters over Ni-based catalysts. These enantioselective surface reactions are controlled by the presence of adsorbed chiral molecules i.e. tartaric acid on the surface of the metal component of the catalyst. The work presented in this thesis focuses on two parts, the synthesis of pure nickel nanoparticles and enantioselective behavior of the modified nickel nanoparticles. The works on the synthesis of pure nickel nanoparticles were carried out using two methods, the reverse microemulsion and the reduction method. It was discovered that the reverse microemulsion method produced nickel oxide nanoparticles, whereas the reduction method produced pure nickel nanoparticles. Chiral modifications of Raney nickel (RNi) and C-supported catalysts were studied. The catalysts were employed in enantioselective hydrogenation of methyl acetoacetate (MAA) to (R) - and (S)-enantiomers of methyl 3-hydroxybutyrate (MHB). The effects of modification and hydrogenation parameters such as concentration of modifier temperature, pressure and solvent on the enantioselectivity of MAA hydrogenation were discussed. For RNi methanol was found to be the best solvent, with tartaric acid concentration 0.2 mol/L for achieving the highest enantiomeric excess under 8 bar at 70 oC. Characteristic features of the in-situ modification of Raney nickel and C-supported Ni were also evaluated and the results obtained were compared with the conventional (pre-modification) approach. Parameters for the conventional and in-situ methods were optimised in a series of experiments for both types of catalysts. The in-situ modified catalyst was found more active for both RNi and C-supported catalysts with 98 % and 42% enantiomeric excess, respectively.

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

NASA Astrophysics Data System (ADS)

Washton, Nancy M.; Brantley, Susan L.; Mueller, Karl T.

2008-12-01

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q 3 groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the "Icelandic" samples and with duration of field weathering for both "Icelandic" and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q 3 sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative 19F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, 27Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.
Platinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving

PubMed Central

Li, Zhi; Yu, Rong; Huang, Jinglu; Shi, Yusheng; Zhang, Diyang; Zhong, Xiaoyan; Wang, Dingsheng; Wu, Yuen; Li, Yadong

2015-01-01

Developing catalysts that provide the effective activation of hydrogen and selective absorption of substrate on metal surface is crucial to simultaneously improve activity and selectivity of hydrogenation reaction. Here we present an unique in situ etching and coordination synthetic strategy for exploiting a functionalized metal-organic framework to incorporate the bimetallic platinum–nickel frames, thereby forming a frame within frame nanostructure. The as-grown metal-organic framework serves as a ‘breath shell' to enhance hydrogen enrichment and activation on platinum–nickel surface. More importantly, this framework structure with defined pores can provide the selective accessibility of molecules through its one-dimensional channels. In a mixture containing four olefins, the composite can selectively transport the substrates smaller than its pores to the platinum–nickel surface and catalyse their hydrogenation. This molecular sieve effect can be also applied to selectively produce imines, which are important intermediates in the reductive imination of nitroarene, by restraining further hydrogenation via cascade processes. PMID:26391605
Effect of nanoscale surface roughness on the bonding energy of direct-bonded silicon wafers

NASA Astrophysics Data System (ADS)

Miki, N.; Spearing, S. M.

2003-11-01

Direct wafer bonding of silicon wafers is a promising technology for manufacturing three-dimensional complex microelectromechanical systems as well as silicon-on-insulator substrates. Previous work has reported that the bond quality declines with increasing surface roughness, however, this relationship has not been quantified. This article explicitly correlates the bond quality, which is quantified by the apparent bonding energy, and the surface morphology via the bearing ratio, which describes the area of surface lying above a given depth. The apparent bonding energy is considered to be proportional to the real area of contact. The effective area of contact is defined as the area sufficiently close to contribute to the attractive force between the two bonding wafers. Experiments were conducted with silicon wafers whose surfaces were roughened by a buffered oxide etch solution (BOE, HF:NH4F=1:7) and/or a potassium hydroxide solution. The surface roughness was measured by atomic force microscopy. The wafers were direct bonded to polished "monitor" wafers following a standard RCA cleaning and the resulting bonding energy was measured by the crack-opening method. The experimental results revealed a clear correlation between the bonding energy and the bearing ratio. A bearing depth of ˜1.4 nm was found to be appropriate for the characterization of direct-bonded silicon at room temperature, which is consistent with the thickness of the water layer at the interface responsible for the hydrogen bonds that link the mating wafers.
Iron Oxide Silica Derived from Sol-Gel Synthesis

PubMed Central

Darmawan, Adi; Smart, Simon; Julbe, Anne; Diniz da Costa, João Carlos

2011-01-01

In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica. PMID:28879999
Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy

NASA Astrophysics Data System (ADS)

Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

2016-10-01

The catalytic hydrogenation of ethylene promoted by a Pt(111) single crystal was studied by using a ultrahigh-vacuum surface-science instrument equipped with a so-called high-pressure cell. Kinetic data were acquired continuously during the catalytic conversion of atmospheric-pressure mixtures of ethylene and hydrogen by using mass spectrometry while simultaneously characterizing the surface species in operando mode by reflection-absorption infrared spectroscopy (RAIRS). Many observations reported in previous studies of this system were corroborated, including the presence of adsorbed alkylidyne intermediates during the reaction and the zero-order dependence of the rate of hydrogenation on the pressure of ethylene. In addition, the high quality of the kinetic data, which could be recorded continuously versus time and processed to calculate time-dependent turnover frequencies (TOFs), afforded a more detailed analysis of the mechanism. Specifically, deuterium labeling could be used to estimate the extent of isotope scrambling reached with mixed-isotope-substituted reactants (C2H4 + D2 and C2D4 + H2). Perhaps the most important new observation from this work is that, although extensive H-D exchange takes place on ethylene before being fully converted to ethane, the average stoichiometry of the final product retains the expected stoichiometry of the gas mixture, that is, four regular hydrogen atoms and two deuteriums per ethane molecule in the case of the experiments with C2H4 + D2. This means that no hydrogen atoms are removed from the surface via their inter-recombination to produce X2 (X = H or D). It is concluded that, under catalytic conditions, hydrogen surface recombination is much slower than ethylene hydrogenation and H-D exchange.
Growth of Desulfovibrio on the Surface of Agar Media

PubMed Central

Iverson, Warren P.

1966-01-01

Growth of Desulfovibrio desulfuricans (API strain) was found to take place in an atmosphere of hydrogen on the agar surface of complex media, including yeast extract (Difco), and Trypticase Soy Agar (BBL) without any added reducing agents. For growth on a 2% yeast extract-agar surface in the absence of hydrogen (nitrogen atmosphere), sodium lactate was required in the medium. Growth on the surface of Trypticase Soy Agar (TSA) under nitrogen took place readily in the absence of an added hydrogen donor. A medium (TSA plus salts) is described based upon the addition of sodium lactate (4 ml per liter), magnesium sulfate (2 g per liter), and ferrous ammonium sulfate (0.05%) to TSA, which appears suitable for the isolation and growth of Desulfovibrio on the surface of agar plates in an atmosphere of hydrogen. Sodium lactate does not appear to be essential in this medium for good growth and sulfate reduction in a hydrogen atmosphere, but is essential in a nitrogen atmosphere. Growth of Desulfovibrio (hydrogen atmosphere) on the agar surface of media commonly used for its cultivation as well as on an inorganic medium containing bicarbonate as a source of carbon is poor and erratic unless inoculated (Desulfovibrio) plates of TSA plus salts are incubated in the same container with plates of these media. This stimulatory effect of incubation with inoculated plates of TSA plus salts medium appears to be due to as yet unidentified volatile material produced by D. desulfuricans when growing on this medium. Another volatile material, or possibly the identical material, appears to act similarly to a hydrogen donor. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 PMID:5955798
Adsorption and dissociation of molecular hydrogen on the (0001) surface of double hexagonal close packed americium

NASA Astrophysics Data System (ADS)

Dholabhai, P. P.; Ray, A. K.

2009-01-01

Hydrogen molecule adsorption on the (0001) surface of double hexagonal packed americium has been studied in detail within the framework of density functional theory using a full-potential all-electron linearized augmented plane wave plus local orbitals method (FP-L/APW+lo). Weak molecular hydrogen adsorptions were observed. Adsorption energies were optimized with respect to the distance of the adsorbates from the surface for three approach positions at three adsorption sites, namely t1 (one-fold top), b2 (two-fold bridge), and h3 (three-fold hollow) sites. Adsorption energies were computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at the fully relativistic level (with spin-orbit coupling SOC). The most stable configuration corresponds to a horizontal adsorption with the molecular approach being perpendicular to a lattice vector. The surface coverage is equivalent to one-fourth of a monolayer (ML), with the adsorption energies at the NSOC and SOC theoretical levels being 0.0997 eV and 0.1022 eV, respectively. The respective distance of the hydrogen molecule from the surface and hydrogen-hydrogen distance was found to be 2.645 Å and 0.789 Å, respectively. The work functions decreased and the net magnetic moments remained almost unchanged in all cases compared with the corresponding quantities of bare dhcp Am (0001) surface. The adsorbate-substrate interactions have been analyzed in detail using the partial charges inside the muffin-tin spheres, difference charge density distributions, and the local density of states. The effects of adsorption on the Am 5f electron localization-delocalization characteristics have been discussed. Reaction barrier for the dissociation of hydrogen molecule has been presented.
Method for the hydrogenation of poly-si

DOEpatents

Wang, Qi

2013-11-12

A method for hydrogenating poly-si. Poly-si is placed into the interior of a chamber. A filament is placed into the interior of a chamber. The base pressure of the interior of the chamber is evacuated, preferably to 10.sup.-6 Torr or less. The poly-si is heated for a predetermined poly-si heating time. The filament is heated by providing an electrical power to the filament. Hydrogen is supplied into the pressurized interior of the chamber comprising the heated poly-si and the heated filament. Atomic hydrogen is produced by the filament at a rate whereby the atomic hydrogen surface density at the poly-si is less than the poly-si surface density. Preferably, the poly-si is covered from the atomic hydrogen produced by the heated filament for a first predetermined covering time. Preferably, the poly-si is then uncovered from the atomic hydrogen produced by the heated filament for a first hydrogenation time.
Plasmonic hydrogen sensor based on integrated microring resonator

NASA Astrophysics Data System (ADS)

Yi, Ya Sha; Wu, Da Chuan

2017-12-01

We have proposed and demonstrated numerically an ultrasmall and highly sensitive plasmonic hydrogen sensor based on an integrated microring resonator, with a footprint size as small as 4×4 μm2. With a palladium (Pd) or platinum (Pt) hydrogen-sensitive layer coated on the inner surface of the microring resonator and the excitation of surface plasmon modes at the interface from the microring resonator waveguide, the device is highly sensitive to low hydrogen concentration variation, and the sensitivity is at least one order of magnitude larger than that of the optical fiber-based hydrogen sensor. We have also investigated the tradeoff between the portion coverage of the Pd/Pt layer and the sensitivity, as well as the width of the hydrogen-sensitive layer. This ultrasmall plasmonic hydrogen sensor holds promise for the realization of a highly compact sensor with integration capability for applications in hydrogen fuel economy.
Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying.

PubMed

Tian, H Y; Buckley, C E; Mulè, S; Paskevicius, M; Dhal, B B

2008-11-26

Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900 °C was also activated in a carbon dioxide atmosphere at 900 °C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77 K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05 nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20 m(2) g(-1) displayed a reasonably high hydrogen uptake at 77 K with a maximum hydrogen sorption of 3.6 wt% at 2.5 MPa. These results suggest that CA are promising candidate hydrogen storage materials.
Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying

NASA Astrophysics Data System (ADS)

Tian, H. Y.; Buckley, C. E.; Mulè, S.; Paskevicius, M.; Dhal, B. B.

2008-11-01

Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900 °C was also activated in a carbon dioxide atmosphere at 900 °C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77 K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05 nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20 m2 g-1 displayed a reasonably high hydrogen uptake at 77 K with a maximum hydrogen sorption of 3.6 wt% at 2.5 MPa. These results suggest that CA are promising candidate hydrogen storage materials.
Release of hydrogen from nanoconfined hydrides by application of microwaves

NASA Astrophysics Data System (ADS)

Sanz-Moral, Luis Miguel; Navarrete, Alexander; Sturm, Guido; Link, Guido; Rueda, Miriam; Stefanidis, Georgios; Martín, Ángel

2017-06-01

The release of hydrogen from solid hydrides by thermolysis can be improved by nanoconfinement of the hydride in a suitable micro/mesoporous support, but the slow heat transfer by conduction through the support can be a limitation. In this work, a C/SiO2 mesoporous material has been synthesized and employed as matrix for nanoconfinement of hydrides. The matrix showed high surface area and pore volume (386 m2/g and 1.41 cm3/g), which enabled the confinement of high concentrations of hydride. Furthermore, by modification of the proportion between C and SiO2, the dielectric properties of the complex could be modified, making it susceptible to microwave heating. As with this heating method the entire sample is heated simultaneously, the heat transfer resistances associated to conduction were eliminated. To demonstrate this possibility, ethane 1,2-diaminoborane (EDAB) was embedded on the C/SiO2 matrix at concentrations ranging from 11 to 31%wt using a wet impregnation method, and a device appropriate for hydrogen release from this material by application of microwaves was designed with the aid of a numerical simulation. Hydrogen liberation tests by conventional heating and microwaves were compared, showing that by microwave heating hydrogen release can be initiated and stopped in shorter times.
Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study.

PubMed

Brown, Craig M; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K; Kepert, Cameron J

2009-05-20

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.
Hydrogen adsorption in HKUST-1: a combined inelastic neutron scattering and first-principles study

NASA Astrophysics Data System (ADS)

Brown, Craig M.; Liu, Yun; Yildirim, Taner; Peterson, Vanessa K.; Kepert, Cameron J.

2009-05-01

Hydrogen adsorption in high surface area nanoporous coordination polymers has attracted a great deal of interest in recent years due to the potential applications in energy storage. Here we present combined inelastic neutron scattering measurements and detailed first-principles calculations aimed at unraveling the nature of hydrogen adsorption in HKUST-1 (Cu3(1,3,5-benzenetricarboxylate)2), a metal-organic framework (MOF) with unsaturated metal centers. We reveal that, in this system, the major contribution to the overall binding comes from the classical Coulomb interaction which is not screened due to the open metal site; this explains the relatively high binding energies and short H2-metal distances observed in MOFs with exposed metal sites as compared to traditional ones. Despite the short distances, there is no indication of an elongation of the H-H bond for the bound H2 molecule at the metal site. We find that both the phonon and rotational energy levels of the hydrogen molecule are closely similar, making the interpretation of the inelastic neutron scattering data difficult. Finally, we show that the orientation of H2 has a surprisingly large effect on the binding potential, reducing the classical binding energy by almost 30%. The implication of these results for the development of MOF materials for better hydrogen storage is discussed.
Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

DOE PAGES

Alia, Shaun M.; Pivovar, Bryan S.

