Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

NASA Astrophysics Data System (ADS)

Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

2017-06-01

The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

DOEpatents

Kunz, Harold R.; Breault, Richard D.

1993-01-01

An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species

DOE PAGES

Martin, Daniel J.; McCarthy, Brian D.; Donley, Carrie L.; ...

2014-12-04

Here, a Ni(ii) complex with nitrogen and sulfur donor ligands degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

The effect of crystal orientation on the aluminum anodes of the aluminum-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin; Leng, Jing; Sun, Zegao; Chen, Chunbo

2015-12-01

Recently, aluminum-air (Al-air) batteries have received attention from researchers as an exciting option for safe and efficient batteries. The electrochemical performance of Aluminum anode remains an active area of investigation. In this paper, the electrochemical properties of polycrystalline Al, Al (001), (110) and (111) single crystals are investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 4 M NaOH and KOH. Hydrogen corrosion rates of the Al anodes are determined by hydrogen collection. Battery performance using the anodes is tested by constant current discharge at 10 mA cm-2. This is the first report showing that the electrochemical properties of Al are closely related to the crystallographic orientation in alkaline electrolytes. The (001) crystallographic plane has good corrosion resistance but (110) is more sensitive. Al (001) single crystals display higher anode efficiency and capacity density. Controlling the crystallographic orientation of the Al anode is another way to improve the performance of Al-air batteries in alkaline electrolytes.

In situ optimization of pH for parts-per-billion electrochemical detection of dissolved hydrogen sulfide using boron doped diamond flow electrodes.

PubMed

Bitziou, Eleni; Joseph, Maxim B; Read, Tania L; Palmer, Nicola; Mollart, Tim; Newton, Mark E; Macpherson, Julie V

2014-11-04

A novel electrochemical approach to the direct detection of hydrogen sulfide (H2S), in aqueous solutions, covering a wide pH range (acid to alkali), is described. In brief, a dual band electrode device is employed, in a hydrodynamic flow cell, where the upstream electrode is used to controllably generate hydroxide ions (OH(-)), which flood the downstream detector electrode and provide the correct pH environment for complete conversion of H2S to the electrochemically detectable, sulfide (HS(-)) ion. All-diamond, coplanar conducting diamond band electrodes, insulated in diamond, were used due to their exceptional stability and robustness when applying extreme potentials, essential attributes for both local OH(-) generation via the reduction of water, and for in situ cleaning of the electrode, post oxidation of sulfide. Using a galvanostatic approach, it was demonstrated the pH locally could be modified by over five pH units, depending on the initial pH of the mobile phase and the applied current. Electrochemical detection limits of 13.6 ppb sulfide were achieved using flow injection amperometry. This approach which offers local control of the pH of the detector electrode in a solution, which is far from ideal for optimized detection of the analyte of interest, enhances the capabilities of online electrochemical detection systems.

Improvement of the efficiency of a space oxygen-hydrogen electrochemical generator

NASA Astrophysics Data System (ADS)

Glukhikh, I. N.; Shcherbakov, A. N.; Chelyaev, V. F.

2014-12-01

This paper describes the method used for cooling of an on-board oxygen-hydrogen electrochemical generator (ECG). Apart from electric power, such a unit produces water of reaction and heat; the latter is an additional load on the thermal control system of a space vehicle. This load is undesirable in long-duration space flights, when specific energy characteristics of on-board systems are the determining factors. It is suggested to partially compensate the energy consumption by the thermal control system of a space vehicle required for cooling of the electrochemical generator through evaporation of water of reaction from the generator into a vacuum (or through ice sublimation if the pressure in the ambient space is lower than that in the triple point of water.) Such method of cooling of an electrochemical generator improves specific energy parameters of an on-board electric power supply system, and, due to the presence of the negative feedback, it makes the operation of this system more stable. Estimates suggest that it is possible to compensate approximately one half of heat released from the generator through evaporation of its water of reaction at the electrical efficiency of the electrochemical generator equal to 60%. In this case, even minor increase in the efficiency of the generator would result in a considerable increase in the efficiency of the evaporative system intended for its cooling.

Redox Control and Hydrogen Production in Sediment Caps Using Carbon Cloth Electrodes

PubMed Central

Sun, Mei; Yan, Fei; Zhang, Ruiling; Reible, Danny D.; Lowry, Gregory V.; Gregory, Kelvin B.

2010-01-01

Sediment caps that degrade contaminants can improve their ability to contain contaminants relative to sand and sorbent-amended caps, but few methods to enhance contaminant degradation in sediment caps are available. The objective of this study was to determine if, carbon electrodes emplaced within a sediment cap at poised potential could create a redox gradient and provide electron donor for the potential degradation of contaminants. In a simulated sediment cap overlying sediment from the Anacostia River (Washington, DC), electrochemically induced redox gradients were developed within 3 days and maintained over the period of the test (~100 days). Hydrogen and oxygen were produced by water electrolysis at the electrode surfaces and may serve as electron donor and acceptor for contaminant degradation. Electrochemical and geochemical factors that may influence hydrogen production were studied. Hydrogen production displayed zero order kinetics with ~75% coulombic efficiency and rates were proportional to the applied potential between 2.5V to 5V and not greatly affected by pH. Hydrogen production was promoted by increasing ionic strength and in the presence of natural organic matter. Graphite electrode-stimulated degradation of tetrachlorobenzene in a batch reactor was dependent on applied voltage and production of hydrogen to a concentration above the threshold for biological dechlorination. These findings suggest that electrochemical reactive capping can potentially be used to create “reactive” sediments caps capable of promoting chemical or biological transformations of contaminants within the cap. PMID:20879761

Electrochemical Visualization of Intracellular Hydrogen Peroxide at Single Cells.

PubMed

He, Ruiqin; Tang, Huifen; Jiang, Dechen; Chen, Hong-yuan

2016-02-16

In this Letter, the electrochemical visualization of hydrogen peroxide inside one cell was achieved first using a comprehensive Au-luminol-microelectrode and electrochemiluminescence. The capillary with a tip opening of 1-2 μm was filled with the mixture of chitosan and luminol, which was coated with the thin layers of polyvinyl chloride/nitrophenyloctyl ether (PVC/NPOE) and gold as the microelectrode. Upon contact with the aqueous hydrogen peroxide, hydrogen peroxide and luminol in contact with the gold layer were oxidized under the positive potential resulting in luminescence for the imaging. Due to the small diameter of the electrode, the microelectrode tip was inserted into one cell and the bright luminescence observed at the tip confirmed the visualization of intracellular hydrogen peroxide. The further coupling of oxidase on the electrode surface could open the field in the electrochemical imaging of intracellular biomolecules at single cells, which benefited the single cell electrochemical detection.

Influence of hydrogen oxidation kinetics on hydrogen environment embrittlement

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

An electrochemical method for determining hydrogen concentrations in metals and some applications

NASA Technical Reports Server (NTRS)

Danford, M. D.

1983-01-01

An electrochemical method was developed for the determination of hydrogen in metals using the EG&G-PARC Model 350A Corrosion Measurement Console. The method was applied to hydrogen uptake, both during electrolysis and electroplating, and to studies of hydrogen elimination and the effect of heat treatment on elimination times. Results from these studies are presented.

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.

Refurbishment of one-person regenerative air revitalization system

NASA Technical Reports Server (NTRS)

Powell, Ferolyn T.

1989-01-01

Regenerative processes for the revitalization of spacecraft atmospheres and reclamation of waste waters are essential for making long-term manned space missions a reality. Processes studied include: static feed water electrolysis for oxygen generation, Bosch carbon dioxide reduction, electrochemical carbon dioxide concentration, vapor compression distillation water recovery, and iodine monitoring. The objectives were to: provide engineering support to Marshall Space Flight Center personnel throughout all phases of the test program, e.g., planning through data analysis; fabricate, test, and deliver to Marshall Space Flight Center an electrochemical carbon dioxide module and test stand; fabricate and deliver an iodine monitor; evaluate the electrochemical carbon dioxide concentrator subsystem configuration and its ability to ensure safe utilization of hydrogen gas; evaluate techniques for recovering oxygen from a product oxygen and carbon dioxide stream; and evaluate the performance of an electrochemical carbon dioxide concentrator module to operate without hydrogen as a method of safe haven operation. Each of the tasks were related in that all focused on providing a better understanding of the function, operation, and performance of developmental pieces of environmental control and life support system hardware.

Pore size engineering applied to starved electrochemical cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Thaller, L. H.

1982-01-01

To maximize performance in starved, multiplate cells, the cell design should rely on techniques which widen the volume tolerance characteristics. These involve engineering capillary pressure differences between the components of an electrochemical cell and using these forces to promote redistribution of electrolyte to the desired optimum values. This can be implemented in practice by prescribing pore size distributions for porous back-up plates, reservoirs, and electrodes. In addition, electrolyte volume management can be controlled by incorporating different pore size distributions into the separator. In a nickel/hydrogen cell, the separator must contain pores similar in size to the small pores of both the nickel and hydrogen electrodes in order to maintain an optimum conductive path for the electrolyte. The pore size distributions of all components should overlap in such a way as to prevent drying of the separator and/or flooding of the hydrogen electrode.

Extraction of Carbon Dioxide and Hydrogen from Seawater by an Electrochemical Acidification Cell. Part 3. Scaled-up Mobile Unit Studies (Calendar Year 2011)

DTIC Science & Technology

2012-05-30

Electrochemical Acidification Cell Part III: Scaled-up Mobile Unit Studies (Calendar Year 2011) May 30, 2012 Approved for public release; distribution is...Hydrogen from Seawater by an Electrochemical Acidification Cell Part III: Scaled-up Mobile Unit Studies (Calendar Year 2011) Heather D. Willauer, Dennis R...Unclassified Unlimited Unclassified Unlimited Unclassified Unlimited 41 Heather D. Willauer (202) 767-2673 Electrochemical acidification cell Carbon

Electrochemical Properties of LaNi(sub 5-x)Ge(sub x) Alloys in Ni-MH Batteries

NASA Technical Reports Server (NTRS)

Bowman, R. C., Jr.; Witham, C.

1997-01-01

Electrochemical studies were performed on LaNi(sub 5-x)Ge(sub x) metal hydride alloys with 0 <= x <= 0.5. We carried out single-electrode studies to understand the effects of the Ge substituent on the hydrogen absorption characteristics, the electrochemical capacity, and the electrochemical kinetics of hydrogen absorption and desorption.

The effect of hydrogen on the parameters of plastic deformation localization in low carbon steel

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

Lunev, Aleksey G., E-mail: agl@ispms.tsc.ru, E-mail: nadjozhkin@ispms.tsc.ru; Nadezhkin, Mikhail V., E-mail: agl@ispms.tsc.ru, E-mail: nadjozhkin@ispms.tsc.ru; Shlyakhova, Galina V., E-mail: shgv@ispms.tsc.ru

2014-11-14

In the present study, the effect of interstitial hydrogen atoms on the mechanical properties and plastic strain localization patterns in tensile tested polycrystals of low-carbon steel Fe-0.07%C has been studied using double exposure speckle photography technique. The main parameters of plastic flow localization at various stages of deformation hardening have been determined in polycrystals of steel electrolytically saturated with hydrogen in a three-electrode electrochemical cell at a controlled constant cathode potential. Also, the effect of hydrogen on changing of microstructure by using optical microscopy has been demonstrated.

Defects Engineered Monolayer MoS 2 for Improved Hydrogen Evolution Reaction

DOE PAGES

Ye, Gonglan; Gong, Yongji; Lin, Junhao; ...

2016-01-13

MoS 2 is a promising, low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. Our work represents an easy method to increase the hydrogen production in electrochemical reaction of MoS 2 via defect engineering, and helps to understand the catalytic properties of MoS 2.

On-site applicability of hydrogen peroxide producing microbial electrochemical cells (MECs) coupled with UV in wastewater disinfection study

EPA Science Inventory

Background: There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals wh...

ON-SITE APPLICABILITY OF HYDROGEN PEROXIDE PRODUCING MICROBIAL ELECTROCHEMICAL CELLS COUPLED WITH UV IN WASTEWATER DISINFECTION STUDY

EPA Science Inventory

There is an increased interest in the application of microbial electrochemical cell (MEC) for the recovery of value-added products such as hydrogen gas and hydrogen peroxide (H2O2) from wastewater. H2O2 has strong oxidation capability and produces hydroxyl radicals when coupled w...

Electrochemical Implications of Defects in Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Hall, Jonathan Peter

The electrochemical behavior of carbon nanotubes (CNTs) containing both intrinsic and extrinsically introduced defects has been investigated through the study of bamboo and hollow multi-walled CNT morphologies. The controlled addition of argon, hydrogen, and chlorine ions in addition to atomic hydrogen and magnesium vapor was used for varying the charge and type of extrinsic defects. To quantify changes in the CNTs upon treatment, Raman spectroscopy and electrochemical techniques were employed. It was indicated from Raman spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and chronopotentiometric experiments that the electrochemical response of hollow type CNTs could be tailored more significantly compared to bamboo type CNTs, which have innately high reactive site densities and are less amenable to modification. Total defect density and edge-plane-like defect concentrations monitored through Raman spectroscopy were used to correlate changes in the electrochemical response of the CNT electrodes as a function of treatment. The implementation of CNT electrodes in a prototypical electrolytic capacitor device was then explored and characterized. Dependencies on source current and redox couple concentration were evaluated, as well as changes in the total capacitance as a function of treatment. Cyclability studies were also performed as a function of source current magnitude to evaluate the longevity of the faradaic currents which typically decrease over time in other similar capacitors. This thesis then concludes with an overall summary of the themes and findings of the research presented in this work.

Flotation process for removal of precipitates from electrochemical chromate reduction unit

DOEpatents

DeMonbrun, James R.; Schmitt, Charles R.; Williams, Everett H.

1976-01-01

This invention is an improved form of a conventional electrochemical process for removing hexavalent chromium or other metal-ion contaminants from cooling-tower blowdown water. In the conventional process, the contaminant is reduced and precipitated at an iron anode, thus forming a mixed precipitate of iron and chromium hydroxides, while hydrogen being evolved copiously at a cathode is vented from the electrochemical cell. In the conventional process, subsequent separation of the fine precipitate has proved to be difficult and inefficient. In accordance with this invention, the electrochemical operation is conducted in a novel manner permitting a much more efficient and less expensive precipitate-recovery operation. That is, the electrochemical operation is conducted under an evolved-hydrogen partial pressure exceeding atmospheric pressure. As a result, most of the evolved hydrogen is entrained as bubbles in the blowdown in the cell. The resulting hydrogen-rich blowdown is introduced to a vented chamber, where the entrained hydrogen combines with the precipitate to form a froth which can be separated by conventional techniques. In addition to the hydrogen, two materials present in most blowdown act as flotation promoters for the precipitate. These are (1) air, with which the blowdown water becomes saturated in the course of normal cooling-tower operation, and (2) surfactants which commonly are added to cooling-tower recirculating-water systems to inhibit the growth of certain organisms or prevent the deposition of insoluble particulates.

Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

PubMed

Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

2014-04-01

Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

Controllable synthesis and electrochemical hydrogen storage properties of Bi2Se3 architectural structures.

PubMed

Sun, Zhengliang; Liufu, Shengcong; Chen, Xihong; Chen, Lidong

2010-05-14

Two kinds of Bi2Se3 nanostructures, 3D rose-like hierarchitectures and monodisperse nanospheres, have been synthesized through adjusting the supersaturation of the precursor solution. Noticeable hydrogen storage capacity, amounting to 185 mA h g-1, has been found for the 3D rose-like hierarchitectures, which arises from the special micro/nano-hierarchitectures with highly crystallized flake-substructures.

Nonaqueous System of Iron-Based Ionic Liquid and DMF for the Oxidation of Hydrogen Sulfide and Regeneration by Electrolysis.

PubMed

Guo, Zhihui; Zhang, Tingting; Liu, Tiantian; Du, Jun; Jia, Bing; Gao, Shujing; Yu, Jiang

2015-05-05

To improve the hydrogen sulfide removal efficiency with the application of an iron-based imidazolium chloride ionic liquid (Fe(III)-IL) as desulfurizer, Fe(II) and N,N-dimethylformamide (DMF) are introduced to Fe(III)-IL to construct a new nonaqueous desulfurization system (Fe(III/II)-IL/DMF). Following desulfurization, the system can be regenerated using the controlled-potential electrolysis method. The addition of Fe(II) in Fe(III)-IL is beneficial for the hydrogen sulfide removal and the electrochemical regeneration of the desulfurizer. The addition of DMF in Fe(III/II)-IL does not change the structure of Fe(III/II)-IL but clearly decreases the acidity, increases the electrolytic current, and decreases the stability of the Fe-Cl bond in Fe(III/II)-IL. Fe(III/II)-IL/DMF can remove hydrogen sulfide and can be regenerated through an electrochemical method more efficiently than can Fe(III/II)-IL. After six cycles, the desulfurization efficiency remains higher than 98%, and the average conversion rate of Fe(II) is essentially unchanged. No sulfur peroxidation occurs, and the system remains stable. Therefore, this new nonaqueous system has considerable potential for removing H2S in pollution control applications.

Potential-sensing electrochemical atomic force microscopy for in operando analysis of water-splitting catalysts and interfaces

NASA Astrophysics Data System (ADS)

Nellist, Michael R.; Laskowski, Forrest A. L.; Qiu, Jingjing; Hajibabaei, Hamed; Sivula, Kevin; Hamann, Thomas W.; Boettcher, Shannon W.

2018-01-01

Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the "surface" electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents.

PubMed

Tessensohn, Malcolm E; Lee, Melvyn; Hirao, Hajime; Webster, Richard D

2015-01-12

Voltammetric experiments with 9,10-anthraquinone and 1,4-benzoquinone performed under controlled moisture conditions indicate that the hydrogen-bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔEp (red) =|Ep (red(1)) -Ep (red(2)) |, which is the potential separation between the two one-electron reduction processes. This electrochemical parameter is inversely related to the strength of the interactions and can be used to differentiate between primary, secondary, tertiary alcohols, and even diols, as it is sensitive to both their steric and electronic properties. The results are highly reproducible across two solvents with substantially different hydrogen-bonding properties (CH3 CN and CH2 Cl2 ) and are supported by density functional theory calculations. This indicates that the numerous solvent-alcohol interactions are less significant than the quinone-alcohol hydrogen-bonding interactions. The utility of ΔEp (red) was illustrated by comparisons between 1) 3,3,3-trifluoro-n-propanol and 1,3-difluoroisopropanol and 2) ethylene glycol and 2,2,2-trifluoroethanol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Defect studies of ZnO single crystals electrochemically doped with hydrogen

NASA Astrophysics Data System (ADS)

Čížek, J.; Žaludová, N.; Vlach, M.; Daniš, S.; Kuriplach, J.; Procházka, I.; Brauer, G.; Anwand, W.; Grambole, D.; Skorupa, W.; Gemma, R.; Kirchheim, R.; Pundt, A.

2008-03-01

Various defect studies of hydrothermally grown (0001) oriented ZnO crystals electrochemically doped with hydrogen are presented. The hydrogen content in the crystals is determined by nuclear reaction analysis and it is found that already 0.3at.% H exists in chemically bound form in the virgin ZnO crystals. A single positron lifetime of 182ps is detected in the virgin crystals and attributed to saturated positron trapping at Zn vacancies surrounded by hydrogen atoms. It is demonstrated that a very high amount of hydrogen (up to ˜30at.%) can be introduced into the crystals by electrochemical doping. More than half of this amount is chemically bound, i.e., incorporated into the ZnO crystal lattice. This drastic increase of the hydrogen concentration is of marginal impact on the measured positron lifetime, whereas a contribution of positrons annihilated by electrons belonging to O-H bonds formed in the hydrogen doped crystal is found in coincidence Doppler broadening spectra. The formation of hexagonal shape pyramids on the surface of the hydrogen doped crystals by optical microscopy is observed and discussed.

Highly hydrogenated graphene through microwave exfoliation of graphite oxide in hydrogen plasma: towards electrochemical applications.

PubMed

Eng, Alex Yong Sheng; Sofer, Zdenek; Šimek, Petr; Kosina, Jiri; Pumera, Martin

2013-11-11

Hydrogenated graphenes exhibit a variety of properties with potential applications in devices, ranging from a tunable band gap to fluorescence, ferromagnetism, and the storage of hydrogen. We utilize a one-step microwave-irradiation process in hydrogen plasma to create highly hydrogenated graphene from graphite oxides. The procedure serves the dual purposes of deoxygenation and concurrent hydrogenation of the carbon backbone. The effectiveness of the hydrogenation process is investigated on three different graphite oxides (GOs), which are synthesized by using the Staudenmaier, Hofmann, and Hummers methods. A systematic characterization of our hydrogenated graphenes is performed using UV/Vis spectroscopy, SEM, AFM, Raman spectroscopy, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), combustible elemental analysis, and electrical conductivity measurements. The highest hydrogenation extent is observed in hydrogenated graphene produced from the Hummers-method GO, with a hydrogen content of 19 atomic % in the final product. In terms of the removal of oxygen groups, microwave exfoliation yields graphenes with very similar oxygen contents despite differences in their parent GOs. In addition, we examine the prospective application of hydrogenated graphenes as electrochemical transducers through a cyclic voltammetry (CV) study. The highly hydrogenated graphenes exhibit fast heterogeneous electron-transfer rates, suggestive of their suitability for electrochemical applications in electrodes, supercapacitors, batteries, and sensors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Sensor Based on Pd/GeO{sub 2} Using a Low Cost Electrochemical Deposition

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

Jawad, M. J.; Hashim, M. R.; Ali, N. K.

2011-05-25

This work reports on a synthesis of sub micron germanium dioxide (GeO{sub 2}) on porous silicon (PS) by electrochemical deposition. n-type Si (100) wafer was used to fabricate (PS) using conventional method of electrochemical etching in HF based solution. A GeCl{sub 4} was directly hydrolyzed by hydrogen peroxide to produce pure GeO{sub 2}, and then electrochemically deposited on PS. Followed by palladium (Pd) contact on GeO{sub 2} /PS was achieved by using RF sputtering technique. The grown GeO{sub 2} crystals were characterized using SEM and EDX. I-V characteristics of Pd/ GeO{sub 2} were recorded before and after hydrogen gas exposuremore » as well as with different H{sub 2} concentrations and different applied temperatures. The sensitivity of Pd/ GeO{sub 2} also has been investigated it could be seen to increase significantly with increased hydrogen concentration while it decreased with increase temperature.« less

Effect of electrochemical redox reaction on growth and metabolism of Saccharomyces cerevisiae as an environmental factor.

PubMed

Na, Kwan Byung; Hwang, Tae Sik; Lee, Sung Hun; Ahn, Dae Hee; Park, Doo Hyun

2007-03-01

The effect of an electrochemically generated oxidation-reduction potential and electric pulse on ethanol production and growth of Saccharomyces cerevisiae ATCC 26603 was experimented and compared with effects of electron mediators (neutral red, benzyl viologen, and thionine), chemical oxidants (hydrogen peroxide and hypochlorite), chemical reductants (sulfite and nitrite), oxygen, and hydrogen. The oxidation (anodic) and reduction (cathodic) potential and electric pulse activated ethanol production and growth, and changed the total soluble protein pattern of the test strain. Neutral red electrochemically reduced activated ethanol production and growth of the test strain, but benzyl viologen and thionine did not. Nitrite inhibited ethanol production but did not influence growth of the test strain. Hydrogen peroxide, hypochlorite, and sulfite did not influence ethanol production and growth of the test strain. Hydrogen and oxygen also did not influence the growth and ethanol production. It shows that the test strain may perceive electrochemically generated oxidation-reduction potential and electric pulse as an environmental factor.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Combined heat and power (cogeneration) plant based on renewable energy sources and electrochemical hydrogen systems

NASA Astrophysics Data System (ADS)

Grigor'ev, S. A.; Grigor'ev, A. S.; Kuleshov, N. V.; Fateev, V. N.; Kuleshov, V. N.

2015-02-01

The layout of a combined heat and power (cogeneration) plant based on renewable energy sources (RESs) and hydrogen electrochemical systems for the accumulation of energy via the direct and inverse conversion of the electrical energy from RESs into the chemical energy of hydrogen with the storage of the latter is described. Some efficient technical solutions on the use of electrochemical hydrogen systems in power engineering for the storage of energy with a cyclic energy conversion efficiency of more than 40% are proposed. It is shown that the storage of energy in the form of hydrogen is environmentally safe and considerably surpasses traditional accumulator batteries by its capacitance characteristics, being especially topical in the prolonged absence of energy supply from RESs, e.g., under the conditions of polar night and breathless weather. To provide the required heat consumption of an object during the peak period, it is proposed to burn some hydrogen in a boiler house.

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound.

PubMed

González-García, José; Banks, Craig E; Sljukić, Biljana; Compton, Richard G

2007-04-01

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction

PubMed Central

Wang, Haotian; Lu, Zhiyi; Xu, Shicheng; Kong, Desheng; Cha, Judy J.; Zheng, Guangyuan; Hsu, Po-Chun; Yan, Kai; Bradshaw, David; Prinz, Fritz B.; Cui, Yi

2013-01-01

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li+ ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity. PMID:24248362

Electrochemical performance and transport properties of a Nafion membrane in a hydrogen-bromine cell environment

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.

1987-01-01

The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.

Electrochemical supramolecular recognition of hemin-carbon composites

NASA Astrophysics Data System (ADS)

Le, Hien Thi Ngoc; Jeong, Hae Kyung

2018-04-01

Hemin-graphite oxide-carbon nanotube (hemin-GO-CNT) and hemin-thermally reduced graphite oxide-carbon nanotube (hemin-TRGO-CNT) composites are synthesized and investigated for the electrochemical supramolecular recognition by electron transfer between biomolecules (dopamine and hydrogen peroxide) and the composite electrodes. Redox reaction mechanisms of two composites with dopamine and hydrogen peroxide are explained in detail by using cyclic voltammetry and differential pulse voltammetry. Hemin-TRGO-CNT displays higher electrochemical detection for dopamine and hydrogen peroxide than that of hemin-GO-CNT, exhibiting enhancement of the electron transfer due to the effective immobilization of redox couple of hemin (Fe2+/Fe3+) on the TRGO-CNT surface.

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

PubMed Central

2013-01-01

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm2 in comparison with that of pristine ATO nanotubes (0.29 mA/cm2) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity. PMID:24047205

Proton transfer in microbial electrolysis cells

DOE PAGES

Borole, Abhijeet P.; Lewis, Alex J.

2017-02-15

Proton transfer and electron transfer are of prime importance in the development of microbial electrochemical cells. While electron transfer is primarily controlled by biology, proton transfer is controlled by process engineering and cell design. To develop commercially feasible technologies around the concept of a bioelectrochemical cell, real feedstocks have to be explored and associated limitations have to be identified. Here in this study, the proton transfer rate was quantified for a microbial electrolysis cell (MEC) and its dependence on process parameters was investigated using a proton balance model. The reaction system consisted of a biomass-derived pyrolytic aqueous stream as amore » substrate producing hydrogen in a flow-through MEC. The proton transfer rate increased with anode flow rate and organic loading rate up to a maximum of 0.36 ± 0.01 moles per m 2 per h, equivalent to a hydrogen production rate of 9.08 L per L per day. Higher rates of hydrogen production, reaching 11.7 ± 0.2 L per L per day were achieved, when additional protons were provided via the cathode buffer. Electrochemical impedance spectroscopy shows that proton transfer was the dominant resistance in the production of hydrogen. The quantification of proton transfer rates for MECs with potential for biorefinery application and the demonstration of high hydrogen production rates approaching those required for commercial consideration indicate the strong potential of this technology for renewable hydrogen production. Understanding the transport phenomenon in bioelectrochemical cells is of great significance since these systems have potential for wide-ranging applications including energy production, bioremediation, chemical and nanomaterial synthesis, electro-fermentation, energy storage, desalination, and produced water treatment. Electron transfer in anode biofilms has been investigated extensively, but proton transfer studies are also important, since many cathodic half reactions require protons as the reactant. Determination of transport rates via proton balance was investigated in microbial electrolysis cells, which can be applied to other forms of microbial electrochemical systems. Lastly, these systems have a unique niche in the development of future biorefineries as a means of recovering energy from waste streams with potential for water recycle, making them an integral part of the water–energy nexus focus area.« less

Proton transfer in microbial electrolysis cells

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

Borole, Abhijeet P.; Lewis, Alex J.

Proton transfer and electron transfer are of prime importance in the development of microbial electrochemical cells. While electron transfer is primarily controlled by biology, proton transfer is controlled by process engineering and cell design. To develop commercially feasible technologies around the concept of a bioelectrochemical cell, real feedstocks have to be explored and associated limitations have to be identified. Here in this study, the proton transfer rate was quantified for a microbial electrolysis cell (MEC) and its dependence on process parameters was investigated using a proton balance model. The reaction system consisted of a biomass-derived pyrolytic aqueous stream as amore » substrate producing hydrogen in a flow-through MEC. The proton transfer rate increased with anode flow rate and organic loading rate up to a maximum of 0.36 ± 0.01 moles per m 2 per h, equivalent to a hydrogen production rate of 9.08 L per L per day. Higher rates of hydrogen production, reaching 11.7 ± 0.2 L per L per day were achieved, when additional protons were provided via the cathode buffer. Electrochemical impedance spectroscopy shows that proton transfer was the dominant resistance in the production of hydrogen. The quantification of proton transfer rates for MECs with potential for biorefinery application and the demonstration of high hydrogen production rates approaching those required for commercial consideration indicate the strong potential of this technology for renewable hydrogen production. Understanding the transport phenomenon in bioelectrochemical cells is of great significance since these systems have potential for wide-ranging applications including energy production, bioremediation, chemical and nanomaterial synthesis, electro-fermentation, energy storage, desalination, and produced water treatment. Electron transfer in anode biofilms has been investigated extensively, but proton transfer studies are also important, since many cathodic half reactions require protons as the reactant. Determination of transport rates via proton balance was investigated in microbial electrolysis cells, which can be applied to other forms of microbial electrochemical systems. Lastly, these systems have a unique niche in the development of future biorefineries as a means of recovering energy from waste streams with potential for water recycle, making them an integral part of the water–energy nexus focus area.« less

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

Overview of the Design, Development, and Application of Nickel-hydrogen Batteries

NASA Technical Reports Server (NTRS)

Thaller, Lawrence H.; Zimmerman, Albert H.

2003-01-01

This document provides an overview of the design, development, and application of nickel-hydrogen (Ni-H2) battery technology for aerospace applications. It complements and updates the information presented in NASA RP-1314, NASA Handbook for Nickel- Hydrogen Batteries, published in 1993. Since that time, nickel-hydrogen batteries have become widely accepted for aerospace energy storage requirements and much more has been learned. The intent of this document is to capture some of that additional knowledge. This document addresses various aspects of nickel-hydrogen technology including the electrochemical reactions, cell component design, and selection considerations; overall cell and battery design considerations; charge control considerations; and manufacturing issues that have surfaced over the years that nickel-hydrogen battery technology has been the major energy storage technology for geosynchronous and low-Earth-orbiting satellites.

Ion/proton-conducting apparatus and method

DOEpatents

Yates, Matthew; Xue, Wei

2014-12-23

A c-axis-oriented HAP thin film synthesized by seeded growth on a palladium hydrogen membrane substrate. An exemplary synthetic process includes electrochemical seeding on the substrate, and secondary and tertiary hydrothermal treatments under conditions that favor growth along c-axes and a-axes in sequence. By adjusting corresponding synthetic conditions, an HAP this film can be grown to a controllable thickness with a dense coverage on the underlying substrate. The thin films have relatively high proton conductivity under hydrogen atmosphere and high temperature conditions. The c-axis oriented films may be integrated into fuel cells for application in the intermediate temperature range of 200-600.degree. C. The electrochemical-hydrothermal deposition technique may be applied to create other oriented crystal materials having optimized properties, useful for separations and catalysis as well as electronic and electrochemical applications, electrochemical membrane reactors, and in chemical sensors. Additional high-density and gas-tight HAP film compositions may be deposited using a two-step deposition method that includes an electrochemical deposition method followed by a hydrothermal deposition method. The two-step method uses a single hydrothermal deposition solution composition. The method may be used to deposit HAP films including but not limited to at least doped HAP films, and more particularly including carbonated HAP films. In addition, the high-density and gas-tight HAP films may be used in proton exchange membrane fuel cells.

An electrochemical model for hot-salt stress-corrosion of titanium alloys

NASA Technical Reports Server (NTRS)

Garfinkle, M.

1972-01-01

An electrochemical model of hot-salt stress-corrosion cracking of titanium alloys is proposed based on an oxygen-concentration cell. Hydrogen embrittlement is proposed as the direct cause of cracking, the hydrogen being generated as the results of the hydrolysis of complex halides formed at the shielded anode of the electrochemical cell. The model found to be consistent with the diverse observations made both in this study and by many investigators in this field.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone.

PubMed

Mozo Mulero, Cristina; Sáez, Alfonso; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (L Pd ) of 0.2 and 0.02 mg cm -2 . The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H 2 SO 4 . Current densities of 10, 15 and 20 mA cm -2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (X R ) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone

PubMed Central

Mozo Mulero, Cristina; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (LPd) of 0.2 and 0.02 mg cm−2. The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H2SO4. Current densities of 10, 15 and 20 mA cm−2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (XR) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity. PMID:29623115

Anodic Oxidative Modification of Egg White for Heat Treatment.

PubMed

Takahashi, Masahito; Handa, Akihiro; Yamaguchi, Yusuke; Kodama, Risa; Chiba, Kazuhiro

2016-08-31

A new functionalization of egg white was achieved by an electrochemical reaction. The method involves electron transfer from thiol groups of egg white protein to form disulfide bonds. The oxidized egg white produced less hydrogen sulfide during heat treatment; with sufficient application of electricity, almost no hydrogen sulfide was produced. In addition, gels formed by heating electrochemically oxidized egg white exhibited unique properties, such as a lower gelation temperature and a softened texture, presumably due to protein aggregation and electrochemically mediated intramolecular disulfide bond formation.

The effect of grain size on aluminum anodes for Al-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin

2015-06-01

Aluminum is an ideal material for metallic fuel cells. In this research, different grain sizes of aluminum anodes are prepared by equal channel angular pressing (ECAP) at room temperature. Microstructure of the anodes is examined by electron backscatter diffraction (EBSD) in scanning electron microscope (SEM). Hydrogen corrosion rates of the Al anodes in 4 mol L-1 NaOH are determined by hydrogen collection method. The electrochemical properties of the aluminum anodes are investigated in the same electrolyte using electrochemical impedance spectroscopy (EIS) and polarization curves. Battery performance is also tested by constant current discharge at different current densities. Results confirm that the electrochemical properties of the aluminum anodes are related to grain size. Finer grain size anode restrains hydrogen evolution, improves electrochemical activity and increases anodic utilization rate. The proposed method is shown to effectively improve the performance of Al-air batteries.

Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

ERIC Educational Resources Information Center

Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

2012-01-01

The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

Enhanced hydrogen production in microbial electrolysis cell with 3D self-assembly nickel foam-graphene cathode.

PubMed

Cai, Weiwei; Liu, Wenzong; Han, Jinglong; Wang, Aijie

2016-06-15

In comparison to precious metal catalyst especially Platinum (Pt), nickel foam (NF) owned cheap cost and unique three-dimensional (3D) structure, however, it was scarcely applied as cathode material in microbial electrolysis cell (MEC) as the intrinsic laggard electrochemical activity for hydrogen recovery. In this study, a self-assembly 3D nickel foam-graphene (NF-G) cathode was fabricated by facile hydrothermal approach for hydrogen evolution in MECs. Electrochemical analysis (linear scan voltammetry and electrochemical impedance spectroscopy) revealed the improved electrochemical activity and effective mass diffusion after coating with graphene. NF-G as cathode in MEC showed a significant enhancement in hydrogen production rate compared with nickel foam at a variety of biases. Noticeably, NF-G showed a comparable averaged hydrogen production rate (1.31 ± 0.07 mL H2 mL(-1) reactor d(-1)) to Platinum/carbon (Pt/C) (1.32 ± 0.07 mL H2 mL(-1) reactor d(-1)) at 0.8 V. Profitable energy recovery could be achieved by NF-G cathode at higher applied voltage, which performed the best hydrogen yield of 3.27 ± 0.16 mol H2 mol(-1) acetate at 0.8 V and highest energy efficiency of 185.92 ± 6.48% at 0.6 V. Copyright © 2016 Elsevier B.V. All rights reserved.