2018-01-01

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing tomore » 250 degrees C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 degrees C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. Furthermore, these techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.« less
Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

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

Alia, Shaun M.; Pivovar, Bryan S.

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing tomore » 250 degrees C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 degrees C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. Furthermore, these techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.« less
Sum frequency generation spectroscopy study of hydrogenated stepped Si(111) surfaces made by molecular hydrogen exposure

NASA Astrophysics Data System (ADS)

Hien, K. T. T.; Sattar, M. A.; Miyauchi, Y.; Mizutani, G.; Rutt, H. N.

2017-09-01

Hydrogen adsorption on stepped Si(111) surfaces 9.5° miscut in the [ 1 ̅ 1 ̅ 2 ] direction has been investigated in situ in a UHV chamber with a base pressure of 10-8 Pa. The H-Si(111)1×1 surface was prepared by exposing the wafer to ultra-pure hydrogen gas at a pressure of 470 Pa. Termination of hydrogen on terraces and steps was observed by sum frequency generation (SFG) with several polarization combinations such as ppp, ssp, pps, spp, psp, sps, pss and sss. Here the 1st, 2nd and 3rd symbols indicate SFG, visible and IR polarizations, respectively. ppp and ssp-SFG clearly showed only two modes: the Si-H stretching vibration terrace mode at 2082 cm-1 (A) and the vertical step dihydride vibration mode at 2094 cm-1 (C1). Interesting points are the appearance of the C1 mode in contrast to the previous SFG spectrum of the H-Si(111)1×1 surface with the same miscut surface angle prepared by wet chemical etching. We suggest that the formation of step dihydride and its orientation on the Si(111) stepped surfaces depend strongly on the preparation method.
Method for improving the stability of amorphous silicon

DOEpatents

Branz, Howard M.

2004-03-30

A method of producing a metastable degradation resistant amorphous hydrogenated silicon film is provided, which comprises the steps of growing a hydrogenated amorphous silicon film, the film having an exposed surface, illuminating the surface using an essentially blue or ultraviolet light to form high densities of a light induced defect near the surface, and etching the surface to remove the defect.
Study of Improvement of Hydrogen Maser Frequency Standard

NASA Technical Reports Server (NTRS)

Crampton, S. B.

1977-01-01

The research work dealt primarily with reducing the atom leakage rate using as storage surfaces the FEP Teflon surfaces conventionally used in contemporary hydrogen maser frequency standards. Some work was also done on a possible alternative to the conventional surfaces, but the results here and elsewhere suggest that the alternative surface is not promising enough to warrant much further work.
Surface-initiated phase transition in solid hydrogen under the high-pressure compression

NASA Astrophysics Data System (ADS)

Lei, Haile; Lin, Wei; Wang, Kai; Li, Xibo

2018-03-01

The large-scale molecular dynamics simulations have been performed to understand the microscopic mechanism governing the phase transition of solid hydrogen under the high-pressure compression. These results demonstrate that the face-centered-cubic-to-hexagonal close-packed phase transition is initiated first at the surfaces at a much lower pressure than in the volume and then extends gradually from the surface to volume in the solid hydrogen. The infrared spectra from the surface are revealed to exhibit a different pressure-dependent feature from those of the volume during the high-pressure compression. It is thus deduced that the weakening intramolecular H-H bonds are always accompanied by hardening surface phonons through strengthening the intermolecular H2-H2 coupling at the surfaces with respect to the counterparts in the volume at high pressures. This is just opposite to the conventional atomic crystals, in which the surface phonons are softening. The high-pressure compression has further been predicted to force the atoms or molecules to spray out of surface to degrade the pressure. These results provide a glimpse of structural properties of solid hydrogen at the early stage during the high-pressure compression.

Analysis of Te and TeO 2 on CdZnTe Nuclear Detectors Treated with Hydrogen Bromide and Ammonium-Based Solutions

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

Drabo, Mebougna L.; Egarievwe, Stephen U.; Okwechime, Ifechukwude O.

Surface defects caused during cutting and polishing in the fabrication of cadmium zinc telluride (CdZnTe) nuclear detectors limit their spectral performance. Chemical treatments are often used to remove surface damages and defects. In this paper, we present the analysis of Te and TeO 2 species on the surfaces of CdZnTe nuclear detectors treated with hydrogen bromide and ammonium-based solutions. The CdZnTe wafers were chemo-mechanically polished in a mixture of hydrogen bromide in hydrogen peroxide and ethylene glycol, followed by a chemical passivation in a mixture of ammonium fluoride and hydrogen peroxide solution. X-ray photoelectron spectroscopy showed significant conversion of Temore » to TeO 2, thus producing a more chemically stable surface. The resistivity of the CdZnTe samples is in the order of 1010 ohms-cm. The current for a given applied voltage increased following the passivation and decreased after a 3-hour period. Results from spectral response measurements showed that the 59.5-keV gamma-peak of Am-241 was stable under the same channel for the surface treatment processes.« less
Analysis of Te and TeO 2 on CdZnTe Nuclear Detectors Treated with Hydrogen Bromide and Ammonium-Based Solutions

DOE PAGES

Drabo, Mebougna L.; Egarievwe, Stephen U.; Okwechime, Ifechukwude O.; ...

2017-04-30

Surface defects caused during cutting and polishing in the fabrication of cadmium zinc telluride (CdZnTe) nuclear detectors limit their spectral performance. Chemical treatments are often used to remove surface damages and defects. In this paper, we present the analysis of Te and TeO 2 species on the surfaces of CdZnTe nuclear detectors treated with hydrogen bromide and ammonium-based solutions. The CdZnTe wafers were chemo-mechanically polished in a mixture of hydrogen bromide in hydrogen peroxide and ethylene glycol, followed by a chemical passivation in a mixture of ammonium fluoride and hydrogen peroxide solution. X-ray photoelectron spectroscopy showed significant conversion of Temore » to TeO 2, thus producing a more chemically stable surface. The resistivity of the CdZnTe samples is in the order of 1010 ohms-cm. The current for a given applied voltage increased following the passivation and decreased after a 3-hour period. Results from spectral response measurements showed that the 59.5-keV gamma-peak of Am-241 was stable under the same channel for the surface treatment processes.« less
Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.
Erosion of graphite surface exposed to hot supersonic hydrogen gas

NASA Technical Reports Server (NTRS)

Sharma, O. P.

1972-01-01

A theoretical model based on laminar boundary layer flow equations was developed to predict the erosion rate of a graphite (AGCarb-101) surface exposed to a hot supersonic stream of hydrogen gas. The supersonic flow in the nozzle outside the boundary layer formed over the surface of the specimen was determined by assuming one-dimensional isentropic conditions. An overall surface reaction rate expression based on experimental studies was used to describe the interaction of hydrogen with graphite. A satisfactory agreement was found between the results of the computation, and the available experimental data. Some shortcomings of the model and further possible improvements are discussed.
Methane formation from the hydrogenation of carbon dioxide on Ni(110) surface--a density functional theoretical study.

PubMed

Bothra, Pallavi; Periyasamy, Ganga; Pati, Swapan K

2013-04-21

The complete hydrogenation mechanisms of CO2 are explored on Ni(110) surface catalyst using density functional theory. We have studied the possible hydrogenation mechanism to form product methane from the stable adsorption-co-adsorption intermediates of CO2 and H2 on Ni(110) surface. Our computations clearly elucidate that the mechanism for the formation of methyl, methoxy and methane moieties from carbon dioxide on the nickel catalyst. Moreover, our studies clearly show that the methane formation via hydroxyl carbonyl intermediate requires a lower energy barrier than via carbon monoxide and formate intermediates on the Ni(110) surface.
Erosion of graphite surface exposed to hot supersonic hydrogen gas

NASA Technical Reports Server (NTRS)

Sharma, O. P.

1972-01-01

A theoretical model based on laminar boundary layer flow equations is developed to predict the erosion rate of a graphite (AGCarb-101) surface exposed to a hot supersonic stream of hydrogen gas. The supersonic flow in the nozzle outside the boundary layer formed over the surface of the specimen is determined by assuming one-dimensional isentropic conditions. An overall surface reaction rate expression based on the experimental studies by Clarke and Fox is used to describe the interaction of hydrogen with graphite. A satisfactory agreement is found between the results of the computation, and the available experimental data. Some shortcomings of the model, and further possible improvements are discussed.
Monolithic Hydrogen Peroxide Catalyst Bed Development

NASA Technical Reports Server (NTRS)

Ponzo, J. B.

2003-01-01

With recent increased industry and government interest in rocket grade hydrogen peroxide as a viable propellant, significant effort has been expended to improve on earlier developments. This effort has been predominately centered in improving heterogeneous. typically catalyst beds; and homogeneous catalysts, which are typically solutions of catalytic substances. Heterogeneous catalyst beds have traditionally consisted of compressed wire screens plated with a catalytic substance, usually silver, and were used m many RCS applications (X-1, Mercury, and Centaur for example). Aerojet has devised a heterogeneous catalyst design that is monolithic (single piece), extremely compact, and has pressure drops equal to or less than traditional screen beds. The design consists of a bonded stack of very thin, photoetched metal plates, silver coated. This design leads to a high surface area per unit volume and precise flow area, resulting in high, stable, and repeatable performance. Very high throughputs have been demonstrated with 90% hydrogen peroxide. (0.60 lbm/s/sq in at 1775-175 psia) with no flooding of the catalyst bed. Bed life of over 900 seconds has also been demonstrated at throughputs of 0.60 lbm/s/sq in across varying chamber pressures. The monolithic design also exhibits good starting performance, short break-in periods, and will easily scale to various sizes.
Molecular dynamics simulations reveal the assembly mechanism of polysaccharides in marine aerosols.

PubMed

Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

2014-12-21

The high Arctic marine environment has recently detected polymer gels in atmospheric aerosol particles and cloud water originating from the surface microlayer of the open leads within the pack ice area. These polysaccharide molecules are water insoluble but water solvated, highly surface-active and highly hydrated (99% water). In order to add to the understanding and to complement missing laboratory characterization of marine polymer gels we have in this work performed an atomistic study of the assembly process and interfacial properties of polysaccharides. Our study reveals a number of salient features of the microscopic process behind polysaccharide assembly into nanogels. With three- and four-repeating units the polysaccharides assemble into a cluster in 50 ns. The aggregates grow quicker by absorbing one or two polymers each time, depending on the unit length and the type of inter-bridging cation. Although both the hydrophobic and hydrophilic domains are contracted, the latter dominates distinctly upon the contraction of solvent accessible surface areas. The establishment of inter-chain hydrogen-bonds is the key to the assembly while ionic bridges can further promote aggregation. During the assembly of the more bent four-unit polymers, intra-chain hydrogen bonds are significantly diminished by Ca(2+). Meanwhile, the percentage of Ca(2+) acting as an ionic bridge is more eminent, highlighting the significance of Ca(2+) ions for longer-chain polysaccharides. The aggregates are able to enhance surface tension more in the presence of Ca(2+) than in the presence of Na(+) owing to their more compact structure. These conclusions all demonstrate that studies of the present kind provide insight into the self-assembly process and interfacial properties of marine gels. We hope this understanding will keep up the interest in the complex and the fascinating relationship between marine microbiology, atmospheric aerosols, clouds and climate.
Influence of pH, bleaching agents, and acid etching on surface wear of bovine enamel

PubMed Central

Soares, Ana Flávia; Bombonatti, Juliana Fraga Soares; Alencar, Marina Studart; Consolmagno, Elaine Cristina; Honório, Heitor Marques; Mondelli, Rafael Francisco Lia

2016-01-01

ABSTRACT Development of new materials for tooth bleaching justifies the need for studies to evaluate the changes in the enamel surface caused by different bleaching protocols. Objective The aim of this study was to evaluate the bovine dental enamel wear in function of different bleaching gel protocols, acid etching and pH variation. Material and Methods Sixty fragments of bovine teeth were cut, obtaining a control and test areas. In the test area, one half received etching followed by a bleaching gel application, and the other half, only the bleaching gel. The fragments were randomly divided into six groups (n=10), each one received one bleaching session with five hydrogen peroxide gel applications of 8 min, activated with hybrid light, diode laser/blue LED (HL) or diode laser/violet LED (VHL) (experimental): Control (C); 35% Total Blanc Office (TBO35HL); 35% Lase Peroxide Sensy (LPS35HL); 25% Lase Peroxide Sensy II (LPS25HL); 15% Lase Peroxide Lite (LPL15HL); and 10% hydrogen peroxide (experimental) (EXP10VHL). pH values were determined by a pHmeter at the initial and final time periods. Specimens were stored, subjected to simulated brushing cycles, and the superficial wear was determined (μm). ANOVA and Tukey´s tests were applied (α=0.05). Results The pH showed a slight decrease, except for Group LPL15HL. Group LPS25HL showed the highest degree of wear, with and without etching. Conclusion There was a decrease from the initial to the final pH. Different bleaching gels were able to increase the surface wear values after simulated brushing. Acid etching before bleaching increased surface wear values in all groups. PMID:27008254
Influence of pH, bleaching agents, and acid etching on surface wear of bovine enamel.

PubMed

Soares, Ana Flávia; Bombonatti, Juliana Fraga Soares; Alencar, Marina Studart; Consolmagno, Elaine Cristina; Honório, Heitor Marques; Mondelli, Rafael Francisco Lia

2016-01-01

Development of new materials for tooth bleaching justifies the need for studies to evaluate the changes in the enamel surface caused by different bleaching protocols. The aim of this study was to evaluate the bovine dental enamel wear in function of different bleaching gel protocols, acid etching and pH variation. Sixty fragments of bovine teeth were cut, obtaining a control and test areas. In the test area, one half received etching followed by a bleaching gel application, and the other half, only the bleaching gel. The fragments were randomly divided into six groups (n=10), each one received one bleaching session with five hydrogen peroxide gel applications of 8 min, activated with hybrid light, diode laser/blue LED (HL) or diode laser/violet LED (VHL) (experimental): Control (C); 35% Total Blanc Office (TBO35HL); 35% Lase Peroxide Sensy (LPS35HL); 25% Lase Peroxide Sensy II (LPS25HL); 15% Lase Peroxide Lite (LPL15HL); and 10% hydrogen peroxide (experimental) (EXP10VHL). pH values were determined by a pHmeter at the initial and final time periods. Specimens were stored, subjected to simulated brushing cycles, and the superficial wear was determined (μm). ANOVA and Tukey´s tests were applied (α=0.05). The pH showed a slight decrease, except for Group LPL15HL. Group LPS25HL showed the highest degree of wear, with and without etching. There was a decrease from the initial to the final pH. Different bleaching gels were able to increase the surface wear values after simulated brushing. Acid etching before bleaching increased surface wear values in all groups.
Effect of surface oxygen vacancy sites on ethanol synthesis from acetic acid hydrogenation on a defective In2O3(110) surface.