Sputtered Pd as hydrogen storage for a chip-integrated microenergy system.

PubMed

Slavcheva, E; Ganske, G; Schnakenberg, U

2014-01-01

The work presents a research on preparation and physical and electrochemical characterisation of dc magnetron sputtered Pd films envisaged for application as hydrogen storage in a chip-integrated hydrogen microenergy system. The influence of the changes in the sputtering pressure on the surface structure, morphology, and roughness was analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AMF). The electrochemical activity towards hydrogen adsorption/desorption and formation of PdH were investigated in 0.5 M H2SO4 using the methods of cyclic voltammetry and galvanostatic polarisation. The changes in the electrical properties of the films as a function of the sputtering pressure and the level of hydrogenation were evaluated before and immediately after the electrochemical charging tests, using a four-probe technique. The research resulted in establishment of optimal sputter regime, ensuring fully reproducible Pd layers with highly developed surface, moderate porosity, and mechanical stability. Selected samples were integrated as hydrogen storage in a newly developed unitized microenergy system and tested in charging (water electrolysis) and discharging (fuel cell) operative mode at ambient conditions demonstrating a stable recycling performance.

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.

First-Principles Approach to Model Electrochemical Reactions: Understanding the Fundamental Mechanisms behind Mg Corrosion

NASA Astrophysics Data System (ADS)

Surendralal, Sudarsan; Todorova, Mira; Finnis, Michael W.; Neugebauer, Jörg

2018-06-01

Combining concepts of semiconductor physics and corrosion science, we develop a novel approach that allows us to perform ab initio calculations under controlled potentiostat conditions for electrochemical systems. The proposed approach can be straightforwardly applied in standard density functional theory codes. To demonstrate the performance and the opportunities opened by this approach, we study the chemical reactions that take place during initial corrosion at the water-Mg interface under anodic polarization. Based on this insight, we derive an atomistic model that explains the origin of the anodic hydrogen evolution.

Facile Fabrication of 3D Layer-by-layer Graphene-gold Nanorod Hybrid Architecture for Hydrogen Peroxide Based Electrochemical Biosensor

DTIC Science & Technology

2015-01-01

measurement techniques such as radioisotope tracing, NMR spectroscopy, and microfluorometry assay [12,25,18]. In recent years, electrochemical biosensors...control number. 1. REPORT DATE 2015 2. REPORT TYPE 3. DATES COVERED 00-00-2015 to 00-00-2015 4. TITLE AND SUBTITLE Facile Fabrication of 3D...Claussen, S. Jedlicka, J.L. Rickus, D.M. Porterfield, J. Neurosci. Methods 189 (2010) 14–22. [17] E.S. McLamore, J. Shi, D. Jaroch, J.C. Claussen, A

Growth mechanism of surface roughed platinum nanowires through electrodeposition current control and their electrochemical applications

NASA Astrophysics Data System (ADS)

Ruan, Dajiang

The aim of this work is to investigate the effect of current density on the grain size and surface morphology of electrodeposited platinum nanowires and their applications. Platinum (Pt) nanowires were fabricated by a galvanostatic electrodeposition method in a porous anodic alumina oxide (AAO) template with different current densities. Both direct current and pulse current electrodeposition were used to synthesize the Pt nanowires. The grain size and surface morphology of the Pt nanowires were studied by field emission scanning electron microscopy (FE-SEM), transmission electron microcopy (TEM) and X-ray diffraction (XRD). The experimental results showed that the current density was the key factor to control the surface roughness. The surface of the Pt nanowires became rougher and the grain sizes were increased by increasing the current densities. From the experimental results, a growth mechanism of Pt nanowires based on progressive nucleation and crystallization was proposed in order to find out the relationship between the surface morphology and current density. The electrochemical properties and catalytic activities of these surface roughed Pt nanowires were investigated in the detection of H20 2 and for the methanol oxidation. Cyclic voltammograms of Pt nanowire modified electrodes were obtained using a potentiostat, which showed that rougher Pt nanowires have higher response and better activity than that of smooth nanowires. For H202 detection, the effect of scan rate and H202 concentration were studied and it was found that the peak current for hydrogen peroxide reduction became larger with the increasing of either scan rate or H202 concentration. It can be inferred that the process of electrocatalytic hydrogen peroxide reduction may be controlled by diffusion of hydrogen peroxide and the Pt nanowire modified glassy carbon electrode (GCE) is well suited for the detection of H202. From the relationship between the peak current and square root of scan rates for methanol oxidation, it can be inferred that the process of electrocatalytic methanol oxidation was controlled by diffusion of methanol. To understand the effect of the morphological feature on the electrocatalytic activity of the Pt nanowire catalysts, the electrochemically active surface area (ECSA) as a function of deposited current density was investigated, which suggests that Pt nanowire catalysts deposited at highest current density had the most ECSA surface morphology of the Pt nanowires. The chronoamperometric curves and electrochemical impedance spectroscopy (EIS) results confirmed that the Pt nanowire catalyst synthesized at higher current density possessed longer durability and gave more efficient electrochemical performance.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

Wilson, Richard M. (Compiler)

1996-01-01

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

NASA Technical Reports Server (NTRS)

Rillema, D. P.

1981-01-01

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling.

PubMed

Rivier, Lucie; Peljo, Pekka; Vannay, Laurent A C; Gschwend, Grégoire C; Méndez, Manuel A; Corminboeuf, Clémence; Scanlon, Micheál D; Girault, Hubert H

2017-02-20

The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp 2 *Ru II (Cp*=C 5 Me 5 ), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions- especially the use of weakly coordinating solvent and counterions-are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amine-free reversible hydrogen storage in formate salts catalyzed by ruthenium pincer complex without pH control or solvent change.

PubMed

Kothandaraman, Jotheeswari; Czaun, Miklos; Goeppert, Alain; Haiges, Ralf; Jones, John-Paul; May, Robert B; Prakash, G K Surya; Olah, George A

2015-04-24

Due to the intermittent nature of most renewable energy sources, such as solar and wind, energy storage is increasingly required. Since electricity is difficult to store, hydrogen obtained by electrochemical water splitting has been proposed as an energy carrier. However, the handling and transportation of hydrogen in large quantities is in itself a challenge. We therefore present here a method for hydrogen storage based on a CO2 (HCO3 (-) )/H2 and formate equilibrium. This amine-free and efficient reversible system (>90 % yield in both directions) is catalyzed by well-defined and commercially available Ru pincer complexes. The formate dehydrogenation was triggered by simple pressure swing without requiring external pH control or the change of either the solvent or the catalyst. Up to six hydrogenation-dehydrogenation cycles were performed and the catalyst performance remained steady with high selectivity (CO free H2 /CO2 mixture was produced). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroenzymatic oxidation of veratryl alcohol by lignin peroxidase.

PubMed

Lee, KiBeom; Moon, Seung-Hyeon

2003-05-08

This paper reports the formation of veratraldehyde by electroenzymatic oxidation of veratryl alcohol (3,4-dimethoxybenzyl alcohol) hybridizing both electrochemical and enzymatic reactions and using lignin peroxidase. The novel electroenzymatic method was found to be effective for replacement of hydrogen peroxide by an electrochemical reactor, which is essential for enzyme activity of lignin peroxidase. The effects of operating parameters such as enzyme dosage, pH, and electric potential were investigated. Further, the kinetics of veratryl alcohol oxidation in an electrochemical reactor were compared to oxidation when hydrogen peroxide was supplied externally.

Maximising biohydrogen yields via continuous electrochemical hydrogen removal and carbon dioxide scrubbing.

PubMed

Massanet-Nicolau, Jaime; Jones, Rhys Jon; Guwy, Alan; Dinsdale, Richard; Premier, Giuliano; Mulder, Martijn J J

2016-10-01

The use of electrochemical hydrogen removal (EHR) together with carbon dioxide removal (CDR) was demonstrated for the first time using a continuous hydrogen producing fermenter. CDR alone was found to increase hydrogen yields from 0.07molH2molhexose to 0.72molH2molhexose. When CDR was combined with EHR, hydrogen yields increased further to 1.79molH2molhexose. The pattern of carbohydrate utilisation and volatile fatty acid (VFA) production are consistent with the hypothesis that increased yields are the result of relieving end product inhibition and inhibition of microbial hydrogen consumption. In situ removal of hydrogen and carbon dioxide as demonstrated here not only increase hydrogen yield but also produces a relatively pure product gas and unlike other approaches can be used to enhance conventional, mesophilic, CSTR type fermentation of low grade/high solids biomass. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

Experimental study of electrochemical fluorination of trichloroethylene

NASA Technical Reports Server (NTRS)

Polisena, C.; Liu, C. C.; Savinell, R. F.

1982-01-01

The electrochemical fluorination of trichloroethylene in anhydrous hydrogen fluoride at 0 C and at constant cell potential was investigated. A microprocessor-aided electrochemical fluorination reactor system that yields highly reproducible results was utilized. The following major two-carbon-chain products were observed: CHCl2-CCl2F, CHCl2-CClF2, CHClF-CCl2F, and CCl2F-CClF2. The first step in the reaction sequence was determined to be fluorine addition to the double bond, followed by replacement of first hydrogen and then chlorine by fluorine. Polymerization reactions yielded higher molecular weight or possible ring-type chlorofluorohydrocarbons. A comparison of the reaction products of electrochemical and chemical fluorinations of trichloroethylene is also discussed.

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

Sputtered Pd as Hydrogen Storage for a Chip-Integrated Microenergy System

PubMed Central

Slavcheva, E.; Ganske, G.; Schnakenberg, U.

2014-01-01

The work presents a research on preparation and physical and electrochemical characterisation of dc magnetron sputtered Pd films envisaged for application as hydrogen storage in a chip-integrated hydrogen microenergy system. The influence of the changes in the sputtering pressure on the surface structure, morphology, and roughness was analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AMF). The electrochemical activity towards hydrogen adsorption/desorption and formation of PdH were investigated in 0.5 M H2SO4 using the methods of cyclic voltammetry and galvanostatic polarisation. The changes in the electrical properties of the films as a function of the sputtering pressure and the level of hydrogenation were evaluated before and immediately after the electrochemical charging tests, using a four-probe technique. The research resulted in establishment of optimal sputter regime, ensuring fully reproducible Pd layers with highly developed surface, moderate porosity, and mechanical stability. Selected samples were integrated as hydrogen storage in a newly developed unitized microenergy system and tested in charging (water electrolysis) and discharging (fuel cell) operative mode at ambient conditions demonstrating a stable recycling performance. PMID:24516356

Conductance bistability of gold nanowires at room temperature

NASA Astrophysics Data System (ADS)

Kiguchi, Manabu; Konishi, Tatsuya; Murakoshi, Kei

2006-03-01

Quantized conductance behavior of gold nanowires was studied under electrochemical potential control. We fabricated 1-nm -long monoatomic wires in solution at room temperature. Electrochemical potential significantly affected the stability of the monoatomic wire and fractional conductance peak occurrence in the conductance histogram. We revealed that the hydrogen adsorption on gold monoatomic wires was a decisive factor of the fractional peak, which was originated from the dynamic structural transition between two bistable states of the monoatomic wire showing the unit and the fractional values of the conductance. We could tune the stability of these bistable states to make the fractional conductance state preferable.

Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

PubMed

Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

2015-07-29

The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

Production of bioelectricity, bio-hydrogen, high value chemicals and bioinspired nanomaterials by electrochemically active biofilms.

PubMed

Kalathil, Shafeer; Khan, Mohammad Mansoob; Lee, Jintae; Cho, Moo Hwan

2013-11-01

Microorganisms naturally form biofilms on solid surfaces for their mutual benefits including protection from environmental stresses caused by contaminants, nutritional depletion or imbalances. The biofilms are normally dangerous to human health due to their inherited robustness. On the other hand, a recent study suggested that electrochemically active biofilms (EABs) generated by electrically active microorganisms have properties that can be used to catalyze or control the electrochemical reactions in a range of fields, such as bioenergy production, bioremediation, chemical/biological synthesis, bio-corrosion mitigation and biosensor development. EABs have attracted considerable attraction in bioelectrochemical systems (BESs), such as microbial fuel cells and microbial electrolysis cells, where they act as living bioanode or biocathode catalysts. Recently, it was reported that EABs can be used to synthesize metal nanoparticles and metal nanocomposites. The EAB-mediated synthesis of metal and metal-semiconductor nanocomposites is expected to provide a new avenue for the greener synthesis of nanomaterials with high efficiency and speed than other synthetic methods. This review covers the general introduction of EABs, as well as the applications of EABs in BESs, and the production of bio-hydrogen, high value chemicals and bio-inspired nanomaterials. Copyright © 2013 Elsevier Inc. All rights reserved.

Electrochemical methane sensor

DOEpatents

Zaromb, S.; Otagawa, T.; Stetter, J.R.

1984-08-27

A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about 1.4 volts vs R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

Active hydrogen evolution through lattice distortion in metallic MoTe2

NASA Astrophysics Data System (ADS)

Seok, Jinbong; Lee, Jun-Ho; Cho, Suyeon; Ji, Byungdo; Kim, Hyo Won; Kwon, Min; Kim, Dohyun; Kim, Young-Min; Oh, Sang Ho; Wng Kim, Sung; Lee, Young Hee; Son, Young-Woo; Yang, Heejun

2017-06-01

Engineering surface atoms of transition metal dichalcogenides (TMDs) is a promising way to design catalysts for efficient electrochemical reactions including the hydrogen evolution reaction (HER). However, materials processing based on TMDs, such as vacancy creation or edge exposure, for active HER, has resulted in insufficient atomic-precision lattice homogeneity and a lack of clear understanding of HER over 2D materials. Here, we report a durable and effective HER at atomically defined reaction sites in 2D layered semimetallic MoTe2 with intrinsic turnover frequency (TOF) of 0.14 s-1 at 0 mV overpotential, which cannot be explained by the traditional volcano plot analysis. Unlike former electrochemical catalysts, the rate-determining step of the HER on the semimetallic MoTe2, hydrogen adsorption, drives Peierls-type lattice distortion that, together with a surface charge density wave, unexpectedly enhances the HER. The active HER using unique 2D features of layered TMDs enables an optimal design of electrochemical catalysts and paves the way for a hydrogen economy.

Hydrogen in thin Pd-based layers deposited on reticulated vitreous carbon-A new system for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Łukaszewski, M.; Żurowski, A.; Czerwiński, A.

Reticulated vitreous carbon (RVC) has been used as a matrix for electrodeposition of thin layers of Pd and Pd-rich Pd-Rh alloys. It was found that RVC substrate does not affect qualitatively hydrogen absorption behavior of Pd-based deposits. Similarly to thin Pd or Pd alloy layers deposited on Au wires, the α-β phase transition controls the overall rate of hydrogen absorption and desorption into/from Pd-based/RVC electrodes. The possibility of the application of these materials as phase charging-discharging systems was investigated. The values of specific pseudocapacitance, specific power and specific energy were comparable with those for supercapacitors utilizing various redox reactions.

Mechanical ball-milling preparation of fullerene/cobalt core/shell nanocomposites with high electrochemical hydrogen storage ability.

PubMed

Bao, Di; Gao, Peng; Shen, Xiande; Chang, Cheng; Wang, Longqiang; Wang, Ying; Chen, Yujin; Zhou, Xiaoming; Sun, Shuchao; Li, Guobao; Yang, Piaoping

2014-02-26

The design and synthesis of new hydrogen storage nanomaterials with high capacity at low cost is extremely desirable but remains challenging for today's development of hydrogen economy. Because of the special honeycomb structures and excellent physical and chemical characters, fullerenes have been extensively considered as ideal materials for hydrogen storage materials. To take the most advantage of its distinctive symmetrical carbon cage structure, we have uniformly coated C60's surface with metal cobalt in nanoscale to form a core/shell structure through a simple ball-milling process in this work. The X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectra, high-solution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectrometry (EDX) elemental mappings, and X-ray photoelectron spectroscopy (XPS) measurements have been conducted to evaluate the size and the composition of the composites. In addition, the blue shift of C60 pentagonal pinch mode demonstrates the formation of Co-C chemical bond, and which enhances the stability of the as-obtained nanocomposites. And their electrochemical experimental results demonstrate that the as-obtained C60/Co composites have excellent electrochemical hydrogen storage cycle reversibility and considerably high hydrogen storage capacities of 907 mAh/g (3.32 wt % hydrogen) under room temperature and ambient pressure, which is very close to the theoretical hydrogen storage capacities of individual metal Co (3.33 wt % hydrogen). Furthermore, their hydrogen storage processes and the mechanism have also been investigated, in which the quasi-reversible C60/Co↔C60/Co-Hx reaction is the dominant cycle process.

In situ study of LaY2Ni9 compound as Ni MH negative-electrode material

NASA Astrophysics Data System (ADS)

Latroche, M.; Isnard, O.

2008-03-01

The behavior of a Ni-MH (metal hydride) negative composite electrode made of LaY2Ni9 active material has been studied dynamically using in situ neutron diffraction during a complete charge-discharge electrochemical cycle. From the analysis of the collected diffraction patterns, the phase identity, phase amount variations and cell volume evolutions have been determined as a function of the electrochemical state of (dis)charge. The active material shows a typical two-phase behavior with equilibrium between a hydrogen-poor α phase and a hydrogen-rich β one. The lower electrochemical reversible capacity as compared to solid-gas properties has been interpreted in terms of hydrogen gas evolving during charge and kinetic limitation due to slow β to α transformation during discharge, which hinders high discharge rates.

A novel versatile microbiosensor for local hydrogen detection by means of scanning photoelectrochemical microscopy.

PubMed

Zhao, Fangyuan; Conzuelo, Felipe; Hartmann, Volker; Li, Huaiguang; Stapf, Stefanie; Nowaczyk, Marc M; Rögner, Matthias; Plumeré, Nicolas; Lubitz, Wolfgang; Schuhmann, Wolfgang

2017-08-15

The development of a versatile microbiosensor for hydrogen detection is reported. Carbon-based microelectrodes were modified with a [NiFe]-hydrogenase embedded in a viologen-modified redox hydrogel for the fabrication of a sensitive hydrogen biosensor By integrating the microbiosensor in a scanning photoelectrochemical microscope, it was capable of serving simultaneously as local light source to initiate photo(bio)electrochemical reactions while acting as sensitive biosensor for the detection of hydrogen. A hydrogen evolution biocatalyst based on photosystem 1-platinum nanoparticle biocomplexes embedded into a specifically designed redox polymer was used as a model for proving the capability of the developed hydrogen biosensor for the detection of hydrogen upon localized illumination. The versatility and sensitivity of the proposed microbiosensor as probe tip allows simplification of the set-up used for the evaluation of complex electrochemical processes and the rapid investigation of local photoelectrocatalytic activity of biocatalysts towards light-induced hydrogen evolution. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Facile and controllable one-step fabrication of molecularly imprinted polymer membrane by magnetic field directed self-assembly for electrochemical sensing of glutathione.

PubMed

Zhu, Wanying; Jiang, Guoyi; Xu, Lei; Li, Bingzhi; Cai, Qizhi; Jiang, Huijun; Zhou, Xuemin

2015-07-30

Based on magnetic field directed self-assembly (MDSA) of the ternary Fe3O4@PANI/rGO nanocomposites, a facile and controllable molecularly imprinted electrochemical sensor (MIES) was fabricated through a one-step approach for detection of glutathione (GSH). The ternary Fe3O4@PANI/rGO nanocomposites were obtained by chemical oxidative polymerization and intercalation of Fe3O4@PANI into the graphene oxide layers via π-π stacking interaction, followed by reduction of graphene oxide in the presence of hydrazine hydrate. In molecular imprinting process, the pre-polymers, including GSH as template molecule, Fe3O4@PANI/rGO nanocomposites as functional monomers and pyrrole as both cross-linker and co-monomer, was assembled through N-H hydrogen bonds and the electrostatic interaction, and then was rapidly oriented onto the surface of MGCE under the magnetic field induction. Subsequently, the electrochemical GSH sensor was formed by electropolymerization. In this work, the ternary Fe3O4@PANI/rGO nanocomposites could not only provide available functionalized sites in the matrix to form hydrogen bond and electrostatic interaction with GSH, but also afford a promoting network for electron transfer. Moreover, the biomimetic sensing membrane could be controlled more conveniently and effectively by adjusting the magnetic field strength. The as-prepared controllable sensor showed good stability and reproducibility for the determination of GSH with the detection limit reaching 3 nmol L(-1) (S/N = 3). In addition, the highly sensitive and selective biomimetic sensor has been successfully used for the clinical determination of GSH in biological samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

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

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

DOE PAGES

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.; ...

2017-10-16

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

High H⁻ ionic conductivity in barium hydride.

PubMed

Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

2015-01-01

With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

Investigation of fusion reactions in palladium and titanium tritide using galvanostatic, coulometric, and hydrogen permeation techniques

NASA Astrophysics Data System (ADS)

Guilinger, T. R.; Kelly, M. J.; Scully, J. R.; Christensen, T. M.; Ingersoll, D.; Knapp, J. A.; Ewing, R. I.; Casey, W. H.; Tsao, S. S.

1990-09-01

We describe several electrochemical methods used to investigate the possibility of cold fusion phenomena in palladium and titanium tritide cathodes. We performed long-term (up to 77 days) electrolysis experiments with electrochemical cells of the University of Utah type at current densities as high as 1 A/cm2, while monitoring neutron and tritium levels. With some cells, we pulsed the current to determine if neutron bursts would result. In another cell, we used titanium tritide as the cathode to determine if D-T reactions yielding neutrons would occur. In no instance were levels of neutrons or tritium significantly above background except in the titanium tritide cell where isotopic exchange, occcurring between the electrode and the electrolyte, resulted in significant tritium levels. We also combined x-ray photoelectron spectroscopy (XPS) and electrochemical hydrogen permeation experiments to determine the effectiveness of various Pd surface treatment procedures on the resultant electrochemical hydrogen absorption efficiency. Electroanalytical and thermal desorption/gas analysis techniques indicated the maximum loading of H in Pd was to a ratio of H∶Pd=0.8.

PdCo alloy nanoparticle-embedded carbon nanofiber for ultrasensitive nonenzymatic detection of hydrogen peroxide and nitrite.

PubMed

Liu, Dong; Guo, Qiaohui; Zhang, Xueping; Hou, Haoqing; You, Tianyan

2015-07-15

PdCo alloy nanoparticle-embedded carbon nanofiber (PdCo/CNF) prepared by electrospinning and thermal treatment was employed as a high-performance platform for the determination of hydrogen peroxide and nitrite. The as-obtained PdCo/CNF were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were employed to investigate the electrochemical behaviors of the resultant biosensor. The proposed PdCo/CNF-based biosensor showed excellent analytical performances toward hydrogen peroxide (detection limit: 0.1 μM; linear range: 0.2 μM-23.5 mM) and nitrite (detection limit: 0.2 μM; linear range: 0.4-30 μM and 30-400 μM). The superior analytical properties could be attributed to the synergic effect and firmly embedment of well-dispersed PdCo alloy nanoparticles. These attractive electrochemical properties make this robust electrode material promising for the development of effective electrochemical sensors. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis and electrochemical study of palladium-based nanomaterials for green energy applications

NASA Astrophysics Data System (ADS)

Ostrom, Cassandra K.

Rising global energy consumption leads to increased environmental impacts. The continued use of current energy resources, e.g. fossil fuels, will exaggerate the cumulative nature of CO2 byproduct emissions in the atmosphere. The development and implementation of a hydrogen economy, as a solution to offset degradative environmental impacts, will likely enable opportunities for maintaining or improving standards of living while significantly lowering carbon emissions. Palladium has proven to be a strong contender as an enabling material that encompasses many aspects of a prospective hydrogen economy, lending promise to applications such as hydrogen purification, storage and fuel cell catalysis. In my M.Sc. study, Pd-based nanomaterials have been synthesized and examined for their applications in hydrogen storage and fuel cell catalysis. The surface properties of synthesized Pd-based nanomaterials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD), X-ray Photoelectron spectroscopy (XPS), and N2 gas adsorption/desorption. Electrochemical analysis of the fabricated materials was performed using cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was employed to characterize the composition of the formed samples. Hydrogen electrosorption onto activated carbon materials modified with different trimetallic dissociation catalysts (Pd-Ag-Cd) was investigated in an acidic medium. A uniform distribution of the Pd-Ag-Cd catalysts was achieved using a facile room temperature sodium borohydride reduction method. By varying the composition of the alloys, synergistic effects between the metal and carbon support resulted in drastic increases in hydrogen sorption capabilities in contrast to bi-metallic PdAg and PdCd catalysts. Utilizing electrochemical methods, the optimal composition of the Pd-Ag-Cd alloys was determined to be Pd80Ag10Cd10, with the highest hydrogen sorption capacity at a hydrogen desorption charge of 18.49 C/cm2˙mg. Further enhancement of the electroactivity of synthesized titanium dioxide nanotubes (TiO2 NTs) was achieved using UV light and electrochemical pretreatment methods. The effects of these pretreatment methods on TiO2 NTs were systematically investigated and compared. Using Pd as a dispersed catalyst, Pd/TiO2 NT electrodes were examined in acidic medium, with both UV and electrochemical pretreatment methods revealing significant enhancements in the electroactivity of the TiO2 NT substrate. The UV pretreated samples were found to dominate, when compared to those that underwent electrochemical pretreatment, in terms of overall efficacy for hydrogen sorption and the electrooxidation of formic acid. Improvements in nanotube conductivity resulted in an effective reduction of noble metal coating loads. Nanostructured PdPb electrocatalysts were loaded directly onto TiO2 NT substrates and tested for their activity towards formic acid oxidation. Comparative studies revealed the enhanced electrochemical oxidation of formic acid on Pd95Pb5/TiO2 NTs in comparison to Pd/TiO2 NTs, resulting in the successful reduction of Pd noble metal load. The work performed in this M. Sc. thesis project reveals that modifications to both Pd catalysts and their associated supports can drastically alter their geometric and electronic properties. This has a major influence on the development of more cost effective materials with enhanced activity for use towards the commercialization of fuel cells.

Isolation of high quality graphene from Ru by solution phase intercalation

NASA Astrophysics Data System (ADS)

Koren, E.; Sutter, E.; Bliznakov, S.; Ivars-Barcelo, F.; Sutter, P.

2013-09-01

We introduce a method for isolating graphene grown on epitaxial Ru(0001)/α-Al2O3. The strong graphene/Ru(0001) coupling is weakened by electrochemically driven intercalation of hydrogen underpotentially deposited in aqueous KOH solution, which allows the penetration of water molecules at the graphene/Ru(0001) interface. Following these electrochemically driven processes, the graphene can be isolated by electrochemical hydrogen evolution and transferred to arbitrary supports. Raman and transport measurements demonstrate the high quality of the transferred graphene. Our results show that intercalation, typically carried out in vacuum, can be extended to solution environments for graphene processing under ambient conditions.

Polyaniline nanowires-gold nanoparticles hybrid network based chemiresistive hydrogen sulfide sensor

NASA Astrophysics Data System (ADS)

Shirsat, Mahendra D.; Bangar, Mangesh A.; Deshusses, Marc A.; Myung, Nosang V.; Mulchandani, Ashok

2009-02-01

We report a sensitive, selective, and fast responding room temperature chemiresistive sensor for hydrogen sulfide detection and quantification using polyaniline nanowires-gold nanoparticles hybrid network. The sensor was fabricated by facile electrochemical technique. Initially, polyaniline nanowires with a diameter of 250-320 nm bridging the gap between a pair of microfabricated gold electrodes were synthesized using templateless electrochemical polymerization using a two step galvanostatic technique. Polyaniline nanowires were then electrochemically functionalized with gold nanoparticles using cyclic voltammetry technique. These chemiresistive sensors show an excellent limit of detection (0.1 ppb), wide dynamic range (0.1-100 ppb), and very good selectivity and reproducibility.

Challenge for lowering concentration polarization in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Suzuki, Toshio; Yamaguchi, Toshiaki; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

2016-01-01

In the scope of electrochemical phenomena, concentration polarization at electrodes is theoretically inevitable, and lowering the concentration overpotential to improve the performance of electrochemical cells has been a continuing challenge. Electrodes with highly controlled microstructure, i.e., high porosity and uniform large pores are therefore essential to achieve high performance electrochemical cells. In this study, state-of-the-art technology for controlling the microstructure of electrodes has been developed for realizing high performance support electrodes of solid oxide fuel cells (SOFCs). The key is controlling the porosity and pore size distribution to improve gas diffusion, while maintaining the integrity of the electrolyte and the structural strength of actual sized electrode supports needed for the target application. Planar anode-supported SOFCs developed in this study realize 5 μm thick dense electrolyte (yttria-stabilized zirconia: YSZ) and the anode substrate (Ni-YSZ) of 53.6 vol.% porosity with a large median pore diameter of 0.911 μm. Electrochemical measurements reveal that the performance of the anode-supported SOFCs improves with increasing anode porosity. This Ni-YSZ anode minimizes the concentration polarization, resulting in a maximum power density of 3.09 W cm-2 at 800 °C using humidified hydrogen fuel without any electrode functional layers.

Electrochemical properties of LaNi{sub 5{minus}x}Ge{sub x} alloys in Ni-MH batteries

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

Witham, C.; Hightower, A.; Fultz, B.

1997-11-01

Electrochemical studies were performed on LaNi{sub 5{minus}x}Ge{sub x} metal hydride alloys with 0 {le} x {le} 0.5. The authors carried out single-electrode studies to understand the effects of the Ge substituent on the hydrogen absorption characteristics, the electrochemical capacity, and the electrochemical kinetics of hydrogen absorption and desorption. The electrochemical characteristics of the Ge-substituted alloys are compared to those of the Sn-substituted alloys reported earlier. LaNi{sub 5{minus}x}Ge{sub x} alloys show compositional trends similar to LaNi{sub 5{minus}x}Sn{sub x} alloys, but unlike the Sn-substituted alloys, Ge-substituted alloys continue to exhibit facile kinetics for hydrogen absorption/desorption at high solute concentrations. Cycle lives ofmore » LaNi{sub 5{minus}x}Ge{sub x} electrodes were measured in 300 mAh laboratory test cells and were found to be superior to the Sn-substituted LaNi{sub 5} and comparable to a Mm(Ni, Co, Mn, Al){sub 5} alloy. The optimum Ge content for LaNi{sub 5{minus}x}Ge{sub x} metal hydride alloys in alkaline rechargeable cells is in the range 0.4 {le} x {le} 0.5.« less

Effects of hydrogen-charging on the properties of S235JR steel

NASA Astrophysics Data System (ADS)

Pietkun-Greber, Izabela

2017-10-01

The paper presents the test results of the S235JR steel susceptibility to damage under the influence of hydrogen. The test of mechanical properties was performed on the basis of a static stretch test of non-hydrogenated samples and after cathodic polarization. Electrochemical measurements for the assessment of corrosion resistance of non-hydrogenated and hydrogenated steels were carried out using open circuit potential measurement and registering of potentiodynamic polarization curves in a three-electrode measuring system. Hydrogenation was carried out for between 3 and 24 hours in a solution of 0.1 N sulfuric acid (VI) with the addition of 2 mg/dm 3 of arsenic oxide (III) at an electric current density of 10 mA/cm2. The hydrogen content in the steel before and after saturation with hydrogen was determined using the analyzer. Fracture samples after tensile test were observed using scanning electron microscope. The results of the research showed that as the hydrogen concentration in the examined steel increased (the lengthening of the saturation time), the deterioration of its mechanical and electrochemical properties occurred.

Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins

DOE PAGES

Ye, Jianchao C.; Ong, Mitchell T.; Heo, Tae Wook; ...

2015-11-05

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp 2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexesmore » in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. Furthermore, these findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.« less

Universal roles of hydrogen in electrochemical performance of graphene: high rate capacity and atomistic origins

PubMed Central

Ye, Jianchao; Ong, Mitchell T.; Heo, Tae Wook; Campbell, Patrick G.; Worsley, Marcus A.; Liu, Yuanyue; Shin, Swanee J.; Charnvanichborikarn, Supakit; Matthews, Manyalibo J.; Bagge-Hansen, Michael; Lee, Jonathan R.I.; Wood, Brandon C.; Wang, Y. Morris

2015-01-01

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. These findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes. PMID:26536830

Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

PubMed

Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

2018-02-22

Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

Method of determining methane and electrochemical sensor therefor

DOEpatents

Zaromb, Solomon; Otagawa, Takaaki; Stetter, Joseph R.

1986-01-01

A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about about 1.4 volts versus R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

Fluorinated graphenes as advanced biosensors - effect of fluorine coverage on electron transfer properties and adsorption of biomolecules

NASA Astrophysics Data System (ADS)

Urbanová, Veronika; Karlický, František; Matěj, Adam; Šembera, Filip; Janoušek, Zbyněk; Perman, Jason A.; Ranc, Václav; Čépe, Klára; Michl, Josef; Otyepka, Michal; Zbořil, Radek

2016-06-01

Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms.Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms. Electronic supplementary information (ESI) available: SEM, HRTEM, and AFM images the sheet in pristine graphene sample, survey XPS spectrum, high resolution C 1s XPS spectrum, and Raman spectrum of pristine graphene precursor used for controlled fluorination, survey and high resolution F 1s XPS spectra of the CF0.084, CF0.158, and CF0.218 samples, EDS chemical mapping of fluorine in CF0.158, contact angle measurement of CF0.084, CF0.158, CF0.218, and HOPG, and additional electrochemical data. See DOI: 10.1039/c6nr00353b

Conducting polymer-based electrochemical biosensors for neurotransmitters: A review.

PubMed

Moon, Jong-Min; Thapliyal, Neeta; Hussain, Khalil Khadim; Goyal, Rajendra N; Shim, Yoon-Bo

2018-04-15

Neurotransmitters are important biochemical molecules that control behavioral and physiological functions in central and peripheral nervous system. Therefore, the analysis of neurotransmitters in biological samples has a great clinical and pharmaceutical importance. To date, various methods have been developed for their assay. Of the various methods, the electrochemical sensors demonstrated the potential of being robust, selective, sensitive, and real time measurements. Recently, conducting polymers (CPs) and their composites have been widely employed in the fabrication of various electrochemical sensors for the determination of neurotransmitters. Hence, this review presents a brief introduction to the electrochemical biosensors, with the detailed discussion on recent trends in the development and applications of electrochemical neurotransmitter sensors based on CPs and their composites. The review covers the sensing principle of prime neurotransmitters, including glutamate, aspartate, tyrosine, epinephrine, norepinephrine, dopamine, serotonin, histamine, choline, acetylcholine, nitrogen monoxide, and hydrogen sulfide. In addition, the combination with other analytical techniques was also highlighted. Detection challenges and future prospective of the neurotransmitter sensors were discussed for the development of biomedical and healthcare applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrogen Sorption Kinetics on Bare and Platinum-Modified Palladium Nanofilms, Grown by Electrochemical Atomic Layer Deposition (E-ALD)

DOE PAGES

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.; ...

2016-01-01

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Electrochemical degradation of trichloroacetic acid in aqueous media: influence of the electrode material.

PubMed

Esclapez, M D; Díez-García, M I; Sàez, V; Bonete, P; González-García, José

2013-01-01

The electrochemical degradation of trichloroacetic acid (TCAA) in water has been analysed through voltammetric studies with a rotating disc electrode and controlled-potential bulk electrolyses. The influence of the mass-transport conditions and initial concentration of TCAA for titanium, stainless steel and carbon electrodes has been studied. It is shown that the electrochemical reduction of TCAA takes place prior to the massive hydrogen evolution in the potential window for all electrode materials studied. The current efficiency is high (> 18%) compared with those normally reported in the literature, and the fractional conversion is above 50% for all the electrodes studied. Only dichloroacetic acid (DCAA) and chloride anions were routinely detected as reduction products for any of the electrodes, and reasonable values of mass balance error were obtained. Of the three materials studied, the titanium cathode gave the best results.

Amperometric sensing of hydrogen peroxide using glassy carbon electrode modified with copper nanoparticles

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

Sophia, J.; Muralidharan, G., E-mail: muraligru@gmail.com

2015-10-15

In this paper, fabrication of glassy carbon electrode (GCE) modified with nano copper particles is discussed. The modified electrode has been tested for the non-enzymatic electrochemical detection of hydrogen peroxide (H{sub 2}O{sub 2}). The copper nanoparticles (Cu NPs) were prepared employing a simple chemical reduction method. The presence of Cu NPs was confirmed through UV–visible (UV–vis) absorption spectroscopy and X-ray diffraction (XRD) analysis. The size and morphology of the particles were investigated using transmission electron microscopy (TEM). The electrochemical properties of the fabricated sensor were studied via cyclic voltammetry (CV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The electrochemical sensor displayedmore » excellent performance features towards H{sub 2}O{sub 2} detection exhibiting wide linear range, low detection limit, swift response time, good reproducibility and stability.« less

A Combustion Products Analyzer for contingency use during thermodegradation events on spacecraft

NASA Technical Reports Server (NTRS)

Limero, Thomas; James, John T.; Beck, Steven; Cromer, Raymond

1991-01-01

This paper will describe the Combustion Products Analyzer (CPA), which is being developed under the direction of the Toxicology Laboratory at Johnson Space Center to provide necessary data on air quality in the Shuttle following a thermodegradation incident. Using separate electrochemical sensors, the CPA monitors four gases (hydrogen fluoride/carbonyl fluoride, hydrogen chloride, hydrogen cyanide, and carbon monoxide), which were selected as the most hazardous compounds likely to be released during thermodegradation of synthetic materials. Electrochemical sensors have been available for several years; the CPA sensors, which are unique because of their small size and zero-gravity compatibility, will be described in detail.

Improvement in low-temperature and instantaneous high-rate output performance of Al-free AB5-type hydrogen storage alloy for negative electrode in Ni/MH battery: Effect of thermodynamic and kinetic regulation via partial Mn substituting

NASA Astrophysics Data System (ADS)

Zhou, Wanhai; Zhu, Ding; Tang, Zhengyao; Wu, Chaoling; Huang, Liwu; Ma, Zhewen; Chen, Yungui

2017-03-01

A series of Al-free Mn-modified AB5-type hydrogen storage alloys have been designed and the effects of thermodynamic stability and electrochemical kinetics on electrochemical performance via Mn substituting have been investigated. Compared with high-Al alloys, the Al-free alloys in this study have better low-temperature performance and instantaneous high-rate output because of the higher surface catalytic ability. After partial substitution of Ni by Mn, both the hydrogen desorption capacity and plateau pressure decrease, and correspondingly results in an improved thermodynamic stability which is adverse to low-temperature delivery. Additionally, with the improvement of charge acceptance ability and anti-corrosion property via Mn substitution, the room-temperature discharge capacity and cycling stability increase slightly. However, Mn adversely affects the electrochemical kinetics and deteriorates both the surface catalytic ability and the bulk hydrogen diffusion ability, leading to the drop of low-temperature dischargeability, high-rate dischargeability and peak power (Ppeak). Based on the thermodynamic and kinetic regulation and overall electrochemical properties, the optimal composition is obtained when x = 0.2, the discharge capacity is 243.6 mAh g-1 at -40 °C with 60 mA g-1, and the Ppeak attains to 969.6 W kg-1 at -40 °C.

Electrochemical separation of hydrogen from reformate using PEM fuel cell technology

NASA Astrophysics Data System (ADS)

Gardner, C. L.; Ternan, M.

This article is an examination of the feasibility of electrochemically separating hydrogen obtained by steam reforming a hydrocarbon or alcohol source. A potential advantage of this process is that the carbon dioxide rich exhaust stream should be able to be captured and stored thereby reducing greenhouse gas emissions. Results are presented for the performance of the anode of proton exchange membrane (PEM) electrochemical cell for the separation of hydrogen from a H 2-CO 2 gas mixture and from a H 2-CO 2-CO gas mixture. Experiments were carried out using a single cell state-of-the-art PEM fuel cell. The anode was fed with either a H 2-CO 2 gas mixture or a H 2-CO 2-CO gas mixture and hydrogen was evolved at the cathode. All experiments were performed at room temperature and atmospheric pressure. With the H 2-CO 2 gas mixture the hydrogen extraction efficiency is quite high. When the gas mixture included CO, however, the hydrogen extraction efficiency is relatively poor. To improve the efficiency for the separation of the gas mixture containing CO, the effect of periodic pulsing on the anode potential was examined. Results show that pulsing can substantially reduce the anode potential thereby improving the overall efficiency of the separation process although the anode potential of the CO poisoned and pulsed cell still lies above that of an unpoisoned cell.

An Integrated Device View on Photo-Electrochemical Solar-Hydrogen Generation.

PubMed

Modestino, Miguel A; Haussener, Sophia

2015-01-01

Devices that directly capture and store solar energy have the potential to significantly increase the share of energy from intermittent renewable sources. Photo-electrochemical solar-hydrogen generators could become an important contributor, as these devices can convert solar energy into fuels that can be used throughout all sectors of energy. Rather than focusing on scientific achievement on the component level, this article reviews aspects of overall component integration in photo-electrochemical water-splitting devices that ultimately can lead to deployable devices. Throughout the article, three generalized categories of devices are considered with different levels of integration and spanning the range of complete integration by one-material photo-electrochemical approaches to complete decoupling by photovoltaics and electrolyzer devices. By using this generalized framework, we describe the physical aspects, device requirements, and practical implications involved with developing practical photo-electrochemical water-splitting devices. Aspects reviewed include macroscopic coupled multiphysics device models, physical device demonstrations, and economic and life cycle assessments, providing the grounds to draw conclusions on the overall technological outlook.

An Enzyme Switch Employing Direct Electrochemical Communication between Horseradish Peroxidase and a Poly(aniline) Film.

PubMed

Bartlett, P N; Birkin, P R; Wang, J H; Palmisano, F; De Benedetto, G

1998-09-01

An enzyme switch, or microelectrochemical enzyme transistor, responsive to hydrogen peroxide was made by connecting two carbon band electrodes (∼10 μm wide, 4.5 mm long separated by a 20-μm gap) with an anodically grown film of poly(aniline). Horseradish peroxidase (EC 1.11.1.7) was either adsorbed onto the poly(aniline) film or immobilized in an insulating poly(1,2-diaminobenzene) polymer grown electrochemically on top of the poly(aniline) film to complete the device. In the completed device, the conductivity of the poly(aniline) film changes from conducting (between - 0.05 and + 0.3 V vs SCE at pH 5) to insulating (>+0.3 V vs SCE at pH 5) on addition of hydrogen peroxide. The change in conductivity is brought about by oxidation of the poly(aniline) film by direct electrochemical communication between the enzyme and the conducting polymer. This was confirmed by measuring the potential of the poly(aniline) film during switching of the conductivity in the presence of hydrogen peroxide. The devices can be reused by rereducing the poly(aniline) electrochemically to a potential below +0.3 V vs SCE. A blind test showed that the device can be used to determine unknown concentrations of H(2)O(2) in solution and that, when used with hydrogen peroxide concentrations below 0.5 mmol dm(-)(3), the same device maybe reused several times. The possible development of devices of this type for use in applications requiring the measurement of low levels of hydrogen peroxide or horseradish peroxidase is discussed.

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.

Design principles for hydrogen evolution reaction catalyst materials

DOE PAGES

Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan; ...

2016-04-19

Design and synthesis of active, stable and cost-effective materials for efficient hydrogen production (hydrogen evolution reaction, HER) is of paramount importance for the successful deployment of hydrogen -based alternative energy technologies. The HER, seemingly one of the simplest electrochemical reactions, has served for decades to bridge the gap between fundamental electrocatalysis and practical catalyst design. However, there are still many open questions that need to be answered before it would be possible to claim that design principles of catalyst materials are fully developed for the efficient hydrogen production. Here in this review, by summarizing key results for the HER onmore » well-characterized electrochemical interfaces in acidic and alkaline media, we have broadened our understanding of the HER in the whole range of pH by considering three main parameters: the nature of the proton donor (H 3O + in acid and H 2O in alkaline), the energy of adsorption of H ad and OH ad, and the presence of spectator species. Simply by considering these three parameters we show that great deal has already been learned and new trends are beginning to emerge, giving some predictive ability with respect to the nature of electrochemical interface and electrocatalytic activity of the HER.« less

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

NASA Astrophysics Data System (ADS)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

Strongly coupled inorganic-nano-carbon hybrid materials for energy storage.

PubMed

Wang, Hailiang; Dai, Hongjie

2013-04-07

The global shift of energy production from fossil fuels to renewable energy sources requires more efficient and reliable electrochemical energy storage devices. In particular, the development of electric or hydrogen powered vehicles calls for much-higher-performance batteries, supercapacitors and fuel cells than are currently available. In this review, we present an approach to synthesize electrochemical energy storage materials to form strongly coupled hybrids (SC-hybrids) of inorganic nanomaterials and novel graphitic nano-carbon materials such as carbon nanotubes and graphene, through nucleation and growth of nanoparticles at the functional groups of oxidized graphitic nano-carbon. We show that the inorganic-nano-carbon hybrid materials represent a new approach to synthesize electrode materials with higher electrochemical performance than traditional counterparts made by simple physical mixtures of electrochemically active inorganic particles and conducting carbon materials. The inorganic-nano-carbon hybrid materials are novel due to possible chemical bonding between inorganic nanoparticles and oxidized carbon, affording enhanced charge transport and increased rate capability of electrochemical materials without sacrificing specific capacity. Nano-carbon with various degrees of oxidation provides a novel substrate for nanoparticle nucleation and growth. The interactions between inorganic precursors and oxidized-carbon substrates provide a degree of control over the morphology, size and structure of the resulting inorganic nanoparticles. This paper reviews the recent development of inorganic-nano-carbon hybrid materials for electrochemical energy storage and conversion, including the preparation and functionalization of graphene sheets and carbon nanotubes to impart oxygen containing groups and defects, and methods of synthesis of nanoparticles of various morphologies on oxidized graphene and carbon nanotubes. We then review the applications of the SC-hybrid materials for high performance lithium ion batteries, rechargeable Li-S and Li-O2 batteries, supercapacitors and ultrafast Ni-Fe batteries, and new electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions.

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.

Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study.

PubMed

Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc

2015-10-29

Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

An electrochemical study of hydrogen uptake and elimination by bare and gold-plated waspaloy

NASA Technical Reports Server (NTRS)

Danford, M. D.; Deramus, G. E., Jr.; Lowery, J. R.

1984-01-01

Two electrochemical methods for the determination of hydrogen concentrations in metals are discussed and evaluated. The take-up of hydrogen at a pressure of 5000 psi by Waspaloy metal was determined experimentally at 24 C. It was found that the metal becomes saturated with hydrogen after an exposure time of about 1 hr. For samples charged with hydrogen at high pressure, most of the hydrogen is contained in the interstitial solid solution of the metal. For electrolytically charged samples, most of the hydrogen is contained as surface and subsurface hydrides. Hydrogen elimination rates were determined for these two cases, with the rate for electrolytically charged samples being greater by over a factor of two. Theoretical effects of high temperature and pressure on hydrogen take-up and elimination by bare and gold plated Waspaloy metal was considered. The breakthrough point for hydrogen at 5000 psi, determined experimentally, lies between a gold thickness of 0.0127 mm (0.0005 in.) and 0.0254 mm (0.001 in.) at 24 C. Electropolishing was found to greatly reduce the uptake of hydrogen at high pressure by Waspaloy metal at 24 C. Possible implications of the results obtained, as they apply to the turbine disk of the space shuttle main engine, are discussed.

Miniature ceramic fuel cell

DOEpatents

Lessing, Paul A.; Zuppero, Anthony C.

1997-06-24

A miniature power source assembly capable of providing portable electricity is provided. A preferred embodiment of the power source assembly employing a fuel tank, fuel pump and control, air pump, heat management system, power chamber, power conditioning and power storage. The power chamber utilizes a ceramic fuel cell to produce the electricity. Incoming hydro carbon fuel is automatically reformed within the power chamber. Electrochemical combustion of hydrogen then produces electricity.

Low-Cost alpha Alane for Hydrogen Storage

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

Fabian, Tibor; Petrie, Mark; Crouch-Baker, Steven

This project was directed towards the further development of the Savannah River National Laboratory (SRNL) lab-scale electrochemical synthesis of the hydrogen storage material alpha-alane and Ardica Technologies-SRI International (SRI) chemical downstream processes that are necessary to meet DoE cost metrics and transition alpha-alane synthesis to an industrial scale. Ardica has demonstrated the use of alpha-alane in a fuel-cell system for the U.S. Army WFC20 20W soldier power system that has successfully passed initial field trials with individual soldiers. While alpha-alane has been clearly identified as a desirable hydrogen storage material, cost-effective means for its production and regeneration on a scalemore » of use applicable to the industry have yet to be established. We focused on three, principal development areas: 1. The construction of a comprehensive engineering techno-economic model to establish the production costs of alpha-alane by both electrochemical and chemical routes at scale. 2. The identification of critical, cost-saving design elements of the electrochemical cell and the quantification of the product yields of the primary electrochemical process. A moving particle-bed reactor design was constructed and operated. 3. The experimental quantification of the product yields of candidate downstream chemical processes necessary to produce alpha-alane to complete the most cost-effective overall manufacturing process. Our techno-economic model shows that under key assumptions most 2015 and 2020 DOE hydrogen storage system cost targets for low and medium power can be achieved using the electrochemical alane synthesis process. To meet the most aggressive 2020 storage system cost target, $1/g, our model indicates that 420 metric tons per year (MT/y) production of alpha-alane is required. Laboratory-scale experimental work demonstrated that the yields of two of the three critical component steps within the overall “electrochemical process” were sufficiently high to meet this production target. In the case of the yield of the third step, the crystallization of alpha-alane from the primary alane-related product of the electrochemical reaction, further development is required.« less

Selective electrochemical generation of hydrogen peroxide from water oxidation

DOE PAGES

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

2015-10-08

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

Controllable synthesis of hierarchical nickel cobalt sulfide with enhanced electrochemical activity

NASA Astrophysics Data System (ADS)

Tie, Jinjin; Han, Jiaxi; Diao, Guiqiang; Liu, Jiwen; Xie, Zhuopeng; Cheng, Gao; Sun, Ming; Yu, Lin

2018-03-01

The composition of nickel cobalt sulfide has great influence on its electrochemical performance. Herein, the nickel cobalt sulfide with different composition and mixed phase were synthesized by one-step solvothermal method through changing the molar ratio of Ni to Co in the reaction system. The electrochemical measurements showed that the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co to be 1.5:1.5 (NCS-2) demonstrates the superior pseudocapacitive performance with a high specific capacitance (6.47 F cm-2 at 10 mA cm-2) and a favorable Coulombic efficiency (∼99%). Whereas, when applied as the catalyst for hydrogen evolution reaction in 1 M KOH aqueous electrolyte, the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co is 1:2 (NCS-1) displays better catalytic activity, and it requires a relatively lower overpotential of 282 mV to deliver the current density of 10 mA cm-2.

Single-Atom Electrocatalysts.

PubMed

Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong; Du, Dan; Lin, Yuehe

2017-11-06

Recent years have witnessed a dramatic increase in the production of sustainable and renewable energy. However, the electrochemical performances of the various systems are limited, and there is an intensive search for highly efficient electrocatalysts by more rational control over the size, shape, composition, and structure. Of particular interest are the studies on single-atom catalysts (SACs), which have sparked new interests in electrocatalysis because of their high catalytic activity, stability, selectivity, and 100 % atom utilization. In this Review, we introduce innovative syntheses and characterization techniques for SACs, with a focus on their electrochemical applications in the oxygen reduction/evolution reaction, hydrogen evolution reaction, and hydrocarbon conversion reactions for fuel cells (electrooxidation of methanol, ethanol, and formic acid). The electrocatalytic performance is further considered at an atomic level and the underlying mechanisms are discussed. The ultimate goal is the tailoring of single atoms for electrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

A number of electrocatalyst combinations were prepared and characterized. These electrocatalysts were formulated to contain platinum combined with transition metal carbide forming elements (W, Mo, V) for cathodes and platinum combined with palladium for anodes. High resolution electron microscopy was used to determine the crystallite size and dispersion of platinum-palladium alloy electrocatalysts in order to provide analytical support for the electrochemical determinations of the particle dispersions. An equation was derived which correlates palladium crystallite size with electrochemical hydrogen adsorption. Based on comparisons of electrocatalyst performances in the presence of pure hydrogen and hydrogen containing carbon monoxide, it was shown that the apparent poisoning of the electrocatalyst by carbon monoxide is influenced by the electrode structure.

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

DOE PAGES

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.; ...

2018-01-17

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

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

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

Bipolar electrochemical mechanism for the propulsion of catalytic nanomotors in hydrogen peroxide solutions.

PubMed

Wang, Yang; Hernandez, Rose M; Bartlett, David J; Bingham, Julia M; Kline, Timothy R; Sen, Ayusman; Mallouk, Thomas E

2006-12-05

Bimetallic nanorods are propelled in aqueous solutions by the catalytic decomposition of hydrogen peroxide to oxygen and water. Several mechanisms (interfacial tension gradients, bubble recoil, viscous Brownian ratchet, self-electrophoresis) have been proposed for the transduction of chemical to mechanical energy in this system. From Tafel plots of anodic and cathodic hydrogen peroxide reactions at various metal (Au, Pt, Rh, Ni, Ru, and Pd) ultramicroelectrodes, we determine the potential at which the anodic and cathodic reaction rates are equal for each metal. These measurements allow one to predict the direction of motion of all possible bimetallic combinations according to the bipolar electrochemical (or self-electrophoretic) mechanism. These predictions are consistent with the observed direction of motion in all cases studied, providing strong support for the mechanism. We also find that segmented nanorods with one Au end and one poly(pyrrole) end containing catalase, an enzyme that decomposes hydrogen peroxide nonelectrochemically, perform the overall catalytic reaction at a rate similar to that of nanorods containing Au and Pt segments. However, in this case there is no observed axial movement, again supporting the bipolar electrochemical propulsion mechanism for bimetallic nanorods.

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.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Corrosion protection of copper by polypyrrole film studied by electrochemical impedance spectroscopy and the electrochemical quartz microbalance

NASA Astrophysics Data System (ADS)

Lei, Yanhua; Ohtsuka, Toshiaki; Sheng, Nan

2015-12-01

Polypyrrole (PPy) films were synthesized on copper in solution of sodium di-hydrogen phosphate and phytate for corrosion protection. The protection properties of PPy films were comparatively investigated in NaCl solution. During two months immersion, the PPy film doped with phytate anions, working as a cationic perm-selective membrane, inhibited the dissolution of copper to 1% of bare copper. Differently, the PPy film doped with di-hydrogen phosphate anions, possessing anionic perm-selectivity, was gradually reduced, and inhibited the dissolution to 7.8% of bare copper. Degradation of the PPy films was studied by comparing the electrochemical impedance spectroscopy change at different immersion time and Raman spectra change after immersion.

Method of detecting defects in ion exchange membranes of electrochemical cells by chemochromic sensors

DOEpatents

Brooker, Robert Paul; Mohajeri, Nahid

2016-01-05

A method of detecting defects in membranes such as ion exchange membranes of electrochemical cells. The electrochemical cell includes an assembly having an anode side and a cathode side with the ion exchange membrane in between. In a configuration step a chemochromic sensor is placed above the cathode and flow isolation hardware lateral to the ion exchange membrane which prevents a flow of hydrogen (H.sub.2) between the cathode and anode side. The anode side is exposed to a first reactant fluid including hydrogen. The chemochromic sensor is examined after the exposing for a color change. A color change evidences the ion exchange membrane has at least one defect that permits H.sub.2 transmission therethrough.

Measuring Hydrogen Concentrations in Metals

NASA Technical Reports Server (NTRS)

Danford, M. D.

1985-01-01

Commercial corrosion-measurement system adapted to electrochemical determination of hydrogen concentrations in metals. New technique based on diffusion of hydrogen through foil specimen of metal. In sample holder, hydrogen produced on one side of foil, either by corrosion reaction or by cathodic current. Hydrogen diffused through foil removed on other side by constant anode potential, which leads to oxidation of hydrogen to water. Anode current is measure of concentration of hydrogen diffusing through foil. System used to study hydrogen uptake, hydrogen elimination by baking, effect of heat treatment, and effect of electroplating on high-strength steels.

Co@Pd core-shell nanoparticles embedded in nitrogen-doped porous carbon as dual functional electrocatalysts for both oxygen reduction and hydrogen evolution reactions.

PubMed

Yang, Hongyu; Tang, Zhenghua; Wang, Kai; Wu, Wen; Chen, Yinghuan; Ding, Zhaoqing; Liu, Zhen; Chen, Shaowei

2018-05-21

Developing efficient bi-functional electrocatalysts for both oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for producing hydrogen and utilizing hydrogen effectively to promote electrochemical energy storage in proton membrane exchange fuel cells (PEMFCs). Herein, we report Co@Pd core-shell nanoparticles encapsulated in porous carbon derived from zeolitic imidazolate framework 67 (ZIF-67) for both ORR and HER. The controlled pyrolysis of ZIF-67 can lead to the formation of Co nanoparticles encapsulated in nitrogen-doped porous carbon (Co NC), which subsequently underwent galvanic replacement with Na 2 PdCl 4 to form Co@Pd core-shell nanoparticles embedded in nitrogen-doped porous carbon (Co@Pd NC). The Co@Pd NC exhibited outperformance in ORR and HER than commercial Pd/C, as manifested by more positive onset potential and larger diffusion-limited current density in ORR tests, as well as a small overpotential to drive a current density of 10 mA cm -2 , and much lower Tafel slope in HER tests. It also demonstrated more robust long-term stability than commercial Pd/C for both ORR and HER. Multiple techniques inter-confirmed that the Pd loading in the sample was very low. The findings can pave a path for fabricating a core-shell structured nanocomposite with ultralow noble metal usage as a bifunctional catalyst for electrochemical energy storage and conversion with high-efficiency and remarkable longevity. Copyright © 2018 Elsevier Inc. All rights reserved.

Real-time electrochemical detection of hydrogen peroxide secretion in live cells by Pt nanoparticles decorated graphene-carbon nanotube hybrid paper electrode.

PubMed

Sun, Yimin; He, Kui; Zhang, Zefen; Zhou, Aijun; Duan, Hongwei

2015-06-15

In this work, we develop a new type of flexible and lightweight electrode based on highly dense Pt nanoparticles decorated free-standing graphene-carbon nanotube (CNT) hybrid paper (Pt/graphene-CNT paper), and explore its practical application as flexible electrochemical biosensor for the real-time tracking hydrogen peroxide (H2O2) secretion by live cells. For the fabrication of flexible nanohybrid electrode, the incorporation of CNT in graphene paper not only improves the electrical conductivity and the mechanical strength of graphene paper, but also increases its surface roughness and provides more nucleation sites for metal nanoparticles. Ultrafine Pt nanoparticles are further decorated on graphene-CNT paper by well controlled sputter deposition method, which offers several advantages such as defined particle size and dispersion, high loading density and strong adhesion between the nanoparticles and the substrate. Consequently, the resultant flexible Pt/graphene-CNT paper electrode demonstrates a variety of desirable electrochemical properties including large electrochemical active surface area, excellent electrocatalytic activity, high stability and exceptional flexibility. When used for nonenzymatic detection of H2O2, Pt/graphene-CNT paper exhibits outstanding sensing performance such as high sensitivity, selectivity, stability and reproducibility. The sensitivity is 1.41 µA µM(-1) cm(-2) with a linear range up to 25 µM and a low detection limit of 10 nM (S/N=3), which enables the resultant biosensor for the real-time tracking H2O2 secretion by live cells macrophages. Copyright © 2015. Published by Elsevier B.V.

A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Ma, Juanjuan; Liu, Lin; Chen, Qian; Yang, Min; Wang, Danping; Tong, Zhiwei; Chen, Zhong

2017-03-01

Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.

Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

NASA Astrophysics Data System (ADS)

Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

2016-03-01

A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

Advanced materials for energy storage.

PubMed

Liu, Chang; Li, Feng; Ma, Lai-Peng; Cheng, Hui-Ming

2010-02-23

Popularization of portable electronics and electric vehicles worldwide stimulates the development of energy storage devices, such as batteries and supercapacitors, toward higher power density and energy density, which significantly depends upon the advancement of new materials used in these devices. Moreover, energy storage materials play a key role in efficient, clean, and versatile use of energy, and are crucial for the exploitation of renewable energy. Therefore, energy storage materials cover a wide range of materials and have been receiving intensive attention from research and development to industrialization. In this Review, firstly a general introduction is given to several typical energy storage systems, including thermal, mechanical, electromagnetic, hydrogen, and electrochemical energy storage. Then the current status of high-performance hydrogen storage materials for on-board applications and electrochemical energy storage materials for lithium-ion batteries and supercapacitors is introduced in detail. The strategies for developing these advanced energy storage materials, including nanostructuring, nano-/microcombination, hybridization, pore-structure control, configuration design, surface modification, and composition optimization, are discussed. Finally, the future trends and prospects in the development of advanced energy storage materials are highlighted.

Gold nanoparticles/4-aminothiophenol interfaces for direct electron transfer of horseradish peroxidase: Enzymatic orientation and modulation of sensitivity towards hydrogen peroxide detection.

PubMed

Huerta-Miranda, G A; Arrocha-Arcos, A A; Miranda-Hernández, M

2018-08-01

Hydrogen peroxide electrochemical detection by horseradish peroxidase has been widely studied. The use of gold nanoparticles to prepare electrode/enzyme bioconjugates has attracted attention due to their catalytic properties. In this work, it is reported the use of gold nanoparticles and 4-aminothiophenol as a scaffold to obtain a suitable matrix for enzyme bioconjugation with horseradish peroxidase. A critical factor in biosensors design and development is the enzymatic electrochemical activity understanding. Comparison of voltammetric studies of the heme prosthetic group showed a reversible electrochemical behavior when the enzymes were immobilized in a well-dispersed gold deposit; on the other hand, a discrete redox response was observed on a randomly deposited gold electrode. These results show that the distance between enzymes is essential. Hydrogen peroxide catalysis and the enzymatic behavior were analyzed considering two types of nanoparticles dispositions. The catalytic behavior observed in the well-dispersed nanoparticles configuration suggests a preserved enzyme folding, a decrease of steric impediments, and appears to be a better immobilization strategy. In contrast, the randomly electrodeposited gold electrode decreased the enzyme orientation and the electrochemical activity. The advantages of this methodology are the electrode fabrication affordable cost and the enzymatic direct electron transfer response improvement. Copyright © 2018 Elsevier B.V. All rights reserved.

Editors' Choice—Field Trials Testing of Mixed Potential Electrochemical Hydrogen Safety Sensors at Commercial California Hydrogen Filling Stations

DOE PAGES

Brosha, Eric Lanich; Romero, Christopher Jesse; Poppe, Daniel; ...

2017-10-27

Hydrogen safety sensors must meet specific performance requirements, mandated by the U.S. Department of Energy, for hydrogen fueling station monitoring. Here, we describe the long-term performance of two zirconia-based mixed potential electrochemical hydrogen gas sensors, developed specifically with a high sensitivity to hydrogen, low cross-sensitivity, and fast response time. Over a two-year period, sensors with tin-doped indium oxide and strontium doped lanthanum chromite electrodes were deployed at two stations in four field trials tests conducted in Los Angeles. The sensors documented the existence of hydrogen plumes ranging in concentration from 100 to as high as 2700 ppm in the areamore » surrounding the dispenser, consistent with depressurization from 700 bar following vehicle refueling. As expected, the hydrogen concentration reported by the mixed potential sensors was influenced by wind direction. Baseline stability testing at a Chino, CA station showed no measureable baseline drift throughout 206 days of uninterrupted data acquisition. The high baseline stability, excellent correlation with logged fueling/depressurization events, and absence of false alarms suggest that the zirconia-based mixed potential sensor platform is a good candidate for protecting hydrogen infrastructure where frequent calibrations or sensor replacement to reduce the false alarm frequency have been shown to be cost prohibitive.« less

Editors' Choice—Field Trials Testing of Mixed Potential Electrochemical Hydrogen Safety Sensors at Commercial California Hydrogen Filling Stations

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

Brosha, Eric Lanich; Romero, Christopher Jesse; Poppe, Daniel

Hydrogen safety sensors must meet specific performance requirements, mandated by the U.S. Department of Energy, for hydrogen fueling station monitoring. Here, we describe the long-term performance of two zirconia-based mixed potential electrochemical hydrogen gas sensors, developed specifically with a high sensitivity to hydrogen, low cross-sensitivity, and fast response time. Over a two-year period, sensors with tin-doped indium oxide and strontium doped lanthanum chromite electrodes were deployed at two stations in four field trials tests conducted in Los Angeles. The sensors documented the existence of hydrogen plumes ranging in concentration from 100 to as high as 2700 ppm in the areamore » surrounding the dispenser, consistent with depressurization from 700 bar following vehicle refueling. As expected, the hydrogen concentration reported by the mixed potential sensors was influenced by wind direction. Baseline stability testing at a Chino, CA station showed no measureable baseline drift throughout 206 days of uninterrupted data acquisition. The high baseline stability, excellent correlation with logged fueling/depressurization events, and absence of false alarms suggest that the zirconia-based mixed potential sensor platform is a good candidate for protecting hydrogen infrastructure where frequent calibrations or sensor replacement to reduce the false alarm frequency have been shown to be cost prohibitive.« less

Fabrication characteristics and hydrogenation behavior of hydrogen storage alloys for sealed Ni-MH batteries

NASA Astrophysics Data System (ADS)

Kim, Ho-Sung; Kim, Jeon Min; Kim, Tae-Won; Oh, Ik-Hyun; Choi, Jeon; Park, Choong Nyeon

2008-08-01

Hydrogen storage alloys based on LmNi4.2Co0.2Mn0.3Al0.3 were fabricated to study the equilibrium hydrogen pressure and electrochemical performance. The surface morphology and structure of the alloys were analyzed by SEM and XRD, and then the hydrogenation behaviors of all alloys were evaluated by PCT and electrochemical half-cell. We studied the hydrogenation behavior of the Lm-based alloy with changes in composition elements such as Mn, Al, and Co and investigated the optimal design for Lm-based alloy in a sealed battery system. As a result of studying the hydrogenation characterization of alloys with the substitution elements, hydrogen storage alloys such as LmNi3.75Co0.15Mn0.5Al0.3 and LmNi3.5Co0.5Mn0.5Al0.5 were obtained to correspond with the characteristics of a sealed battery with a higher capacity, long life cycle, lower internal pressure, and lower battery cost. The capacity preservation rate of LmNi3.5Co0.5Mn0.5Al0.5 was greatly improved to 92.7% (255 mAh/g) at 60 cycles, indicating a low equilibrium hydrogen pressure of 0.03 atm in PCT devices.

HYDROGENATION OF OLEFINS USING PALLADIUM NANOPARTICLES PREPARED WITH PULSE ELECTROCHEMICAL DEPOSITION

EPA Science Inventory

Electrochemistry has been used to synthesize nano-structured materials. In this project, we have conducted the application of electrochemistry for the synthesis of nano-palladium catalysts that may have application in the area of green chemistry. The electrochemical technique use...

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water

PubMed Central

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles. PMID:28182635

Electrochemically reduced water exerts superior reactive oxygen species scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water.

PubMed

Hamasaki, Takeki; Harada, Gakuro; Nakamichi, Noboru; Kabayama, Shigeru; Teruya, Kiichiro; Fugetsu, Bunshi; Gong, Wei; Sakata, Ichiro; Shirahata, Sanetaka

2017-01-01

Electrochemically reduced water (ERW) is produced near a cathode during electrolysis and exhibits an alkaline pH, contains richly dissolved hydrogen, and contains a small amount of platinum nanoparticles. ERW has reactive oxygen species (ROS)-scavenging activity and recent studies demonstrated that hydrogen-dissolved water exhibits ROS-scavenging activity. Thus, the antioxidative capacity of ERW is postulated to be dependent on the presence of hydrogen levels; however, there is no report verifying the role of dissolved hydrogen in ERW. In this report, we clarify whether the responsive factor for antioxidative activity in ERW is dissolved hydrogen. The intracellular ROS scavenging activity of ERW and hydrogen-dissolved water was tested by both fluorescent stain method and immuno spin trapping assay. We confirm that ERW possessed electrolysis intensity-dependent intracellular ROS-scavenging activity, and ERW exerts significantly superior ROS-scavenging activity in HT1080 cells than the equivalent level of hydrogen-dissolved water. ERW retained its ROS-scavenging activity after removal of dissolved hydrogen, but lost its activity when autoclaved. An oxygen radical absorbance capacity assay, the 2,2-diphenyl-1-picrylhydrazyl assay and chemiluminescence assay could not detect radical-scavenging activity in both ERW and hydrogen-dissolved water. These results indicate that ERW contains electrolysis-dependent hydrogen and an additional antioxidative factor predicted to be platinum nanoparticles.

Voltammetric and impedance behaviours of surface-treated nano-crystalline diamond film electrodes

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

Liu, F. B.; Jing, B.; Cui, Y.

2015-04-15

The electrochemical performances of hydrogen- and oxygen-terminated nano-crystalline diamond film electrodes were investigated by cyclic voltammetry and AC impedance spectroscopy. In addition, the surface morphologies, phase structures, and chemical states of the two diamond films were analysed by scanning probe microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. The results indicated that the potential window is narrower for the hydrogen-terminated nano-crystalline diamond film than for the oxygen-terminated one. The diamond film resistance and capacitance of oxygen-terminated diamond film are much larger than those of the hydrogen-terminated diamond film, and the polarization resistances and double-layer capacitance corresponding to oxygen-terminated diamond filmmore » are both one order of magnitude larger than those corresponding to the hydrogen-terminated diamond film. The electrochemical behaviours of the two diamond film electrodes are discussed.« less

Multi-Scale Ordered Cell Structure for Cost Effective Production of Hydrogen by HTWS

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

Elangovan, Elango; Rao, Ranjeet; Colella, Whitney

Production of hydrogen using an electrochemical device provides for large scale, high efficiency conversion and storage of electrical energy. When renewable electricity is used for conversion of steam to hydrogen, a low-cost and low emissions pathway to hydrogen production emerges. This project was intended to demonstrate a high efficiency High Temperature Water Splitting (HTWS) stack for the electrochemical production of low cost H2. The innovations investigated address the limitations of the state of the art through the use of a novel architecture that introduces macro-features to provide mechanical support of a thin electrolyte, and micro-features of the electrodes to lowermore » polarization losses. The approach also utilizes a combination of unique sets of fabrication options that are scalable to achieve manufacturing cost objectives. The development of HTWS process and device is guided by techno-economic and life cycle analyses.« less

Hydrogen evolution using palladium sulfide (PdS) nanocorals as photoanodes in aqueous solution.

PubMed

Barawi, M; Ferrer, I J; Ares, J R; Sánchez, C

2014-11-26

Palladium sulfide (PdS) nanostructures are proposed to be used as photoanodes in photoelectrochemical cells (PECs) for hydrogen evolution due to their adequate transport and optical properties shown in previous works. Here, a complete morphological and electrochemical characterization of PdS films has been performed by different techniques. PdS flatband potential (Vfb=-0.65±0.05 V vs NHE) was determined by electrochemical impedance spectroscopy measurements in aqueous Na2SO3 electrolyte, providing a description of the energy levels scheme at the electrolyte-semiconductor interface. This energy levels scheme confirms PdS as a compound able to photogenerate hydrogen in a PEC. At last, photogenerated hydrogen rates are measured continuously by mass spectrometry as a function of the external bias potential under illumination, reaching values up to 4.4 μmolH2/h at 0.3 V vs Ag/AgCl.

A Ti-V-based bcc phase alloy for use as metal hydride electrode with high discharge capacity

NASA Astrophysics Data System (ADS)

Yu, X. B.; Wu, Z.; Xia, B. J.; Xu, N. X.