PubMed

Lyu, Huisheng; Liu, Jiatao; Chen, Yifei; Li, Guiming; Jiang, Haoxi; Zhang, Minhua

2018-03-07

Developing a new type of low-cost and high-efficiency non-noble metal catalyst is beneficial for industrially massive synthesis of alcohols from carboxylic acids which can be obtained from renewable biomass. In this work, the effect of active oxygen vacancies on ethanol synthesis from acetic acid hydrogenation over defective In 2 O 3 (110) surfaces has been studied using periodic density functional theory (DFT) calculations. The relative stabilities of six surface oxygen vacancies from O v1 to O v6 on the In 2 O 3 (110) surface were compared. D1 and D4 surfaces with respective O v1 and O v4 oxygen vacancies were chosen to map out the reaction paths from acetic acid to ethanol. A reaction cycle mechanism between the perfect and defective states of the In 2 O 3 surface was found to catalyze the formation of ethanol from acetic acid hydrogenation. By H 2 reduction the oxygen vacancies on the In 2 O 3 surface play key roles in promoting CH 3 COO* hydrogenation and C-O bond breaking in acetic acid hydrogenation. The acetic acid, in turn, benefits the creation of oxygen vacancies, while the C-O bond breaking of acetic acid refills the oxygen vacancy and, thereby, sustains the catalytic cycle. The In 2 O 3 based catalysts were shown to be advantageous over traditional noble metal catalysts in this paper by theoretical analysis.
A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures.

PubMed

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-24

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.
A mechanical-force-driven physical vapour deposition approach to fabricating complex hydride nanostructures

NASA Astrophysics Data System (ADS)

Pang, Yuepeng; Liu, Yongfeng; Gao, Mingxia; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Zhu, Min; Pan, Hongge

2014-03-01

Nanoscale hydrides desorb and absorb hydrogen at faster rates and lower temperatures than bulk hydrides because of their high surface areas, abundant grain boundaries and short diffusion distances. No current methods exist for the direct fabrication of nanoscale complex hydrides (for example, alanates, borohydrides) with unique morphologies because of their extremely high reducibility, relatively low thermodynamic stability and complicated elemental composition. Here, we demonstrate a mechanical-force-driven physical vapour deposition procedure for preparing nanoscale complex hydrides without scaffolds or supports. Magnesium alanate nanorods measuring 20-40 nm in diameter and lithium borohydride nanobelts measuring 10-40 nm in width are successfully synthesised on the basis of the one-dimensional structure of the corresponding organic coordination polymers. The dehydrogenation kinetics of the magnesium alanate nanorods are improved, and the nanorod morphology persists through the dehydrogenation-hydrogenation process. Our findings may facilitate the fabrication of such hydrides with improved hydrogen storage properties for practical applications.
Fabrication and characterization of magnesium and calcium trimesate complexes via ion-exchange and one-pot self-assembly reaction

NASA Astrophysics Data System (ADS)

Ozer, Demet; Oztas, Nursen Altuntas; Köse, Dursun A.; Şahin, Onur

2018-03-01

Using two different synthesis methods, two diversified magnesium and calcium complexes were successfully prepared. When the ion exchange method was used, C9H14MgO11.H2O and C18H30Ca3O24 complexes were obtained. When the one-pot self-assembly reaction was used, C18H34Mg3O26.4H2O and C9H12CaO10 complexes were produced. The structural characterizations were performed by using X-ray diffraction, FT-IR and elemental analyses. Thermal behavior of complexes were also determined via TGA method. The both complexes of magnesium and calcium trimesate have micro and mesoporosity with low porosity because of hydrogen bonds. Then hydrogen storage capacities of complexes were also determined. The differences in synthesis method result in the differences on complexes structure, morphology (shape, particle size and specific surface area) and hydrogen storage capacities.
Zwitterionic-surfactant-stabilized palladium nanoparticles as catalysts in the hydrogen transfer reductive amination of benzaldehydes.

PubMed

Drinkel, Emma E; Campedelli, Roberta R; Manfredi, Alex M; Fiedler, Haidi D; Nome, Faruk

2014-03-21

Palladium nanoparticles (NPs) stabilized by a zwitterionic surfactant are revealed here to be good catalysts for the reductive amination of benzaldehydes using formate salts as hydrogen donors in aqueous isopropanol. In terms of environmental impact and economy, metallic NPs offer several advantages over homogeneous and traditional heterogeneous catalysts. NPs usually display greater activity due to the increased metal surface area and sometimes exhibit enhanced selectivity. Thus, it is possible to use very low loadings of expensive metal. The methodology eliminates the use of a hydrogen gas atmosphere or toxic or expensive reagents. A range of aromatic aldehydes were converted to benzylamines when reacted with primary and secondary amines in the presence of the Pd NPs, which also displayed good activity when supported on alumina. In every case, the Pd NPs could be easily recovered and reused up to three more times, and at the end of the process, the product was metal-free.
A novel approach of chemical mechanical polishing for cadmium zinc telluride wafers.

PubMed

Zhang, Zhenyu; Wang, Bo; Zhou, Ping; Kang, Renke; Zhang, Bi; Guo, Dongming

2016-05-26

A novel approach of chemical mechanical polishing (CMP) is developed for cadmium zinc telluride (CdZnTe or CZT) wafers. The approach uses environment-friendly slurry that consists of mainly silica, hydrogen peroxide, and citric acid. This is different from the previously reported slurries that are usually composed of strong acid, alkali, and bromine methanol, and are detrimental to the environment and operators. Surface roughness 0.5 nm and 4.7 nm are achieved for Ra and peak-to-valley (PV) values respectively in a measurement area of 70 × 50 μm(2), using the developed novel approach. Fundamental polishing mechanisms are also investigated in terms of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. Hydrogen peroxide dominates the passivating process during the CMP of CZT wafers, indicating by the lowest passivation current density among silica, citric acid and hydrogen peroxide solution. Chemical reaction equations are proposed during CMP according to the XPS and electrochemical measurements.
A novel approach of chemical mechanical polishing for cadmium zinc telluride wafers

PubMed Central

Zhang, Zhenyu; Wang, Bo; Zhou, Ping; Kang, Renke; Zhang, Bi; Guo, Dongming

2016-01-01

A novel approach of chemical mechanical polishing (CMP) is developed for cadmium zinc telluride (CdZnTe or CZT) wafers. The approach uses environment-friendly slurry that consists of mainly silica, hydrogen peroxide, and citric acid. This is different from the previously reported slurries that are usually composed of strong acid, alkali, and bromine methanol, and are detrimental to the environment and operators. Surface roughness 0.5 nm and 4.7 nm are achieved for Ra and peak-to-valley (PV) values respectively in a measurement area of 70 × 50 μm2, using the developed novel approach. Fundamental polishing mechanisms are also investigated in terms of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. Hydrogen peroxide dominates the passivating process during the CMP of CZT wafers, indicating by the lowest passivation current density among silica, citric acid and hydrogen peroxide solution. Chemical reaction equations are proposed during CMP according to the XPS and electrochemical measurements. PMID:27225310
Self-assembly synthesis of precious-metal-free 3D ZnO nano/micro spheres with excellent photocatalytic hydrogen production from solar water splitting

NASA Astrophysics Data System (ADS)

Guo, Si-yao; Zhao, Tie-jun; Jin, Zu-quan; Wan, Xiao-mei; Wang, Peng-gang; Shang, Jun; Han, Song

2015-10-01

A simple and straightforward solution growth routine is developed to prepare microporous 3D nano/micro ZnO microsphere with a large BET surface area of 288 m2 g-1 at room temperature. The formation mechanism of the hierarchical 3D nano/micro ZnO microsphere and its corresponding hydrogen evolution performance has been deeply discussed. In particular, this novel hierarchical 3D ZnO microspheres performs undiminished hydrogen evolution for at least 24 h under simulated solar light illumination, even under the condition of no precious metal as cocatalyst. Since the complex production process of photocatalysts and high cost of precious metal cocatalyst remains a major constraint that hinders the application of solar water splitting, this 3D nano/micro ZnO microspheres could be expected to be applicable in the precious-metal-free solar water splitting system due to its merits of low cost, simple procedure and high catalytic activity.
Tensile properties of titanium electrolytically charged with hydrogen

NASA Technical Reports Server (NTRS)

Smith, R. J.; Otterson, D. A.

1971-01-01

Yield strength, ultimate tensile strength, and elongation were studied for annealed titanium electrolytically charged with hydrogen. The hydrogen was present as a surface hydride layer. These tensile properties were generally lower for uncharged titanium than for titanium with a continuous surface hydride; they were greater for uncharged titanium than for titanium with an assumed discontinuous surface hydride. We suggest that the interface between titanium and titanium hydride is weak. And the hydride does not necessarily impair strength and ductility of annealed titanium. The possibility that oxygen and/or nitrogen can embrittle titanium hydride is discussed.
Effect of a microstructure and surface hydrogen alloying of a VT6 alloy on diffusion welding

NASA Astrophysics Data System (ADS)

Senkevich, K. S.; Skvortsova, S. V.; Kudelina, I. M.; Knyazev, M. I.; Zasypkin, V. V.

2014-01-01

The effect of a structural type (lamellar, fine, gradient) and additional surface alloying with hydrogen on the diffusion bonding of titanium alloy VT6 samples is studied. It is shown that the surface alloying of VT6 alloy parts with hydrogen allows one to decrease the diffusion welding temperature by 50-100°C, to obtain high-quality pore-free bonding, and to remove the "structural" boundary between materials to be welded that usually forms during welding of titanium alloys with a lamellar structure.

Experimental Studies of Hydrogenation and Other Reactions on Surfaces Under Astrophysically Relevant Conditions

NASA Technical Reports Server (NTRS)

Vidali, Gianfranco

1998-01-01

The goal of our project is to study hydrogen recombination reactions on solid surfaces under conditions that are relevant in astrophysics. Laboratory experiments were conducted using low-flux, cold atomic H and D beams impinging on a sample kept under ultra high vacuum conditions. Realistic analogues of interstellar dust grains were used. Our results show that current models for hydrogen recombination reactions have to be modified to take into account the role of activated diffusion of H on surfaces even at low temperature.
Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.
Surface properties of hydrogenated nanodiamonds: a chemical investigation.

PubMed

Girard, H A; Petit, T; Perruchas, S; Gacoin, T; Gesset, C; Arnault, J C; Bergonzo, P

2011-06-28

Hydrogen terminations (C-H) confer to diamond layers specific surface properties such as a negative electron affinity and a superficial conductive layer, opening the way to specific functionalization routes. For example, efficient covalent bonding of diazonium salts or of alkene moieties can be performed on hydrogenated diamond thin films, owing to electronic exchanges at the interface. Here, we report on the chemical reactivity of fully hydrogenated High Pressure High Temperature (HPHT) nanodiamonds (H-NDs) towards such grafting, with respect to the reactivity of as-received NDs. Chemical characterizations such as FTIR, XPS analysis and Zeta potential measurements reveal a clear selectivity of such couplings on H-NDs, suggesting that C-H related surface properties remain dominant even on particles at the nanoscale. These results on hydrogenated NDs open up the route to a broad range of new functionalizations for innovative NDs applications development. This journal is © the Owner Societies 2011
Reduction of friction stress of ethylene glycol by attached hydrogen ions

PubMed Central

Li, Jinjin; Zhang, Chenhui; Deng, Mingming; Luo, Jianbin

2014-01-01

In the present work, it is shown that the friction stress of ethylene glycol can decrease by an order of magnitude to achieve superlubricity if there are hydrogen ions attached on the friction surfaces. An ultra-low friction coefficient (μ = 0.004) of ethylene glycol between Si3N4 and SiO2 can be obtained with the effect of hydrogen ions. Experimental result indicates that the hydrogen ions adsorbed on the friction surfaces forming a hydration layer and the ethylene glycol in the contact region forming an elastohydrodynamic film are the two indispensable factors for the reduction of friction stress. The mechanism of superlubricity is attributed to the extremely low shear strength of formation of elastohydrodynamic film on the hydration layer. This finding may introduce a new approach to reduce friction coefficient of liquid by attaching hydrogen ions on friction surfaces. PMID:25428584
Hydrogen adsorption site on the Ni?110?-p(1 × 2)-H surface from time-of-flight scattering and recoiling spectrometry (TOF-SARS)

NASA Astrophysics Data System (ADS)

Bu, H.; Roux, C. D.; Rabalais, J. W.

The adsorption site of hydrogen on the Ni{110}-p(1 × 2)-H surface resulting from saturation exposure to H 2 at ˜ 310-350 K has been investigated by time-of-flight scattering and recoiling spectrometry (TOF-SARS). The recoiled neutral plus ion hydrogen atom flux resulting from 2-5 keV Ar + or Ne + pulsed ion beams incident on the surface was monitored as a function of crystal azimuthal angle and beam incidence angle. From classical trajectory calculations and shadowing and blocking analyses, it is concluded that hydrogen atoms are localized at the pseudo-three-fold sites on the (1 × 2) missing-row (MR) reconstructed Ni{110} surface; the (1 × 2) MR reconstruction is induced by hydrogen adsorption shown elsewhere [Surf. Sci. 259 (1991) 253]. Only the pseudo-three-fold site is consistent with all of the experimental data. The coordinates of the hydrogen adsorption site with respect to the nickel lattice were determined. The lateral distance of hydrogen from the 1st-layer Ni <1 overline10> rows is 1.56 ± 0.12 Å and the vertical distance above the substrate is 0.21 ± 0.12 Å, providing NiH bond lengths of 2.0 Å to the two-layer Ni atoms and 1.5 Å to the 2nd-layer Ni atom.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.
Plasma-assisted oxide removal from ruthenium-coated EUV optics

NASA Astrophysics Data System (ADS)

Dolgov, A.; Lee, C. J.; Bijkerk, F.; Abrikosov, A.; Krivtsun, V. M.; Lopaev, D.; Yakushev, O.; van Kampen, M.