2004-07-01

The electrochemical characteristics of single bcc phase Ti-30V-15Cr-15Mn alloy were investigated. It was demonstrated that the single bcc phase alloy has high electrochemical discharge performance at high temperature. Its discharge capacity is closely related with temperature and discharge current. The first discharge capacities of 580-814 mAh g-1 of the alloy powder were obtained at discharge current of 45-10 mA g-1 in 6 M KOH solution at 353 K. Although the electrochemical cycle life of the alloy is unsatisfactory at present, it opens up prospects for developing a new hydrogen storage alloy with high hydrogen capacity for use as high performance metal hydride electrodes in rechargeable Ni-MH battery.

A Ti-V-based bcc phase alloy for use as metal hydride electrode with high discharge capacity.

PubMed

Yu, X B; Wu, Z; Xia, B J; Xu, N X

2004-07-08

The electrochemical characteristics of single bcc phase Ti-30V-15Cr-15Mn alloy were investigated. It was demonstrated that the single bcc phase alloy has high electrochemical discharge performance at high temperature. Its discharge capacity is closely related with temperature and discharge current. The first discharge capacities of 580-814 mAh g(-1) of the alloy powder were obtained at discharge current of 45-10 mA g(-1) in 6 M KOH solution at 353 K. Although the electrochemical cycle life of the alloy is unsatisfactory at present, it opens up prospects for developing a new hydrogen storage alloy with high hydrogen capacity for use as high performance metal hydride electrodes in rechargeable Ni-MH battery.

Corrosion kinetics and topography analysis of Ti-6Al-4V alloy subjected to different mouthwash solutions.

PubMed

Faverani, Leonardo Perez; Barao, Valentim Adelino Ricardo; Pires, Maria Flávia Araújo; Yuan, Judy Chia-Chun; Sukotjo, Cortino; Mathew, Mathew T; Assunção, Wirley Gonçalves

2014-10-01

This study evaluated the corrosion kinetics and surface topography of Ti-6Al-4V alloy exposed to mouthwash solutions (0.12% chlorhexidine digluconate, 0.053% cetylpyridinium chloride and 3% hydrogen peroxide) compared to artificial saliva (pH6.5) (control). Twenty Ti-6Al-4V alloy disks were used and divided into 4 groups (n=5). For the electrochemical assay, standard tests as open circuit potential and electrochemical impedance spectroscopy (EIS) were applied at baseline, 7 and 14days after immersion in the solutions. Scanning electron microscopy, atomic force microscopy and profilometry (average roughness - Ra) were used for surface characterization. Total weight loss of disks was calculated. Data were analyzed by ANOVA and Bonferroni's test (α=0.05). Hydrogen peroxide generated the lowest polarization resistance (Rp) values for all periods (P<0.05). For the capacitance (Cdl), similar results were observed among groups at baseline (P=0.098). For the 7 and 14-day periods, hydrogen peroxide promoted the highest Cdl values (P<0.0001). Hydrogen peroxide promoted expressive superficial changes and greater Ra values than the others (P<0.0001). It could be concluded that solutions containing cetylpyridinium chloride and chlorhexidine digluconate might be the mouthwashes of choice during the post-operatory period of dental implants. However, hydrogen peroxide is counter-indicated in these situations. Further studies evaluating the dynamics of these solutions (tribocorrosion) and immersing the disks in daily cycles (two or three times a day) to mimic a clinical situation closest to the application of mouthwashes in the oral cavity are warranted to prove our results. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

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

Lee, June Key, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.

2015-05-14

Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ∼35%. Further removal of hydrogen seems to be involved in the breaking ofmore » Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.« less

Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

NASA Astrophysics Data System (ADS)

Lee, June Key; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok; Ryu, Sang-Wan; Jeong, Tak; Jung, Eunjin; Kim, Hyunsoo

2015-05-01

Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ˜35%. Further removal of hydrogen seems to be involved in the breaking of Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, Joseph C.; Wang, Francis T.; Hickman, Robert G.; Lewis, Patricia R.

1996-01-01

An electrochemical cell/electrolyte/mediator combination for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required.

Fuel Cells for Society

NASA Technical Reports Server (NTRS)

1999-01-01

Through a SBIR contract with Lewis Research Center, ElectroChem, Inc. developed a hydrogen/oxygen fuel cell. The objective for Lewis Research Center's collaboration with ElectroChem was to develop a fuel cell system that could deliver 200-W (minimum) approximately to 10kWh of electrical energy.

Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach

PubMed Central

Lee, Hiang Kwee; Koh, Charlynn Sher Lin; Lee, Yih Hong; Liu, Chong; Phang, In Yee; Han, Xuemei; Tsung, Chia-Kuang; Ling, Xing Yi

2018-01-01

Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF’s water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor–abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries. PMID:29536047

Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution

PubMed Central

Tsai, Charlie; Li, Hong; Park, Sangwook; Park, Joonsuk; Han, Hyun Soo; Nørskov, Jens K.; Zheng, Xiaolin; Abild-Pedersen, Frank

2017-01-01

Recently, sulfur (S)-vacancies created on the basal plane of 2H-molybdenum disulfide (MoS2) using argon plasma exposure exhibited higher intrinsic activity for the electrochemical hydrogen evolution reaction than the edge sites and metallic 1T-phase of MoS2 catalysts. However, a more industrially viable alternative to the argon plasma desulfurization process is needed. In this work, we introduce a scalable route towards generating S-vacancies on the MoS2 basal plane using electrochemical desulfurization. Even though sulfur atoms on the basal plane are known to be stable and inert, we find that they can be electrochemically reduced under accessible applied potentials. This can be done on various 2H-MoS2 nanostructures. By changing the applied desulfurization potential, the extent of desulfurization and the resulting activity can be varied. The resulting active sites are stable under extended desulfurization durations and show consistent HER activity. PMID:28429782

Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution

DOE PAGES

Tsai, Charlie; Li, Hong; Park, Sangwook; ...

2017-04-21

Recently, sulfur (S)-vacancies created on the basal plane of 2H-molybdenum disulfide (MoS 2) using argon plasma exposure exhibited higher intrinsic activity for the electrochemical hydrogen evolution reaction than the edge sites and metallic 1T-phase of MoS 2 catalysts. But, a more industrially viable alternative to the argon plasma desulfurization process is needed. In this work, we introduce a scalable route towards generating S-vacancies on the MoS 2 basal plane using electrochemical desulfurization. We found that they can be electrochemically reduced under accessible applied potentials, even though sulfur atoms on the basal plane are known to be stable and inert. Thismore » can be done on various 2H-MoS 2 nanostructures. Furthermore, by changing the applied desulfurization potential, the extent of desulfurization and the resulting activity can be varied. The resulting active sites are stable under extended desulfurization durations and show consistent HER activity.« less

Towards an Electrochemical Immunosensor System with Temperature Control for Cytokine Detection.

PubMed

Metzner, Julia; Luckert, Katrin; Lemuth, Karin; Hämmerle, Martin; Moos, Ralf

2018-04-24

The cytokine interleukin-13 (IL-13) plays a major role in airway inflammation and is a target of new anti-asthmatic drugs. Hence, IL-13 determination could be interesting in assessing therapy success. Thus, in this work an electrochemical immunosensor for IL-13 was developed and integrated into a fluidic system with temperature control for read-out. Therefore, two sets of results are presented. First, the sensor was set up in sandwich format on single-walled carbon nanotube electrodes and was read out by applying the hydrogen peroxide⁻hydroquinone⁻horseradish peroxidase (HRP) system. Second, a fluidic system was built up with an integrated heating function realized by Peltier elements that allowed a temperature-controlled read-out of the immunosensor in order to study the influence of temperature on the amperometric read-out. The sensor was characterized at the temperature optimum of HRP at 30 °C and at 12 °C as a reference for lower performance. These results were compared to a measurement without temperature control. At the optimum operation temperature of 30 °C, the highest sensitivity (slope) was obtained compared to lower temperatures and a limit of detection of 5.4 ng/mL of IL-13 was calculated. Taken together, this approach is a first step towards an automated electrochemical immunosensor platform and shows the potential of a temperature-controlled read-out.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

Process for electrochemically gasifying coal using electromagnetism

DOEpatents

Botts, Thomas E.; Powell, James R.

1987-01-01

A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

Coulometric titration of potassium hydrogen phthalate in a non-aqueous solution, with a vitreous carbon anode.

PubMed

Jennings, V J; Dodson, A; Tedds, G

1974-06-01

A vitreous carbon anode has been used as working electrode in the coulometric titration of potassium hydrogen phthalate in glacial acetic acid-acetic anhydride medium with protous generated electrochemical oxidation of quinol.

Electrochemical gating-induced reversible and drastic resistance switching in VO2 nanowires

PubMed Central

Sasaki, Tsubasa; Ueda, Hiroki; Kanki, Teruo; Tanaka, Hidekazu

2015-01-01

Reversible and drastic modulation of the transport properties in vanadium dioxide (VO2) nanowires by electric field-induced hydrogenation at room temperature was demonstrated using the nanogaps separated by humid air in field-effect transistors with planer-type gates (PG-FET). These PG-FETs allowed us to investigate behavior of revealed hydrogen intercalation and diffusion aspects with time and spatial evolutions in nanowires. These results show that air nanogaps can operate as an electrochemical reaction field, even in a gaseous atmosphere, and offer new directions to explore emerging functions for electronic and energy devices in oxides. PMID:26584679

High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

NASA Astrophysics Data System (ADS)

Abbas, Qamar; Béguin, François

2016-06-01

We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

Mediated electrochemical oxidation of organic wastes without electrode separators

DOEpatents

Farmer, J.C.; Wang, F.T.; Hickman, R.G.; Lewis, P.R.

1996-05-14

An electrochemical cell/electrolyte/mediator combination is described for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required. 3 figs.

Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Nd-Mg-Ni-Based NdMg12-Type Alloys Synthesized via Mechanical Milling

NASA Astrophysics Data System (ADS)

Zhang, Yanghuan; Shang, Hongwei; Hou, Zhonghui; Yuan, Zeming; Yang, Tai; Qi, Yan

2016-12-01

In this study, Mg was partially substituted by Ni with the intent of improving the hydrogen storage kinetics performance of NdMg12-type alloy. Mechanical milling technology was adopted to fabricate the nanocrystalline and amorphous NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys. The effects of Ni content and milling duration on the microstructures and hydrogen storage kinetics of as-milled alloys have been systematically investigated. The structures were characterized by XRD and HRTEM. The electrochemical hydrogen storage properties were tested by an automatic galvanostatic system. Moreover, the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter connected with a H2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. The results reveal that the increase of Ni content dramatically ameliorates the gaseous and electrochemical hydrogen storage kinetics performance of the as-milled alloys. Furthermore, high rate discharge ability (HRD) reach the maximum value with the variation of milling time. The maximum HRDs of the NdMg11Ni + x wt pct Ni ( x = 100, 200) alloys are 80.24 and 85.17 pct. The improved gaseous hydrogen storage kinetics of alloys via increasing Ni content and milling time can be attributed to a decrease in the hydrogen desorption activation energy.

Carbon dots-decorated multiwalled carbon nanotubes nanocomposites as a high-performance electrochemical sensor for detection of H2O2 in living cells.

PubMed

Bai, Jing; Sun, Chunhe; Jiang, Xiue

2016-07-01

A novel enzyme-free hydrogen peroxide sensor composed of carbon dots (CDs) and multi-walled carbon nanotubes (MWCNTs) was prepared. It was found that the carbon dots-decorated multi-walled carbon nanotubes nanocomposites (CDs/MWCNTs) modified glassy carbon (GC) electrode (CDs/MWCNTs/GCE) exhibited a significant synergistic electrocatalytic activity towards hydrogen peroxide reduction as compared to carbon dots or multi-walled carbon nanotubes alone, and the CDs/MWCNTs/GCE has shown a low detection limit as well as excellent stability, selectivity, and reproducibility. These remarkable analytical advantages enable the practical application of CDs/MWCNTs/GCE for the real-time tracking of hydrogen peroxide (H2O2) released from human cervical cancer cells with satisfactory results. The enhanced electrochemical activity can be assigned to the edge plane-like defective sites and lattice oxygen in the CDs/MWCNTs nanocomposites due to the small amount of decoration of carbon dots on the multi-walled carbon nanotubes. Based on a facile preparation method and with good electrochemical properties, the CDs/MWCNTs nanocomposites represent a new class of carbon electrode for electrochemical sensor applications. Graphical Abstract CDs/MWCNTs exhibited good electrocatalytic activity and stability to H2O2 reduction and can be used for real-time detection of H2O2 released from living cells.

Hydrogen peroxide as sustainable fuel: electrocatalysts for production with a solar cell and decomposition with a fuel cell.

PubMed

Yamada, Yusuke; Fukunishi, Yurie; Yamazaki, Shin-ichi; Fukuzumi, Shunichi

2010-10-21

Hydrogen peroxide was electrochemically produced by reducing oxygen in an aqueous solution with [Co(TCPP)] as a catalyst and photovoltaic solar cell operating at 0.5 V. Hydrogen peroxide thus produced is utilized as a fuel for a one-compartment fuel cell with Ag-Pb alloy nanoparticles as the cathode.

Enhanced Photoelectrochemical Behavior of H-TiO2 Nanorods Hydrogenated by Controlled and Local Rapid Thermal Annealing

NASA Astrophysics Data System (ADS)

Wang, Xiaodan; Estradé, Sonia; Lin, Yuanjing; Yu, Feng; Lopez-Conesa, Lluis; Zhou, Hao; Gurram, Sanjeev Kumar; Peiró, Francesca; Fan, Zhiyong; Shen, Hao; Schaefer, Lothar; Braeuer, Guenter; Waag, Andreas

2017-05-01

Recently, colored H-doped TiO2 (H-TiO2) has demonstrated enhanced photoelectrochemical (PEC) performance due to its unique crystalline core—disordered shell nanostructures and consequent enhanced conduction behaviors between the core-shell homo-interfaces. Although various hydrogenation approaches to obtain H-TiO2 have been developed, such as high temperature hydrogen furnace tube annealing, high pressure hydrogen annealing, hydrogen-plasma assisted reaction, aluminum reduction and electrochemical reduction etc., there is still a lack of a hydrogenation approach in a controlled manner where all processing parameters (temperature, time and hydrogen flux) were precisely controlled in order to improve the PEC performance of H-TiO2 and understand the physical insight of enhanced PEC performance. Here, we report for the first time a controlled and local rapid thermal annealing (RTA) approach to prepare hydrogenated core-shell H-TiO2 nanorods grown on F:SnO2 (FTO) substrate in order to address the degradation issue of FTO in the typical TiO2 nanorods/FTO system observed in the conventional non-RTA treated approaches. Without the FTO degradation in the RTA approach, we systematically studied the intrinsic relationship between the annealing temperature, structural, optical, and photoelectrochemical properties in order to understand the role of the disordered shell on the improved photoelectrochemical behavior of H-TiO2 nanorods. Our investigation shows that the improvement of PEC performance could be attributed to (i) band gap narrowing from 3.0 to 2.9 eV; (ii) improved optical absorption in the visible range induced by the three-dimensional (3D) morphology and rough surface of the disordered shell; (iii) increased proper donor density; (iv) enhanced electron-hole separation and injection efficiency due to the formation of disordered shell after hydrogenation. The RTA approach developed here can be used as a suitable hydrogenation process for TiO2 nanorods/FTO system for important applications such as photocatalysis, hydrogen generation from water splitting and solar energy conversion.

Enhanced Photoelectrochemical Behavior of H-TiO2 Nanorods Hydrogenated by Controlled and Local Rapid Thermal Annealing.

PubMed

Wang, Xiaodan; Estradé, Sonia; Lin, Yuanjing; Yu, Feng; Lopez-Conesa, Lluis; Zhou, Hao; Gurram, Sanjeev Kumar; Peiró, Francesca; Fan, Zhiyong; Shen, Hao; Schaefer, Lothar; Braeuer, Guenter; Waag, Andreas

2017-12-01

Recently, colored H-doped TiO 2 (H-TiO 2 ) has demonstrated enhanced photoelectrochemical (PEC) performance due to its unique crystalline core-disordered shell nanostructures and consequent enhanced conduction behaviors between the core-shell homo-interfaces. Although various hydrogenation approaches to obtain H-TiO 2 have been developed, such as high temperature hydrogen furnace tube annealing, high pressure hydrogen annealing, hydrogen-plasma assisted reaction, aluminum reduction and electrochemical reduction etc., there is still a lack of a hydrogenation approach in a controlled manner where all processing parameters (temperature, time and hydrogen flux) were precisely controlled in order to improve the PEC performance of H-TiO 2 and understand the physical insight of enhanced PEC performance. Here, we report for the first time a controlled and local rapid thermal annealing (RTA) approach to prepare hydrogenated core-shell H-TiO 2 nanorods grown on F:SnO 2 (FTO) substrate in order to address the degradation issue of FTO in the typical TiO 2 nanorods/FTO system observed in the conventional non-RTA treated approaches. Without the FTO degradation in the RTA approach, we systematically studied the intrinsic relationship between the annealing temperature, structural, optical, and photoelectrochemical properties in order to understand the role of the disordered shell on the improved photoelectrochemical behavior of H-TiO 2 nanorods. Our investigation shows that the improvement of PEC performance could be attributed to (i) band gap narrowing from 3.0 to 2.9 eV; (ii) improved optical absorption in the visible range induced by the three-dimensional (3D) morphology and rough surface of the disordered shell; (iii) increased proper donor density; (iv) enhanced electron-hole separation and injection efficiency due to the formation of disordered shell after hydrogenation. The RTA approach developed here can be used as a suitable hydrogenation process for TiO 2 nanorods/FTO system for important applications such as photocatalysis, hydrogen generation from water splitting and solar energy conversion.

Systems and methods for selective hydrogen transport and measurement

DOEpatents

Glatzmaier, Gregory C

2013-10-29

Systems and methods for selectively removing hydrogen gas from a hydrogen-containing fluid volume are disclosed. An exemplary system includes a proton exchange membrane (PEM) selectively permeable to hydrogen by exclusively conducting hydrogen ions. The system also includes metal deposited as layers onto opposite sides or faces of the PEM to form a membrane-electrode assembly (MEA), each layer functioning as an electrode so that the MEA functions as an electrochemical cell in which the ionic conductors are hydrogen ions, and the MEA functioning as a hydrogen selective membrane (HSM) when located at the boundary between a hydrogen-containing fluid volume and a second fluid.

The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

NASA Technical Reports Server (NTRS)

Liu, C. C.

1983-01-01

A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

Computational Fluid Dynamics Modeling of Nickel Hydrogen Batteries

NASA Technical Reports Server (NTRS)

Cullion, R.; Gu, W. B.; Wang, C. Y.; Timmerman, P.

2000-01-01

An electrochemical Ni-H2 battery model has been expanded to include thermal effects. A thermal energy conservation equation was derived from first principles. An electrochemical and thermal coupled model was created by the addition of this equation to an existing multiphase, electrochemical model. Charging at various rates was investigated and the results validated against experimental data. Reaction currents, pressure changes, temperature profiles, and concentration variations within the cell are predicted numerically and compared with available data and theory.

Development of a tritium monitor combined with an electrochemical tritium pump using a proton conducting oxide

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

Tanaka, M.; Sugiyama, T.

2015-03-15

The detection of low level tritium is one of the key issues for tritium management in tritium handling facilities. Such a detection can be performed by tritium monitors based on proton conducting oxide technique. We tested a tritium monitoring system composed of a commercial proportional counter combined with an electrochemical hydrogen pump equipped with CaZr{sub 0.9}In{sub 0.1}O{sub 3-α} as proton conducting oxide. The hydrogen pump operated at 973 K under electrolysis conditions using tritiated water vapor (HTO). The proton conducting oxide extracts tritium molecules (HT) from HTO and tritium concentration is measured by the proportional counter. The advantage of themore » proposed tritium monitoring system is that it is able to convert HTO into molecular hydrogen.« less

Process for electrochemically gasifying coal

DOEpatents

Botts, T.E.; Powell, J.R.

1985-10-25

A process is claimed for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution. 7 figs.

Electrochemical Upgrading of Bio-Oil

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

Elangovan, S.; Larsen, Dennis; Bay, Insoo

Bio-oil produced by fast pyrolysis of biomass is a potential source of low carbon, renewable hydrocarbon fuel. However, the properties such as low heating value, incomplete volatility, acidity, instability, and incompatibility with standard fuels restrict its use. The undesirable properties of pyrolysis oil result from its chemical composition that mostly consists of different classes of oxygenated organic compounds. Current process of Hydrodeoxygenation to remove oxygen involves high-temperature, high-pressure processing in the presence of hydrogen and catalyst. An alternative process of deoxygenation of bio-oil using solid-state, oxygen conductor based electrochemical cell is under investigation. The electrolysis process removes oxygen from themore » oxygenated organic molecule as well from steam to produce hydrogen in-situ allowing for a distributed, small scale integrated upgrading unit. Mixtures of model compounds and a slip stream of pyrolysis vapor were tested. The results show the potential for integrating a pyrolyzer and an electrochemical device for stabilizing pyrolysis oil.« less

Hydrogen detection study. [for environmental control/life support systems

NASA Technical Reports Server (NTRS)

Shumar, J. W.; Powell, J. D.

1974-01-01

The effectiveness was assessed of a hydrogen (H2) detection concept for regenerative environmental control life support systems (EC/LSS). The concept evaluated was that utilized for the electrochemical depolarized concentrator (EDC) design, constructed, and tested for the EC/LSS space station prototype program. The EDC contains combustible gas detectors (CGDs) which were evaluated with H2. The CGDs were evaluated for linearity, position sensitivity, reproducibility, ambient effects, repeatability, speed of response, recovery time, and interchangeability. The effectiveness of CGDs located within the EDC for sensing H2 leaks at various line replaceable units in the subsystem was determined. The effects of H2 leak rate, H2 concentration of leaking gas and air currents in the vicinity of the EDC were determined. Proposed improvements for the H2 detection concept were documented and alternative H2 detection approaches were identified and analyzed.

Electrochemical mercerization, souring, and bleaching of textiles

DOEpatents

Cooper, J.F.

1995-10-10

Economical, pollution-free treatment of textiles occurs in a low voltage electrochemical cell that mercerizes (or scours), sours, and optionally bleaches without effluents and without the purchase of bulk caustic, neutralizing acids, or bleaches. The cell produces base in the cathodic chamber for mercerization and an equivalent amount of acid in the anodic chamber for neutralizing the fabric. Gas diffusion electrodes are used for one or both electrodes and may simultaneously generate hydrogen peroxide for bleaching. The preferred configuration is a stack of bipolar electrodes, in which one or both of the anode and cathode are gas diffusion electrodes, and where no hydrogen gas is evolved at the cathode. 5 figs.

Electrochemical impregnation and cycle life of lightweight nickel electrodes for nickel-hydrogen cells

NASA Technical Reports Server (NTRS)

Britton, Doris L.

1990-01-01

Development of a high specific energy nickel electrode is the main goal of the lightweight nickel electrode program at NASA-Lewis. The approach was 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. Lightweight plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products that are fabricated into nickel electrodes by electrochemically impregnating them with active material. The electrodes are life cycle tested in a low Earth orbit regime at 40 and 80 percent depths-of-discharge.

Electrochemical impregnation and cycle life of lightweight nickel electrodes for nickel-hydrogen cells

NASA Technical Reports Server (NTRS)

Britton, Doris L.

1990-01-01

Development of a high specific energy nickel electrode is the main goal of the lightweight nickel electrode program at NASA-Lewis. The approach was 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. Lightweight plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products that are fabricated into nickel electrodes by electrochemically impregnating them with active material. The electrodes are life cycle tested in a low earth orbit regime at 40 and 80 percent depths-of-discharge.

Electrochemical mercerization, souring, and bleaching of textiles

DOEpatents

Cooper, John F.

1995-01-01

Economical, pollution-free treatment of textiles occurs in a low voltage electrochemical cell that mercerizes (or scours), sours, and optionally bleaches without effluents and without the purchase of bulk caustic, neutralizing acids, or bleaches. The cell produces base in the cathodic chamber for mercerization and an equivalent amount of acid in the anodic chamber for neutralizing the fabric. Gas diffusion electrodes are used for one or both electrodes and may simultaneously generate hydrogen peroxide for bleaching. The preferred configuration is a stack of bipolar electrodes, in which one or both of the anode and cathode are gas diffusion electrodes, and where no hydrogen gas is evolved at the cathode.

Library of electrocatalytic sites in nano-structured domains: electrocatalysis of hydrogen peroxide.

PubMed

Pandey, Prem C; Singh, Bhupendra

2008-12-01

Electrochemical detection of hydrogen peroxide at eight types of ormosil-modified electrodes, referred as hexacyanoferrate-system; Prussian blue systems (PB-1, PB-2, and PB-3), palladium (Pd-) system, graphite (Gr-) system, gold nanoparticle (AuNPs) system and palladium-gold nanoparticle (Pd-AuNPs) system were studied. The results on electrochemical detection suggested that hydrogen peroxide does not undergo homogeneous electrochemical mediation; however, the presence of redox mediator within nano-structured domains facilitates the electro-analysis of the same via redox electrocatalysis. Four approaches causing manipulation in nano-structured domains are described: (a) increase in the molecular size of the components generating nano-structured domains; (b) modulation via chemical reactivity; (c) modulation by non-reactive moieties and known nanoparticles; and (d) modulation by mixed approaches (a-c), all leading to decrease in a nano-structured domains. The results demonstrated that an increase in the size of nano-structured domains or decrease in micro-porous geometry increases the efficiency of electrocatalysis. The basic reaction protocol adopted in generating nano-structured domains, followed by manipulation protocols, supported the introduction of a library for creating electrocatalytic sites with varying electrocatalytic efficiency within the same basic nano-structured platform.

Preparation of NiCoP Hollow Quasi-Polyhedra and Their Electrocatalytic Properties for Hydrogen Evolution in Alkaline Solution.

PubMed

Li, Yapeng; Liu, Jindou; Chen, Chen; Zhang, Xiaohua; Chen, Jinhua

2017-02-22

Double metal phosphide (NiCoP) with hollow quasi-polyhedron structure was prepared by acidic etching and precipitation of ZIF-67 polyhedra and further phosphorization treatment with NaH 2 PO 2 . The morphology and microstructure of NiCoP quasi-polyhedron and its precursors were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and a micropore and chemisorption analyzer. Electrocatalytic properties were examined by typical electrochemical methods, such as linear sweep voltammetry, cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy in 1.0 M KOH aqueous solution. Results reveal that, compared with CoP hollow polyhedra, NiCoP hollow quasi-polyhedra exhibit better electrochemical properties for hydrogen evolution with a low onset overpotential of 74 mV and a small Tafel slope of 42 mV dec -1 . When the current density is 10 mA cm -2 , the corresponding overpotential is merely 124 mV, and 93% of its electrocatalytic activity can be maintained for 12 h. This indicates that NiCoP with hollow quasi-polyhedron structure, bimetallic merit, and low cost may be a good candidate as electrocatalyst in the practical application of hydrogen evolution.

Combined Photoemission Spectroscopy and Electrochemical Study of a Mixture of (Oxy)carbides as Potential Innovative Supports and Electrocatalysts.

PubMed

Calvillo, Laura; Valero-Vidal, Carlos; Agnoli, Stefano; Sezen, Hikmet; Rüdiger, Celine; Kunze-Liebhäuser, Julia; Granozzi, Gaetano

2016-08-03

Active and stable non-noble metal materials, able to substitute Pt as catalyst or to reduce the Pt amount, are vitally important for the extended commercialization of energy conversion technologies, such as fuel cells and electrolyzers. Here, we report a fundamental study of nonstoichiometric tungsten carbide (WxC) and its interaction with titanium oxycarbide (TiOxCy) under electrochemical working conditions. In particular, the electrochemical activity and stability of the WxC/TiOxCy system toward the ethanol electrooxidation reaction (EOR) and hydrogen evolution reaction (HER) are investigated. The chemical changes caused by the applied potential are established by combining photoemission spectroscopy and electrochemistry. WxC is not active toward the ethanol electrooxidation reaction at room temperature but it is highly stable under these conditions thanks to the formation of a passive thin film on the surface, consisting mainly of WO2 and W2O5, which prevents the full oxidation of WxC. In addition, WxC is able to adsorb ethanol, forming ethoxy groups on the surface, which constitutes the first step for the ethanol oxidation. The interaction between WxC and TiOxCy plays an important role in the electrochemical stability of WxC since specific orientations of the substrate are able to stabilize WxC and prevent its corrosion. The beneficial interaction with the substrate and the specific surface chemistry makes tungsten carbide a good electrocatalyst support or cocatalyst for direct ethanol fuel cells. However, WxC is active toward the HER and chemically stable under hydrogen reduction conditions, since no changes in the chemical composition or dissolution of the film are observed. This makes tungsten carbide a good candidate as electrocatalyst support or cocatalyst for the electrochemical production of hydrogen.

Lewis Research Center battery overview

NASA Technical Reports Server (NTRS)

Odonnell, Patricia

1993-01-01

The topics covered are presented in viewgraph form and include the following: the Advanced Communications Technology Satellite; the Space Station Freedom (SSF) photovoltaic power module division; Ni/H2 battery and cell design; individual pressure vessel (IPV) nickel-hydrogen cell testing SSF support; the LeRC Electrochemical Technology Branch; improved design IPV nickel-hydrogen cells; advanced technology for IPV nickel-hydrogen flight cells; a lightweight nickel-hydrogen cell; bipolar nickel-hydrogen battery development and technology; aerospace nickel-metal hydride cells; the NASA Sodium-Sulfur Cell Technology Flight Experiment; and the lithium-carbon dioxide battery thermodynamic model.

Control of malodorous hydrogen sulfide compounds using microbial fuel cell.

PubMed

Eaktasang, Numfon; Min, Hyeong-Sik; Kang, Christina; Kim, Han S

2013-10-01

In this study, a microbial fuel cell (MFC) was used to control malodorous hydrogen sulfide compounds generated from domestic wastewaters. The electricity production demonstrated a distinct pattern of a two-step increase during 170 h of system run: the first maximum current density was 118.6 ± 7.2 mA m⁻² followed by a rebound of current density increase, reaching the second maximum of 176.8 ± 9.4 mA m⁻². The behaviors of the redox potential and the sulfate level in the anode compartment indicated that the microbial production of hydrogen sulfide compounds was suppressed in the first stage, and the hydrogen sulfide compounds generated from the system were removed effectively as a result of their electrochemical oxidation, which contributed to the additional electricity production in the second stage. This was also directly supported by sulfur deposits formed on the anode surface, which was confirmed by analyses on those solids using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy as well as an elemental analyzer. To this end, the overall reduction efficiencies for HS⁻ and H₂S(g) were as high as 67.5 and 96.4 %, respectively. The correlations among current density, redox potential, and sulfate level supported the idea that the electricity signal generated in the MFC can be utilized as a potential indicator of malodor control for the domestic wastewater system.

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.

Uniform manganese hexacyanoferrate hydrate nanocubes featuring superior performance for low-cost supercapacitors and nonenzymatic electrochemical sensors

NASA Astrophysics Data System (ADS)

Pang, Huan; Zhang, Yizhou; Cheng, Tao; Lai, Wen-Yong; Huang, Wei

2015-09-01

Uniform manganese hexacyanoferrate hydrate nanocubes are prepared via a simple chemical precipitation method at room temperature. Due to both micro/mesopores of the Prussian blue analogue and nanocubic structures, the manganese hexacyanoferrate hydrate nanocubes allow the efficient charge transfer and mass transport for electrolyte solution and chemical species. Thus, the manganese hexacyanoferrate hydrate nanocube electrode shows a good rate capability and cycling stability for electrochemical capacitors. Furthermore, electrodes modified with manganese hexacyanoferrate hydrate nanocubes demonstrate a sensitive electrochemical response to hydrogen peroxide (H2O2) in buffer solutions with a high selectivity.Uniform manganese hexacyanoferrate hydrate nanocubes are prepared via a simple chemical precipitation method at room temperature. Due to both micro/mesopores of the Prussian blue analogue and nanocubic structures, the manganese hexacyanoferrate hydrate nanocubes allow the efficient charge transfer and mass transport for electrolyte solution and chemical species. Thus, the manganese hexacyanoferrate hydrate nanocube electrode shows a good rate capability and cycling stability for electrochemical capacitors. Furthermore, electrodes modified with manganese hexacyanoferrate hydrate nanocubes demonstrate a sensitive electrochemical response to hydrogen peroxide (H2O2) in buffer solutions with a high selectivity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04322k

Virtual electrochemical nitric oxide analyzer using copper, zinc superoxide dismutase immobilized on carbon nanotubes in polypyrrole matrix.

PubMed

Madasamy, Thangamuthu; Pandiaraj, Manickam; Balamurugan, Murugesan; Karnewar, Santosh; Benjamin, Alby Robson; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Kotamraju, Srigiridhar; Karunakaran, Chandran

2012-10-15

In this work, we have designed and developed a novel and cost effective virtual electrochemical analyzer for the measurement of NO in exhaled breath and from hydrogen peroxide stimulated endothelial cells using home-made potentiostat. Here, data acquisition system (NI MyDAQ) was used to acquire the data from the electrochemical oxidation of NO mediated by copper, zinc superoxide dismutase (Cu,ZnSOD). The electrochemical control programs (graphical user-interface software) were developed using LabVIEW 10.0 to sweep the potential, acquire the current response and process the acquired current signal. The Cu,ZnSOD (SOD1) immobilized on the carbon nanotubes in polypyrrole modified platinum electrode was used as the NO biosensor. The electrochemical behavior of the SOD1 modified electrode exhibited the characteristic quasi-reversible redox peak at the potential, +0.06 V vs. Ag/AgCl. The biological interferences were eliminated by nafion coated SOD1 electrode and then NO was measured selectively. Further, this biosensor showed a wide linear range of response over the concentration of NO from 0.1 μM to 1 mM with a detection limit of 0.1 μM and high sensitivity of 1.1 μA μM(-1). The electroanalytical results obtained here using the developed virtual electrochemical instrument were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. 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.

Structures and Electrochemical Hydrogen Storage Properties of the As-Spun RE-Mg-Ni-Co-Al-Based AB2-Type Alloys Applied to Ni-MH Battery

NASA Astrophysics Data System (ADS)

Zhang, Yanghuan; Yuan, Zeming; Shang, Hongwei; Li, Yaqin; Qi, Yan; Zhao, Dongliang

2017-05-01

In this paper, the La0.8- x Ce0.2Y x MgNi3.5Co0.4Al0.1 ( x = 0, 0.05, 0.1, 0.15, 0.2) alloys were synthesized via smelting and melt spinning. The effect of Y content on the structure and electrochemical hydrogen storage characteristics of the as-cast and spun alloys was investigated. The identifications of XRD and SEM demonstrate that the experimental alloys possess a major phase LaMgNi4 and a minor phase LaNi5. The variation of Y content results in an obvious transformation of the phase abundance rather than phase composition in the alloys, namely LaMgNi4 phase increases while LaNi5 phase decreases with Y content growing. Furthermore, the replacement of Y for La causes the lattice constants and cell volume to clearly decrease and markedly refines the alloy grains. The electrochemical tests reveal that these alloys can obtain the maximum values of discharge capacity at the first cycling without any activation needed. With Y content growing, the discharge capacity of the alloys obviously declines, but its cycle stability remarkably improves. Moreover, the electrochemical dynamics of the alloys, involving the high-rate discharge ability, hydrogen diffusion coefficient ( D), limiting current density ( I L), and charge transfer rate, initially augment and then decrease with rising Y content.

A convenient method for determining the concentration of hydrogen in water: use of methylene blue with colloidal platinum

PubMed Central

2012-01-01

A simple titration (oxidimetry) method using a methylene blue-platinum colloid reagent is effective in determining the concentration of hydrogen gas in an aqueous solution. The method performs as effectively as the more complex and expensive electrochemical method. PMID:22273079

Space Electrochemical Research and Technology Conference: Abstracts

NASA Technical Reports Server (NTRS)

1989-01-01

The objectives of the conference were to examine current technologies, research efforts, and advanced ideas, and to identify technical barriers which affect the advancement of electrochemical energy storage systems for space applications. Papers were presented and workshops were conducted in four technical areas: advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, the nickel electrode, and advanced rechargeable batteries.

Renewable hydrogen production via thermochemical/electrochemical coupling

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

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

PubMed

Badalyan, Artavazd; Stahl, Shannon S

2016-07-21

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1–2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2′-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2′-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

NASA Astrophysics Data System (ADS)

Badalyan, Artavazd; Stahl, Shannon S.