2018-04-01

An experimental study of oxide reduction at the surface of ruthenium layers on top of multilayer mirrors and thin Ru/Si films is presented. Oxidation and reduction processes were observed under conditions close to those relevant for extreme ultraviolet lithography. The oxidized ruthenium surface was exposed to a low-temperature hydrogen plasma, similar to the plasma induced by extreme ultraviolet radiation. The experiments show that hydrogen ions are the main reducing agent. Furthermore, the addition of hydrogen radicals increases the reduction rate beyond that expected from simple flux calculations. We show that low-temperature hydrogen plasmas can be effective for reducing oxidized top surfaces. Our proof-of-concept experiments show that an in situ, EUV-generated plasma cleaning technology is feasible.
Stabilization of Hydrogen Production via Methanol Steam Reforming in Microreactor by Al2O3 Nano-Film Enhanced Catalyst Adhesion.

PubMed

Jeong, Heondo; Na, Jeong-Geol; Jang, Min Su; Ko, Chang Hyun

2016-05-01

In hydrogen production by methanol steam reforming reaction with microchannel reactor, Al2O3 thin film formed by atomic layer deposition (ALD) was introduced on the surface of microchannel reactor prior to the coating of catalyst particles. Methanol conversion rate and hydrogen production rate, increased in the presence of Al2O3 thin film. Over-view and cross-sectional scanning electron microscopy study showed that the adhesion between catalyst particles and the surface of microchannel reactor enhanced due to the presence of Al2O3 thin film. The improvement of hydrogen production rate inside the channels of microreactor mainly came from the stable fixation of catalyst particles on the surface of microchannels.
Growth Kinetics of the S Sub H Center on Magnesium Oxide Using Electron Paramagnetic Resonance

NASA Technical Reports Server (NTRS)

Jayne, J. P.

1971-01-01

Electron paramagnetic resonance spectroscopy was used to study the growth of S sub H centers on magnesium oxide powder which had hydrogen adsorbed on its surface. The centers were produced by ultraviolet radiation. The effects of both radiation intensity and hydrogen pressure were also studied. At constant hydrogen pressure and radiation dose, the initial S sub H center growth rate was found to be zero order. Beyond the initial region the growth rate deviated from zero order and finally approached saturation. The results are interpreted in terms of a model which assumes that the S sub H center is a hydrogen atom associated with a surface vacancy. Saturation appears to result from a limited supply of surface vacancies.
Performance model of a recirculating stack nickel hydrogen cell

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1994-01-01

A theoretical model of the nickel hydrogen battery cell has been utilized to describe the chemical and physical changes during charge and overcharge in a recirculating stack nickel hydrogen cell. In particular, the movement of gas and electrolyte have been examined as a function of the amount of electrolyte put into the cell stack during cell activation, and as a function of flooding in regions of the gas screen in this cell design. Additionally, a two-dimensional variation on this model has been utilized to describe the effects of non-uniform loading in the nickel-electrode on the movement of gas and electrolyte within the recirculating stack nickel hydrogen cell. The type of nonuniform loading that has been examined here is that associated with higher than average loading near the surface of the sintered nickel electrode, a condition present to some degree in many nickel electrodes made by electrochemical impregnation methods. The effects of high surface loading were examined primarily under conditions of overcharge, since the movement of gas and electrolyte in the overcharging condition was typically where the greatest effects of non-uniform loading were found. The results indicate that significant changes in the capillary forces between cell components occur as the percentage of free volume in the stack filled by electrolyte becomes very high. These changes create large gradients in gas-filled space and oxygen concentrations near the boundary between the separator and the hydrogen electrode when the electrolyte fill is much greater than about 95 percent of the stack free volume. At lower electrolyte fill levels, these gaseous and electrolyte gradients become less extreme, and shift through the separator towards the nickel electrode. Similarly, flooding of areas in the gas screen cause higher concentrations of oxygen gas to approach the platinum/hydrogen electrode that is opposite the back side of the nickel electrode. These results illustrate the need for appropriate pore size distributions, and the maintenance of both convective electrolyte and gas flow paths through the stack, if the recirculating stack nickel hydrogen cell design is to work properly.
Cryopumping of hydrogen in vacuum chambers is aided by catalytic oxidation of hydrogen

NASA Technical Reports Server (NTRS)

Childs, J. H.; Grobman, J.; Rayle, W.

1964-01-01

Vacuum test facilities are required for high speed cryopumping of gaseous hydrogen at low pressures. One method involves the catalytic oxidation of hydrogen and condensation of the resulting water on a liquid nitrogen-cooled surface.
Fluid insulation to prevent ice formation in heat exchangers

NASA Technical Reports Server (NTRS)

Coffinberry, G. A.

1973-01-01

Heat transfer surfaces were insulated to maintain air side surface temperature above freezing. Double wall tubes, with annular space between tubes, were filled with static liquid hydrogen. Low thermal conductivity of this hydrogen provided thermal resistance.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yinshan; Zhu, Men; Laventure, Audrey

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less
Thermodynamics and kinetics of graphene chemistry: a graphene hydrogenation prototype study.

PubMed

Pham, Buu Q; Gordon, Mark S

2016-12-07

The thermodynamic and kinetic controls of graphene chemistry are studied computationally using a graphene hydrogenation reaction and polyaromatic hydrocarbons to represent the graphene surface. Hydrogen atoms are concertedly chemisorped onto the surface of graphene models of different shapes (i.e., all-zigzag, all-armchair, zigzag-armchair mixed edges) and sizes (i.e., from 16-42 carbon atoms). The second-order Z-averaged perturbation theory (ZAPT2) method combined with Pople double and triple zeta basis sets are used for all calculations. It is found that both the net enthalpy change and the barrier height of graphene hydrogenation at graphene edges are lower than at their interior surfaces. While the thermodynamic product distribution is mainly determined by the remaining π-islands of functionalized graphenes (Phys. Chem. Chem. Phys., 2013, 15, 3725-3735), the kinetics of the reaction is primarily correlated with the localization of the electrostatic potential of the graphene surface.
Radiation Shielding Materials Containing Hydrogen, Boron, and Nitrogen: Systematic Computational and Experimental Study. Phase I

NASA Technical Reports Server (NTRS)

Thibeault, Sheila A.; Fay, Catharine C.; Lowther, Sharon E.; Earle, Kevin D.; Sauti, Godfrey; Kang, Jin Ho; Park, Cheol; McMullen, Amelia M.

2012-01-01

The key objectives of this study are to investigate, both computationally and experimentally, which forms, compositions, and layerings of hydrogen, boron, and nitrogen containing materials will offer the greatest shielding in the most structurally robust combination against galactic cosmic radiation (GCR), secondary neutrons, and solar energetic particles (SEP). The objectives and expected significance of this research are to develop a space radiation shielding materials system that has high efficacy for shielding radiation and that also has high strength for load bearing primary structures. Such a materials system does not yet exist. The boron nitride nanotube (BNNT) can theoretically be processed into structural BNNT and used for load bearing structures. Furthermore, the BNNT can be incorporated into high hydrogen polymers and the combination used as matrix reinforcement for structural composites. BNNT's molecular structure is attractive for hydrogen storage and hydrogenation. There are two methods or techniques for introducing hydrogen into BNNT: (1) hydrogen storage in BNNT, and (2) hydrogenation of BNNT (hydrogenated BNNT). In the hydrogen storage method, nanotubes are favored to store hydrogen over particles and sheets because they have much larger surface areas and higher hydrogen binding energy. The carbon nanotube (CNT) and BNNT have been studied as potentially outstanding hydrogen storage materials since 1997. Our study of hydrogen storage in BNNT - as a function of temperature, pressure, and hydrogen gas concentration - will be performed with a hydrogen storage chamber equipped with a hydrogen generator. The second method of introducing hydrogen into BNNT is hydrogenation of BNNT, where hydrogen is covalently bonded onto boron, nitrogen, or both. Hydrogenation of BN and BNNT has been studied theoretically. Hyper-hydrogenated BNNT has been theoretically predicted with hydrogen coverage up to 100% of the individual atoms. This is a higher hydrogen content than possible with hydrogen storage; however, a systematic experimental hydrogenation study has not been reported. A combination of the two approaches may be explored to provide yet higher hydrogen content. The hydrogen containing BNNT produced in our study will be characterized for hydrogen content and thermal stability in simulated space service environments. These new materials systems will be tested for their radiation shielding effectiveness against high energy protons and high energy heavy ions at the HIMAC facility in Japan, or a comparable facility. These high energy particles simulate exposure to SEP and GCR environments. They will also be tested in the LaRC Neutron Exposure Laboratory for their neutron shielding effectiveness, an attribute that determines their capability to shield against the secondary neutrons found inside structures and on lunar and planetary surfaces. The potential significance is to produce a radiation protection enabling technology for future exploration missions. Crew on deep space human exploration missions greater than approximately 90 days cannot remain below current crew Permissible Exposure Limits without shielding and/or biological countermeasures. The intent of this research is to bring the Agency closer to extending space missions beyond the 90-day limit, with 1 year as a long-term goal. We are advocating a systems solution with a structural materials component. Our intent is to develop the best materials system for that materials component. In this Phase I study, we have shown, computationally, that hydrogen containing BNNT is effective for shielding against GCR, SEP, and neutrons over a wide range of energies. This is why we are focusing on hydrogen containing BNNT as an innovative advanced concept. In our future work, we plan to demonstrate, experimentally, that hydrogen, boron, and nitrogen based materials can provide mechanically strong, thermally stable, structural materials with effective radiation shielding against GCR, SEP, and neutrons.
Extent of hydrogen coverage of Si(001) under chemical vapor deposition conditions from ab initio approaches

NASA Astrophysics Data System (ADS)

Rosenow, Phil; Tonner, Ralf

2016-05-01

The extent of hydrogen coverage of the Si(001) c(4 × 2) surface in the presence of hydrogen gas has been studied with dispersion corrected density functional theory. Electronic energy contributions are well described using a hybrid functional. The temperature dependence of the coverage in thermodynamic equilibrium was studied computing the phonon spectrum in a supercell approach. As an approximation to these demanding computations, an interpolated phonon approach was found to give comparable accuracy. The simpler ab initio thermodynamic approach is not accurate enough for the system studied, even if corrections by the Einstein model for surface vibrations are considered. The on-set of H2 desorption from the fully hydrogenated surface is predicted to occur at temperatures around 750 K. Strong changes in hydrogen coverage are found between 1000 and 1200 K in good agreement with previous reflectance anisotropy spectroscopy experiments. These findings allow a rational choice for the surface state in the computational treatment of chemical reactions under typical metal organic vapor phase epitaxy conditions on Si(001).
Extent of hydrogen coverage of Si(001) under chemical vapor deposition conditions from ab initio approaches

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

Rosenow, Phil; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de

2016-05-28

The extent of hydrogen coverage of the Si(001) c(4 × 2) surface in the presence of hydrogen gas has been studied with dispersion corrected density functional theory. Electronic energy contributions are well described using a hybrid functional. The temperature dependence of the coverage in thermodynamic equilibrium was studied computing the phonon spectrum in a supercell approach. As an approximation to these demanding computations, an interpolated phonon approach was found to give comparable accuracy. The simpler ab initio thermodynamic approach is not accurate enough for the system studied, even if corrections by the Einstein model for surface vibrations are considered. Themore » on-set of H{sub 2} desorption from the fully hydrogenated surface is predicted to occur at temperatures around 750 K. Strong changes in hydrogen coverage are found between 1000 and 1200 K in good agreement with previous reflectance anisotropy spectroscopy experiments. These findings allow a rational choice for the surface state in the computational treatment of chemical reactions under typical metal organic vapor phase epitaxy conditions on Si(001).« less
A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

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

Masud, J; Nguyen, TV; Singh, N

Rhodium sulfide (Rh2S3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh2S3 at high temperatures (600 degrees C to 850 degrees C) in presence of argon resulted in the transformation of Rh2S3 into Rh3S4, Rh17S15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H2SO4 and HBr solutions. The thermally treated catalysts show high activity for themore » hydrogen reactions. The exchange current densities (i(o)) of the synthesized RhxSy catalysts in H-2-saturated 1M H2SO4 and 1M HBr for HER and HOR were 0.9 mA/cm(2) to 1.0 mA/cm(2) and 0.8 to 0.9 mA/cm(2), respectively. The lower i(o) values obtained in 1M HBr solution compared to in H2SO4 might be due to the adsorption of Br- on the active surface. Stable electrochemical active surface area (ECSA) of RhxSy catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements. (C) The Author(s) 2015. Published by ECS. All rights reserved.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Gao; Jiang, Deen; Kumar, Santosh

We here investigate the catalytic properties of water-soluble Aun(SG)m nanocluster catalysts (H-SG = glutathione) of different sizes, including Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and captopril-capped Au25(Capt)18 nanoclusters. These Aun(SR)m nanoclusters (-SR represents thiolate generally) are used as homogeneous catalysts (i.e., without supports) in the chemoselective hydrogenation of 4-nitrobenzaldehyde (4-NO2PhCHO) to 4-nitrobenzyl alcohol (4-NO2PhCH2OH) in water with H2 gas (20 bar) as the hydrogen source. These nanocluster catalysts, except Au18(SG)14, remain intact after the catalytic reaction, evidenced by UV-vis spectra which are characteristic of each sized nanoclusters and thus serve as spectroscopic fingerprints . We observe a drastic size-dependence and steric effectmore » of protecting ligands on the gold nanocluster catalysts in the hydrogenation reaction. Density functional theory (DFT) modeling of the 4-nitrobenzaldehyde adsorption shows that both the CHO and NO2 groups are in close interact with the S-Au-S staples on the gold nanocluster surface; the adsorption of the 4-nitrobenzaldehyde molecule on the four different sized Aun(SR)m nanoclusters are moderately strong and similar in strength. The DFT results suggest that the catalytic activity of the Aun(SR)m nanoclusters is primarily determined by the surface area of the Au nanocluster, consistent with the observed trend of the conversion of 4-nitrobenzaldehyde versus the cluster size. Overall, this work offers the molecular insight into the hydrogenation of 4-nitrobenzaldehyde and the catalytically active site structure on gold nanocluster catalysts.« less
A Rh xS y/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

DOE PAGES

Masud, Jahangir; Nguyena, Trung V.; Singh, Nirala; ...

2015-02-01

Rhodium sulfide (Rh 2S 3) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh 2S 3 at high temperatures (600°C to 850°C) in presence of argon resulted in the transformation of Rh 2S 3 into Rh 3S 4, Rh 17S 15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H 2SO 4 and HBr solutions. Themore » thermally treated catalysts show high activity for the hydrogen reactions. The exchange current densities (i o) of the synthesized Rh xS y catalysts in H 2-saturated 1M H 2SO 4 and 1M HBr for HER and HOR were 0.9 mA/cm 2 to 1.0 mA/cm 2 and 0.8 to 0.9 mA/cm 2, respectively. The lower i o values obtained in 1M HBr solution compared to in H 2SO 4 might be due to the adsorption of Br - on the active surface. Stable electrochemical active surface area (ECSA) of Rh xS y catalyst was obtained for CV scan limits between 0 V and 0.65 V vs. RHE. Scans with upper voltage limit beyond 0.65 V led to decreased and unreproducible ECSA measurements.« less

Synthesis of renewable diesel through hydrodeoxygenation reaction from nyamplung oil (Calophyllum Inophyllum oil) using NiMo/Z and NiMo/C catalysts with rapid heating and cooling method

NASA Astrophysics Data System (ADS)

Susanto, B. H.; Prakasa, M. B.; Shahab, M. H.

2016-11-01

The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. The result of NiMo/Z 575 °C characterizations are 33.73 m2/gram surface area and 31.80 nm crystal size. By used NiMo/C 700 °C catalyst for 30 minutes which had surface area of 263.21 m2/gram, had 31.77 nm crystal size, and good morphology, obtained catalyst with high activity, selectivity, and stability. After catalyst activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 °C, 12 bar, and 800 rpm. The result of conversion was 81.99%, yield was 68.08%, and selectivity was 84.54%.
Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.
A Joint Theory and Experimental Project in the Synthesis and Testing of Porous COFs for On-Board Vehicular Hydrogen Storage

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

Yaghi, Omar M.; Goddard, William A.

2013-06-29

Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g/L) densities to be achieved by 2015. From our continuous efforts on hydrogen storage, it is believed that metalation of highly porous solids with high-valence metals is promising and provides a rational direction to realize high volumetric hydrogen density near room temperature. This grant was focusedmore » on the study of high surface area covalent organic frameworks (COFs) with these specific objectives (1) to introduce potential metal binding sites through the COF synthesis and (2) to implement metalation experiments and evaluate their respective hydrogen adsorption properties. To maximize our efforts, simulation calculations were also performed (prior to experiments) for the prediction of binding enthalpy of hydrogen for molecular building units containing transition metals and promising COF structures to increase volumetric hydrogen uptake at room temperature. In this effort, first molecular building units with optimal binding energy for hydrogen storage (20 kJ/mol) were designed by quantum mechanical (QM) methods. Employing these results, it was revealed that one of metalated COFs takes up 60 g/L (total) of H2 at 100 bar and 298 K. To realize proposed COF structures, chemistry of COF synthesis has been developed; for instance, new air stable COFs were synthesized via hydrazone (COF-41 to 43) and imine condensation (COF-301, 320, 340, and 366) and some of them were tested the effect on metalation. Finally, a new triazine COF with high volumetric hydrogen uptake capacity was presented as a proposed future direction.« less
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.
Hydrogen-Induced Plastic Deformation in ZnO

NASA Astrophysics Data System (ADS)

Lukáč, F.; Čížek, J.; Vlček, M.; Procházka, I.; Anwand, W.; Brauer, G.; Traeger, F.; Rogalla, D.; Becker, H.-W.

In the present work hydrothermally grown ZnO single crystals covered with Pd over-layer were electrochemically loaded with hydrogen and the influence of hydrogen on ZnO micro structure was investigated by positron annihilation spectroscopy (PAS). Nuclear reaction analysis (NRA) was employed for determination of depth profile of hydrogen concentration in the sample. NRA measurements confirmed that a substantial amount of hydrogen was introduced into ZnO by electrochemical charging. The bulk hydrogen concentration in ZnO determined by NRA agrees well with the concentration estimated from the transported charge using the Faraday's law. Moreover, a subsurface region with enhanced hydrogen concentration was found in the loaded crystals. Slow positron implantation spectroscopy (SPIS) investigations of hydrogen-loaded crystal revealed enhanced concentration of defects in the subsurface region. This testifies hydrogen-induced plastic deformation of the loaded crystal. Absorbed hydrogen causes a significant lattice expansion. At low hydrogen concentrations this expansion is accommodated by elastic straining, but at higher concentrations hydrogen-induced stress exceeds the yield stress in ZnO and plastic deformation of the loaded crystal takes place. Enhanced hydrogen concentration detected in the subsurface region by NRA is, therefore, due to excess hydrogen trapped at open volume defects introduced by plastic deformation. Moreover, it was found that hydrogen-induced plastic deformation in the subsurface layer leads to typical surface modification: formation of hexagonal shape pyramids on the surface due to hydrogen-induced slip in the [0001] direction.
Cloning single wall carbon nanotubes for hydrogen storage

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

Tour, James M; Kittrell, Carter

2012-08-30

The purpose of this research is to development the technology required for producing 3-D nano-engineered frameworks for hydrogen storage based on sp 2 carbon media, which will have high gravimetric and especially high volumetric uptake of hydrogen, and in an aligned fibrous array that will take advantage of the exceptionally high thermal conductivity of sp 2 carbon materials to speed up the fueling process while minimizing or eliminating the need for internal cooling systems. A limitation for nearly all storage media using physisorption of the hydrogen molecule is the large amount of surface area (SA) occupied by each H 2more » molecule due to its large zero-point vibrational energy. This creates a conundrum that in order to maximize SA, the physisorption media is made more tenuous and the density is decreased, usually well below 1 kg/L, so that there comes a tradeoff between volumetric and gravimetric uptake. Our major goal was to develop a new type of media with high density H 2 uptake, which favors volumetric storage and which, in turn, has the capability to meet the ultimate DoE H 2 goals.« less
Hydrogen ions associated with the dry deposition of pollen

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

Noll, K.E.; Khalili, E.K.

The data provided in this paper demonstrates that pollen can generate significant amounts of hydrogen ions when added to water and that the deposition of tree pollen in forested areas represents a significant hydrogen ion source. Measurements of dry deposition of pollen were made during the months of May and June, 1987 in Northern Wisconsin, using a smooth surrogate surface. Rain samples were also collected. Deposited particles were weighed to determine mass fluxes, then washed and ion chromatographed for SO {sub 4} = and NO {sub 3} {minus} analysis. Species of pollen collected from different types of trees during themore » sampling period were analyzed for SO{sub 4} = NO {sub 3} and other trace constituents. The micrograms of hydrogen ions (protons) generated per gram for different types of pollen added to water, were measured. From 56 to 566 gm were generated per gram or pollen added. The amount generated varied with pollen type. Based on this information, the equivalent protons from the dry deposition of pollen were calculated and compared with the wet deposition proton data. The sulfate, nitrate, and protons associated with dry deposition were of a magnitude comparable with wet deposition.« less
Process for removing copper in a recoverable form from solid scrap metal

DOEpatents

Hartman, Alan D.; Oden, Laurance L.; White, Jack C.

1995-01-01

A process for removing copper in a recoverable form from a copper/solid ferrous scrap metal mix is disclosed. The process begins by placing a copper/solid ferrous scrap metal mix into a reactor vessel. The atmosphere within the reactor vessel is purged with an inert gas or oxidizing while the reactor vessel is heated in the area of the copper/solid ferrous scrap metal mix to raise the temperature within the reactor vessel to a selected elevated temperature. Air is introduced into the reactor vessel and thereafter hydrogen chloride is introduced into the reactor vessel to obtain a desired air-hydrogen chloride mix. The air-hydrogen chloride mix is operable to form an oxidizing and chloridizing atmosphere which provides a protective oxide coating on the surface of the solid ferrous scrap metal in the mix and simultaneously oxidizes/chloridizes the copper in the mix to convert the copper to a copper monochloride gas for transport away from the solid ferrous scrap metal. After the copper is completely removed from the copper/solid ferrous scrap metal mix, the flows of air and hydrogen chloride are stopped and the copper monochloride gas is collected for conversion to a recoverable copper species.
Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes.

PubMed

Lobo, Rui F M; Santos, Diogo M F; Sequeira, Cesar A C; Ribeiro, Jorge H F

2012-02-06

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi 3.6 Co 0.85 Al 0.3 Mn 0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam-thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.
Enhanced carbon monoxide utilization in methanation process

DOEpatents

Elek, Louis F.; Frost, Albert C.

1984-01-01

Carbon monoxide - containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is subsequently reacted with steam or hydrogen to form methane. Surprisingly, hydrogen and water vapor present in the feed gas do not adversely affect CO utilization significantly, and such hydrogen actually results in a significant increase in CO utilization.
Study of wettability and cell viability of H implanted stainless steel

NASA Astrophysics Data System (ADS)

Shafique, Muhammad Ahsan; Ahmad, Riaz; Rehman, Ihtesham Ur

2018-03-01

In the present work, the effect of hydrogen ion implantation on surface wettability and biocompatibility of stainless steel is investigated. Hydrogen ions are implanted in the near-surface of stainless steel to facilitate hydrogen bonding at different doses with constant energy of 500 KeV, which consequently improve the surface wettability. Treated and untreated sample are characterized for surface wettability, incubation of hydroxyapatite and cell viability. Contact angle (CA) study reveals that surface wettability increases with increasing H-ion dose. Raman spectroscopy shows that precipitation of hydroxyapatite over the surface increase with increasing dose of H-ions. Cell viability study using MTT assay describes improved cell viability in treated samples as compared to the untreated sample. It is found that low dose of H-ions is more effective for cell proliferation and the cell count decreases with increasing ion dose. Our study demonstrates that H ion implantation improves the surface wettability and biocompatibility of stainless steel.
Elucidation of metal-ion accumulation induced by hydrogen bonds on protein surfaces by using porous lysozyme crystals containing Rh(III) ions as the model surfaces.

PubMed

Ueno, Takafumi; Abe, Satoshi; Koshiyama, Tomomi; Ohki, Takahiro; Hikage, Tatsuo; Watanabe, Yoshihito

2010-03-01

Metal-ion accumulation on protein surfaces is a crucial step in the initiation of small-metal clusters and the formation of inorganic materials in nature. This event is expected to control the nucleation, growth, and position of the materials. There remain many unknowns, as to how proteins affect the initial process at the atomic level, although multistep assembly processes of the materials formation by both native and model systems have been clarified at the macroscopic level. Herein the cooperative effects of amino acids and hydrogen bonds promoting metal accumulation reactions are clarified by using porous hen egg white lysozyme (HEWL) crystals containing Rh(III) ions, as model protein surfaces for the reactions. The experimental results reveal noteworthy implications for initiation of metal accumulation, which involve highly cooperative dynamics of amino acids and hydrogen bonds: i) Disruption of hydrogen bonds can induce conformational changes of amino-acid residues to capture Rh(III) ions. ii) Water molecules pre-organized by hydrogen bonds can stabilize Rh(III) coordination as aqua ligands. iii) Water molecules participating in hydrogen bonds with amino-acid residues can be replaced by Rh(III) ions to form polynuclear structures with the residues. iv) Rh(III) aqua complexes are retained on amino-acid residues through stabilizing hydrogen bonds even at low pH (approximately 2). These metal-protein interactions including hydrogen bonds may promote native metal accumulation reactions and also may be useful in the preparation of new inorganic materials that incorporate proteins.
The dynamical properties of a Rydberg hydrogen atom between two parallel metal surfaces

NASA Astrophysics Data System (ADS)

Liu, Wei; Li, Hong-Yun; Yang, Shan-Ying; Lin, Sheng-Lu

2011-03-01

This paper presents the dynamical properties of a Rydberg hydrogen atom between two metal surfaces using phase space analysis methods. The dynamical behaviour of the excited hydrogen atom depends sensitively on the atom—surface distance d. There exists a critical atom—surface distance dc = 1586 a.u. When the atom—surface distance d is larger than the critical distance dc, the image charge potential is less important than the Coulomb potential, the system is near-integrable and the electron motion is regular. As the distance d decreases, the system will tend to be non-integrable and unstable, and the electron might be captured by the metal surfaces. Project supported by the National Natural Science Foundation of China (Grant No. 10774093) and the Natural Science Foundation of Shandong Province (Grant No. ZR2009FZ006).
Molecular dynamics simulations of hydrogen bombardment of tungsten carbide surfaces

NASA Astrophysics Data System (ADS)

Träskelin, P.; Juslin, N.; Erhart, P.; Nordlund, K.

2007-05-01

The interaction between energetic hydrogen and tungsten carbide (WC) is of interest both due to the use of hydrogen-containing plasmas in thin-film manufacturing and due to the presence of WC in the divertor of fusion reactors. In order to study this interaction, we have carried out molecular dynamics simulations of the low-energy bombardment of deuterium impinging onto crystalline as well as amorphous WC surfaces. We find that prolonged bombardment leads to the formation of an amorphous WC surface layer, regardless of the initial structure of the WC sample. Loosely bound hydrocarbons, which can erode by swift chemical sputtering, are formed at the surface. Carbon-terminated surfaces show larger sputtering yields than tungsten-terminated surfaces. In both cumulative and noncumulative simulations, C is seen to sputter preferentially. Implications for mixed material erosion in ITER are discussed.
Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

2013-08-01

The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage.The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage. Electronic supplementary information (ESI) available: Detailed methods of preparation of GOBINPPA, SEM images, IR spectra, TGA, nitrogen adsorption-desorption isotherms, pore size distribution, gravimetric hydrogen adsorption, carbon dioxide adsorption isotherms, and virial analysis of the adsorption data for GOBIN materials. See DOI: 10.1039/c3nr01480k
Porous palladium coated conducting polymer nanoparticles for ultrasensitive hydrogen sensors

NASA Astrophysics Data System (ADS)