2016-07-01

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

The role of Hydrogen and Creep in Intergranular Stress Corrosion Cracking of Alloy 600 and Alloy 690 in PWR Primary Water Environments ? a Review

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

Rebak, R B; Hua, F H

2004-07-12

Intergranular attack (IGA) and intergranular stress corrosion cracking (IGSCC) of Alloy 600 in PWR steam generator environment has been extensively studied for over 30 years without rendering a clear understanding of the essential mechanisms. The lack of understanding of the IGSCC mechanism is due to a complex interaction of numerous variables such as microstructure, thermomechanical processing, strain rate, water chemistry and electrochemical potential. Hydrogen plays an important role in all these variables. The complexity, however, significantly hinders a clearer and more fundamental understanding of the mechanism of hydrogen in enhancing intergranular cracking via whatever mechanism. In this work, an attemptmore » is made to review the role of hydrogen based on the current understanding of grain boundary structure and chemistry and intergranular fracture of nickel alloys, effect of hydrogen on electrochemical behavior of Alloy 600 and Alloy 690 (e.g. the passive film stability, polarization behavior and open-circuit potential) and effect of hydrogen on PWSCC behavior of Alloy 600 and Alloy 690. Mechanistic studies on the PWSCC are briefly reviewed. It is concluded that further studies on the role of hydrogen on intergranular cracking in both inert and primary side environments are needed. These studies should focus on the correlation of the results obtained at different laboratories by different methods on materials with different metallurgical and chemical parameters.« less

Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes

PubMed Central

Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

2015-01-01

In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 μm to 12 μm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 μm rough surface PtNWA presented the largest sensitivity (654 μA·mM−1·cm−2) among all the nanowires studied, and showed a limit of detection of 2.4 μM. The 12 μm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors. PMID:26404303

Solar-Electrochemical Power System for a Mars Mission

NASA Technical Reports Server (NTRS)

Withrow, Colleen A.; Morales, Nelson

1994-01-01

This report documents a sizing study of a variety of solar electrochemical power systems for the intercenter NASA study known as 'Mars Exploration Reference Mission'. Power systems are characterized for a variety of rovers, habitation modules, and space transport vehicles based on requirements derived from the reference mission. The mission features a six-person crew living on Mars for 500 days. Mission power requirements range from 4 kWe to 120 kWe. Primary hydrogen and oxygen fuel cells, regenerative hydrogen and oxygen fuel cells, sodium sulfur batteries advanced photovoltaic solar arrays of gallium arsenide on germanium with tracking and nontracking mechanisms, and tent solar arrays of gallium arsenide on germanium are evaluated and compared.

Real-time monitoring of H2O2 release from single cells using nanoporous gold microelectrodes decorated with platinum nanoparticles.

PubMed

Xiao, Chong; Liu, Yan-Ling; Xu, Jia-Quan; Lv, Song-Wei; Guo, Shan; Huang, Wei-Hua

2015-06-07

Here, we report a self-supported nanoporous gold microelectrode decorated with well-dispersed and tiny platinum nanoparticles as an electrochemical nonenzymatic hydrogen peroxide biosensor. Nanoporous gold was fabricated by electrochemical alloying/dealloying and then small-sized platinum nanoparticles were electrodeposited uniformly on them. This novel hybrid nanostructure endows the sensor with high sensitivity and selectivity towards the reduction of hydrogen peroxide with a low detection limit of 0.3 nM. The sensor has been successfully applied for the measurement of H2O2 release from a single isolated human breast cancer cell, demonstrating its great potential for further physiological and pathological applications.

Novel aqueous dual-channel aluminum-hydrogen peroxide battery

NASA Astrophysics Data System (ADS)

Marsh, Catherine; Licht, Stuart

1994-06-01

A dual-channel aluminum hydrogen peroxide battery is introduced with an open-circuit voltage of 1.9 volts, polarization losses of 0.9 mV cm(exp 2) mA(exp -1), and power densities of 1 W/cm(exp 2). Catholyte and anolyte cell compartments are separated by an Ir/Pd modified porous nickel cathode. Separation of catholyte and anolyte chambers prevents hydrogen peroxide poisoning of the aluminum anode. The battery is expressed by aluminum oxidation and aqueous solution phase hydrogen peroxide reduction for an overall battery discharge consisting of 2Al + 3H2O2 + 2OH(-) yields 2AlO2(-) + 4H2O E = 2.3 V. The search for electrical propulsion sources which fit the requirements for electrically powered vehicles has blurred the standard characteristics associated with electrochemical storage systems. Presently, electrochemical systems comprised of mechanically rechargeable primary batteries, secondary batteries, and fuel cells are candidates for electrochemical propulsion sources. While important advances in energy and power density continue for nonaqueous and molten electrolytes, aqueous electrolyte batteries often have an advantage in simplicity, conductivity, cost effectiveness, and environmental impact. Systems coupling aluminum anodes and aqueous electrolytes have been investigated. These systems include: aluminum/silver oxide, aluminum/manganese dioxide, aluminum air, aluminum/hydrogen peroxide aqueous batteries, and the recently introduced aluminum/ferricyanide and aluminum sulfur aqueous batteries. Conventional aqueous systems such as the nickel cadmium and lead-acid batteries are characterized by their relatively low energy densities and adverse environmental impact. Other systems have substantially higher theoretical energy capacities. While aluminum-silver oxide has demonstrated the highest steady-state power density, its high cost is an impediment for widespread utilization for electric propulsion.

Hydrogen Generator

NASA Technical Reports Server (NTRS)

1978-01-01

Another spinoff from spacecraft fuel cell technology is the portable hydrogen generator shown. Developed by General Electric Company, it is an aid to safer operation of systems that use hydrogen-for example, gas chromatographs, used in laboratory analysis of gases. or flame ionization detectors used as $ollution monitors. The generator eliminates the need for high-pressure hydrogen storage bottles, which can be a safety hazard, in laboratories, hospitals and industrial plants. The unit supplies high-purity hydrogen by means of an electrochemical process which separates the hydrogen and oxygen in distilled water. The oxygen is vented away and the hydrogen gas is stored within the unit for use as needed. GE's Aircraft Equipment Division is producing about 1,000 of the generators annually.

Regenerative fuel cells for space applications

NASA Technical Reports Server (NTRS)

Appleby, A. John

1987-01-01

After several years of development of the regenerative fuel cell (RFC) as the electrochemical storage system to be carried by the future space station, the official stance has now been adopted that nickel hydrogen batteries would be a better system choice. RFCs are compared with nickel hydrogen and other battery systems for space platform applications.

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates.

PubMed

Chadderdon, Xiaotong H; Chadderdon, David J; Matthiesen, John E; Qiu, Yang; Carraher, Jack M; Tessonnier, Jean-Philippe; Li, Wenzhen

2017-10-11

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

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

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions ofmore » each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.« less

Palliative effects of H2 on SOFCs operating with carbon containing fuels

NASA Astrophysics Data System (ADS)

Reeping, Kyle W.; Bohn, Jessie M.; Walker, Robert A.

2017-12-01

Chlorine can accelerate degradation of solid oxide fuel cell (SOFC) Ni-based anodes operating on carbon containing fuels through several different mechanisms. However, supplementing the fuel with a small percentage of excess molecular hydrogen effectively masks the degradation to the catalytic activity of the Ni and carbon fuel cracking reaction reactions. Experiments described in this work explore the chemistry behind the "palliative" effect of hydrogen on SOFCs operating with chlorine-contaminated, carbon-containing fuels using a suite of independent, complementary techniques. Operando Raman spectroscopy is used to monitor carbon accumulation and, by inference, Ni catalytic activity while electrochemical techniques including electrochemical impedance spectroscopy and voltammetry are used to monitor overall cell performance. Briefly, hydrogen not only completely hides degradation observed with chlorine-contaminated carbon-containing fuels, but also actively removes adsorbed chlorine from the surface of the Ni, allowing for the methane cracking reaction to continue, albeit at a slower rate. When hydrogen is removed from the fuel stream the cell fails immediately due to chlorine occupation of methane/biogas reaction sites.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

DOE PAGES

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.; ...

2017-09-13

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions ofmore » each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.« less

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.

Poly (3,4-ethylenedioxythiophene) graphene oxide composite coatings for controlling magnesium implant corrosion.

PubMed

Catt, Kasey; Li, Huaxiu; Cui, X Tracy

2017-01-15

Magnesium (Mg) is a promising biodegradable implant material because of its appropriate mechanical properties and safe degradation products. However, in vivo corrosion speed and hydrogen gas production need to be controlled for uses in biomedical applications. Here we report the development of a conducting polymer 3,4-ethylenedioxythiphene (PEDOT) and graphene oxide (GO) composite coating as a corrosion control layer. PEDOT/GO was electropolymerized on Mg samples in ethanol media. The coated Mg samples were subjected to various corrosion tests. The PEDOT/GO coating significantly reduced the rate of corrosion as evidenced by lower Mg ion concentration and pH of the corrosion media. In addition, the coating decreased the evolved hydrogen. Electrochemical analysis of the corroding samples showed more positive corrosion potential, a decreased corrosion current, and an increase in the polarization resistance. PEDOT/GO corrosion protection is attributed to three factors; an initial passive layer preventing solution ingress, buildup of negative charges in the film, and formation of corrosion protective Mg phosphate layer through redox coupling with Mg corrosion. To explore the biocompatibility of the coated implants in vitro, corrosion media from PEDOT/GO coated or uncoated Mg samples were exposed to cultured neurons where PEDOT/GO coated samples showed decreased toxicity. These results suggest that PEDOT/GO coating will be an effective treatment for controlling corrosion of Mg based medical implants. Coating Mg substrates with a PEDOT/GO composite coating showed a significant decrease in corrosion rate. While conducting polymer coatings have been used to prevent corrosion on various metals, there has been little work on the use of these coatings for Mg. Additionally, to our knowledge, there has not been a report of the combined used of conducting polymer and GO as a corrosion control layer. Corrosion control is attributed to an initial barrier layer followed by electrochemical coupling of the PEDOT/GO coating with the substrate to facilitate the formation of a protective phosphate layer. This coupling also resulted in a decrease in hydrogen produced during corrosion, which could further improve the host tissue integration of Mg implants. This work elaborates on the potential for electroactive polymers to serve as corrosion control methods. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Electrochemical process and production of novel complex hydrides

DOEpatents

Zidan, Ragaiy

2013-06-25

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

Electrochemical cell for rebalancing REDOX flow system

NASA Technical Reports Server (NTRS)

Thaller, L. H. (Inventor)

1979-01-01

An electrically rechargeable REDOX cell or battery system including one of more rebalancing cells is described. Each rebalancing cell is divided into two chambers by an ion permeable membrane. The first chamber is fed with gaseous hydrogen and a cathode fluid which is circulated through the cathode chamber of the REDOX cell is also passed through the second chamber of the rebalancing cell. Electrochemical reactions take place on the surface of insert electrodes in the first and second chambers to rebalance the electrochemical capacity of the anode and cathode fluids of the REDOX system.

Efficient and Selective Electrochemical and Photoelectrochemical Reduction of 5-Hydroxymethylfurfural to 2,5-Bis(hydroxymethyl)furan using Water as the Hydrogen Source

DOE PAGES

Roylance, John J.; Kim, Tae Woo; Choi, Kyoung-Shin

2016-02-17

Reductive biomass conversion has been conventionally conducted using H 2 gas under high-temperature and-pressure conditions. Here, efficient electrochemical reduction of 5-hydroxymethylfurfural (HMF), a key intermediate for biomass conversion, to 2,5-bis(hydroxymethyl)furan (BHMF), an important monomer for industrial processes, was demonstrated using Ag catalytic electrodes. This process uses water as the hydrogen source under ambient conditions and eliminates the need to generate and consume H 2 for hydrogenation, providing a practical and efficient route for BHMF production. By systematic investigation of HMF reduction on the Ag electrode surface, BHMF production was achieved with the Faradaic efficiency and selectivity nearing 100%, and plausiblemore » reduction mechanisms were also elucidated. Furthermore, construction of a photoelectrochemical cell (PEC) composed of an n-type BiVO 4 semiconductor anode, which uses photogenerated holes for water oxidation, and a catalytic Ag cathode, which uses photoexcited electrons from BiVO 4 for the reduction of HMF to BHMF, was demonstrated to utilize solar energy to significantly decrease the external voltage necessary for HMF reduction. This shows the possibility of coupling electrochemical HMF reduction and solar energy conversion, which can provide more efficient and environmentally benign routes for reductive biomass conversion.« less

The Electrochemical Properties of Sr(Ti,Fe)O 3-δ for Anodes in Solid Oxide Fuel Cells

DOE PAGES

Nenning, Andreas; Volgger, Lukas; Miller, Elizabeth; ...

2017-02-18

Reduction-stable mixed ionic and electronic conductors such as Sr(Ti,Fe)O 3-δ (STF) are promising materials for application in anodes of solid oxide fuel cells. The defect chemistry of STF and its properties as solid oxide fuel cell (SOFC) cathode have been studied thoroughly, while mechanistic investigations of its electrochemical properties as SOFC anode material are still scarce. In this study, thin film model electrodes of STF with 30% and 70% Fe content were investigated in H 2+H 2O atmosphere by electrochemical impedance spectroscopy. Lithographically patterned thin film Pt current collectors were applied on top or beneath the STF thin films tomore » compensate for the low electronic conductivity under reducing conditions. Oxygen exchange resistances, electronic and ionic conductivities and chemical capacitances were quantified and discussed in a defect chemical model. Increasing Fe content increases the electro-catalytic activity of the STF surface as well as the electronic and ionic conductivity. Current collectors on top also increase the electrochemical activity due to a highly active Pt-atmosphere-STF triple phase boundary. Furthermore, the electrochemical activity depends decisively on the H 2:H 2O mixing ratio and the polarization. Lastly, Fe 0 nanoparticles may evolve on the surface in hydrogen rich atmospheres and increase the hydrogen adsorption rate.« less

Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

NASA Astrophysics Data System (ADS)

Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

2018-01-01

Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

Top-Down and Bottom-Up Approaches in Engineering 1 T Phase Molybdenum Disulfide (MoS2 ): Towards Highly Catalytically Active Materials.

PubMed

Chua, Chun Kiang; Loo, Adeline Huiling; Pumera, Martin

2016-09-26

The metallic 1 T phase of MoS2 has been widely identified to be responsible for the improved performances of MoS2 in applications including hydrogen evolution reactions and electrochemical supercapacitors. To this aim, various synthetic methods have been reported to obtain 1 T phase-rich MoS2 . Here, the aim is to evaluate the efficiencies of the bottom-up (hydrothermal reaction) and top-down (chemical exfoliation) approaches in producing 1 T phase MoS2 . It is established in this study that the 1 T phase MoS2 produced through the bottom-up approach contains a high proportion of 1 T phase and demonstrates excellent electrochemical and electrical properties. Its performance in the hydrogen evolution reaction and electrochemical supercapacitors also surpassed that of 1 T phase MoS2 produced through a top-down approach. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface structure and electrochemical characteristics of Ti-V-Cr bcc-type solid solution alloys sintered with Ni

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

Tsuji, Yoichiro; Yamamoto, Osamu; Matsuda, Hiromu

2000-07-01

Ti-V-Cr bcc-type solid solution alloys can absorb a large amount of hydrogen and be applied to active materials of the negative electrode in Ni-MH batteries. However, because of the insolubility of Ni into these alloys, the electrochemical characteristics like discharge capacity and cycle life were poor. In order to increase the discharge capacity of hydrogen absorbing alloy electrodes, Ti-V-Cr bcc-type alloy powders were sintered with Ni in order to form Ni contained surface layer on the alloy surface. As sintering temperature rose up, the surface composition changed from TiNi to Ti{sub 2}Ni. TiNi surface layer showed better electrochemical characteristics. Formore » the Ni adding method, Ni electroless plating was preferred because of good adhesion. As a result of optimized conditions, a discharge capacity of 570 mAh/g and an improvement of cycle life were achieved.« less

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.

Ti(Ni,Cu) pseudobinary compounds as efficient negative electrodes for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Emami, Hoda; Cuevas, Fermin; Latroche, Michel

2014-11-01

The effect of Ni by Cu substitution on the structural, solid-gas and electrochemical hydrogenation properties of TiNi has been investigated. Pseudo-binary TiNi1-xCux (x ≤ 0.5) compounds have been synthesized by induction melting. They crystallize in B2 structure above 350 K and either in B19‧ (x < 0.1) or B19 (0.2 ≤ x ≤ 0.5) at room temperature (RT). For all compounds, Pressure-Composition Isotherms at 423 K exhibit a single slopping plateau pressure within the range 10-3-1 MPa of hydrogen pressure revealing a metal to hydride transformation. Both the hydrogenation capacity and the hydride stability decrease with Cu-content. The hydrided pseudobinary compounds crystallize in the tetragonal S.G. I4/mmm structure as for TiNi hydride. The electrochemical discharge capacity increases with Cu content from 150 mAh g-1 for TiNi up to 300 mAh g-1 for TiNi0.8Cu0.2 and then decreases again for larger Cu amounts. Electrochemical isotherms and in-situ neutron diffraction measurements at RT demonstrate that such a capacity increase results from a metal to hydride phase transformation in which the hydride phase is destabilized by Cu substitution. The TiNi0.8Cu0.2 compound exhibits interesting cycling stability for 30 cycles and good high-rate capability at D/2 rate. This compound has promising electrochemical properties as compared to commercial LaNi5-type alloys with the advantage of being rare-earth metal free.

Electrochemistry in the mimicry of oxidative drug metabolism by cytochrome P450s.

PubMed

Nouri-Nigjeh, Eslam; Bischoff, Rainer; Bruins, Andries P; Permentier, Hjalmar P

2011-05-01

Prediction of oxidative drug metabolism at the early stages of drug discovery and development requires fast and accurate analytical techniques to mimic the in vivo oxidation reactions by cytochrome P450s (CYP). Direct electrochemical oxidation combined with mass spectrometry, although limited to the oxidation reactions initiated by charge transfer, has shown promise in the mimicry of certain CYP-mediated metabolic reactions. The electrochemical approach may further be utilized in an automated manner in microfluidics devices facilitating fast screening of oxidative drug metabolism. A wide range of in vivo oxidation reactions, particularly those initiated by hydrogen atom transfer, can be imitated through the electrochemically-assisted Fenton reaction. This reaction is based on O-O bond activation in hydrogen peroxide and oxidation by hydroxyl radicals, wherein electrochemistry is used for the reduction of molecular oxygen to hydrogen peroxide, as well as the reduction of Fe(3+) to Fe(2+). Metalloporphyrins, as surrogates for the prosthetic group in CYP, utilizing metallo-oxo reactive species, can also be used in combination with electrochemistry. Electrochemical reduction of metalloporphyrins in solution or immobilized on the electrode surface activates molecular oxygen in a manner analogous to the catalytical cycle of CYP and different metalloporphyrins can mimic selective oxidation reactions. Chemoselective, stereoselective, and regioselective oxidation reactions may be mimicked using electrodes that have been modified with immobilized enzymes, especially CYP itself. This review summarizes the recent attempts in utilizing electrochemistry as a versatile analytical and preparative technique in the mimicry of oxidative drug metabolism by CYP. © 2011 Bentham Science Publishers Ltd.

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.

Electrochemical energy engineering: a new frontier of chemical engineering innovation.

PubMed

Gu, Shuang; Xu, Bingjun; Yan, Yushan

2014-01-01

One of the grand challenges facing humanity today is a safe, clean, and sustainable energy system where combustion no longer dominates. This review proposes that electrochemical energy conversion could set the foundation for such an energy system. It further suggests that a simple switch from an acid to a base membrane coupled with innovative cell designs may lead to a new era of affordable electrochemical devices, including fuel cells, electrolyzers, solar hydrogen generators, and redox flow batteries, for which recent progress is discussed using the authors' work as examples. It also notes that electrochemical energy engineering will likely become a vibrant subdiscipline of chemical engineering and a fertile ground for chemical engineering innovation. To realize this vision, it is necessary to incorporate fundamental electrochemistry and electrochemical engineering principles into the chemical engineering curriculum.

Enhanced performance of Zn(II)-doped lead-acid batteries with electrochemical active carbon in negative mass

NASA Astrophysics Data System (ADS)

Xiang, Jiayuan; Hu, Chen; Chen, Liying; Zhang, Dong; Ding, Ping; Chen, Dong; Liu, Hao; Chen, Jian; Wu, Xianzhang; Lai, Xiaokang

2016-10-01

The effect and mechanism of Zn(II) on improving the performances of lead-acid cell with electrochemical active carbon (EAC) in negative mass is investigated. The hydrogen evolution of the cell is significantly reduced due to the deposition of Zn on carbon surface and the increased porosity of negative mass. Zn(II) additives can also improve the low-temperature and high-rate capacities of the cell with EAC in negative mass, which ascribes to the formation of Zn on lead and carbon surface that constructs a conductive bridge among the active mass. Under the co-contribution of EAC and Zn(II), the partial-state-of-charge cycle life is greatly prolonged. EAC optimizes the NAM structure and porosity to enhance the charge acceptance and retard the lead sulfate accumulation. Zn(II) additive reduces the hydrogen evolution during charge process and improves the electric conductivity of the negative electrode. The cell with 0.6 wt% EAC and 0.006 wt% ZnO in negative mass exhibits 90% reversible capacity of the initial capacity after 2100 cycles. In contrast, the cell with 0.6 wt% EAC exhibits 84% reversible capacity after 2100 cycles and the control cell with no EAC and Zn(II) exhibits less than 80% reversible capacity after 1350 cycles.

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

Junhua Jiang; Ted Aulich

An electrolytic renewable nitrogen fertilizer process that utilizes wind-generated electricity, N{sub 2} extracted from air, and syngas produced via the gasification of biomass to produce nitrogen fertilizer ammonia was developed at the University of North Dakota Energy & Environmental Research Center. This novel process provides an important way to directly utilize biosyngas generated mainly via the biomass gasification in place of the high-purity hydrogen which is required for Haber Bosch-based production of the fertilizer for the production of the widely used nitrogen fertilizers. Our preliminary economic projection shows that the economic competitiveness of the electrochemical nitrogen fertilizer process strongly dependsmore » upon the cost of hydrogen gas and the cost of electricity. It is therefore expected the cost of nitrogen fertilizer production could be considerably decreased owing to the direct use of cost-effective 'hydrogen-equivalent' biosyngas compared to the high-purity hydrogen. The technical feasibility of the electrolytic process has been proven via studying ammonia production using humidified carbon monoxide as the hydrogen-equivalent vs. the high-purity hydrogen. Process optimization efforts have been focused on the development of catalysts for ammonia formation, electrolytic membrane systems, and membrane-electrode assemblies. The status of the electrochemical ammonia process is characterized by a current efficiency of 43% using humidified carbon monoxide as a feedstock to the anode chamber and a current efficiency of 56% using high-purity hydrogen as the anode gas feedstock. Further optimization of the electrolytic process for higher current efficiency and decreased energy consumption is ongoing at the EERC.« less

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, Hann S.; Sather, Norman F.

1988-01-01

A process for reducing the amount of halogens and halogen acids in high temperature combustion gases and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, H.S.; Sather, N.F.

1987-08-21

A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Electrochemical production of ozone and hydrogen peroxide

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1999-01-01

Methods of using ozone have been developed which sterilize instruments and medical wastes, oxidize organics found in wastewater, clean laundry, break down contaminants in soil into a form more readily digested by microbes, kill microorganisms present in food products, and destroy toxins present in food products. The preferred methods for killing microorganisms and destroying toxins use pressurized, humidified, and concentrated ozone produced by an electrochemical cell.

Detecting and measuring metabolic byproducts by electrochemical sensing

NASA Technical Reports Server (NTRS)

Wilkins, J. R.; Stoner, G. E.

1974-01-01

Method of detecting certain groups of bacteria is based on sensing buildup in molecular hydrogen. Apparatus is easy to assemble and use, and it has added advantage that hydrogen evolution by test micro-organisms can be measured automatically and accurately. System has been used to detect and enumerate variety of gram-negative bacteria of enterobacteriaceae group.

Clinical evaluation of a miniaturized desktop breath hydrogen analyzer.

PubMed

Duan, L P; Braden, B; Clement, T; Caspary, W F; Lembcke, B

1994-10-01

A small desktop electrochemical H2 analyzer (EC-60-Hydrogen monitor) was compared with a stationary electrochemical H2 monitor (GMI-exhaled Hydrogen monitor). The EC-60-H2 monitor shows a high degree of precision for repetitive (n = 10) measurements of standard hydrogen mixtures (CV 1-8%). The response time for completion of measurement is shorter than that of the GMI-exhaled H2 monitor (37 sec. vs 53 sec.; p < 0.0001), while reset times are almost identical (54 sec. vs 51 sec. n.s). In a clinical setting, breath H2-concentrations measured with the EC-60-H2 monitor and the GMI-exhaled H2 monitor were in excellent agreement with a linear correlation (Y = 1.12X + 1.022, r2 = 0.9617, n = 115). With increasing H2-concentrations the EC-60-H2 monitor required larger sample volumes for maintaining sufficient precision, and sample volumes greater than 200 ml were required with H2-concentrations > 30 ppm. For routine gastrointestinal function testing, the EC-60-H2 monitor is an satisfactory and reliable, easy to use and inexpensive desktop breath hydrogen analyzer, whereas in patients with difficulty in cooperating (children, people with severe pulmonary insufficiency), special care has to be applied to obtain sufficiently large breath samples.

Flower-like hydrogenated TiO2(B) nanostructures as anode materials for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhonghua; Zhou, Zhenfang; Nie, Sen; Wang, Honghu; Peng, Hongrui; Li, Guicun; Chen, Kezheng

2014-12-01

Flower-like hydrogenated TiO2(B) nanostructures have been synthesized via a facile solvothermal approach combined with hydrogenation treatment. The obtained TiO2(B) nanostructures show uniform and hierarchical flower-like morphology with a diameter of 124 ± 5 nm, which are further constructed by primary nanosheets with a thickness of 10 ± 1.2 nm. The Ti3+ species and/or oxygen vacancies are well introduced into the structures of TiO2(B) after hydrogen reduction, resulting in an enhancement in the electronic conductivity (up to 2.79 × 10-3 S cm-1) and the modified surface electrochemical activity. When evaluated for lithium storage capacity, the hydrogenated TiO2(B) nanostructures exhibit enhanced electrochemical energy storage performances compared to the pristine TiO2(B) nanostructures, including high capacity (292.3 mA h g-1 at 0.5C), excellent rate capability (179.6 mA h g-1 at 10C), and good cyclic stability (98.4% capacity retention after 200 cycles at 10C). The reasons for these improvements are explored in terms of the increased electronic conductivity and the facilitation of lithium ion transport arising from the introduction of oxygen vacancies and the unique flower-like morphologies.

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

2018-02-01

In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

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.

The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

PubMed

Galicia, Policarpo; Batina, Nikola; González, Ignacio

2006-07-27

This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

Electrochemically assisted localized etching of ZnO single crystals in water using a catalytically active Pt-coated atomic force microscopy probe

NASA Astrophysics Data System (ADS)

Shibata, Takayuki; Yamamoto, Kota; Sasano, Junji; Nagai, Moeto

2017-09-01

This paper presents a nanofabrication technique based on the electrochemically assisted chemical dissolution of zinc oxide (ZnO) single crystals in water at room temperature using a catalytically active Pt-coated atomic force microscopy (AFM) probe. Fabricated grooves featured depths and widths of several tens and several hundreds of nanometers, respectively. The material removal rate of ZnO was dramatically improved by controlling the formation of hydrogen ions (H+) on the surface of the catalytic Pt-coated probe via oxidation of H2O molecules; this reaction can be enhanced by applying a cathodic potential to an additional Pt-wire working electrode in a three-electrode configuration. Consequently, ZnO can be dissolved chemically in water as a soluble Zn2+ species via a reaction with H+ species present in high concentrations in the immediate vicinity of the AFM tip apex.

Electrochemical probing of high-level radioactive waste tanks containing washed sludge and precipitates

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

Bickford, D.F.; Congdon, J.W.; Oblath, S.B.

1987-01-01

At the U.S. Department of Energy's Savannah River Plant, corrosion of carbon steel storage tanks containing alkaline, high-level radioactive waste is controlled by specification of limits on waste composition and temperature. Processes for the preparation of waste for final disposal will result in waste with low corrosion inhibitor concentrations and, in some cases, high aromatic organic concentrations, neither of which are characteristic of previous operations. Laboratory tests, conducted to determine minimum corrosion inhibitor levels indicated pitting of carbon steel near the waterline for proposed storage conditions. In situ electrochemical measurements of full-scale radioactive process demonstrations have been conducted to assessmore » the validity of laboratory tests. Probes included pH, Eh (potential relative to a standard hydrogen electrode), tank potential, and alloy coupons. In situ results are compared to those of the laboratory tests, with particular regard given to simulated solution composition.« less

The development of an electrochemical technique for in situ calibrating of combustible gas detectors

NASA Technical Reports Server (NTRS)

Shumar, J. W.; Lantz, J. B.; Schubert, F. H.

1976-01-01

A program to determine the feasibility of performing in situ calibration of combustible gas detectors was successfully completed. Several possible techniques for performing the in situ calibration were proposed. The approach that showed the most promise involved the use of a miniature water vapor electrolysis cell for the generation of hydrogen within the flame arrestor of a combustible gas detector to be used for the purpose of calibrating the combustible gas detectors. A preliminary breadboard of the in situ calibration hardware was designed, fabricated and assembled. The breadboard equipment consisted of a commercially available combustible gas detector, modified to incorporate a water vapor electrolysis cell, and the instrumentation required for controlling the water vapor electrolysis and controlling and calibrating the combustible gas detector. The results showed that operation of the water vapor electrolysis at a given current density for a specific time period resulted in the attainment of a hydrogen concentration plateau within the flame arrestor of the combustible gas detector.

Vapor-fed microfluidic hydrogen generator.

PubMed

Modestino, M A; Dumortier, M; Hosseini Hashemi, S M; Haussener, S; Moser, C; Psaltis, D

2015-05-21

Water-splitting devices that operate with humid air feeds are an attractive alternative for hydrogen production as the required water input can be obtained directly from ambient air. This article presents a novel proof-of-concept microfluidic platform that makes use of polymeric ion conductor (Nafion®) thin films to absorb water from air and performs the electrochemical water-splitting process. Modelling and experimental tools are used to demonstrate that these microstructured devices can achieve the delicate balance between water, gas, and ionic transport processes required for vapor-fed devices to operate continuously and at steady state, at current densities above 3 mA cm(-2). The results presented here show that factors such as the thickness of the Nafion films covering the electrodes, convection of air streams, and water content of the ionomer can significantly affect the device performance. The insights presented in this work provide important guidelines for the material requirements and device designs that can be used to create practical electrochemical hydrogen generators that work directly under ambient air.

Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

DOE PAGES

Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; ...

2017-03-10

Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. Thismore » shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.« less

Chemical, electrochemical and photochemical molecular water oxidation catalysts.

PubMed

Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Sala, Xavier

2015-11-01

Hydrogen release from the splitting of water by simply using sunlight as the only energy source is an old human dream that could finally become a reality. This process involves both the reduction and oxidation of water into hydrogen and oxygen, respectively. While the first process has been fairly overcome, the conversion of water into oxygen has been traditionally the bottleneck process hampering the development of a sustainable hydrogen production based on water splitting. Fortunately, a revolution in this field has occurred during the past decade, since many research groups have been conducting an intense research in this area. Thus, while molecular, well-characterized catalysts able to oxidize water were scarce just five years ago, now a wide range of transition metal based compounds has been reported as active catalysts for this transformation. This review reports the most prominent key advances in the field, covering either examples where the catalysis is triggered chemically, electrochemically or photochemically. Copyright © 2014 Elsevier B.V. All rights reserved.

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

A methodology for thermodynamic simulation of high temperature, internal reforming fuel cell systems

NASA Astrophysics Data System (ADS)

Matelli, José Alexandre; Bazzo, Edson

This work presents a methodology for simulation of fuel cells to be used in power production in small on-site power/cogeneration plants that use natural gas as fuel. The methodology contemplates thermodynamics and electrochemical aspects related to molten carbonate and solid oxide fuel cells (MCFC and SOFC, respectively). Internal steam reforming of the natural gas hydrocarbons is considered for hydrogen production. From inputs as cell potential, cell power, number of cell in the stack, ancillary systems power consumption, reformed natural gas composition and hydrogen utilization factor, the simulation gives the natural gas consumption, anode and cathode stream gases temperature and composition, and thermodynamic, electrochemical and practical efficiencies. Both energetic and exergetic methods are considered for performance analysis. The results obtained from natural gas reforming thermodynamics simulation show that the hydrogen production is maximum around 700 °C, for a steam/carbon ratio equal to 3. As shown in the literature, the found results indicate that the SOFC is more efficient than MCFC.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developments in hydrogenation technology for fine-chemical and pharmaceutical applications.

PubMed

Machado, R M; Heier, K R; Broekhuis, R R

2001-11-01

The continuous innovation in hydrogenation technology is testimony to its growing importance in the manufacture of specialty and fine chemicals. New developments in equipment, process intensification and catalysis represent major themes that have undergone recent advances. Developments in chiral catalysis, methods to support and fix homogeneous catalysts, novel reactor and mixing technology, high-throughput screening, supercritical processing, spectroscopic and electrochemical online process monitoring, monolithic and structured catalysts, and sonochemical activation methods illustrate the scope and breadth of evolving technology applied to hydrogenation.

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.

Uniform manganese hexacyanoferrate hydrate nanocubes featuring superior performance for low-cost supercapacitors and nonenzymatic electrochemical sensors.

PubMed

Pang, Huan; Zhang, Yizhou; Cheng, Tao; Lai, Wen-Yong; Huang, Wei

2015-10-14

Uniform manganese hexacyanoferrate hydrate nanocubes are prepared via a simple chemical precipitation method at room temperature. Due to both micro/mesopores of the Prussian blue analogue and nanocubic structures, the manganese hexacyanoferrate hydrate nanocubes allow the efficient charge transfer and mass transport for electrolyte solution and chemical species. Thus, the manganese hexacyanoferrate hydrate nanocube electrode shows a good rate capability and cycling stability for electrochemical capacitors. Furthermore, electrodes modified with manganese hexacyanoferrate hydrate nanocubes demonstrate a sensitive electrochemical response to hydrogen peroxide (H2O2) in buffer solutions with a high selectivity.

Anodically Grown Binder-Free Nickel Hexacyanoferrate Film: Toward Efficient Water Reduction and Hexacyanoferrate Film Based Full Device for Overall Water Splitting.

PubMed

Bui, Hoa Thi; Shrestha, Nabeen K; Khadtare, Shubhangi; Bathula, Chinna D; Giebeler, Lars; Noh, Yong-Young; Han, Sung-Hwan

2017-05-31

One of the challenges in obtaining hydrogen economically by electrochemical water splitting is to identify and substitute cost-effective earth-abundant materials for the traditionally used precious-metal-based water-splitting electrocatalysts. Herein, we report the electrochemical formation of a thin film of nickel-based Prussian blue analogue hexacyanoferrate (Ni-HCF) through the anodization of a nickel substrate in ferricyanide electrolyte. As compared to the traditionally used Nafion-binder-based bulk film, the anodically obtained binder-free Ni-HCF film demonstrates superior performance in the electrochemical hydrogen evolution reaction (HER), which is highly competitive with that shown by a Pt-plate electrode. The HER onset and the benchmark cathodic current density of 10 mA cm -2 were achieved at small overpotentials of 15 mV and 0.2 V (not iR-corrected), respectively, in 1 M KOH electrolyte, together with the long-term electrochemical durability of the film. Further, a metal-HCF-electrode-based full water-splitting device consisting of the binder-free Ni-HCF film on a Ni plate and a one-dimensional Co-HCF film on carbon paper as the electrodes for the HER and the oxygen evolution reaction (OER), respectively, was designed and was found to demonstrate very promising performance for overall water splitting.

An in situ carbonization-replication method to synthesize mesostructured WO3/C composite as nonprecious-metal anode catalyst in PEMFC.