Lee, Jun Seop; Kim, Sung Gun; Cho, Sunghun; Jang, Jyongsik

2015-12-01

Hydrogen, a clean-burning fuel, is of key importance to various industrial applications, including fuel cells and in the aerospace and automotive industries. However, hydrogen gas is odorless, colorless, and highly flammable; thus appropriate safety protocol implementation and monitoring are essential. Highly sensitive hydrogen leak detection and surveillance sensor systems are needed; additionally, the ability to maintain uniformity through repetitive hydrogen sensing is becoming increasingly important. In this report, we detail the fabrication of porous palladium coated conducting polymer (3-carboxylate polypyrrole) nanoparticles (Pd@CPPys) to detect hydrogen gas. The Pd@CPPys are produced by means of facile alkyl functionalization and chemical reduction of a pristine 3-carboxylate polypyrrole nanoparticle-contained palladium precursor (PdCl2) solution. The resulting Pd@CPPy-based sensor electrode exhibits ultrahigh sensitivity (0.1 ppm) and stability toward hydrogen gas at room temperature due to the palladium sensing layer.Hydrogen, a clean-burning fuel, is of key importance to various industrial applications, including fuel cells and in the aerospace and automotive industries. However, hydrogen gas is odorless, colorless, and highly flammable; thus appropriate safety protocol implementation and monitoring are essential. Highly sensitive hydrogen leak detection and surveillance sensor systems are needed; additionally, the ability to maintain uniformity through repetitive hydrogen sensing is becoming increasingly important. In this report, we detail the fabrication of porous palladium coated conducting polymer (3-carboxylate polypyrrole) nanoparticles (Pd@CPPys) to detect hydrogen gas. The Pd@CPPys are produced by means of facile alkyl functionalization and chemical reduction of a pristine 3-carboxylate polypyrrole nanoparticle-contained palladium precursor (PdCl2) solution. The resulting Pd@CPPy-based sensor electrode exhibits ultrahigh sensitivity (0.1 ppm) and stability toward hydrogen gas at room temperature due to the palladium sensing layer. Electronic supplementary information (ESI) available: BET surface area and pore distribution of palladium architectures without CPPyNPs; Hydrogen sensing ability of palladium architectures without CPPyNPs; HR-TEM image of Pd@CPPy_C16 after 100 cycle exposure of H2. See DOI: 10.1039/c5nr06193h
Mechanism of wiggling enhancement due to HBr gas addition during amorphous carbon etching

NASA Astrophysics Data System (ADS)

Kofuji, Naoyuki; Ishimura, Hiroaki; Kobayashi, Hitoshi; Une, Satoshi

2015-06-01

The effect of gas chemistry during etching of an amorphous carbon layer (ACL) on wiggling has been investigated, focusing especially on the changes in residual stress. Although the HBr gas addition reduces critical dimension loss, it enhances the surface stress and therefore increases wiggling. Attenuated total reflectance Fourier transform infrared spectroscopy revealed that the increase in surface stress was caused by hydrogenation of the ACL surface with hydrogen radicals. Three-dimensional (3D) nonlinear finite element method analysis confirmed that the increase in surface stress is large enough to cause the wiggling. These results also suggest that etching with hydrogen compound gases using an ACL mask has high potential to cause the wiggling.
A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

PubMed

Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

2017-04-05

The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.
Improvement and analysis of the hydrogen-cerium redox flow cell

DOE PAGES

Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

2016-08-03

In this paper, the H 2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm -2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50more » °C. Finally, the H 2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.« less
Direct hydrogenation and one-pot reductive amidation of nitro compounds over Pd/ZnO nanoparticles as a recyclable and heterogeneous catalyst

NASA Astrophysics Data System (ADS)

Hosseini-Sarvari, Mona; Razmi, Zahra

2015-01-01

A novel Pd supported on ZnO nanoparticles was readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% which was determined by ICP analysis and atomic absorption spectroscopy (AAS). Percentage of accessible Pd as active catalyst is also estimated to 2.72% based on the thermogravimetric (TG) analysis. This nano-sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for direct hydrogenation and one-pot reductive amidation of nitro compounds without the use of any ligands under atmospheric pressure. The catalyst can be recovered and recycled several times without marked loss of activity.

InP nanopore arrays for photoelectrochemical hydrogen generation.

PubMed

Li, Qiang; Zheng, Maojun; Zhang, Bin; Zhu, Changqing; Wang, Faze; Song, Jingnan; Zhong, Miao; Ma, Li; Shen, Wenzhong

2016-02-19

We report a facile and large-scale fabrication of highly ordered one-dimensional (1D) indium phosphide (InP) nanopore arrays (NPs) and their application as photoelectrodes for photoelectrochemical (PEC) hydrogen production. These InP NPs exhibit superior PEC performance due to their excellent light-trapping characteristics, high-quality 1D conducting channels and large surface areas. The photocurrent density of optimized InP NPs is 8.9 times higher than that of planar counterpart at an applied potential of +0.3 V versus RHE under AM 1.5G illumination (100 mW cm(-2)). In addition, the onset potential of InP NPs exhibits 105 mV of cathodic shift relative to planar control. The superior performance of the nanoporous samples is further explained by Mott-Schottky and electrochemical impedance spectroscopy ananlysis.
Synthesis and characterization of hydrogen-bond acidic functionalized graphene

NASA Astrophysics Data System (ADS)

Yang, Liu; Han, Qiang; Pan, Yong; Cao, Shuya; Ding, Mingyu

2014-05-01

Hexafluoroisopropanol phenyl group functionalized materials have great potential in the application of gas-sensitive materials for nerve agent detection, due to the formation of strong hydrogen-bonding interactions between the group and the analytes. In this paper, take full advantage of ultra-large specific surface area and plenty of carbon-carbon double bonds and hexafluoroisopropanol phenyl functionalized graphene was synthesized through in situ diazonium reaction between -C=C- and p-hexafluoroisopropanol aniline. The identity of the as-synthesis material was confirmed by transmission electron microscopy, Raman spectroscopy, ultraviolet visible spectroscopy, X-ray photoelectron spectroscopy and thermo gravimetric analysis. The synthesis method is simply which retained the excellent physical properties of original graphene. In addition, the novel material can be assigned as an potential candidate for gas sensitive materials towards organophosphorus nerve agent detection.
Thermodynamics of GaN(s)-NH3(v)+N2(v)+H2(v) system - Electronic aspects of the processes at GaN(0001) surface

NASA Astrophysics Data System (ADS)

Kempisty, Pawel; Strak, Pawel; Sakowski, Konrad; Krukowski, Stanislaw

2017-08-01

Comprehensive analysis of GaN(0001) surface in equilibrium with ammonia/hydrogen mixture was undertaken using results of ab initio calculations. Adsorption energies of the species derived from ammonia and molecular hydrogen and their stable sites were obtained. It was shown that the adsorption process type and energy depend on the position of Fermi level at the surface. Hydrogen decomposes into two separate H atoms, always adsorbed in the positions on top of the surface Ga atoms (On-top). Ammonia adsorption at GaN(0001) surface proceeds molecularly to ammonia in the On-top position or dissociatively into NH2 radicals in bridge (NH2-bridge) or On-top positions or into NH radicals in H3 (NH-H3) site. Presence of these species affects Fermi level pinning at the surface due to creation of new surface states. The Fermi level pinning in function of the surface attached species concentration was determined using extended electron counting rule (EECR). Results of ab initio calculations fully proved validity of the EECR predictions. Thermodynamic analysis of the surface in equilibrium with molecular hydrogen and ammonia vapor mixture is made giving the range of ammonia and hydrogen pressures, corresponding to Fermi level pinned at Ga-broken bond state for NH-H3&H and NH3&H and NH2-bridge&H coverage and at VBM for NH3 & H coverage. As the region of Fermi level pinned at Ga broken bond state corresponds to very low pressures, at pressures close to normal, GaN(0001) surface is almost totally covered by H, NH3 and NH2 located in On-top positions. It is also shown however that dominant portion of the hydrogen and ammonia pressures corresponds to Fermi level not pinned. Among them are these corresponding to MOVPE and HVPE growth conditions in which the surface is almost fully covered by NH3, NH2 and H species in On-top positions.
Mechanisms by Which Humidity Alters Ductility

DTIC Science & Technology

1982-06-01

Example Results and Discussion.,........,,,,,,,, .... 10 2.2 Effects of Ambient Water Vapor and Internal Hydrogen op Surface Microplasticity and Crack...Localized Microplastic Deformation of the Surface of Al 2219-T851,,. ,.. ... ,,. ... ,,* ,, .. ..... .. .... 55 4.2 Effects of Ambient Humidity and Internal...Hydrogen on Surface Local Microplastic Behavior ..... 00. ,00..... ..06...... 56 4.3 Relationship of Localized Plasticity to Crack Initiation and
The impact of multiphase behaviour on coke deposition in heavy oil hydroprocessing catalysts

NASA Astrophysics Data System (ADS)

Zhang, Xiaohui

Coke deposition in heavy oil catalytic hydroprocessing remains a serious problem. The influence of multiphase behaviour on coke deposition is an important but unresolved question. A model heavy oil system (Athabasca vacuum bottoms (ABVB) + decane) and a commercial heavy oil hydrotreating catalyst (NiMo/gamma-Al 2O3) were employed to study the impact of multiphase behaviour on coke deposition. The model heavy oil mixture exhibits low-density liquid + vapour (L1V), high-density liquid + vapour (L2V), as well as low-density liquid + high-density liquid + vapour (L1L2V) phase behaviour at a typical hydroprocessing temperature (380°C). The L2 phase only arises for the ABVB composition range from 10 to 50 wt %. The phase behaviour undergoes transitions from V to L2V, to L1L2V, to L1V with increasing ABVB compositions at the pressure examined. The addition of hydrogen into the model heavy oil mixtures at a fixed mass ratio (0.0057:1) does not change the phase behaviour significantly, but shifts the phase regions and boundaries vertically from low pressure to high pressure. In the absence of hydrogen, the carbon content, surface area and pore volume losses for catalyst exposed to the L1 phase are greater than for the corresponding L2 phase despite a higher coke precursor concentration in L2 than in L1. By contrast, in the presence of hydrogen, the carbon content, surface area and pore volume losses for the catalyst exposed to the L2 phase are greater than for the corresponding L1 phase. The higher hydrogen concentration in L1 appears to reverse the observed results. In the presence of hydrogen, L2 was most closely associated with coke deposition, L1 less associated with coke deposition, and V least associated with coke deposition. Coke deposition is maximized in the phase regions where the L2 phase arises. This key result is inconsistent with expectation and coke deposition models where the extent of coke deposition, at otherwise fixed reaction conditions, is asserted to be proportional to the nominal concentration of coke precursor present in the feed. These new findings are very significant both with respect to providing guidance concerning possible operation improvement for existing processes and for the development of new upgrading processes.
Effect of Chloride Anions on the Synthesis and Enhanced Catalytic Activity of Silver Nanocoral Electrodes for CO 2 Electroreduction

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

Hsieh, Yu-Chi; Senanayake, Sanjaya D.; Zhang, Yu

2015-09-04

Metallic silver (Ag) is known as an efficient electrocatalyst for the conversion of carbon dioxide (CO 2) to carbon monoxide (CO) in aqueous or nonaqueous electrolytes. However, polycrystalline silver electrocatalysts require significant overpotentials in order to achieve high selectivity toward CO 2 reduction, as compared to the side reaction of hydrogen evolution. Here we report a high-surface-area Ag nanocoral catalyst, fabricated by an oxidation–reduction method in the presence of chloride anions in an aqueous medium, for the electro-reduction of CO 2 to CO with a current efficiency of 95% at the low overpotential of 0.37 V and the current densitymore » of 2 mA cm –2. A lower limit of TOF of 0.4 s –1 and TON > 8.8 × 10 4 (over 72 h) was estimated for the Ag nanocoral catalyst at an overpotential of 0.49 V. The Ag nanocoral catalyst demonstrated a 32-fold enhancement in surface-area-normalized activity, at an overpotential of 0.49 V, as compared to Ag foil. We found that, in addition to the effect on nanomorphology, the adsorbed chloride anions play a critical role in the observed enhanced activity and selectivity of the Ag nanocoral electrocatalyst toward CO 2 reduction. Synchrotron X-ray photoelectron spectroscopy (XPS) studies along with a series of control experiments suggest that the chloride anions, remaining adsorbed on the catalyst surface under electrocatalytic conditions, can effectively inhibit the side reaction of hydrogen evolution and enhance the catalytic performance for CO 2 reduction.« less
Plasma-surface interaction in negative hydrogen ion sources

NASA Astrophysics Data System (ADS)

Wada, Motoi

2018-05-01

A negative hydrogen ion source delivers more beam current when Cs is introduced to the discharge, but a continuous operation of the source reduces the beam current until more Cs is added to the source. This behavior can be explained by adsorption and ion induced desorption of Cs atoms on the plasma grid surface of the ion source. The interaction between the ion source plasma and the plasma grid surface of a negative hydrogen ion source is discussed in correlation to the Cs consumption of the ion source. The results show that operation with deuterium instead of hydrogen should require more Cs consumption and the presence of medium mass impurities as well as ions of the source wall materials in the arc discharge enlarges the Cs removal rate during an ion source discharge.
Heterolytic Activation of Hydrogen Promoted by Ruthenium Nanoparticles immobilized on Basic Supports and Hydrogenation of Aromatic Compounds

NASA Astrophysics Data System (ADS)

Fang, Minfeng

Despite the aggressive development and deployment of new renewable and nuclear technologies, petroleum-derived transportation fuels---gasoline, diesel and jet fuels---will continue to dominate the markets for decades. Environmental legislation imposes severe limits on the tolerable proportion of aromatics, sulfur and nitrogen contents in transportation fuels, which is difficult to achieve with current refining technologies. Catalytic hydrogenation plays an important role in the production of cleaner fuels, both as a direct means to reduce the aromatics and as a key step in the hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) processes. However, conventional catalysts require drastic conditions and/or are easily poisoned by S or N aromatics. Therefore, there is still a need for new efficient catalysts for hydrogenation reactions relevant to the production of cleaner fossil fuels. Our catalyst design involves metallic nanoparticles intimately associated with a basic support, with the aim of creating a nanostructure capable of promoting the heterolytic activation of hydrogen and ionic hydrogenation mechanisms, as a strategy to avoid catalyst poisoning and enhance catalytic activity. We have designed and prepared a new nanostructured catalytic material composed of RuNPs immobilized on the basic polymer P4VPy. We have demonstrated that the Ru/P4VPy catalyst can promote heterolytic hydrogen activation and a unique surface ionic hydrogenation mechanism for the efficient hydrogenation of N-aromatics. This is the first time these ionic hydrogenation pathways have been demonstrated on solid surfaces. For the RuNPs surfaces without basic sites in close proximity, the conventional homolytic H2 splitting is otherwise involved. Using the mechanistic concepts from Ru/P4VPy, we have designed and prepared the Ru/MgO catalyst, with the aim to improve the catalytic efficiency for the hydrogenation of heteroatom aromatics operating by the ionic hydrogenation mechanism. The Ru/MgO catalyst significantly improves the catalytic efficiency for hydrogenation of a variety of N-/S-heteroaromatics and mono-/polycyclic aromatic hydrocarbons representative of components of petroleum-derived fuels. The catalyst is superior to the few other known supported noble metal catalysts for these reactions. Mechanistic studies also point to the ionic hydrogenation mechanism on the Ru/MgO surfaces. In addition, the Ru/MgO catalyst is highly recyclable and long-lived.
Chemical structural analysis of diamondlike carbon films: I. Surface growth model

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The surface growth mechanisms of diamondlike carbon (DLC) films has been clarified. DLC films were synthesized in atmospheres with a fixed methane-to-argon ratio at different temperatures up to 700 °C by the photoemission-assisted glow discharge of photoemission-assisted plasma-enhanced chemical vapor deposition. The electrical resistivity of the films decreased logarithmically as the synthesis temperature was increased. Conversely, the dielectric constant of the films increased and became divergent at high temperature. However, the very high electrical resistivity of the film synthesized at 150 °C was retained even after post-annealing treatments at temperatures up to 500 °C, and divergence of the dielectric constant was not observed. Such films exhibited excellent thermal stability and retained large amounts of hydrogen, even after post-annealing treatments. These results suggest that numerous hydrogen atoms were incorporated into the DLC films during synthesis at low temperatures. Hydrogen atoms terminate carbon dangling bonds in the films to restrict π-conjugated growth. During synthesis at high temperature, hydrogen was desorbed from the interior of the growing films and π-conjugated conductive films were formed. Moreover, hydrogen radicals were chemisorbed by carbon atoms at the growing DLC surface, leading to removal of carbon atoms from the surface as methane gas. The methane molecules decomposed into hydrocarbons and hydrogen radicals through the attack of electrons above the surface. Hydrogen radicals contributed to the etching reaction cycle of the film; the hydrocarbon radicals were polymerized by reacting with other radicals and the methane source. The polymer radicals remained above the film, preventing the supply of the methane source and disrupting the action of argon ions. At high temperatures, the resultant DLC films were rough and thin.
First-principles quantum mechanical investigations: Catalytic reactions of furfural on Pd(111) and at the water/Pd(111) interface

NASA Astrophysics Data System (ADS)

Xue, Wenhua

Bio-oils have drawn more and more attention from scientists as a promising new clean, cheap energy source. One of the most interesting relevant issues is the effect of catalysts on the catalytic reactions that are used for producing bio-oils. Furfural, as a very important intermediate during these reactions, has attracted significant studies. However, the effect of catalysts, including particularly the liquid/solid interface formed by a metal catalyst and liquid water, in the catalytic reactions involving furfural still remains elusive. In this research, we performed ab initio molecular dynamics simulations and first-principles density-functional theory calculations to investigate the atomic-scale mechanisms of catalytic hydrogenation of furfural on the palladium surface and at the liquid/state interface formed by the palladium surface and liquid water. We studied all the possible mechanisms that lead to formation of furfuryl alcohol (FOL), formation of tetrahydrofurfural (THFAL), and formation of tetrahydrofurfurfuryl alcohol (THFOL). We found that liquid water plays a significant role in the hydrogenation reactions. During the reaction in the presence of water and the palladium catalyst, in particular, water directly participates in the hydrogenation of the aldehyde group of furfural and facilitates the formation of FOL by reducing the activation energy. Our calculations show that water provides hydrogen for the hydrogenation of the aldehyde group, and at the same time, a pre-existing hydrogen atom, which is resulted from dissociation of molecular hydrogen (experimentally, molecular hydrogen is always supplied for hydrogenation) on the palladium surface, is bonded to water, making the water molecule intact in structure. In the absence of water, on the other hand, formation of FOL and THFAL on the palladium surface involves almost the same energy barriers, suggesting a comparable selectivity. Overall, as water reduces the activation energy for the formation of FOL while increases the energy barrier slightly for hydrogenation of the furan ring, water changes the reaction selectivity and promotes the formation of furfuryl alcohol.
Electron Emission and Ion Desorption Spectroscopy of Clean and Oxidized Ti(0001).

DTIC Science & Technology

1984-03-30

of science and technology ranging from electrocatalysis and photocatalysis to medicine. In the former cases, Ti oxides are used both as active...the bulk hydrogen . The only impurity left after this procedure was surface hydrogen , evidenced by UPS (17) and ESD-TOF (time-of-flight) measurements...The surface concentration of hydrogen could be significantly reduced by slight exposure to oxygen (, 4 L) followed by heating to ’- 7000C and quenching
Relationship Between Topography and the Eastern Equatorial Hydrogen Signal on Mars

NASA Astrophysics Data System (ADS)

Clevy, J. R.; Elphic, R. C.; Feldman, W. C.; Kattenhorn, S. A.

2005-12-01

Epithermal neutron flux data received from the Neutron Spectrometer, part of the Gamma Ray Spectrometer suite on board NASA's Mars Odyssey, indicates elevated equatorial hydrogen deposits partially encircle the Schiaparelli Basin. Deconvolution of the hydrogen signal statistically increased the resolution over the spectrometer's original 600 km footprint. The resulting map of hydrogen concentrations was further refined by ignoring all data <8.9% Water Equivalent Hydrogen (WEH). In so doing, this study provides the most detailed map to date of the hydrogen concentration maxima in this region and serves as a guide for future exploration. Projecting the Eastern Equatorial Hydrogen map onto the digital elevation model for the Schiaparelli Basin reveals several areas of interest. For simplification, these areas are identified by clock position relative to Schiaparelli. At the twelve o'clock position, a maximum exceeding 10% WEH occupies the upper, northern slope of a saddle between Henry Crater and unnamed craters west of Henry. Viking images of the nameless craters demonstrate wind streaks from the north veer to the southwest here, following topography. Surface drainage channels are apparent on the slope below the local WEH maximum. The 2:30 maximum lies over Tuscaloosa Crater and Verde Vallis. This >10% WEH maximum has the greatest aerial extent, roughly 200 km in diameter. At 5 o'clock, the fringing range adjacent to Brazos Valles lies within the surficially dark region called Sinus Sabaeus. It should be noted that projection of the albedo map over the terrain reveals dark grains concentrating in low areas, presumably having moved short distances by wind and gravity. The absence or presence of these grains does not seem to affect the measured WEH concentration as the signal's local maximum, about 10.2%, crosses areas of high and low albedo without an increase or decrease in signal strength. At 6 o'clock, two 10.4% WEH maxima line the north-facing slope of another mountain range. Both maxima are elongated, east to west. The maximum at the top of the peak overlaps the cirque-like bowl of an unnamed, degraded crater. Below the collapsed north wall of this crater sits another maximum, 100 km long by 50 km wide. The eastern end of this lower maximum contains a crater with a 6 km wide, 40 km long drainage channel leading out of the crater and down the slope toward Schiaparelli. The final WEH maximum, at 6:30, is 150 km wide by 180 km long and is centered over Evros Vallis. The maximum extends beyond Sabaeus into Noachis Terra without visibly increasing or decreasing at the albedo boundary. From this study it is clear that albedo features do not control the hydrogen signal. WEH concentrations were found both within and outside Sabaeus. It is also apparent that drainage channels are present near each maximum. This proximity may implicate areas of high WEH as the source of channel-carving fluids. Finally, WEH is not tied to a specific stratigraphic layer. The locations of the maxima can be grouped into north-facing slopes, both peaks and saddles, and broad plains containing well-developed drainage systems flowing away from the WEH maxima. The former could indicate up-slope orographic deposition of hydrogen in the form of water ice as air masses rise and cool, preferentially coating north-facing slopes. High signals in low plains may be related to subsequent drainage when temperatures were warm enough to permit flow without immediate sublimation.
Quantitative Structure Retention Relationships of Polychlorinated Dibenzodioxins and Dibenzofurans

DTIC Science & Technology

1991-08-01

be a projection onto the X-Y plane. The algorithm for this calculation can be found in Stouch and Jurs (22), but was further refined by Rohrbaugh and...throughspace distances. WPSA2 (c) Weighted positive charged surface area. MOMH2 (c) Second major moment of inertia with hydrogens attached. CSTR 3 (d) Sum...of the models. The robust regression analysis method calculates a regression model using a least median squares algorithm which is not as susceptible
Nanocrystalline mesoporous SMO thin films prepared by sol gel process for MEMS-based hydrogen sensor

NASA Astrophysics Data System (ADS)

Gong, Jianwei; Fei, Weifeng; Seal, Sudipta; Chen, Quanfang

2004-01-01

MEMS based SnO2 gas sensor with sol gel synthesized mesoporous nanocrystalline (<10 nm) semiconductor thin (100~150 nm) film has been recently developed. The SnO2 nano film is fabricated with the combination of polymeric sol gel chemistry with block copolymers used for structure directing agents. The novel hydrogen sensor has a fast response time (1s) and quick recovery time (3s), as well as good sensitivity (about 90%), comparing to other hydrogen sensors developed. The improved capabilities are credited to the large surface to volume ratio of gas sensing thin film with nano sized porous surface topology, which can greatly increase the sensitivity even at relatively low working temperature. The gas sensing film is deposited onto a thin dielectric membrane of low thermal conductivity, which provides good thermal isolation between substrate and the gas-sensitive heated area on the membrane. In this way the power consumption can be kept very low. Since the fabrication process is completely compatible with IC industry, it makes mass production possible and greatly reduces the cost. The working temperature of the new sensor can be reduced as low as 100°C. The low working temperature posse advantages such as lower power consumption, lower thermal induced signal shift as well as safe detection in certain environments where temperature is strictly limited.
Research Staff | Hydrogen and Fuel Cells | NREL

Science.gov Websites

laboratory's research areas contribute to this work. Research Areas and Technical Leads NREL's hydrogen and fuel cell research and development is organized into eight research areas. Technical leaders work
Molecular dynamics study of biodegradation of azo dyes via their interactions with AzrC azoreductase.

PubMed

Haghshenas, Hamed; Kay, Maryam; Dehghanian, Fariba; Tavakol, Hossein

2016-01-01

Azo dyes are one of the most important class of dyes, which have been widely used in industries. Because of the environmental pollution of azo dyes, many studies have been performed to study their biodegradation using bacterial systems. In present work, the AzrC of mesophilic gram-positive Bacillus sp. B29 has been considered to study its interaction with five common azo dyes (orange G, acid red 88, Sudan I, orange I, and methyl red). The molecular dynamics simulations have been employed to study the interaction between AzrC and azo dyes. The trajectory was confirmed using root mean square deviation and the root mean square fluctuation analyses. Then, the hydrogen bond and alanine scanning analyses were performed to reveal active site residues. Phe105 (A), Phe125 (B), Phe172 (B), and Pro132 (B) have been found as the most important hydrophobic residues whereas Asn104 (A), Tyr127 (B), and Asn187 (A) have key role in making hydrogen bond. The results of molecular mechanics Poisson-Boltzmann surface area and molecular mechanics generalized Born surface area calculations proved that the hydrophobic azo dyes like Acid red 88 binds more tightly to the AzrC protein. The calculated data suggested MR A 121 (B) I as a potential candidate for improving the AzrC-MR interactions.
Hydrogen uptake causes molecular "avalanches" in palladium | Argonne

Science.gov Websites

experimental and calculated strain distributions in the hydrogen-poor phase. The strains are consistent with a trapped hydrogen-rich surface layer. Middle: Comparison between experimental and calculated strain transformation. Comparison between experimental and calculated strain distributions in the hydrogen-poor phase
Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.
Low Temperature Synthesized H2Ti3O7 Nanotubes with a High CO2 Adsorption Property by Amine Modification.

PubMed

Ota, Misaki; Hirota, Yuichiro; Uchida, Yoshiaki; Sakamoto, Yasuhiro; Nishiyama, Norikazu

2018-06-12

Carbon dioxide (CO 2 ) capture and storage (CCS) technologies have been attracting attention in terms of tackling with global warming. To date, various CO 2 capture technologies including solvents, membranes, cryogenics, and solid adsorbents have been proposed. Currently, a liquid adsorption method for CO 2 using amine solution (monoethanolamine) has been practically used. However, this liquid phase CO 2 adsorption process requires heat regeneration, and it can cause many problems such as corrosion of equipment and degradation of the solution. Meanwhile, solid adsorption methods using porous materials are more advantageous over the liquid method at these points. In this context, we here evaluated if hydrogen titanate (H 2 Ti 3 O 7 ) nanotubes and the surface modification effectively capture CO 2 . For this aim, we first developed a facile synthesis method of H 2 Ti 3 O 7 nanotubes different from any conventional methods. Briefly, they were converted from the precursors-amorphous TiO 2 nanoparticles at room temperature (25 °C). We then determined the outer and the inner diameters of the H 2 Ti 3 O 7 nanotubes as 3.0 and 0.7 nm, respectively. It revealed that both values were much smaller than the reported ones; thus the specific surface area showed the highest value (735 m 2 /g). Next, the outer surface of H 2 Ti 3 O 7 nanotubes was modified using ethylenediamine to examine if CO 2 adsorption capacity increases. The ethylendiamine-modified H 2 Ti 3 O 7 nanotubes showed a higher CO 2 adsorption capacity (50 cm 3 /g at 0 °C, 100 kPa). We finally concluded that the higher CO 2 adsorption capacity could be explained, not only by the high specific surface area of the nanotubes but also by tripartite hydrogen bonding interactions among amines, CO 2 , and OH groups on the surface of H 2 Ti 3 O 7 .
The effect of stress on hydrogen uptake and desorption by A-286

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1991-01-01

The uptake and desorption of hydrogen by A-286 as a function of stress was studied using electrochemical methods. It was found that the apparent surface hydrogen concentration, the mean hydrogen concentration, and the hydrogen distribution uniformity all increased up to a stress level 50 percent of yield and decreased thereafter. The value of the hydrogen diffusion coefficient was relatively unaffected by stress while the percent of trapped hydrogen appeared to decrease with increasing stress.

Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes

PubMed Central

Lobo, Rui F. M.; Santos, Diogo M. F.; Sequeira, Cesar A. C.; Ribeiro, Jorge H. F.

2012-01-01

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption. PMID:28817043
Synthesis of methanol from CO2 hydrogenation promoted by dissociative adsorption of hydrogen on a Ga3Ni5(221) surface.