PubMed

Cui, Xiangzhi; Hua, Zile; Wei, Chenyang; Shu, Zhu; Zhang, Liangxia; Chen, Hangrong; Shi, Jianlin

2013-02-01

A meostructured WO(3)/C composite with crystalline framework and high electric conductivity has been synthesized by a new in situ carbonization-replication route using the block copolymer (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)) present in situ in the pore channels of mesoporous silica template as carbon source. X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetry differential thermal analysis, and N(2) adsorption techniques were adopted for the structural characterization. Cyclic voltammetry, chronoamperometry, and single-cell test for hydrogen electrochemical oxidation were adopted to characterize the electrochemical activities of the mesoporous WO(3)/C composite. The carbon content and consequent electric conductivity of these high-surface-area (108-130 m(2) g(-1)) mesostructured WO(3)/C composite materials can be tuned by variation of the duration of heat treatment, and the composites exhibited high and stable electrochemical catalytic activity. The single-cell test results indicated that the mesostructured WO(3)/C composites showed clear electrochemical catalytic activity toward hydrogen oxidation at 25 °C, which makes them potential non-precious-metal anode catalysts in proton exchange membrane fuel cell. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simple electro-assisted immobilization of ciprofloxacin on carbon nanotube modified electrodes: its selective hydrogen peroxide electrocatalysis.

PubMed

Sornambikai, Sundaram; Kumar, Annamalai Senthil

2014-09-01

Ciprofloxacin (Cf) is a synthetic fourth generation fluoroquinolone class antibiotic used for the treatment of gram-positive, gram-negative and mycobacterium species infections. Electrochemical characteristic of the Cf antibiotic on carbon nanotube modified glassy carbon electrode (GCE/CNT) in pH 7 phosphate buffer solution has been investigated. Electrochemically oxidized radical byproduct of the Cf drug, which is formed as intermediate, gets immobilized on the GCE/CNT (GCE/Cf@CNT) and showed stable and well defined surface confined redox peak at -0.220 V versus Ag/AgCl. Control electrochemical experiment with unmodified GCE failed to show any such immobilization and redox features. Physicochemical characterizations of the Cf@CNT by transmission electron microscope, scanning electron microscope, infrared spectroscopy, UV-Vis and gas chromatography coupled mass spectroscopic analyses of Cf@CNT collectively revealed presence of native form of the Cf antibiotic molecule onto the CNT. The interaction between the Cf molecule and the CNT tubes are revealed from the decreased intensity in the Raman spectrum. The GCE/Cf@CNT showed excellent electrocatalytic response to hydrogen peroxide reduction reaction in pH 7 phosphate buffer solution. Amperometric i-t analysis for the detection of H2O2 showed a current linearity plot upto [H2O2] = 200 μM at an applied potential - 0.1 V versus Ag/AgCl with a current sensitivity value 678 μA mM(-1) cm(-2). No interferences were noticed with ascorbic acid, uric acid, cysteine and nitrite. The present study can be highly helpful to understand the interaction between the Cf and H2O2 in physiological systems and for the removal of Cf from the antibiotic polluted water samples especially in the aquaculture and agricultural systems.

Immobilization of nanobeads on a surface to control the size, shape and distribution of pores in electrochemically generated sol-gel films.

PubMed

Ciabocco, Michela; Berrettoni, Mario; Zamponi, Silvia; Cox, James A

2015-07-01

Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly(styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES) and using (CH 3 ) 3 SiOCH 3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm -3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH 3 ) 3 SiOCH 3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru(CN) 6 4- at scan rates above 5 mVs -1 yielded currents controlled primarily by linear diffusion. Below 5 mVs -1 , convection rather than the expected factor, radial diffusion, apparently limited the current.

One-pot synthesis of MoS2/In2S3 ultrathin nanoflakes with mesh-shaped structure on indium tin oxide as photocathode for enhanced photo-and electrochemical hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Sun, Baoliang; Shan, Fei; Jiang, Xinxin; Ji, Jing; Wang, Feng

2018-03-01

A bifunctional MoS2/In2S3 hybrid composite that has both photo- and electrocatalytic activity toward hydrogen evolution reaction (HER) is prepared by a facile one pot hydrothermal method. The characterizations by scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM) and Photoluminescence (PL) shows that the MoS2/In2S3 hybrid exhibits ultrathin nanoflakes with mesh-shaped structure on transparent conductive substrates, and the as prepared catalyst composite obviously improves the separation of electro-hole pairs. The as prepared hybrid nanosheets with Mo:In of 1/2 integrate In-doped MoS2 to reduce the stacking and increase the active surface area. The novel mesh-shaped nanostructure with a moderate degree of disorder provides not only simultaneously intrinsic conductivity and defects but also higher electrochemically active surface area (ECSA). By electrochemical measurements, such as linear sweep voltammetry (LSV), electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV), we find that the MoS2/In2S3 hybrid possesses much better photo/electrochemical activity than pristine MoS2 or In2S3. MoS2/In2S3 ultrathin nanoflaks are anticipated to be a superior photoelectrocatalyst for PEC cells, and the rational use of the MoS2/In2S3 cathode offers a new avenue toward achieving effective photo-assistant electrocatalytic activity.

An overview—Functional nanomaterials for lithium rechargeable batteries, supercapacitors, hydrogen storage, and fuel cells

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

Liu, Hua Kun, E-mail: hua@uow.edu.au

2013-12-15

Graphical abstract: Nanomaterials play important role in lithium ion batteries, supercapacitors, hydrogen storage and fuel cells. - Highlights: • Nanomaterials play important role for lithium rechargeable batteries. • Nanostructured materials increase the capacitance of supercapacitors. • Nanostructure improves the hydrogenation/dehydrogenation of hydrogen storage materials. • Nanomaterials enhance the electrocatalytic activity of the catalysts in fuel cells. - Abstract: There is tremendous worldwide interest in functional nanostructured materials, which are the advanced nanotechnology materials with internal or external dimensions on the order of nanometers. Their extremely small dimensions make these materials unique and promising for clean energy applications such as lithiummore » ion batteries, supercapacitors, hydrogen storage, fuel cells, and other applications. This paper will highlight the development of new approaches to study the relationships between the structure and the physical, chemical, and electrochemical properties of functional nanostructured materials. The Energy Materials Research Programme at the Institute for Superconducting and Electronic Materials, the University of Wollongong, has been focused on the synthesis, characterization, and applications of functional nanomaterials, including nanoparticles, nanotubes, nanowires, nanoporous materials, and nanocomposites. The emphases are placed on advanced nanotechnology, design, and control of the composition, morphology, nanostructure, and functionality of the nanomaterials, and on the subsequent applications of these materials to areas including lithium ion batteries, supercapacitors, hydrogen storage, and fuel cells.« less

Understanding trends in electrochemical carbon dioxide reduction rates

DOE PAGES

Liu, Xinyan; Xiao, Jianping; Peng, Hongjie; ...

2017-05-22

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbonmore » monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.« less

Understanding trends in electrochemical carbon dioxide reduction rates

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

Liu, Xinyan; Xiao, Jianping; Peng, Hongjie

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbonmore » monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.« less

Electrochemically deposited Cu2O cubic particles on boron doped diamond substrate as efficient photocathode for solar hydrogen generation

NASA Astrophysics Data System (ADS)

Mavrokefalos, Christos K.; Hasan, Maksudul; Rohan, James F.; Compton, Richard G.; Foord, John S.

2017-06-01

Herein, we report a novel photocathode for the water splitting reaction. The electrochemical deposition of Cu2O particles on boron doped diamond (BDD) electrodes and the subsequent decoration with NiO nanoparticles by a dip coating method to act as co-catalyst for hydrogen evolution reaction is described. The morphology analysis by scanning electron microscope (SEM) revealed that Cu2O particles are cubic and decorated sporadically with NiO nanoparticles. X-ray photoelectron spectroscopy (XPS) confirmed the electronic interaction at the interface between Cu2O and NiO through a binding energy shift of the main Cu 2p peak. The photoelectrochemical (PEC) performance of NiO-Cu2O/BDD showed a much higher current density (-0.33 mA/cm2) and photoconversion efficiency (0.28%) compared to the unmodified Cu2O/BDD electrode, which are only -0.12 mA/cm2 and 0.06%, respectively. The enhancement in PEC performance is attributable to the synergy of NiO as an electron conduction mediator leading to the enhanced charge separation and transfer to the reaction interface for hydrogen evolution as evidenced by electrochemical impedance spectroscopy (EIS) and charge carrier density calculation. Stability tests showed that the NiO nanoparticles loading content on Cu2O surface is a crucial parameter in this regard.

Hydrogen peroxide biosensor based on microperoxidase-11 immobilized in a silica cavity array electrode.

PubMed

Tian, Shu; Zhou, Qun; Gu, Zhuomin; Gu, Xuefang; Zhao, Lili; Li, Yan; Zheng, Junwei

2013-03-30

Hydrogen peroxide biosensor based on the silica cavity array modified indium-doped tin oxide (ITO) electrode was constructed. An array of silica microcavities was fabricated by electrodeposition using the assembled polystyrene particles as template. Due to the resistance gradient of the silica cavity structure, the silica cavity exhibits a confinement effect on the electrochemical reactions, making the electrode function as an array of "soft" microelectrodes. The covalently immobilized microperoxidase-11(MP-11) inside these SiO2 cavities can keep its physiological activities, the electron transfer between the MP-11 and electrode was investigated through electrochemical method. The cyclic voltammetric curve shows a quasi-reversible electrochemical redox behavior with a pair of well-defined redox peaks, the cathodic and anodic peaks are located at -0.26 and -0.15V. Furthermore, the modified electrode exhibits high electrocatalytic activity toward the reduction of hydrogen peroxide and also shows good analytical performance for the amperometric detection of H2O2 with a linear range from 2×10(-6) to 6×10(-4)M. The good reproducibility and long-term stability of this novel electrode not only offer an opportunity for the detection of H2O2 in low concentration, but also provide a platform to construct various biosensors based on many other enzymes. Copyright © 2013 Elsevier B.V. All rights reserved.

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy

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

Sheng, WC; Zhuang, ZB; Gao, MR

2015-01-08

The hydrogen oxidation/evolution reactions are two of the most fundamental reactions in distributed renewable electrochemical energy conversion and storage systems. The identification of the reaction descriptor is therefore of critical importance for the rational catalyst design and development. Here we report the correlation between hydrogen oxidation/evolution activity and experimentally measured hydrogen binding energy for polycrystalline platinum examined in several buffer solutions in a wide range of electrolyte pH from 0 to 13. The hydrogen oxidation/evolution activity obtained using the rotating disk electrode method is found to decrease with the pH, while the hydrogen binding energy, obtained from cyclic voltammograms, linearlymore » increases with the pH. Correlating the hydrogen oxidation/evolution activity to the hydrogen binding energy renders a monotonic decreasing hydrogen oxidation/evolution activity with the hydrogen binding energy, strongly supporting the hypothesis that hydrogen binding energy is the sole reaction descriptor for the hydrogen oxidation/evolution activity on monometallic platinum.« less

In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

NASA Astrophysics Data System (ADS)

Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

2017-03-01

La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

Bimetallic Cobalt-Based Phosphide Zeolitic Imidazolate Framework: CoP x Phase-Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting

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

Song, Junhua; Zhu, Chengzhou; Xu, Bo Z.

Cobalt-based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co2P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co-host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance hasmore » been achieved with mild Cu doping in Cu0.3Co2.7P/nitrogen-doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm–2 and satisfying stability for OER. Cu0.3Co2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu0.3Co2.7P/NC paired electrodes shows 60% larger current density than Pt/ RuO2 couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis-based energy conversion.« less

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

NASA Astrophysics Data System (ADS)

Cordova, Isvar Abraxas

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy. Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD's thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2's bandgap, can have a strong dependence on TiO2's thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH 3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency. In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Effect of Hydrogen Charging on the Stress Corrosion Behavior of 2205 Duplex Stainless Steel Under 3.5 wt.% NaCl Thin Electrolyte Layer

NASA Astrophysics Data System (ADS)

Zhao, Tianliang; Liu, Zhiyong; Hu, Shanshan; Du, Cuiwei; Li, Xiaogang

2017-05-01

The effect of hydrogen charging on the stress corrosion cracking (SCC) behavior of 2205 duplex stainless steel (DSS) under 3.5 wt.% NaCl thin electrolyte layer was investigated on precharged samples through hydrogen determination, electrochemical measurement, and slow strain rate tensile test. Results show that hydrogen charging weakens the passive film without inducing any obvious trace of localized anodic dissolution. Therefore, hydrogen charging increases the SCC susceptibility of 2205 DSS mainly through mechanism of hydrogen embrittlement rather than mechanism of localized anodic dissolution. 2205 DSS shows a more susceptibility to hydrogen under the TEL when hydrogen charging current density (HCCD) is between 20 and 50 mA cm-2. The increasing trend is remarkable when hydrogen charging current density increases from 20 to 50 mA cm-2 and fades after 50 mA cm-2.

Electrochemical behavior of zinc particles with silica based coatings as anode material for zinc air batteries with improved discharge capacity

NASA Astrophysics Data System (ADS)

Schmid, M.; Willert-Porada, M.

2017-05-01

Silica coatings on zinc particles as anode material for alkaline zinc air batteries are expected to reduce early formation of irreversible ZnO passivation layers during discharge by controlling zinc dissolution and precipitation of supersaturated zincates, Zn(OH)42-. Zinc particles were coated with SiO2 (thickness: 15 nm) by chemical solution deposition and with Zn2SiO4 (thickness: 20 nm) by chemical vapor deposition. These coatings formed a Si(OH)4 gel in aqueous KOH and retarded hydrogen evolution by 40%. By treatment in aqueous KOH and drying afterwards, the silica coatings were changed into ZnO-K2O·SiO2 layers. In this work, the electrochemical performance of such coated zinc particles is investigated by different electrochemical methods in order to gain a deeper understanding of the mechanisms of the coatings, which reduce zinc passivation. In particular, zinc utilization and changes in internal resistance are investigated. Moreover, methods for determination of diffusion coefficients, charge carrier numbers and activation energies for electrochemical oxidation are determined. SiO2-coated zinc particles show improved discharge capacity (CVD-coated zinc: 69% zinc utilization, CSD-coated zinc: 62% zinc utilization) as compared to as-received zinc (57% zinc utilization) at C/20 rate, by reducing supersaturation of zincates. Additionally, KOH-modified SiO2-coated zinc particles enhance rechargeability after 100% depth-of-discharge.

Hydrogen-based electrochemical energy storage

DOEpatents

Simpson, Lin Jay

2013-08-06

An energy storage device (100) providing high storage densities via hydrogen storage. The device (100) includes a counter electrode (110), a storage electrode (130), and an ion conducting membrane (120) positioned between the counter electrode (110) and the storage electrode (130). The counter electrode (110) is formed of one or more materials with an affinity for hydrogen and includes an exchange matrix for elements/materials selected from the non-noble materials that have an affinity for hydrogen. The storage electrode (130) is loaded with hydrogen such as atomic or mono-hydrogen that is adsorbed by a hydrogen storage material such that the hydrogen (132, 134) may be stored with low chemical bonding. The hydrogen storage material is typically formed of a lightweight material such as carbon or boron with a network of passage-ways or intercalants for storing and conducting mono-hydrogen, protons, or the like. The hydrogen storage material may store at least ten percent by weight hydrogen (132, 134) at ambient temperature and pressure.

Non-Faradaic electrochemical promotion of catalytic methane reforming for methanol production

DOEpatents

Fan, Qinbai

2016-11-22

A method of converting methane to methanol at low temperatures utilizes a reactor including an anode, a cathode, a membrane separator between the anode and cathode, a metal oxide catalyst at the anode and a hydrogen recovery catalyst at the cathode. The method can convert methane to methanol at as rate exceeding the theoretical Faradaic rate due to the contribution of an electrochemical reaction occurring in tandem with a Faradaic reaction.

JPRS Report, Science & Technology, USSR: Chemistry

DTIC Science & Technology

1990-11-30

1990 2 USSR: Chemistry High Temperature Electrochemical Synthesis of Intermetallic Titanium Iron Compounds [V. I. Shapoval, L. I. Zarubitskaya, et al...Method for Increasing Level of Hydrogen Sulfide Purging From Coke Oven Gas [N. K. Smolyakov; KOKS I KHIMIYA, No 1, Jan 90] 18 Increasing...TVERDOGO TOPLIVA No 3, May-Jun 90] 19 Effect of Iron -ore Catalysts in Processes of Hydrogenation of Coal and Polycyclic Hydrocarbons [V. I

Effect of low water content in protic ionic liquid on ions electrosorption in porous carbon: application to electrochemical capacitors.

PubMed

Gorska, B; Timperman, L; Anouti, M; Béguin, F

2017-05-10

The effect of low water content (<20, 150, 1000, 10 000 ppm) in triethylammonium bis[(trifluoromethyl)sulfonyl]imide - [(C 2 H 5 ) 3 N + H][TFSI - ] - protic ionic liquid (PIL) on the performance of activated carbon (AC) electrodes as well as AC/AC electrochemical capacitors (ECs) is reported. Under negative polarization, hydrogen electrosorption onto carbon is enhanced along with the increase of water content in PIL, whereas the resulting desorption peaks are shifted to lower potential values, evidencing lower sorption energy when hydrogen is stored from moisture containing PIL. Cyclic voltammetry (CV) investigations on PIL-based ECs demonstrated that the evolution of the Stern layer nanostructure at positive and negative potentials is asymmetrical. The results revealed comparable electrochemical performance for PIL containing 150 and 1000 ppm of H 2 O, due to similar operation of the positive electrode, where [TFSI - ] anions are adsorbed in the outer Helmholtz plane, and the negative one, where hydrogen is stored through the reduction of the intermediate hydronium cation. By contrast, a cell with "dry" PIL (<20 ppm of water) displayed a distinctive operation due to hydrogen electrosorption directly through reduction of the protonated cation, and selective adsorption of [TFSI - ] anions, which occurs thanks to the high polarizability and image force (IF) created by their induced charge. Galvanostatic cycling with potential limitation (GCPL) showed comparable capacitance values whatever the water content in PILs up to 1000 ppm, yet electrochemical impedance spectroscopy (EIS) revealed higher capacitance as well as better retention at higher frequencies with the PIL containing 150 ppm of water. Hence, 150 ppm is reasoned to be an optimal value for diffusion and adsorption of ions. The nature of current collectors (aluminum or stainless steel) has a determining role in their polarization behavior, and consequently the potential range of electrodes as well as ion diffusion into the activated carbon porosity, influencing the observed capacitance values (C EIS/2.0V : 170 vs. 128 F g -1 , for Al and SSt, respectively).

ZnO-Based Amperometric Enzyme Biosensors

PubMed Central

Zhao, Zhiwei; Lei, Wei; Zhang, Xiaobing; Wang, Baoping; Jiang, Helong

2010-01-01

Nanostructured ZnO with its unique properties could provide a suitable microenvironment for immobilization of enzymes while retaining their biological activity, and thus lead to an expanded use of this nanomaterial for the construction of electrochemical biosensors with enhanced analytical performance. ZnO-based enzyme electrochemical biosensors are summarized in several tables for an easy overview according to the target biosensing analyte (glucose, hydrogen peroxide, phenol and cholesterol), respectively. Moreover, recent developments in enzyme electrochemical biosensors based on ZnO nanomaterials are reviewed with an emphasis on the fabrications and features of ZnO, approaches for biosensor construction (e.g., modified electrodes and enzyme immobilization) and biosensor performances. PMID:22205864

Hydrogen effects in duplex stainless steel welded joints - electrochemical studies

NASA Astrophysics Data System (ADS)

Michalska, J.; Łabanowski, J.; Ćwiek, J.

2012-05-01

In this work results on the influence of hydrogen on passivity and corrosion resistance of 2205 duplex stainless steel (DSS) welded joints are described. The results were discussed by taking into account three different areas on the welded joint: weld metal (WM), heat-affected zone (HAZ) and parent metal. The corrosion resistance was qualified with the polarization curves registered in a synthetic sea water. The conclusion is that, hydrogen may seriously deteriorate the passive film stability and corrosion resistance to pitting of 2205 DSS welded joints. The presence of hydrogen in passive films increases corrosion current density and decreases the potential of the film breakdown. It was also found that degree of susceptibility to hydrogen degradation was dependent on the hydrogen charging conditions. WM region has been revealed as the most sensitive to hydrogen action.

A survey and analysis of commercially available hydrogen sensors

NASA Technical Reports Server (NTRS)

Hunter, Gary W.

1992-01-01

The performance requirements for hydrogen detection in aerospace applications often exceed those of more traditional applications. In order to ascertain the applicability of existing hydrogen sensors to aerospace applications, a survey was conducted of commercially available point-contact hydrogen sensors, and their operation was analyzed. The operation of the majority of commercial hydrogen sensors falls into four main categories: catalytic combustion, electrochemical, semiconducting oxide sensors, and thermal conductivity detectors. The physical mechanism involved in hydrogen detection for each main category is discussed in detail. From an understanding of the detection mechanism, each category of sensor is evaluated for use in a variety of space and propulsion environments. In order to meet the needs of aerospace applications, the development of point-contact hydrogen sensors that are based on concepts beyond those used in commercial sensors is necessary.

Water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2017-12-05

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

Polyoxometalate water oxidation catalysts and methods of use thereof

DOEpatents

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2014-09-02

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

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.

Energy and fuels from electrochemical interfaces

NASA Astrophysics Data System (ADS)

Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.; Markovic, Nenad M.

2017-01-01

Advances in electrocatalysis at solid-liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.

Performance evaluation of SPE electrolyzer for Space Station life support

NASA Technical Reports Server (NTRS)

Erickson, A. C.; Puskar, M. C.; Zagaja, J. A.; Miller, P. S.

1987-01-01

An static water-vapor feed electrolyzer has been developed as a candidate for Space Station life-support oxygen generation. The five-cell electrolysis module has eliminated the need for phase separation devices, pumps, and deionizers by transporting only water vapor to the solid polymer electrolyte cells. The introduction of an innovative electrochemical hydrogen pump allows the use of low-pressure reclaimed water to generate gas pressures of up to 230 psia. The electrolyzer has been tested in a computer-controlled test stand featuring continuous, cyclic, and standby operation (including automatic shutdown with fault detection).

High loading MnO2 nanowires on graphene paper: facile electrochemical synthesis and use as flexible electrode for tracking hydrogen peroxide secretion in live cells.

PubMed

Dong, Shuang; Xi, Jiangbo; Wu, Yanan; Liu, Hongwei; Fu, Chaoyang; Liu, Hongfang; Xiao, Fei

2015-01-01

Recent progress in flexible and lightweight electrochemical sensor systems requires the development of paper-like electrode materials. Here, we report a facile and green synthesis of a new type of MnO2 nanowires-graphene nanohybrid paper by one-step electrochemical method. This strategy demonstrates a collection of unique features including the effective electrochemical reduction of graphene oxide (GO) paper and the high loading of MnO2 nanowires on electrochemical reduced GO (ERGO) paper. When used as flexible electrode for nonenzymatic detection of hydrogen peroxide (H2O2), MnO2-ERGO paper exhibits high electrocatalytic activity toward the redox of H2O2 as well as excellent stability, selectivity and reproducibility. The amperometric responses are linearly proportional to H2O2 concentration in the range 0.1-45.4 mM, with a detection limit of 10 μM (S/N=3) and detection sensitivity of 59.0 μA cm(-2) mM(-1). These outstanding sensing performances enable the practical application of MnO2-ERGO paper electrode for the real-time tracking H2O2 secretion by live cells macrophages. Therefore, the proposed graphene-based nanohybrid paper electrode with intrinsic flexibility, tailorable shapes and adjustable properties can contribute to the full realization of high-performance flexible electrode material used in point-of-care testing devices and portable instruments for in-vivo clinical diagnostics and on-site environmental monitoring. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydroxyl radical generation in electro-Fenton process with a gas-diffusion electrode: Linkages with electro-chemical generation of hydrogen peroxide and iron redox cycle.

PubMed

Yatagai, Tomonori; Ohkawa, Yoshiko; Kubo, Daichi; Kawase, Yoshinori

2017-01-02

The hydroxyl radical generation in an electro-Fenton process with a gas-diffusion electrode which is strongly linked with electro-chemical generation of hydrogen peroxide and iron redox cycle was studied. The OH radical generation subsequent to electro-chemical generations of H 2 O 2 was examined under the constant potential in the range of Fe 2+ dosage from 0 to 1.0 mM. The amount of generated OH radical initially increased and gradually decreased after the maximum was reached. The initial rate of OH radical generation increased for the Fe 2+ dosage <0.25 mM and at higher Fe 2+ dosages remained constant. At higher Fe 2+ dosages the precipitation of Fe might inhibit the enhancement of OH radical generation. The experiments for decolorization and total organic carbon (TOC) removal of azo-dye Orange II by the electro-Fenton process were conducted and the quick decolorization and slow TOC removal of Orange II were found. To quantify the linkages of OH radical generation with dynamic behaviors of electro-chemically generated H 2 O 2 and iron redox cycle and to investigate effects of OH radical generation on the decolorization and TOC removal of Orange II, novel reaction kinetic models were developed. The proposed models could satisfactory clarify the linkages of OH radical generation with electro-chemically generated H 2 O 2 and iron redox cycle and simulate the decolorization and TOC removal of Orange II by the electro-Fenton process.

Imaging nanobubble nucleation and hydrogen spillover during electrocatalytic water splitting.

PubMed

Hao, Rui; Fan, Yunshan; Howard, Marco D; Vaughan, Joshua C; Zhang, Bo

2018-06-05

Nucleation and growth of hydrogen nanobubbles are key initial steps in electrochemical water splitting. These processes remain largely unexplored due to a lack of proper tools to probe the nanobubble's interfacial structure with sufficient spatial and temporal resolution. We report the use of superresolution microscopy to image transient formation and growth of single hydrogen nanobubbles at the electrode/solution interface during electrocatalytic water splitting. We found hydrogen nanobubbles can be generated even at very early stages in water electrolysis, i.e., ∼500 mV before reaching its thermodynamic reduction potential. The ability to image single nanobubbles on an electrode enabled us to observe in real time the process of hydrogen spillover from ultrathin gold nanocatalysts supported on indium-tin oxide.

Sodium ion pumps and hydrogen production in glutamate fermenting anaerobic bacteria.

PubMed

Boiangiu, Clara D; Jayamani, Elamparithi; Brügel, Daniela; Herrmann, Gloria; Kim, Jihoe; Forzi, Lucia; Hedderich, Reiner; Vgenopoulou, Irini; Pierik, Antonio J; Steuber, Julia; Buckel, Wolfgang

2005-01-01

Anaerobic bacteria ferment glutamate via two different pathways to ammonia, carbon dioxide, acetate, butyrate and molecular hydrogen. The coenzyme B12-dependent pathway in Clostridium tetanomorphum via 3-methylaspartate involves pyruvate:ferredoxin oxidoreductase and a novel enzyme, a membrane-bound NADH:ferredoxin oxidoreductase. The flavin- and iron-sulfur-containing enzyme probably uses the energy difference between reduced ferredoxin and NADH to generate an electrochemical Na+ gradient, which drives transport processes. The other pathway via 2-hydroxyglutarate in Acidaminococcus fermentans and Fusobacterium nucleatum involves glutaconyl-CoA decarboxylase, which uses the free energy of decarboxylation to generate also an electrochemical Na+ gradient. In the latter two organisms, similar membrane-bound NADH:ferredoxin oxidoreductases have been characterized. We propose that in the hydroxyglutarate pathway these oxidoreductases work in the reverse direction, whereby the reduction of ferredoxin by NADH is driven by the Na+ gradient. The reduced ferredoxin is required for hydrogen production and the activation of radical enzymes. Further examples show that reduced ferredoxin is an agent, whose reducing energy is about 1 ATP 'richer' than that of NADH. Copyright 2005 S. Karger AG, Basel.

Effect of the Sm content on the structure and electrochemical properties of La 1.3 - xSm xCaMg 0.7Ni 9 ( x = 0-0.3) hydrogen storage alloys

NASA Astrophysics Data System (ADS)

Tang, Rui; Wei, Xuedong; Liu, Yongning; Zhu, Changchun; Zhu, Jiewu; Yu, Guang

La 1.3 - xSm xCaMg 0.7Ni 9 (x = 0-0.3) hydrogen storage alloys were prepared by inductive melting and the effect of the Sm content on the structure and electrochemical properties was investigated in the paper. The Sm substitution for La in La 1.3 - xSm xCaMg 0.7Ni 9 (x = 0-0.3) alloys does not change the main phase structure (the rhombohedral PuNi 3-type structure), but leads to a shrinkage of unit cell and a decrease of hydrogen storage capacity. With the increase of the Sm content in the alloys, the maximum discharge capacity of electrode decreases from 400.2 (x = 0) to 346.6 mAh g -1 (x = 0.3), but the high-rate dischargeability and cycling stability is improved. After 100 cycles, the capacity retention rate increases from 75 (x = 0) to 85% (x = 0.3).

Polyethylene/Potassium Titanate Separators For Ni/H2 Cells

NASA Technical Reports Server (NTRS)

Scott, William E.

1995-01-01

Experimental separators fabricated on paper-making machine. Two-layer, paperlike composite of polyethylene fibers and potassium titanate pigment shows promise for replacing asbestos as separator material in nickel/hydrogen electrochemical cells.

Tested Demonstrations.

ERIC Educational Resources Information Center

Roffia, Sergio; And Others

1988-01-01

Reports two electrochemical demonstrations. Uses a hydrogen-oxygen fuel cell to power a clock. Includes description of methods and materials. Investigates the "potato clock" used with different fruits. Lists emf and current for various fruit and electrode combinations. (ML)

Biodegradability engineering of biodegradable Mg alloys: Tailoring the electrochemical properties and microstructure of constituent phases

PubMed Central

Cha, Pil-Ryung; Han, Hyung-Seop; Yang, Gui-Fu; Kim, Yu-Chan; Hong, Ki-Ha; Lee, Seung-Cheol; Jung, Jae-Young; Ahn, Jae-Pyeong; Kim, Young-Yul; Cho, Sung-Youn; Byun, Ji Young; Lee, Kang-Sik; Yang, Seok-Jo; Seok, Hyun-Kwang

2013-01-01

Crystalline Mg-based alloys with a distinct reduction in hydrogen evolution were prepared through both electrochemical and microstructural engineering of the constituent phases. The addition of Zn to Mg-Ca alloy modified the corrosion potentials of two constituent phases (Mg + Mg2Ca), which prevented the formation of a galvanic circuit and achieved a comparable corrosion rate to high purity Mg. Furthermore, effective grain refinement induced by the extrusion allowed the achievement of much lower corrosion rate than high purity Mg. Animal studies confirmed the large reduction in hydrogen evolution and revealed good tissue compatibility with increased bone deposition around the newly developed Mg alloy implants. Thus, high strength Mg-Ca-Zn alloys with medically acceptable corrosion rate were developed and showed great potential for use in a new generation of biodegradable implants. PMID:23917705

Combining theory and experiment in electrocatalysis: Insights into materials design

DOE PAGES

Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.; ...

2017-01-12

Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. This review discusses design strategies for state-of-the-art heterogeneous electrocatalysts and associated materials for several different electrochemical transformations involving water, hydrogen, and oxygen, using theory as a means to rationalize catalyst performance. By examining the common principles that govern catalysis for different electrochemical reactions, we describe a systematic framework that clarifies trends in catalyzing these reactions, serving as a guide to new catalyst development while highlighting key gaps that need to be addressed. Here, we conclude by extending this framework to emerging cleanmore » energy reactions such as hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, where the development of improved catalysts could allow for the sustainable production of a broad range of fuels and chemicals.« less

Selectivity and resistance to poisons of commercial hydrogen sensors

DOE PAGES

Palmisano, V.; Weidner, E.; Boon-Brett, L.; ...

2015-03-20

The resistance of several models of catalytic, workfunction-based metal-oxide-semiconductor and electrochemical hydrogen sensors to chemical contaminants such as SO 2, H 2S, NO 2 and hexamethyldisiloxane (HMDS) has been investigated. These sensor platforms are among the most commonly used for the detection of hydrogen. The evaluation protocols were based on the methods recommended in the ISO 26142:2010 standard. Permanent alteration of the sensor response to the target analyte (H 2) following exposure to potential poisons at the concentrations specified in ISO 26142 was rarely observed. Although a shift in the baseline response was often observed during exposure to the potentialmore » poisons, only in a few cases did this shift persist after removal of the contaminants. Overall, the resistance of the sensors to poisoning was good. However, a change in sensitivity to hydrogen was observed in the electrochemical platform after exposure to NO 2 and for a catalytic sensor during exposure to SO 2. The siloxane resistance test prescribed in ISO 26142, based on exposure to 10 ppm HMDS, may possibly not properly reflect sensor robustness to siloxanes. In conclusion, further evaluation of the resistance of sensors to other Si-based contaminants and other exposure profiles (e.g., concentration, exposure times) is needed.« less

Studies on metal hydride electrodes containing no binder additives

NASA Astrophysics Data System (ADS)

Rogulski, Z.; Dłubak, J.; Karwowska, M.; Krebs, M.; Pytlik, E.; Schmalz, M.; Gumkowska, A.; Czerwiński, A.

Electrochemical properties of hydrogen storage alloys (AB 5 type: LaMm-Ni 4.1Al 0.3Mn 0.4Co 0.45) were studied in 6 M KOHaq using Limited Volume Electrode (LVE) method. Working electrodes were prepared by pressing alloy powder (without binding and conducting additives) into a metal net wire serving as a support and as a current collector. Cyclic voltammetry curves reveal well defined hydrogen sorption and desorption peaks which are separated from other faradic processes, such as surface oxidation. Voltammograms of LVE resemble the curves obtained by various authors for single particle metal alloy electrodes. Hydrogen diffusion coefficient calculated at room temperature for LV electrodes and for 100% state of charge reaches a constant value of ca. 3.3 × 10 -9 and 2.1 × 10 -10 cm 2 s -1, for chronoamperometric and chronopotentiometric measurements, respectively. A comparison of the electrodes with average alloy particle sizes of ca. 50 and 4 μm allows us to conclude that at room temperature hydrogen storage capability of AB 5 alloy studied is independent on the alloy particle size. On the other hand, reduction of the particle size increases alloy capacity at temperatures below -10 °C and reduces time of electrochemical activation of the electrode.

In-situ diagnostic tools for hydrogen transfer leak characterization in PEM fuel cell stacks part II: Operational applications

NASA Astrophysics Data System (ADS)

Niroumand, Amir M.; Homayouni, Hooman; DeVaal, Jake; Golnaraghi, Farid; Kjeang, Erik

2016-08-01

This paper describes a diagnostic tool for in-situ characterization of the rate and distribution of hydrogen transfer leaks in Polymer Electrolyte Membrane (PEM) fuel cell stacks. The method is based on reducing the air flow rate from a high to low value at a fixed current, while maintaining an anode overpressure. At high air flow rates, the reduction in air flow results in lower oxygen concentration in the cathode and therefore reduction in cell voltages. Once the air flow rate in each cell reaches a low value at which the cell oxygen-starves, the voltage of the corresponding cell drops to zero. However, oxygen starvation results from two processes: 1) the electrochemical oxygen reduction reaction which produces current; and 2) the chemical reaction between oxygen and the crossed over hydrogen. In this work, a diagnostic technique has been developed that accounts for the effect of the electrochemical reaction on cell voltage to identify the hydrogen leak rate and number of leaky cells in a fuel cell stack. This technique is suitable for leak characterization during fuel cell operation, as it only requires stack air flow and voltage measurements, which are readily available in an operational fuel cell system.

Enhanced Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg₂Ni-type Alloy by Melt Spinning.

PubMed

Zhang, Yang-Huan; Li, Bao-Wei; Ren, Hui-Ping; Li, Xia; Qi, Yan; Zhao, Dong-Liang

2011-01-18

Mg₂Ni-type Mg₂Ni 1-x Co x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were fabricated by melt spinning technique. The structures of the as-spun alloys were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys was tested by an automatic galvanostatic system. The results show that the as-spun (x = 0.1) alloy exhibits a typical nanocrystalline structure, while the as-spun (x = 0.4) alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni notably intensifies the glass forming ability of the Mg₂Ni-type alloy. The melt spinning treatment notably improves the hydriding and dehydriding kinetics as well as the high rate discharge ability (HRD) of the alloys. With an increase in the spinning rate from 0 (as-cast is defined as spinning rate of 0 m/s) to 30 m/s, the hydrogen absorption saturation ratio () of the (x = 0.4) alloy increases from 77.1 to 93.5%, the hydrogen desorption ratio () from 54.5 to 70.2%, the hydrogen diffusion coefficient (D) from 0.75 × 10 - 11 to 3.88 × 10 - 11 cm²/s and the limiting current density I L from 150.9 to 887.4 mA/g.

Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples.

PubMed

Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

2014-04-23

For the first time, high-surface-area (approximately 1465 m(2) g(-1)), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900 °C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2(-)) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results.

Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples

NASA Astrophysics Data System (ADS)

Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

2014-04-01

For the first time, high-surface-area (approximately 1465 m2 g-1), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900°C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2-) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results.

Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO 2

DOE PAGES

Passalacqua, Rosalba; Parathoner, Siglinda; Centi, Gabriele; ...

2016-08-04

The study of the electrochemical behavior (in the presence of N 2 or CO 2) of size-controlled naked Cu 5 and Cu 20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO 2 on them. Cu 20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu 5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu 5 nanoclusters coordinate effectively CO 2 (hydrogen carbonate) in solution, differentmore » from Cu 20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu 5 nanoclusters to reduce CO 2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO 2.« less

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

DOE PAGES

Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; ...

2017-05-08

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolyzers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using Density Functional Theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that aremore » tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. Finally, the results suggest design principles for a new class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.« less

Electrochemical behaviour of naked sub-nanometre sized copper clusters and effect of CO 2

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

Passalacqua, Rosalba; Parathoner, Siglinda; Centi, Gabriele

The study of the electrochemical behavior (in the presence of N 2 or CO 2) of size-controlled naked Cu 5 and Cu 20 nanoclusters, prepared using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques, evidences some relevant results regarding the redox behavior of these sub-nanometre sized copper particles and the effect of CO 2 on them. Cu 20 nanoclusters show anodic redox processes occurring at much lower potential with respect to Cu 5 nanoclusters, which behave relatively similar to much larger Cu particles. However, Cu 5 nanoclusters coordinate effectively CO 2 (hydrogen carbonate) in solution, differentmore » from Cu 20 nanoclusters and larger Cu particles. This effect, rather than the redox behavior, is apparently connected to the ability of Cu 5 nanoclusters to reduce CO 2 under cathodic conditions at low overpotential. In conclusion, although preliminary, these results provide rather exciting indications on the possibility of realizing low overpotential electrocatalytic conversion of CO 2.« less

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

NASA Astrophysics Data System (ADS)

Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; Markovic, Nenad M.; Greeley, Jeffrey

2017-06-01

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolysers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using density functional theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. The results suggest design principles for this class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

National labs team to develop better, cheaper fuel cells | Argonne National

Science.gov Websites

electricity through the reaction of hydrogen and oxygen - their only emission being the water formed when the Electrochemical Energy Science CTRCenter for Transportation Research CRIChain Reaction Innovations CIComputation

Electrochemical and thermal grafting of alkyl grignard reagents onto (100) silicon surfaces.

PubMed

Vegunta, Sri Sai S; Ngunjiri, Johnpeter N; Flake, John C

2009-11-03

Passivation of (100) silicon surfaces using alkyl Grignard reagents is explored via electrochemical and thermal grafting methods. The electrochemical behavior of silicon in methyl or ethyl Grignard reagents in tetrahydrofuran is investigated using cyclic voltammetry. Surface morphology and chemistry are investigated using atomic force microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that electrochemical pathways provide an efficient and more uniform passivation method relative to thermal methods, and XPS results demonstrate that electrografted terminations are effective at limiting native oxide formation for more than 55 days in ambient conditions. A two-electron per silicon mechanism is proposed for electrografting a single (1:1) alkyl group per (100) silicon atom. The mechanism includes oxidation of two Grignard species and subsequent hydrogen abstraction and alkylation reaction resulting in a covalent attachment of alkyl groups with silicon.

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

Rational Design of an Electron-Reservoir Pt(II) Complex for Efficient Photocatalytic Hydrogen Production from Water.

PubMed

Whang, Dong Ryeol; Park, Soo Young

2015-10-12

Herein we report a Pt(II) complex containing a 4,4'-bis[4-(triphenylsilyl)phenyl]-2,2'-bipyridine ligand as a molecular catalyst for water splitting. Systematic studies of the electrochemical and electronic properties of this catalyst, in comparison with two control complexes, reveal electron-reservoir characteristics upon two-electron reduction. A turnover number of 510,000 was recorded by employing this complex as a water reduction catalyst in combination with a state-of-the-art photosensitizer and N,N-dimethylaniline as a sacrificial electron donor, which represents a large improvement over the control complexes that do not contain the tetraphenylsilyl ligand substitution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Progress in utilisation of graphene for electrochemical biosensors.

PubMed

Lawal, Abdulazeez T

2018-05-30

This review discusses recent graphene (GR) electrochemical biosensor for accurate detection of biomolecules, including glucose, hydrogen peroxide, dopamine, ascorbic acid, uric acid, nicotinamide adenine dinucleotide, DNA, metals and immunosensor through effective immobilization of enzymes, including glucose oxidase, horseradish peroxidase, and haemoglobin. GR-based biosensors exhibited remarkable performance with high sensitivities, wide linear detection ranges, low detection limits, and long-term stabilities. Future challenges for the field include miniaturising biosensors and simplifying mass production are discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Review of electrochemical impregnation for nickel cadmium cells. [aerospace applications

NASA Technical Reports Server (NTRS)

Gross, S.

1977-01-01

A method of loading active material within the electrodes of nickel cadmium cells is examined. The basic process of electrochemical impregnation of these electrodes is detailed, citing the principle that when current is applied reactions occur which remove hydrogen ions from solution, making the interior of the plaque less acidic. Electrodes result which are superior in energy density, stability, and life. The technology is reviewed and illustrated with typical performance data. Recommendations are made for additional research and development.

Novel metal-filled polyimide electrodes

NASA Technical Reports Server (NTRS)

Furtsch, T. A.; Finklea, H. O.; Taylor, L. T.

1984-01-01

Palladium-coated polyimide films are evaluated as electrochemical electrodes. The film electrodes exhibit essentially identical behavior compared to bulk palladium electrodes. In aqueous 0.5M H2SO4, current peaks due to oxide formation, oxide stripping, hydrogen adsorption, and H2 oxidation are observed. The ferri/ferrocyanide redox couple is grossly irreversible in the same electrolyte. Reversible electrochemical behavior is obtained for Fe(EDTA)(1-/2-) in 1M KCl/H2O, and for ferrocene/ferricenium in 0.1M TEAP/dimethylacetamide.

Layering and Ordering in Electrochemical Double Layers

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

Liu, Yihua; Kawaguchi, Tomoya; Pierce, Michael S.

Electrochemical double layers (EDL) form at electrified interfaces. While Gouy-Chapman model describes moderately charged EDL, formation of Stern layers was predicted for highly charged EDL. Our results provide structural evidence for a Stern layer of cations, at potentials close to hydrogen evolution in alkali fluoride and chloride electrolytes. Layering was observed by x-ray crystal truncation rods and atomic-scale recoil responses of Pt(111) surface layers. Ordering in the layer is confirmed by glancing-incidence in-plane diffraction measurements.

Effect of Thermomechanical Processing and Crystallographic Orientation on the Corrosion Behavior of API 5L X70 Pipeline Steel

NASA Astrophysics Data System (ADS)

Ohaeri, Enyinnaya; Omale, Joseph; Eduok, Ubong; Szpunar, Jerzy

2018-04-01

This work presents the electrochemical response of X70 pipeline steel substrates thermomechanically processed at different conditions. The WE sample was hot rolled at a temperature range of 850 °C to 805 °C and cooled at a rate of 42.75 °C/s. Another sample WD was hot rolled from 880 °C to 815 °C and cooled at a faster rate of 51.5 °C/s. Corrosion tests were conducted electrochemically by potentiodynamic polarization in hydrogen-charged and non-hydrogen-charged environments. A lower corrosion rate was measured with hydrogen charging due to the rapid formation of corrosion product film on pipeline substrate, but WE specimen emerged as the most susceptible to corrosion with and without hydrogen charging. Variations in thermomechanical rolling conditions influenced grain orientation, protective film properties, corrosion, and cracking behavior on both specimens. Cracks were seen in both specimens after hydrogen charging, but specimen WE experienced a more intense deterioration of protective corrosion product film and subsequent cracking. A large part of specimen WD retained its protective corrosion product film after the polarization test, and sites where spalling occurred resulted in pitting with less cracking. Despite weak crystallographic texture noticed in both specimens, WD showed a higher intensity of corrosion-resistant 111||ND-oriented grains, while WE showed a more random distribution of 111||ND-, 011||ND-, and 001||ND-oriented grains with a lower intensity.

Coupling thermoelectricity and electrocatalysis for hydrogen production via PbTesbnd PbS/TiO2 heterojunction

NASA Astrophysics Data System (ADS)

Liu, Zhongqing; Cao, Xiaohao; Wang, Bin; Xia, Min; Lin, Sidney; Guo, Zhanhu; Zhang, Xiaoming; Gao, Shiyuan

2017-02-01

PbTesbnd PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTesbnd PbS/TiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTesbnd PbS/TNAs, the two electrode system in which PbTesbnd PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 °C and 1.0 V bath voltage, the system registers 6.1 mL cm-2 h-1 rate of hydrogen generation, consuming electric power of 26.2 kW h kg-1 H2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling.

Effect of Thermomechanical Processing and Crystallographic Orientation on the Corrosion Behavior of API 5L X70 Pipeline Steel

NASA Astrophysics Data System (ADS)

Ohaeri, Enyinnaya; Omale, Joseph; Eduok, Ubong; Szpunar, Jerzy

2018-06-01

This work presents the electrochemical response of X70 pipeline steel substrates thermomechanically processed at different conditions. The WE sample was hot rolled at a temperature range of 850 °C to 805 °C and cooled at a rate of 42.75 °C/s. Another sample WD was hot rolled from 880 °C to 815 °C and cooled at a faster rate of 51.5 °C/s. Corrosion tests were conducted electrochemically by potentiodynamic polarization in hydrogen-charged and non-hydrogen-charged environments. A lower corrosion rate was measured with hydrogen charging due to the rapid formation of corrosion product film on pipeline substrate, but WE specimen emerged as the most susceptible to corrosion with and without hydrogen charging. Variations in thermomechanical rolling conditions influenced grain orientation, protective film properties, corrosion, and cracking behavior on both specimens. Cracks were seen in both specimens after hydrogen charging, but specimen WE experienced a more intense deterioration of protective corrosion product film and subsequent cracking. A large part of specimen WD retained its protective corrosion product film after the polarization test, and sites where spalling occurred resulted in pitting with less cracking. Despite weak crystallographic texture noticed in both specimens, WD showed a higher intensity of corrosion-resistant 111|| ND-oriented grains, while WE showed a more random distribution of 111|| ND-, 011|| ND-, and 001|| ND-oriented grains with a lower intensity.

Fabrication and electrochemical performance of nickel- and gadolinium-doped ceria-infiltrated La0·2Sr0·8TiO3 anodes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Min-Jin; Shin, Jae-Hwa; Ji, Mi-Jung; Hwang, Hae-Jin

2018-01-01

In this work, nickel and gadolinium-doped ceria (GDC)-infiltrated lanthanum strontium titanate (LST) anodes are fabricated, and their electrode performances under a hydrogen atmosphere is investigated in terms of the Ni:GDC ratios and cell operating temperature. The Ni/GDC-infiltrated LST anode exhibits excellent electrode performance in comparison with the Ni- or GDC-infiltrated anodes, which is attributed to the synergistic effect of an extended triple-phase boundary length by GDC and good catalytic activity for hydrogen oxidation because of the Ni particles. The polarization resistances (Rp) of Ni/GDC-infiltrated LST are 0.07, 0.08, and 0.12 Ω cm2 at 800, 750, and 700 °C, respectively, which are approximately three orders of magnitude lower than that of the LST anode (68.5 Ω cm2 at 700 °C). The effect of Ni and GDC on the electrochemical performance of LST was also investigated by using electrochemical impedance spectroscopy (EIS). The anode polarization resistance (Rp) is confirmed to be dependent on the content and dispersion state (microstructure) of the Ni and GDC nanoparticles.

A nanocomposite-based electrochemical sensor for non-enzymatic detection of hydrogen peroxide

PubMed Central

Du, Xin; Chen, Yuan; Dong, Wenhao; Han, Bingkai; Liu, Min; Chen, Qiang; Zhou, Jun

2017-01-01

Hydrogen peroxide (H2O2) plays important signaling roles in normal physiology and disease. However, analyzing the actions of H2O2 is often impeded by the difficulty in detecting this molecule. Herein, we report a novel nanocomposite-based electrochemical sensor for non-enzymatic detection of H2O2. Graphene oxide (GO) was selected as the dopant for the synthesis of polyaniline (PANI), leading to the successful fabrication of a water-soluble and stable GO-PANI composite. GO-PANI was subsequently subject to cyclic voltammetry to generate reduced GO-PANI (rGO-PANI), enhancing the conductivity of the material. Platinum nanoparticles (PtNPs) were then electrodeposited on the surface of the rGO-PANI-modified glassy carbon electrode (GCE) to form an electrochemical H2O2 sensor. Compared to previously reported sensors, the rGO-PANI-PtNP/GCE exhibited an expanded linear range, higher sensitivity, and lower detection limit in the quantification of H2O2. In addition, the sensor displayed outstanding reproducibility and selectivity in real-sample examination. Our study suggests that the rGO-PANI-PtNP/GCE may have broad utility in H2O2 detection under physiological and pathological conditions. PMID:28035076

Electrochemical removal of biofilms from titanium dental implant surfaces.

PubMed

Schneider, Sebastian; Rudolph, Michael; Bause, Vanessa; Terfort, Andreas

2018-06-01

The infection of dental implants may cause severe inflammation of tissue and even bone degradation if not treated. For titanium implants, a new, minimally invasive approach is the electrochemical removal of the biofilms including the disinfection of the metal surface. In this project, several parameters, such as electrode potentials and electrolyte compositions, were varied to understand the underlying mechanisms. Optimal electrolytes contained iodide as well as lactic acid. Electrochemical experiments, such as cyclic voltammetry or measurements of open circuit potentials, were performed in different cell set-ups to distinguish between different possible reactions. At the applied potentials of E < -1.4 V, the hydrogen evolution reaction dominated at the implant surface, effectively lifting off the bacterial films. In addition, several disinfecting species are formed at the anode, such as triiodide and hydrogen peroxide. Ex situ tests with model biofilms of E. coli clearly demonstrated the effectiveness of the respective anolytes in killing the bacteria, as determined by the LIVE/DEAD™ assay. Using optimized electrolysis parameters of 30 s at 7.0 V and 300 mA, a 14-day old wildtype biofilm could be completely removed from dental implants in vitro. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

NASA Astrophysics Data System (ADS)

Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

2018-04-01

In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

Interferences in electrochemical hydride generation of hydrogen selenide

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Belarra, M. A.; Castillo, J. R.

2001-12-01

Interferences from Cu(II), Zn(II), Pt(IV), As(III) and nitrate on electrochemical hydride generation of hydrogen selenide were studied using a tubular flow-through generator, flow injection sample introduction and quartz tube atomic absorption spectrometry. Comparison with conventional chemical generation using tetrahydroborate was also performed. Lead and reticulated vitreous carbon (RVC), both in particulate form, were used as cathode materials. Signal supressions up to 60-75%, depending on the cathode material, were obtained in the presence of up to 200 mg l-1 of nitrate due to the competitive reduction of the anion. Interference from As(III) was similar in electrochemical and chemical generation, being related to the quartz tube atomization process. Zinc did not interfere up to Se/Zn ratios 1:100, whereas copper and platinum showed suppression levels up to 50% for Se/interferent ratios 1:100. Total signal suppression was observed in presence of Se/Cu ratios 1:100 when RVC cathodes were used. No memory effects were observed in any case. Scanning electron microscopy and squared wave voltametry studies supported the interference mechanism based on the decomposition of the hydride on the dispersed particles of the reduced metal.

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

PubMed

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

Pulse electrochemical meso/micro/nano ultraprecision machining technology.

PubMed

Lee, Jeong Min; Kim, Young Bin; Park, Jeong Woo

2013-11-01

This study demonstrated meso/micro/nano-ultraprecision machining through electrochemical reactions using intermittent DC pulses. The experiment focused on two machining methods: (1) pulse electrochemical polishing (PECP) of stainless steel, and (2) pulse electrochemical nano-patterning (PECNP) on a silicon (Si) surface, using atomic force microscopy (AFM) for fabrication. The dissolution reaction at the stainless steel surface following PECP produced a very clean, smooth workpiece. The advantages of the PECP process included improvements in corrosion resistance, deburring of the sample surface, and removal of hydrogen from the stainless steel surface as verified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). In PECNP, the electrochemical reaction generated within water molecules produced nanoscale oxide textures on a Si surface. Scanning probe microscopy (SPM) was used to evaluate nanoscale-pattern processing on a Si wafer surface produced by AFM-PECNP For both processes using pulse electrochemical reactions, three-dimensional (3-D) measurements and AFM were used to investigate the changes on the machined surfaces. Preliminary results indicated the potential for advancing surface polishing techniques and localized micro/nano-texturing technology using PECP and PECNP processes.

Destructive impact of molecular noise on nanoscale electrochemical oscillators

NASA Astrophysics Data System (ADS)

Cosi, Filippo G.; Krischer, Katharina

2017-06-01

We study the loss of coherence of electrochemical oscillations on meso- and nanosized electrodes with numeric simulations of the electrochemical master equation for a prototypical electrochemical oscillator, the hydrogen peroxide reduction on Pt electrodes in the presence of halides. On nanoelectrodes, the electrode potential changes whenever a stochastic electron-transfer event takes place. Electrochemical reaction rate coefficients depend exponentially on the electrode potential and become thus fluctuating quantities as well. Therefore, also the transition rates between system states become time-dependent which constitutes a fundamental difference to purely chemical nanoscale oscillators. Three implications are demonstrated: (a) oscillations and steady states shift in phase space with decreasing system size, thereby also decreasing considerably the oscillating parameter regions; (b) the minimal number of molecules necessary to support correlated oscillations is more than 10 times as large as for nanoscale chemical oscillators; (c) the relation between correlation time and variance of the period of the oscillations predicted for chemical oscillators in the weak noise limit is only fulfilled in a very restricted parameter range for the electrochemical nano-oscillator.

Self-supported three-dimensional Cu/Cu2O-CuO/rGO nanowire array electrodes for an efficient hydrogen evolution reaction.

PubMed

Ye, Lin; Wen, Zhenhai

2018-06-14

We report the fabrication of self-supported Cu/Cu2O-CuO/rGO nanowire arrays on commercial porous copper foam, which exhibit excellent activity and durability for electrochemical hydrogen evolution, presenting a small onset potential of 84 mV and a low overpotential of 105 mV at a current density of 10 mA cm-2.

Electrochemical Separation, Pumping, and Storage of Hydrogen or Oxygen into Nanocapillaries Via High Pressure MEA Seals

DTIC Science & Technology

2015-10-13

Fabrication (3) Integrate Membrane & (4) Fill with Hydrogen Shaped Al Aluminum Oxide Nanocapillary Array CNT Coated Pore Wall Complete Gas Storage...nanocapillary arrays are produced through aluminum anodization . The nanocapillary arrays are capped with either a PEM or an alkaline (anion) exchange...24,600 psi)  Circumferential Stress  Proportional to  Pore radius  Wall thickness Aluminum AAO AAO /CNT Nanocapillary Array (Not to scale

Hydrogen production from sugar beet juice using an integrated biohydrogen process of dark fermentation and microbial electrolysis cell.

PubMed

Dhar, Bipro Ranjan; Elbeshbishy, Elsayed; Hafez, Hisham; Lee, Hyung-Sool

2015-12-01

An integrated dark fermentation and microbial electrochemical cell (MEC) process was evaluated for hydrogen production from sugar beet juice. Different substrate to inoculum (S/X) ratios were tested for dark fermentation, and the maximum hydrogen yield was 13% of initial COD at the S/X ratio of 2 and 4 for dark fermentation. Hydrogen yield was 12% of initial COD in the MEC using fermentation liquid end products as substrate, and butyrate only accumulated in the MEC. The overall hydrogen production from the integrated biohydrogen process was 25% of initial COD (equivalent to 6 mol H2/mol hexoseadded), and the energy recovery from sugar beet juice was 57% using the combined biohydrogen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ultrafine hydrogen storage powders

DOEpatents

Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

2000-06-13

A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

Enhancing the sensitivity of needle-implantable electrochemical glucose sensors via surface rebuilding.

PubMed

Vaddiraju, Santhisagar; Legassey, Allen; Qiang, Liangliang; Wang, Yan; Burgess, Diane J; Papadimitrakopoulos, Fotios

2013-03-01

Needle-implantable sensors have shown to provide reliable continuous glucose monitoring for diabetes management. In order to reduce tissue injury during sensor implantation, there is a constant need for device size reduction, which imposes challenges in terms of sensitivity and reliability, as part of decreasing signal-to-noise and increasing layer complexity. Herein, we report sensitivity enhancement via electrochemical surface rebuilding of the working electrode (WE), which creates a three-dimensional nanoporous configuration with increased surface area. The gold WE was electrochemically rebuilt to render its surface nanoporous followed by decoration with platinum nanoparticles. The efficacy of such process was studied using sensor sensitivity against hydrogen peroxide (H2O2). For glucose detection, the WE was further coated with five layers, namely, (1) polyphenol, (2) glucose oxidase, (3) polyurethane, (4) catalase, and (5) dexamethasone-releasing poly(vinyl alcohol)/poly(lactic-co-glycolic acid) composite. The amperometric response of the glucose sensor was noted in vitro and in vivo. Scanning electron microscopy revealed that electrochemical rebuilding of the WE produced a nanoporous morphology that resulted in a 20-fold enhancement in H2O2 sensitivity, while retaining >98% selectivity. This afforded a 4-5-fold increase in overall glucose response of the glucose sensor when compared with a control sensor with no surface rebuilding and fittable only within an 18 G needle. The sensor was able to reproducibly track in vivo glycemic events, despite the large background currents typically encountered during animal testing. Enhanced sensor performance in terms of sensitivity and large signal-to-noise ratio has been attained via electrochemical rebuilding of the WE. This approach also bypasses the need for conventional and nanostructured mediators currently employed to enhance sensor performance. © 2013 Diabetes Technology Society.

Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water.

PubMed

Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel; Tatin, Arnaud

2015-06-02

Substitution of the four paraphenyl hydrogens of iron tetraphenylporphyrin by trimethylammonio groups provides a water-soluble molecule able to catalyze the electrochemical conversion of carbon dioxide into carbon monoxide. The reaction, performed in pH-neutral water, forms quasi-exclusively carbon monoxide with very little production of hydrogen, despite partial equilibration of CO2 with carbonic acid-a low pKa acid. This selective molecular catalyst is endowed with a good stability and a high turnover frequency. On this basis, prescribed composition of CO-H2 mixtures can be obtained by adjusting the pH of the solution, optionally adding an electroinactive buffer. The development of these strategies will be greatly facilitated by the fact that one operates in water. The same applies for the association of the cathode compartment with a proton-producing anode by means of a suitable separator.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Electrochemical separation and concentration of hydrogen sulfide from gas mixtures

DOEpatents

Winnick, Jack; Sather, Norman F.; Huang, Hann S.

1984-10-30

A method of removing sulfur oxides of H.sub.2 S from high temperature gas mixtures (150.degree.-1000.degree. C.) is the subject of the present invention. An electrochemical cell is employed. The cell is provided with inert electrodes and an electrolyte which will provide anions compatible with the sulfur containing anions formed at the anode. The electrolyte is also selected to provide inert stable cations at the temperatures encountered. The gas mixture is passed by the cathode where the sulfur gases are converted to SO.sub.4 -- or, in the case of H.sub.2 S, to S--. The anions migrate to the anode where they are converted to a stable gaseous form at much greater concentration levels (>10X). Current flow may be effected by utilizing an external source of electrical energy or by passing a reducing gas such as hydrogen past the anode.

ELECTROCHEMICAL SEPARATION AND CONCENTRATION OF HYDROGEN SULFIDE FROM GAS MIXTURES

DOEpatents

Winnick, Jack; Sather, Norman F.; Huang, Hann S.

1984-10-30

A method of removing sulfur oxides of H.sub.2 S from high temperature gas mixtures (150.degree.-1000.degree. C.) is the subject of the present invention. An electrochemical cell is employed. The cell is provided with inert electrodes and an electrolyte which will provide anions compatible with the sulfur containing anions formed at the anode. The electrolyte is also selected to provide inert stable cations at the temperatures encountered. The gas mixture is passed by the cathode where the sulfur gases are converted to SO.sub.4 -- or, in the case of H.sub.2 S, to S--. The anions migrate to the anode where they are converted to a stable gaseous form at much greater concentration levels (>10X). Current flow may be effected by utilizing an external source of electrical energy or by passing a reducing gas such as hydrogen past the anode.

The correlation of cathodic peak potentials of vitamin K(3) derivatives and their calculated electron affinities. The role of hydrogen bonding and conformational changes.

PubMed

Nasiri, Hamid Reza; Panisch, Robin; Madej, M Gregor; Bats, Jan W; Lancaster, C Roy D; Schwalbe, Harald

2009-06-01

2-methyl-1,4-naphtoquinone 1 (vitamin K(3), menadione) derivatives with different substituents at the 3-position were synthesized to tune their electrochemical properties. The thermodynamic midpoint potential (E(1/2)) of the naphthoquinone derivatives yielding a semi radical naphthoquinone anion were measured by cyclic voltammetry in the aprotic solvent dimethoxyethane (DME). Using quantum chemical methods, a clear correlation was found between the thermodynamic midpoint potentials and the calculated electron affinities (E(A)). Comparison of calculated and experimental values allowed delineation of additional factors such as the conformational dependence of quinone substituents and hydrogen bonding which can influence the electron affinities (E(A)) of the quinone. This information can be used as a model to gain insight into enzyme-cofactor interactions, particularly for enzyme quinone binding modes and the electrochemical adjustment of the quinone motif.

Space Electrochemical Research and Technology Conference, 2nd, Cleveland, OH, Apr. 11-13, 1989, Proceedings

NASA Technical Reports Server (NTRS)

O'Donnell, Patricia M. (Editor)

1990-01-01

Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.

Electrochemical reduction of toluene to methylcyclohexane for use as an energy carrier

NASA Astrophysics Data System (ADS)

Matsuoka, Koji; Miyoshi, Kota; Sato, Yasushi

2017-03-01

The electrochemical reduction of liquid toluene to methylcyclohexane (MCH) was investigated using a membrane electrode assembly (MEA) and high active-area catalysts commonly used in proton exchange membrane fuel cells (PEMFC). The current density on Pt/C was higher than on PtRu/C, which was comparable to that of alkaline water electrolysis. The potential of hydrogen evolution was shifted negatively by the presence of toluene and MCH. Therefore, the toluene reduction reaction was almost perfectly separated from the hydrogen evolution reaction. Toluene was perfectly reduced to MCH at around 0 V vs. RHE on PtRu/C and no by-products were detected in the solutions after electrolysis. MCH was produced at a Faradaic efficiency of more than 96% by carefully keeping the potential above -30 mV vs. RHE. Through this electrolytic process, we were able to reduce the concentration of toluene from 100% to 7.6%.

Generalized platform for antibody detection using the antibody catalyzed water oxidation pathway.

PubMed

Welch, M Elizabeth; Ritzert, Nicole L; Chen, Hongjun; Smith, Norah L; Tague, Michele E; Xu, Youyong; Baird, Barbara A; Abruña, Héctor D; Ober, Christopher K

2014-02-05

Infectious diseases, such as influenza, present a prominent global problem including the constant threat of pandemics that initiate in avian or other species and then pass to humans. We report a new sensor that can be specifically functionalized to detect antibodies associated with a wide range of infectious diseases in multiple species. This biosensor is based on electrochemical detection of hydrogen peroxide generated through the intrinsic catalytic activity of all antibodies: the antibody catalyzed water oxidation pathway (ACWOP). Our platform includes a polymer brush-modified surface where specific antibodies bind to conjugated haptens with high affinity and specificity. Hydrogen peroxide provides an electrochemical signal that is mediated by Resorufin/Amplex Red. We characterize the biosensor platform, using model anti-DNP antibodies, with the ultimate goal of designing a versatile device that is inexpensive, portable, reliable, and fast. We demonstrate detection of antibodies at concentrations that fall well within clinically relevant levels.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

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

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Degradation of 2,4,6-trinitrotoluene by immobilized horseradish peroxidase and electrogenerated peroxide.

PubMed

Beom Lee, Ki; Bock Gu, Man; Moon, Seung Hyeon

2003-03-01

This paper presents horseradish peroxidase (HRP)-catalyzed removal of 2,4,6-trinitrotoluene (TNT) by an electrochemical packed-bed flow reactor operated in a circulating batch mode with the help of in situ generated hydrogen peroxide. HRP immobilized on the reticulated vitreous carbon electrode was prepared for the cyclic voltammetry of 2,4,6-TNT. Effects of pH and temperature on the TNT electroreduction in 0.2M phosphate buffer saturated with oxygen were examined. HRP immobilized carbon electrode was capable of catalyzing the oxidation and detoxification of 44 microM TNT in aqueous solution under optimized conditions. The removal rate of TNT for the electroenzymatic method was much greater than for electrochemical and biochemical methods. Stoichiometric and kinetic studies indicated that the hydrogen peroxide was utilized more effectively in the electroenzymatic method. Denitrification as intermediate reaction was also investigated.

Layered transition metal dichalcogenide electrochemistry: journey across the periodic table.

PubMed

Chia, Xinyi; Pumera, Martin

2018-06-08

Studies on layered transition metal dichalcogenides (TMDs), in particular for Group VIB TMDs like MoS2 and WS2, have long reached a crescendo in the realms of electrochemical applications initiated by their remarkable catalytic and electronic properties. One area that garnered considerable attention is the fervent pursuit of layered TMDs as electrocatalysts for hydrogen evolution reaction (HER), driven by global efforts towards reducing carbon footprint and attaining hydrogen economy. This Tutorial Review captures the essence of electrochemistry of different classes of layered TMDs and metal chalcogenides across the period table and showcases their tuneable electrochemical and HER catalytic attributes that are governed by the elemental composition, structure and anisotropy. Of interest to the assiduously studied Group VIB TMDs, we describe the role of elemental constituents and material purity in aspects of surface composition and structure, on their electrochemistry. Across families of layered TMDs in the periodic table, we highlight the apparent trends in their electrochemical and electrocatalytic properties through diligent comparison. Inevitably, these trends vary according to the type of chalcogen or transition metal that constitutes the eventual TMD. Beyond layered TMDs, we discuss the electrochemistry and recent progress in HER electrocatalysis of other layered metal chalcogenides that are overshadowed by the success of Group VIB TMDs. At the pinnacle of the emergent applications of layered TMDs, it is prudent to demystify the intrinsic electrochemical behaviour that originates from the participation of the elemental constitution of transition metal or chalcogen. Moreover, knowledge of the catalytic and electronic properties of the various TMD families and emerging trends across the period or down the group is of paramount importance when introducing or refining their prospective uses. The annotations in this Tutorial Review are envisioned to promote discourse into the catalytic and electrochemical trends of TMDs that is currently absent.

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.

An electrochemical rebalance cell for Redox systems

NASA Technical Reports Server (NTRS)

Acevedo, J. C.; Stalnaker, D. K.

1983-01-01

An electrochemical rebalance cell for maintaining electrochemical balance, at the system level, of the acidified aqueous iron chloride and chromium chloride reactant solutions in the redox energy storage system was constructed and evaluated. The electrochemical reaction for the cathode is Fe(+3) + e(-) yields Fe(+2), and that for the anode is 1/2H2 yields H(+) + e(-). The iron (carbon felt) electrode and the hydrogen (platinized carbon) electrode are separated by an anion exchange membrane. The performance of the rebalance cell is discussed as well as the assembly of a single rebalance cell and multicell stacks. Various cell configurations were tested and the results are presented and discussed. The rebalance cell was also used to demonstrate its ability, as a preparative tool, for making high purity solutions of soluble reduced metal ionic species. Preparations of titanium, copper, vanadium and chromium ions in acidified solutions were evaluated.

Three-Dimensional Architectures Constructed from Transition-Metal Dichalcogenide Nanomaterials for Electrochemical Energy Storage and Conversion.

PubMed

Yun, Qinbai; Lu, Qipeng; Zhang, Xiao; Tan, Chaoliang; Zhang, Hua

2018-01-15

Transition-metal dichalcogenides (TMDs) have attracted considerable attention in recent years because of their unique properties and promising applications in electrochemical energy storage and conversion. However, the limited number of active sites as well as blocked ion and mass transport severely impair their electrochemical performance. The construction of three-dimensional (3D) architectures from TMD nanomaterials has been proven to be an effective strategy to solve the aforementioned problems as a result of their large specific surface areas and short ion and mass transport distances. This Review summarizes the commonly used routes to build 3D TMD architectures and highlights their applications in electrochemical energy storage and conversion, including batteries, supercapacitors, and electrocatalytic hydrogen evolution. The challenges and outlook in this research area are also discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stress Corrosion Cracking Study of Aluminum Alloys Using Electrochemical Noise Analysis

NASA Astrophysics Data System (ADS)

Rathod, R. C.; Sapate, S. G.; Raman, R.; Rathod, W. S.

2013-12-01

Stress corrosion cracking studies of aluminum alloys AA2219, AA8090, and AA5456 in heat-treated and non heat-treated condition were carried out using electrochemical noise technique with various applied stresses. Electrochemical noise time series data (corrosion potential vs. time) was obtained for the stressed tensile specimens in 3.5% NaCl aqueous solution at room temperature (27 °C). The values of drop in corrosion potential, total corrosion potential, mean corrosion potential, and hydrogen overpotential were evaluated from corrosion potential versus time series data. The electrochemical noise time series data was further analyzed with rescaled range ( R/ S) analysis proposed by Hurst to obtain the Hurst exponent. According to the results, higher values of the Hurst exponents with increased applied stresses showed more susceptibility to stress corrosion cracking as confirmed in case of alloy AA 2219 and AA8090.

Enhanced Electronic Communication and Electrochemical Sensitivity Benefiting from the Cooperation of Quadruple Hydrogen Bonding and π-π Interactions in Graphene/Multi-Walled Carbon Nanotube Hybrids.

PubMed

Wang, Qiguan; Wang, Sumin; Shang, Jiayin; Qiu, Shenbao; Zhang, Wenzhi; Wu, Xinming; Li, Jinhua; Chen, Weixing; Wang, Xinhai

2017-02-22

By designing a molecule labeled as UPPY with both ureidopyrimidinone (UP) and pyrene (PY) units, the supramolecular self-assembly of multiwalled carbon nanotube (MWNT) and reduced graphene oxide (rGO) was driven by the UP quadruple hydrogen-bonding and PY-based π-π interactions to form a novel hybrid of rGO-UPPY-MWNT in which the morphology of rGO-wrapped MWNT was found. Bridged by the two kinds of noncovalent bonding, enhanced electronic communication occurred in rGO-UPPY-MWNT. Also, under the cooperation of UP quadruple hydrogen-bonding and PY-based π-π interactions, higher electrical conductivity and better charge transfer were observed for rGO-UPPY-MWNT, compared with the rGO-MWNT composite without such noncovalent bonds, and that with just single PY-based π-π interaction (rGO-PY-MWNT) or UP quadruple hydrogen bond (rGO-UP-MWNT). Specifically, the electrical conductivity of rGO-PY-MWNT hybrids was increased approximately sevenfold, and the interfacial charge transfer resistance was nearly decreased by 1 order of magnitude compared with rGO-MWNT, rGO-UP-MWNT, and rGO-PY-MWNT. Resulting from its excellent electrical conductivity and charge transfer properties, the rGO-UPPY-MWNT modified electrode exhibited enhanced electrochemical activity toward dopamine with detection limit as low as 20 nM.