PubMed

Tang, Qingli; Shen, Zhemin; Huang, Liang; He, Ting; Adidharma, Hertanto; Russell, Armistead G; Fan, Maohong

2017-07-19

Catalytic carbon dioxide (CO 2 ) hydrogenation to liquid fuels including methanol (CH 3 OH) has attracted great attention in recent years. In this work, density functional theory (DFT) calculations have been employed to study the reaction mechanisms of CO 2 hydrogenation to CH 3 OH on Ga 3 Ni 5 (221) surfaces. The results show that all intermediates except for the O atom prefer to adsorb on Ni sites, and dissociative adsorption of hydrogen (H 2 ) on the Ga 3 Ni 5 (221) surface is almost barrierless and highly exothermic, favoring CO 2 hydrogenation. Moreover, the presence of Ga indeed enhances the dissociative adsorption of H 2 , and this is verified by the projected density of states (PDOS) analysis. Importantly, three possible reaction pathways based on formate (HCOO) and hydrocarboxyl (COOH) formations and reverse water gas shift (rWGS) with carbon monoxide (CO) hydrogenation have been discussed. It is found that CO 2 reduction to CH 3 OH in these pathways prefers to occur entirely via the Langmuir-Hinshelwood (L-H) mechanism. COOH generation is the most favorable pathway because the HCOO and rWGS with CO hydrogenation pathways have high energy barriers and the resulting HCOOH intermediate in the HCOO pathway is unstable. In the COOH reaction pathway, CO 2 is firstly hydrogenated to trans-COOH, followed by the formation of COH via three isomers of COHOH, its hydrogenation to trans-HCOH, and then the production of CH 3 OH via a CH 2 OH intermediate.
Laser Surface Melting of Stainless Steel Anodes for Reduced Hydrogen Outgassing (Postprint)

DTIC Science & Technology

2016-12-29

including baking [8– 12], vacuum baking [8,11,13,14], polishing [8,14], and surface treatments to create oxide or other protective surface films. Elec...quantity [15] and may necessitate an additional bake to thoroughly degas the surface [8]. The purpose of the work described here was to determine the...9] M. Bernardini, Air bake -out to reduce hydrogen outgassing from stainless steel, J. Vac. Sci. Technol. A Vacuum, Surfaces, Film 16 (1998) 188–193.4
Computer Animation of a Chemical Reaction.

ERIC Educational Resources Information Center

Eaker, Charles W.; Jacobs, Edwin L.

1982-01-01

Taking a prototype chemical reaction (molecular hydrogen plus hydrogen atom), constructs an accurate semiempirical, generalized diatomics-in-molecules potential energy surface, calculates motions of these atoms on this surface using REACTS trajectory program, and presents results as moving picture on a microcomputer graphics system. Provides…
Negative-hydrogen-ion production from a nanoporous 12CaO • 7Al2O3 electride surface

NASA Astrophysics Data System (ADS)

Sasao, Mamiko; Moussaoui, Roba; Kogut, Dmitry; Ellis, James; Cartry, Gilles; Wada, Motoi; Tsumori, Katsuyoshi; Hosono, Hideo

2018-06-01

A high production rate of negative hydrogen ions (H‑) was observed from a nanoporous 12CaO • 7Al2O3 (C12A7) electride surface immersed in hydrogen/deuterium low-pressure plasmas. The target was negatively biased at 20–130 V, and the target surface was bombarded by H3 + ions from the plasma. The production rate was compared with that from a clean molybdenum surface. Using the pseudo-exponential work-function dependence of the H‑ production rate, the total H‑ yield from the C12A7 electride surface bombarded at 80 V was evaluated to be 25% of that from a cesiated molybdenum surface with the lowest work-function. The measured H‑ energy spectrum indicates that the major production mechanism is desorption by sputtering. This material has potential to be used as a production surface of cesium-free negative ion sources for accelerators, heating beams in nuclear fusion, and surface modification for industrial applications.
Hydrogen evolution from aqueous-phase photocatalytic reforming of ethylene glycol over Pt/TiO2 catalysts: Role of Pt and product distribution

NASA Astrophysics Data System (ADS)

Li, Fuying; Gu, Quan; Niu, Yu; Wang, Renzhang; Tong, Yuecong; Zhu, Shuying; Zhang, Hualei; Zhang, Zizhong; Wang, Xuxu

2017-01-01

Pt nanoparticles were loaded on anatase TiO2 by the photodeposition method to investigate their photocatalytic activity for H2 evolution in an aqueous solution containing a certain amount of ethylene glycol (EG) as the sacrificial agent. The surface properties and chemical states of the Pt/TiO2 sample were characterized by X-ray powder diffraction analysis, Brunauer-Emmett-Teller surface area analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and electrochemical resistance. The aqueous-phase photocatalytic EG reforming using Pt/TiO2 and anatase TiO2 generated not only H2 and CO2, but also CO, CH4, C2H6, and C2H4. Moreover, the amount of formate and acetate complexes in the solution increased gradually. The EG adsorption and gas-phase intermediates during photocatalytic reaction processes were investigated by the in situ FTIR spectrum. Finally, the photocatalytic EG reforming reaction mechanism was elucidated. This helped to better understand the role of a sacrificial agent in a photocatalytic hydrogen production.
Synthesis of core-shell AlOOH hollow nanospheres by reacting Al nanoparticles with water

NASA Astrophysics Data System (ADS)

Lozhkomoev, A. S.; Glazkova, E. A.; Bakina, O. V.; Lerner, M. I.; Gotman, I.; Gutmanas, E. Y.; Kazantsev, S. O.; Psakhie, S. G.

2016-05-01

A novel route for the synthesis of boehmite nanospheres with a hollow core and the shell composed of highly crumpled AlOOH nanosheets by oxidizing Al nanopowder in pure water under mild processing conditions is described. The stepwise events of Al transformation into boehmite are followed by monitoring the pH in the reaction medium. A mechanism of formation of hollow AlOOH nanospheres with a well-defined shape and crystallinity is proposed which includes the hydration of the Al oxide passivation layer, local corrosion of metallic Al accompanied by hydrogen evolution, the rupture of the protective layer, the dissolution of Al from the particle interior and the deposition of AlOOH nanosheets on the outer surface. In contrast to previously reported methods of boehmite nanoparticle synthesis, the proposed method is simple, and environmentally friendly and allows the generation of hydrogen gas as a by-product. Due to their high surface area and high, slit-shaped nanoporosity, the synthesized AlOOH nanostructures hold promise for the development of more effective catalysts, adsorbents, vaccines and drug carriers.
Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

NASA Astrophysics Data System (ADS)

Damle, Ashok S.

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H 2 followed by equilibrium reconstitution to methane appears to be reasonable one.
Bactericidal Efficacy of Hydrogen Peroxide-Based Disinfectants Against Gram-Positive and Gram-Negative Bacteria on Stainless Steel Surfaces.

PubMed

Ríos-Castillo, Abel G; González-Rivas, Fabián; Rodríguez-Jerez, José J

2017-10-01

In order to develop disinfectant formulations that leverage the effectiveness of hydrogen peroxide (H 2 O 2 ), this study evaluated the bactericidal efficacy of hydrogen peroxide-based disinfectants against Gram-positive and Gram-negative bacteria on stainless steel surfaces. Low concentration of hydrogen peroxide as 0.5% with a cationic polymer, ethoxylated fatty alcohol, and ethyl alcohol had bactericidal efficacy (reductions ≥ 4 log 10 CFU/mL) against Escherichia coli, Staphylococcus aureus, Enterococcus hirae, and Pseudomonas aeruginosa. Hydrogen peroxide-based disinfectants were more effective against E. hirae and P. aeruginosa than to S. aureus. However, the efficacy of hydrogen peroxide against catalase positive bacteria such as S. aureus was increased when this compound was formulated with low concentrations of benzalkonium chloride or ethyl alcohol, lactic acid, sodium benzoate, cationic polymer, and salicylic acid. This study demonstrates that the use of hydrogen peroxide with other antimicrobial products, in adequate concentrations, had bactericidal efficacy in Gram-positive and Gram-negative bacteria on stainless steel surfaces, enabling to reduce the effective concentration of hydrogen peroxide. In the same way, the use of hydrogen peroxide-based disinfectants could reduce the concentrations of traditional disinfectants as quaternary ammonium compounds and therefore a reduction of their chemical residues in the environment after being used. The study of the bactericidal properties of environmentally nontoxic disinfectants such as hydrogen peroxide, sole or in formulations with other disinfectants against Gram-positive and Gram-negative bacteria can enhance the efficacy of various commonly used disinfectant formulations with the hygiene benefits that it entails. Also, the use of hydrogen peroxide formulations can reduce the concentration levels of products that generate environmental residues. © 2017 Institute of Food Technologists®.
Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640
First principles study of gallium cleaning for hydrogen-contaminated α-Al2O3(0001) surfaces.

PubMed

Yang, Rui; Rendell, Alistair P

2013-05-15

The use of gallium for cleaning hydrogen-contaminated Al2O3 surfaces is explored by performing first principles density functional calculations of gallium adsorption on a hydrogen-contaminated Al-terminated α-Al2O3(0001) surface. Both physisorbed and chemisorbed H-contaminated α-Al2O3(0001) surfaces with one monolayer (ML) gallium coverage are investigated. The thermodynamics of gallium cleaning are considered for a variety of different asymptotic products, and are found to be favorable in all cases. Physisorbed H atoms have very weak interactions with the Al2O3 surface and can be removed easily by the Ga ML. Chemisorbed H atoms form stronger interactions with the surface Al atoms. Bonding energy analysis and departure simulations indicate, however, that chemisorbed H atoms can be effectively removed by the Ga ML. Copyright © 2013 Wiley Periodicals, Inc.
Water's Interfacial Hydrogen Bonding Structure Reveals the Effective Strength of Surface-Water Interactions.

PubMed

Shin, Sucheol; Willard, Adam P

2018-06-05

We combine all-atom molecular dynamics simulations with a mean field model of interfacial hydrogen bonding to analyze the effect of surface-water interactions on the structural and energetic properties of the liquid water interface. We show that the molecular structure of water at a weakly interacting ( i.e., hydrophobic) surface is resistant to change unless the strength of surface-water interactions are above a certain threshold. We find that below this threshold water's interfacial structure is homogeneous and insensitive to the details of the disordered surface, however, above this threshold water's interfacial structure is heterogeneous. Despite this heterogeneity, we demonstrate that the equilibrium distribution of molecular orientations can be used to quantify the energetic component of the surface-water interactions that contribute specifically to modifying the interfacial hydrogen bonding network. We identify this specific energetic component as a new measure of hydrophilicity, which we refer to as the intrinsic hydropathy.
How much hydrogen is there in a white dwarf?

NASA Technical Reports Server (NTRS)

Macdonald, James; Vennes, Stephane

1991-01-01

Stratified hydrogen/helium envelope models in diffusive equilibrium are calculated for a 0.6-solar-mass white dwarf for effective temperatures between 10,000 and 80,000 K in order to investigate the observational constraints placed on the total hydrogen mass. Convective mixing is included ab initio in the calculations, and synthetic spectra are used for comparing these models with observational materials. It is shown that evolutionary changes in the surface composition of white dwarfs cannot be explained by a model in which a small amount of hydrogen floats to the surface from initially being mixed in the outer parts of a helium envelope. It is pointed out that the shape of the hydrogen lines can be used for constraining theories of convective overshoot.
Purification of Hydrogen

DOEpatents

Newton, A S

1950-12-05

Disclosed is a process for purifying hydrogen containing various gaseous impurities by passing the hydrogen over a large surface of uranium metal at a temperature above the decomposition temperature of uranium hydride, and below the decomposition temperature of the compounds formed by the combination of the uranium with the impurities in the hydrogen.
The application of diffusion theory to the analysis of hydrogen desorption data at 25 deg C

NASA Technical Reports Server (NTRS)

Danford, M. D.

1985-01-01

The application of diffusion theory to the analysis of hydrogen desorption data (coulombs of H2 desorbed versus time) has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, are studied in this work. For the nickel base alloys, it is found that the hydrogen distributions after electrolytic charging conforms closely to those which would be predicted by diffusion theory. For Waspaloy samples charged at 5,000 psi, it is found that the hydrogen distributions are essentially the same as those obtained by electrolytic charging. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, are essentially uniform in nature, which would not be predicted by diffusion theory. A possible explanation has been proposed. Finally, it is found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the fast hydrogen is not due to surface and sub-surface hydride formation, as was originally proposed.
High speed hydrogen/graphite interaction

NASA Technical Reports Server (NTRS)

Kelly, A. J.; Hamman, R.; Sharma, O. P.; Harrje, D. T.

1974-01-01

Various aspects of a research program on high speed hydrogen/graphite interaction are presented. Major areas discussed are: (1) theoretical predictions of hydrogen/graphite erosion rates; (2) high temperature, nonequilibrium hydrogen flow in a nozzle; and (3) molecular beam studies of hydrogen/graphite erosion.
Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.
Diffusion Analysis Of Hydrogen-Desorption Measurements

NASA Technical Reports Server (NTRS)

Danford, Merlin D.

1988-01-01

Distribution of hydrogen in metal explains observed desorption rate. Report describes application of diffusion theory to anaylsis of experimental data on uptake and elimination of hydrogen in high-strength alloys of 25 degree C. Study part of program aimed at understanding embrittlement of metals by hydrogen. Two nickel-base alloys, Rene 41 and Waspaloy, and one ferrous alloy, 4340 steel, studied. Desorption of hydrogen explained by distribution of hydrogen in metal. "Fast" hydrogen apparently not due to formation of hydrides on and below surface as proposed.
Solvation of excess electrons trapped in charge pockets on molecular surfaces

NASA Astrophysics Data System (ADS)

Jalbout, Abraham F.

This work considers the ability of hydrogen fluoride (HF) to solvate excess electrons located on cyclic hydrocarbon surfaces. The principle applied involves the formation of systems in which excess electrons can be stabilized not only on concentrated molecular surface charge pockets but also by HF. Recent studies have shown that OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), at the same time, the hydrogen atoms on the opposite side of this surface form a pocket of positive charge can attract the excess electron. This density can be further stabilized by the addition of an HF molecule that can form an 'anion with an internally solvated electron' (AISE) state. These systems are shown to be stable with respect to vertical electron detachment (VDE).
Automated extraction of single H atoms with STM: tip state dependency

NASA Astrophysics Data System (ADS)

Møller, Morten; Jarvis, Samuel P.; Guérinet, Laurent; Sharp, Peter; Woolley, Richard; Rahe, Philipp; Moriarty, Philip

2017-02-01

The atomistic structure of the tip apex plays a crucial role in performing reliable atomic-scale surface and adsorbate manipulation using scanning probe techniques. We have developed an automated extraction routine for controlled removal of single hydrogen atoms from the H:Si(100) surface. The set of atomic extraction protocols detect a variety of desorption events during scanning tunneling microscope (STM)-induced modification of the hydrogen-passivated surface. The influence of the tip state on the probability for hydrogen removal was examined by comparing the desorption efficiency for various classifications of STM topographs (rows, dimers, atoms, etc). We find that dimer-row-resolving tip apices extract hydrogen atoms most readily and reliably (and with least spurious desorption), while tip states which provide atomic resolution counter-intuitively have a lower probability for single H atom removal.

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