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

Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

PubMed

Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

2013-07-19

A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

Nanoparticle-based electrochemical sensors for the detection of lactate and hydrogen peroxide

NASA Astrophysics Data System (ADS)

Uzunoglu, Aytekin

In the present study, electrochemical sensors for the detection of lactate and hydrogen peroxide were constructed by exploiting the physicochemical properties of metal ad metal oxide nanoparticles. This study can be divided into two main sections. While chapter 2, 3, and 4 report on the construction of electrochemical lactate biosensors using CeO2 and CeO2-based mixed metal oxide nanoparticles, chapter 5 and 6 show the development of electrochemical hydrogen peroxide sensors by the decoration of the electrode surface with palladium-based nanoparticles. First generation oxidase enzyme-based sensors suffer from oxygen dependency which results in errors in the response current of the sensors in O2-lean environments. To address this challenge, the surface of the sensors must be modified with oxygen rich materials. In this regard, we developed a novel electrochemical lactate biosensor design by exploiting the oxygen storage capacity of CeO2 and CeO 2-CuO nanoparticles. By the introduction of CeO2 nanoparticles into the enzyme layer of the sensors, negative interference effect of ascorbate which resulted from the formation of oxygen-lean regions was eliminated successfully. When CeO2-based design was exposed to higher degree of O2 -depleted environments, however, the response current of the biosensors experienced an almost 21 % decrease, showing that the OSC of CeO2 was not high enough to sustain the enzymatic reactions. When CeO2-CuO nanoparticles, which have 5 times higher OSC than pristine CeO2, were used as an oxygen supply in the enzyme layer, the biosensors did not show any drop in the performance when moving from oxygen-rich to oxygen-lean conditions. In the second part of the study, PdCu/SPCE and PdAg/rGO-based electrochemical H2O2 sensors were designed and their performances were evaluated to determine their sensitivity, linear range, detection limit, and storage stability. In addition, practical applicability of the sensors was studied in human serum. The chronoamperometry results showed that the PdCu/SPCE sensors yielded a high sensitivity (396.7 microA mM -1 cm-2), a wide linear range (0.5 -11 mM), and a low limit of detection (0.7 microM) at the applied potential of -0.3 V. For PdAg/rGO sensors, a high sensitivity of 247.6 +/- 2.7 microA˙mM -1˙cm-2 was obtained towards H2O 2 in a linear range of 0.05 mM to 28 mM.

From flavoenzymes to devices: The role of electronic effects in recognition

NASA Astrophysics Data System (ADS)

Deans, Robert

Acylated aminopyridines provide models for specific flavoenzyme-cofactor interactions, allowing isolation and observation of the effects of hydrogen bonding on flavin NMR. To determine the relative hydrogen bond affinities of O(2) and O(4) of the flavin, a 2-aminopyridine based receptor was investigated. Additionally, this receptor allowed the effects of hydrogen bonding at O(2) and O(4) on the electron distribution in the flavin nucleus to be determined using sp{13}C NMR. A new family of receptors for flavins based on 6-aryl-2,4-(acyldiamino)-s-triazines was synthesized. In these synthetic hosts, systematic variation of the spatially remote substituents on the 6-aryl ring altered the hydrogen bond donating abilities of the amide functionality and the hydrogen bond accepting properties of the triazine N(3). This variation resulted in a strong modulation of the efficiency of flavin binding, with association constants for the receptor flavin complexes ranging over an 8-fold range. In addition, the communication of electronic information over extended distances was also investigated. Polymers can provide relevant media for the modeling of biological processes, including molecular recognition. To explore this possibility, a diaminotriazine-functionalized polymer was synthesized, starting from Merrifield's peptide resin. This polymer selectively bound a flavin derivative through hydrogen bonding, efficiently extracting it from a chloroform solution, as monitored by UV-vis extraction studies. The temperature profile of this polymer-flavin binding was also investigated and compared to the analogous solution-phase triazine-flavin dyad. Hydrogen bonding and aromatic stacking are fundamental interactions in molecular recognition. These interactions are sensitive to the redox states of the components of the host-guest complex. To explore the interplay of recognition and redox processes, a system consisting of two hosts and one guest, where guest binding interactions (hydrogen bonding and aromatic stacking) were modulated via choice of redox state was examined. Proper choice of receptors then provided a device where the competition between the two hosts was controlled by the redox state of the guest. The efficient reversal of host preference in this assembly provided an electrochemically-controlled three-component, two-pole, molecular switch.

Tailoring the Kinetics of the Photoinitiated Cationic Polymerization of Polyoctahedral Oligomeric Silsesquioxane (POSS)-Containing Epoxy Monomers

NASA Astrophysics Data System (ADS)

Iordanov, Liubomir

Within the aircraft industry, high strength steels have been used for aircraft components (e.g., main landing gear, fasteners, etc). These steels have traditionally been protected using cadmium electroplating. As a result of the carcinogenic nature of cadmium, its use has been severely restricted. Electroplated ZnNi has been identified as a replacement material for the cadmium coating. Demonstration plating lines have been implemented in both Air Force and NAVAIR depots. However, the effects of hydrogen generated from differences in electrochemical potential between the ZnNi coating and exposed steel at a defect site have raised concern. The objective of this work is to determine the potential effect of hydrogen on the susceptibility of ZnNi coated 4340 steel to Hydrogen Embrittlement. In this work, susceptibility of the substrate AISI 4340 steel to HE as a function of cathodic potential will be shown. Slow strain rate tests (SSRT) of smooth bar samples made of high strength AISI 4340 are being conducted to determine susceptibility to HE. In the first set of SSR experiments, bare steel samples were exposed to a NaCl immersion environment while being held at one of five different electrochemical potentials. The effect of potential on time to failure and other properties will be explored. A second set of SSR tests were performed under atmospheric exposure conditions at 84% RH. This value of RH is above the deliquescence point of NaCl and was controlled within the enclosed SSR test cell using a saturated solution of Sodium Sulfate at the bottom of the cell. NaCl salt was deposited on the SSR sample gauge section by a salt spray technique. Filter paper soaked in saturated NaCl solution was used to act as a salt bridge for the reference and counter electrodes under atmospheric condition. The effect of electrochemical potential on the cracking behavior of the atmospherically exposed samples will also be described. SEM characterization of the fractured samples was performed to validate embrittlement. Results from this effort will be used by both the Air Force and Navy to assess the need for enhanced risk based inspection of ZnNi coated steel parts. Engineering modeling was done for different defect sizes on the sample and results were used to validate engineering modeling approaches to predict corrosion and cracking performance during system design.

3D CFD ELECTROCHEMICAL AND HEAT TRANSFER MODEL OF AN INTERNALLY MANIFOLDED SOLID OXIDE ELECTROLYSIS CELL

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

Grant L. Hawkes; James E. O'Brien; Greg Tao

2011-11-01

A three-dimensional computational fluid dynamics (CFD) electrochemical model has been created to model high-temperature electrolysis cell performance and steam electrolysis in an internally manifolded planar solid oxide electrolysis cell (SOEC) stack. This design is being evaluated at the Idaho National Laboratory for hydrogen production from nuclear power and process heat. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified formore » this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, operating potential, steam-electrode gas composition, oxygen-electrode gas composition, current density and hydrogen production over a range of stack operating conditions. Single-cell and five-cell results will be presented. Flow distribution through both models is discussed. Flow enters from the bottom, distributes through the inlet plenum, flows across the cells, gathers in the outlet plenum and flows downward making an upside-down ''U'' shaped flow pattern. Flow and concentration variations exist downstream of the inlet holes. Predicted mean outlet hydrogen and steam concentrations vary linearly with current density, as expected. Effects of variations in operating temperature, gas flow rate, oxygen-electrode and steam-electrode current density, and contact resistance from the base case are presented. Contour plots of local electrolyte temperature, current density, and Nernst potential indicate the effects of heat transfer, reaction cooling/heating, and change in local gas composition. Results are discussed for using this design in the electrolysis mode. Discussion of thermal neutral voltage, enthalpy of reaction, hydrogen production, cell thermal efficiency, cell electrical efficiency, and Gibbs free energy are discussed and reported herein.« less

Enhancement of hydrogen oxidation activity at a nickel coated carbon beads electrode by cobalt and iron

NASA Astrophysics Data System (ADS)

Chatterjee, A. K.; Banerjee, R.; Sharon, M.

The electrochemical characteristics of a porous ceramic that is coated with carbon beads, impregnated with Ni, Fe and Co catalyst and operated as a hydrogen electrode for an alkaline fuel cell (AFC) are studied. To improve the catalytic activity and electrode performance, Ni is bimetallized with Co as well as Fe. Chemical vapour deposition (CVD) of turpentine oil, a renewable natural precursor, is used to grow the carbon beads. Various compositions of Ni-Co and Ni-Fe (10:90, 50:50, 90:10) are electroplated over the carbon-coated ceramic substrate. The detailed surface profile and elemental composition of the electrodes are studied by SEM, TEM, XRD and XRF analysis. Vander-Pauw resistivity measurements of the electrodes showed an increase in the conductivity of Ni electrode by addition of Co and Fe. The electrochemical performance is investigated by measuring hydrogen dissociation voltage, half-cell and full-cell current-potential characteristics and chrono-potentiometry in 30% KOH solution. The activity of the NI electrode is improved by addition of small amounts of Co and Fe. The best performance is obtained using an electrode coated with 90:10 ratios of Ni-Co and Ni-Fe bimetallic composition.

The improvement of SiO2 nanotubes electrochemical behavior by hydrogen atmosphere thermal treatment

NASA Astrophysics Data System (ADS)

Spataru, Nicolae; Anastasescu, Crina; Radu, Mihai Marian; Balint, Ioan; Negrila, Catalin; Spataru, Tanta; Fujishima, Akira

2018-06-01

Highly defected SiO2 nanotubes (SiO2-NT) were obtained by a simple sol-gel procedure followed by calcination. Boron-doped diamond (BDD) polycrystalline films coated with SiO2-NT were used as working electrodes and, unexpectedly, cyclic voltammetric experiments have shown that the concentration of both positive and negative defects at the surface is high enough to enable redox processes involving positively charged Ru(bpy)32+/3+ to occur. Conversely, no electrochemical activity was put into evidence for Fe(CN)63-/4- species, most likely as a result of the strong electrostatic repulsion exerted by the negatively charged SiO2 surface. The concentration of surface defects was further increased by a subsequent thermal treatment in a hydrogen atmosphere which, as EIS measurements have shown, significantly promotes Ru(bpy)32+ anodic oxidation. Digital simulation of the voltammetric responses demonstrated that this treatment does not lead to a similar increase of the number of electron-donor sites. It was also found that methanol anodic oxidation at hydrogenated SiO2-NT-supported platinum results in Tafel slopes of 116-220 mV decade-1, comparable to those reported for both conventional PtRu and Pt-oxide catalysts.

Influence of electrolyte composition and temperature on behaviour of AB5 hydrogen storage alloy used as negative electrode in Ni-MH batteries

NASA Astrophysics Data System (ADS)

Karwowska, Malgorzata; Jaron, Tomasz; Fijalkowski, Karol J.; Leszczynski, Piotr J.; Rogulski, Zbigniew; Czerwinski, Andrzej

2014-10-01

The AB5-type metal alloy (Mm-Ni4.1Al0.2Mn0.4Co0.45) has been investigated in different electrolytes (LiOH, NaOH, KOH, RbOH, CsOH). All of the electrochemical measurements have been performed using limited volume electrode technique (LVE). Thickness of the working electrode is nearly equal to the diameter of the grain (ca. 50 μm). Hydrogen diffusion coefficient has been determined using chronoamperometry. Hydrogen diffusion coefficient calculated for 100% state of charge reaches maximum value in KOH (DH = 4.65·10-10 cm2 s-1). We have obtained the highest value of capacity for the electrode in KOH and the lowest - in CsOH. The temperature influence on alloy capacity has been also tested. The alloy has been also characterised with SEM coupled with EDS, TGA/DSC and powder XRD. The unit cell of MmNi4.1Al0.2Mn0.4Co0.45 have been refined in the Cu5.4Yb0.8 structure type (a modified LaNi5 structure); the structure is unaffected by the electrochemical treatment.

Misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ for the hydrogen evolution reaction: beyond van der Waals heterostructures.

PubMed

Chua, Chun Kiang; Sofer, Zdeněk; Jankovský, Ondřej; Pumera, Martin

2015-03-16

Recent research on stable 2D nanomaterials has led to the discovery of new materials for energy-conversion and energy-storage applications. A class of layered heterostructures known as misfit-layered chalcogenides consists of well-defined atomic layers and has previously been applied as thermoelectric materials for use as high-temperature thermoelectric batteries. The performance of such misfit-layered chalcogenides in electrochemical applications, specifically the hydrogen evolution reaction, is currently unexplored. Herein, a misfit-layered chalcogenide consisting of CoO2 layers interleaved with an SrO-BiO-BiO-SrO rock-salt block and having the formula Bi1.85 Sr2 Co1.85 O7.7-δ is synthesized and examined for its structural and electrochemical properties. The hydrogen-evolution performance of misfit-layered Bi1.85 Sr2 Co1.85 O7.7-δ , which has an overpotential of 589 mV and a Tafel slope of 51 mV per decade, demonstrates the promising potential of misfit-layered chalcogenides as electrocatalysts instead of classical carbon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Space Electrochemical Research and Technology (SERT), 1989

NASA Technical Reports Server (NTRS)

Baldwin, Richard S. (Editor)

1989-01-01

The proceedings of NASA's second Space Electrochemical Research and Technology Conference are presented. The objectives of the conference were to examine current technologies, research efforts, and advanced ideas, and to identify technical barriers which affect the advancement of electrochemical energy storage systems for space applications. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, with the intention of coalescing views and findings into conclusions on progress in the field, prospects for future advances, areas overlooked, and the directions of future efforts. Related overviews were presented in the areas of NASA advanced mission models. Papers were presented and workshops conducted in four technical areas: advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, the nickel electrode, and advanced rechargable batteries.

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

Jagannathan, Kaushik; Benson, David M.; Robinson, David B.

Nanofilms of Pd were grown using an electrochemical form of atomic layer deposition (E-ALD) on 100 nm evaporated Au films on glass. Multiple cycles of surface-limited redox replacement (SLRR) were used to grow deposits. Each SLRR involved the underpotential deposition (UPD) of a Cu atomic layer, followed by open circuit replacement via redox exchange with tetrachloropalladate, forming a Pd atomic layer: one E-ALD deposition cycle. That cycle was repeated in order to grow deposits of a desired thickness. 5 cycles of Pd deposition were performed on the Au on glass substrates, resulting in the formation of 2.5 monolayers of Pd.more » Those Pd films were then modified with varying coverages of Pt, also formed using SLRR. The amount of Pt was controlled by changing the potential for Cu UPD, and by increasing the number of Pt deposition cycles. Hydrogen absorption was studied using coulometry and cyclic voltammetry in 0.1 M H 2SO 4 as a function of Pt coverage. The presence of even a small fraction of a Pt monolayer dramatically increased the rate of hydrogen desorption. However, this did not reduce the films’ hydrogen storage capacity. The increase in desorption rate in the presence of Pt was over an order of magnitude.« less

Electrochemical vapor deposition of semiconductors from gas phase with a solid membrane cell.

PubMed

Cho, Sung Ki; Fan, Fu-Ren F; Bard, Allen J

2015-05-27

We demonstrate the feasibility of semiconductor deposition via the electrochemical reduction of gaseous precursors by the use of an anhydrous proton-conducting membrane, the solid acid CsHSO4, at 165 °C. This membrane electrode assembly was operated within the oxidation of hydrogen on a porous Pt anode and the deposition of Si or Ge under bias at the cathode from chloride-based gaseous precursors; SiCl4 and GeCl4 in an Ar flow with a reduction potential over -1.0 V (vs RHE).

Device and method for the measurement of gas permeability through membranes

DOEpatents

Agarwal, Pradeep K.; Ackerman, John; Borgialli, Ron; Hamann, Jerry; Muknahalliptna, Suresh

2006-08-08

A device for the measuring membrane permeability in electrical/electrochemical/photo-electrochemical fields is provided. The device is a permeation cell and a tube mounted within the cell. An electrode is mounted at one end of the tube. A membrane is mounted within the cell wherein a corona is discharged from the electrode in a general direction toward the membrane thereby generating heated hydrogen atoms adjacent the membrane. A method for measuring the effects of temperature and pressure on membrane permeability and selectivity is also provided.

Synthesis and enhanced electrochemical catalytic performance of monolayer WS2(1-x) Se2x with a tunable band gap.

PubMed

Fu, Qi; Yang, Lei; Wang, Wenhui; Han, Ali; Huang, Jian; Du, Pingwu; Fan, Zhiyong; Zhang, Jingyu; Xiang, Bin

2015-08-26

The first realization of a tunable band-gap in monolayer WS2(1-x) Se2x is demonstrated. The tuning of the bandgap exhibits a strong dependence of S and Se content, as proven by PL spectroscopy. Because of its remarkable electronic structure, monolayer WS2(1-x) Se2x exhibits novel electrochemical catalytic activity and offers long-term electrocatalytic stability for the hydrogen evolution reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Passivation of Si(111) surfaces with electrochemically grafted thin organic films

NASA Astrophysics Data System (ADS)

Roodenko, K.; Yang, F.; Hunger, R.; Esser, N.; Hinrichs, K.; Rappich, J.

2010-09-01

Ultra thin organic films (about 5 nm thick) of nitrobenzene and 4-methoxydiphenylamine were deposited electrochemically on p-Si(111) surfaces from benzene diazonium compounds. Studies based on atomic force microscopy, infrared spectroscopic ellipsometry and x-ray photoelectron spectroscopy showed that upon exposure to atmospheric conditions the oxidation of the silicon interface proceed slower on organically modified surfaces than on unmodified hydrogen passivated p-Si(111) surfaces. Effects of HF treatment on the oxidized organic/Si interface and on the organic layer itself are discussed.

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

PubMed

Jin, Zhaoyu; Li, Panpan; Xiao, Dan

2017-02-08

Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reflections on some Recent Studies of Materials of Importance in Aqueous Electrochemical Energy-Storage Systems

DTIC Science & Technology

1979-01-01

includes oxidative pyrolysis of water vapour , to destroy the organic Impurities of water vapour , and careful redistillation. With pyrodistilled... gallium or the poisonous arsenic or the scarce ruthenium, if practical hydrogen production or photoelectrochemlcal

Resonance-Raman spectro-electrochemistry of intermediates in molecular artificial photosynthesis of bimetallic complexes.

PubMed

Zedler, Linda; Guthmuller, Julien; Rabelo de Moraes, Inês; Kupfer, Stephan; Krieck, Sven; Schmitt, Michael; Popp, Jürgen; Rau, Sven; Dietzek, Benjamin

2014-05-25

The sequential order of photoinduced charge transfer processes and accompanying structure changes were analyzed by UV-vis and resonance-Raman spectroscopy of intermediates of a Ru(ii) based photocatalytic hydrogen evolving system obtained by electrochemical reduction.

A Simple and Inexpensive Solar Energy Experiment.

ERIC Educational Resources Information Center

Evans, J. H.; Pedersen, L. G.

1979-01-01

An experiment is presented which utilizes the current solid state technology to demonstrate electrochemical generation of hydrogen gas, direct generation of electricity for pumping water, and energy conversion efficiency. The experimental module costs about $100 and can be used repeatedly. (BB)

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.).

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Hydrogen Oxidation-Selective Electrocatalysis by Fine Tuning of Pt Ensemble Sites to Enhance the Durability of Automotive Fuel Cells.

PubMed

Yun, Su-Won; Park, Shin-Ae; Kim, Tae-June; Kim, Jun-Hyuk; Pak, Gi-Woong; Kim, Yong-Tae

2017-02-08

A simple, inexpensive approach is proposed for enhancing the durability of automotive proton exchange membrane fuel cells by selective promotion of the hydrogen oxidation reaction (HOR) and suppression of the oxygen reduction reaction (ORR) at the anode in startup/shutdown events. Dodecanethiol forms a self-assembled monolayer (SAM) on the surface of Pt particles, thus decreasing the number of Pt ensemble sites. Interestingly, by controlling the dodecanethiol concentration during SAM formation, the number of ensemble sites can be precisely optimized such that it is sufficient for the HOR but insufficient for the ORR. Thus, a Pt surface with an SAM of dodecanethiol clearly effects HOR-selective electrocatalysis. Clear HOR selectivity is demonstrated in unit cell tests with the actual membrane electrode assembly, as well as in an electrochemical three-electrode setup with a thin-film rotating disk electrode configuration. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy and fuels from electrochemical interfaces

DOE PAGES

Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.; ...

2016-12-20

Advances in electrocatalysis at solid–liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, in this paper, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate–hydroxide binding energy and the interactions inmore » the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Lastly, links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.« less

Water Splitting Using Porous Silicon Photo-electrodes for Hydrogen Production

NASA Astrophysics Data System (ADS)

Ali, M.; Starkov, V. V.; Gosteva, E. A.; Druzhinin, A. V.; Sattar, S.

2017-11-01

This paper presents the efficiency study results of using gradient-porous silicon structures with different morphology, as photo-anodes for photo-electrochemical dissociation of water. The results of a study of the physicochemical properties of gradient-porous silicon structures show the relatively low cost and simplicity of the technological process, as well as the possibility of forming structures with predefined properties, allow the creation of effective devices for artificial photosynthesis based on porous silicon for subsequent use in hydrogen energy.

PCE dechlorination by non-Dehalococcoides in a microbial electrochemical system.

PubMed

Yu, Jaecheul; Park, Younghyun; Nguyen, Van Khanh; Lee, Taeho

2016-08-01

The bioremediation of tetrachloroethene (perchloroethene; PCE) contaminated sites generally requires a supply of some fermentable organic substrates as an electron donor. On the other hand, organic substrates can induce the massive growth of microorganisms around the injection wells, which can foul the contaminated subsurface environment. In this study, PCE dechlorination to ethene was performed in a microbial electrochemical system (MES) using the electrode (a cathode polarized at -500 mV vs. standard hydrogen electrode) as the electron donor. Denaturing gel gradient electrophoresis and pyrosequencing revealed a variety of non-Dehalococcoides bacteria dominant in MES, such as Acinetobacter sp. (25.7 % for AS1 in suspension of M3), Rhodopseudomonas sp. (10.5 % for AE1 and 10.1 % for AE2 in anodic biofilm of M3), Pseudomonas aeruginosa (22.4 % for BS1 in suspension of M4), and Enterobacter sp. (21.7 % for BE1 in anodic biofilm of M4) which are capable of electron transfer, hydrogen production and dechlorination. The Dehalococcoides group, however, was not detected in this system. Therefore, these results suggest that a range of bacterial species outside the Dehalococcoides can play an important role in the microbial electrochemical dechlorination process, which may lead to innovative bioremediation technology.

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

PubMed

Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

2018-01-10

Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Co3O4 conical nanotube and its application in calcium ion biosensor

NASA Astrophysics Data System (ADS)

Yuan, Hongwen; Ma, Chi; Geng, Junlong; Zhang, Liqiang; Cui, Hai; Liu, Cunzhi

2018-02-01

Calcium ion (Ca2+) is an important ion involved in body life activities, and its content detection in biomedical field owns great significance. In this study, we fabricated Co3O4 conical nanotube on F-doped tin oxide (FTO) substrate for detecting Ca2+. Co3O4 is fabricated through a hydrothermal method and demonstrates a regular hexagon structure, with a length of 5-10 μm and wall thickness of 30 nm. The structure and morphology of Co3O4 were characterized by X-ray diffraction (XRD), scanning electron microscope, and transmission electron microscopy, respectively. In addition, then, we used electrochemical technique to characterize the Ca2+ concentration in the simulated body fluid. The detection of Ca2+ is originated from the electrochemical reaction of hydrogen peroxide using Co3O4 as a catalyst, in which Ca2+ plays a significant role for accelerating the decomposition of hydrogen peroxide catalytic performance. By monitoring the electron transfer signals changes during the electrochemical reaction, we can quickly quantify the Ca2+ concentrations. It is found that this Ca2+ sensor owns a wide detection range (0.1-1.1 mM), a low detection limit (3.767 μM), and good anti-interference ability.

High performance robust F-doped tin oxide based oxygen evolution electro-catalysts for PEM based water electrolysis

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

Datta, Moni Kanchan; Kadakia, Karan; Velikokhatnyi, Oleg I

2013-01-01

Identification and development of non-noble metal based electro-catalysts or electro-catalysts comprising compositions with significantly reduced amounts of expensive noble metal contents (e.g. IrO{sub 2}, Pt) with comparable electrochemical performance to the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would signify a major breakthrough in hydrogen generation via water electrolysis. Development of such systems would lead to two primary outcomes: first, a reduction in the overall capital costs of PEM based water electrolyzers, and second, attainment of the targeted hydrogen production costs (<$3.00/gge delivered by 2015) comparable to conventional liquid fuels. In line with these goals,more » by exploiting a two-pronged theoretical first principles and experimental approach herein, we demonstrate for the very first time a solid solution of SnO{sub 2}:10 wt% F containing only 20 at.% IrO{sub 2} [e.g. (Sn{sub 0.80}Ir{sub 0.20})O{sub 2}:10F] displaying remarkably similar electrochemical activity and comparable or even much improved electrochemical durability compared to pure IrO{sub 2}, the accepted gold standard in oxygen evolution electro-catalysts for PEM based water electrolysis. We present the results of these studies.« less

Electrochemical decomposition of fluorinated wetting agents in plating industry waste water.

PubMed

Fath, Andreas; Sacher, Frank; McCaskie, John E

2016-01-01

Electrochemical decomposition of fluorinated surfactants (PFAS, perfluorinated alkyl substances) used in the plating industry was analyzed and the decomposition process parameters optimized at the laboratory scale and production scale of a 500-liter reactor using lead electrodes. The method and system was successfully demonstrated under production conditions to treat PFAS) with up to 99% efficiency in the concentration range of 1,000-20,000 μg/l (1 ppm-20 ppm). The treatment also reduced hexavalent chromium (Cr(6+)) ions to trivalent chromium (Cr(3+)) ions in the wastewater. If the PFAS-containing wastewater is mixed with other wastewater streams, specifically from nickel plating drag out solution or when pH values >5, the treatment process is ineffective. For the short chain PFAS, (perfluorobutylsulfonate) the process was less efficient than C6-C8 PFAS. The process is automated and has safety procedures and controls to prevent hazards. The PFAS were decomposed to hydrogen fluoride (HF) under the strong acid electrochemical operating conditions. Analytical tests showed no evidence of organic waste products remaining from the process. Conventional alternative PFAS removal systems were tested on the waste streams and compared with each other and with the-E-destruct (electrochemical oxidation) process. For example, ion exchange resin (IX resin) treatment of wastewater to complex and remove PFAS was found to be seven times more efficient when compared to the conventional activated carbon absorption (C-treat) process. However, the E-destruct process is higher in capacity, exhibits longer service life and lower operating costs than either IX or C-treat methods for elimination of PFAS from these electroplating waste streams.

Enhanced electrochemical nanoring electrode for analysis of cytosol in single cells.

PubMed

Zhuang, Lihong; Zuo, Huanzhen; Wu, Zengqiang; Wang, Yu; Fang, Danjun; Jiang, Dechen

2014-12-02

A microelectrode array has been applied for single cell analysis with relatively high throughput; however, the cells were typically cultured on the microelectrodes under cell-size microwell traps leading to the difficulty in the functionalization of an electrode surface for higher detection sensitivity. Here, nanoring electrodes embedded under the microwell traps were fabricated to achieve the isolation of the electrode surface and the cell support, and thus, the electrode surface can be modified to obtain enhanced electrochemical sensitivity for single cell analysis. Moreover, the nanometer-sized electrode permitted a faster diffusion of analyte to the surface for additional improvement in the sensitivity, which was evidenced by the electrochemical characterization and the simulation. To demonstrate the concept of the functionalized nanoring electrode for single cell analysis, the electrode surface was deposited with prussian blue to detect intracellular hydrogen peroxide at a single cell. Hundreds of picoamperes were observed on our functionalized nanoring electrode exhibiting the enhanced electrochemical sensitivity. The success in the achievement of a functionalized nanoring electrode will benefit the development of high throughput single cell electrochemical analysis.

Restructuring of an Ir(210) electrode surface by potential cycling

PubMed Central

Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

2014-01-01

Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

Restructuring of an Ir(210) electrode surface by potential cycling.

PubMed

Soliman, Khaled A; Kolb, Dieter M; Kibler, Ludwig A; Jacob, Timo

2014-01-01

This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s(-1) between -0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation.

Electroactive Au@Ag nanoparticles driven electrochemical sensor for endogenous H2S detection.

PubMed

Zhao, Yuan; Yang, Yaxin; Cui, Linyan; Zheng, Fangjie; Song, Qijun

2018-05-26

In this work, a novel and facile electrochemical sensor is reported for the highly selective and sensitive detection of dissolved hydrogen sulfide (H 2 S), attributing to the redox reaction between Au@Ag core-shell nanoparticles (Au@Ag NPs) and H 2 S. Electroactive Au@Ag NPs not only possess excellent conductivity, but exhibit great electrochemical reactivity at 0.26 V due to the electrochemical oxidation from Ag° to Ag + . In the presence of H 2 S, the Ag shell of Au@Ag NPs can be oxidized to Ag 2 S, resulting in the decrease of differential pulse voltammetry (DPV) peak at 0.26 V. The electrochemical sensor exhibits a wide linear response range from 0.1 nM to 500 nM. The limit of detection (LOD) for H 2 S is as low as 0.04 nM. The developed sensor shows significant prospects in the study of pathological processes related to the mechanism of H 2 S production. Copyright © 2018. Published by Elsevier B.V.

Pt/Pd electrocatalyst electrons for fuel cells

DOEpatents

Stonehart, P.

1981-11-03

This invention relates to improved electrochemical cells and to novel electrodes for use therein. In particular, the present invention comprises a fuel cell used primarily for the consumption of impure hydrogen fuels containing carbon monoxide or carbonaceous fuels where the electrode in contact with the fuel is not substantially poisoned by carbon monoxide. The anode of the fuel cell comprises a Pd/Pt alloy supported on a graphitized or partially graphitized carbon material. Fuel cells which comprise as essential elements a fuel electrode, an oxidizing electrode, and an electrolyte between said electrodes are devices for the direct production of electricity through the electrochemical combustion of a fuel and oxidant. These devices are recognized for their high efficiency as energy conversion units, since unlike conventional combustion engines, they are not subject to the limitations of the Carnot heat cycle. It is the primary object of the present invention to provide an electrode having high electrochemical activity for an electrochemical cell. It is another object of the present invention to provide an electrode having an electro-catalyst which is highly resistant to the corrosive environment of an electrochemical cell.

Ultrasonic-electrodeposition of PtPd alloy nanoparticles on ionic liquid-functionalized graphene paper: towards a flexible and versatile nanohybrid electrode

NASA Astrophysics Data System (ADS)

Sun, Yimin; Zheng, Huaming; Wang, Chenxu; Yang, Mengmeng; Zhou, Aijun; Duan, Hongwei

2016-01-01

Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors.Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors. Electronic supplementary information (ESI) available: The stress-strain curve of the IL-rGOP, EDX spectrum of PtPd/IL-rGOP, the particle size and size distribution of Pt, PtPd and Pd nanoparticles electrodeposited on IL-rGOP derived from SEM, and the structural parameters of Pt, PtPd and Pd nanoparticles electrodeposited on IL-rGOP derived from XRD, influence of the potential interfering species towards glucose detection. See DOI: 10.1039/c5nr06912b

Hierarchical Cu2O foam/g-C3N4 photocathode for photoelectrochemical hydrogen production

NASA Astrophysics Data System (ADS)

Ma, Xinzhou; Zhang, Jingtao; Wang, Biao; Li, Qiuguo; Chu, Sheng

2018-01-01

Solar photoelectrochemical (PEC) hydrogen production is a promising way for solving energy and environment problems. Earth-abundant Cu2O is a potential light absorber for PEC hydrogen production. In this article, hierarchical porous Cu2O foams are prepared by thermal oxidation of the electrochemically deposited Cu foams. PEC performances of the Cu2O foams are systematically studied and discussed. Benefiting from their higher light harvesting and more efficient charge separation, the Cu2O foams demonstrate significantly enhanced photocurrents and photostability compared to their film counterparts. Moreover, by integrating g-C3N4, hierarchical Cu2O foam/g-C3N4 composites are prepared with further improved photocurrent and photostability, appearing to be potential photocathodes for solar PEC hydrogen production. This study may provide a new and useful insight for the development of Cu2O-based photocathodes for PEC hydrogen production.

[NiFe] hydrogenases: a common active site for hydrogen metabolism under diverse conditions.

PubMed

Shafaat, Hannah S; Rüdiger, Olaf; Ogata, Hideaki; Lubitz, Wolfgang

2013-01-01

Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. The most abundant hydrogenases contain a [NiFe] active site; these proteins are generally biased towards hydrogen oxidation activity and are reversibly inhibited by oxygen. However, there are [NiFe] hydrogenase that exhibit unique properties, including aerobic hydrogen oxidation and preferential hydrogen production activity; these proteins are highly relevant in the context of biotechnological devices. This review describes four classes of these "nonstandard" [NiFe] hydrogenases and discusses the electrochemical, spectroscopic, and structural studies that have been used to understand the mechanisms behind this exceptional behavior. A revised classification protocol is suggested in the conclusions, particularly with respect to the term "oxygen-tolerance". This article is part of a special issue entitled: metals in bioenergetics and biomimetics systems. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Processes for making dense, spherical active materials for lithium-ion cells

DOEpatents

Kang, Sun-Ho [Naperville, IL; Amine, Khalil [Downers Grove, IL

2011-11-22

Processes are provided for making dense, spherical mixed-metal carbonate or phosphate precursors that are particularly well suited for the production of active materials for electrochemical devices such as lithium ion secondary batteries. Exemplified methods include precipitating dense, spherical particles of metal carbonates or metal phosphates from a combined aqueous solution using a precipitating agent such as ammonium hydrogen carbonate, sodium hydrogen carbonate, or a mixture that includes sodium hydrogen carbonate. Other exemplified methods include precipitating dense, spherical particles of metal phosphates using a precipitating agent such as ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, or a mixture of any two or more thereof. Further provided are compositions of and methods of making dense, spherical metal oxides and metal phosphates using the dense, spherical metal precursors. Still further provided are electrodes and batteries using the same.

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres

PubMed Central

Gerstl, Matthias; Nenning, Andreas; Iskandar, Riza; Rojek-Wöckner, Veronika; Bram, Martin; Hutter, Herbert; Opitz, Alexander Karl

2016-01-01

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur. PMID:28773771

Effects of nitrogen- and oxygen-containing functional groups of activated carbon nanotubes on the electrochemical performance in supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Haiyan; Song, Huaihe; Chen, Xiaohong; Zhang, Su; Zhou, Jisheng; Ma, Zhaokun

2015-07-01

A kind of nitrogen- and oxygen-containing activated carbon nanotubes (ACNTs) has been prepared by carbonization and activation of polyaniline nanotubes obtained by rapidly mixed reaction. The ACNTs show oxygen content of 15.7% and nitrogen content of 2.97% (atomic ratio). The ACNTs perform high capacitance and good rate capability (327 F g-1 at the current density of 10 A g-1) when used as the electrode materials for supercapacitors. Hydrogen reduction has been further used to investigate the effects of surface functional groups on the electrochemical performance. The changes for both structural component and electrochemical performance reveal that the quinone oxygen, pyridinic nitrogen, and pyrrolic nitrogen of carbon have the most obvious influence on the capacitive property because of their pseudocapacitive contributions.

Electrochemically-driven large amplitude pH cycling for acid-base driven DNA denaturation and renaturation.

PubMed

Wang, Yong-Chun; Lin, Cong-Bin; Su, Jian-Jia; Ru, Ying-Ming; Wu, Qiao; Chen, Zhao-Bin; Mao, Bing-Wei; Tian, Zhao-Wu

2011-06-15

In this paper, we present an electrochemically driven large amplitude pH alteration method based on a serial electrolytic cell involving a hydrogen permeable bifacial working electrode such as Pd thin foil. The method allows solution pH to be changed periodically up to ±4~5 units without additional alteration of concentration and/or composition of the system. Application to the acid-base driven cyclic denaturation and renaturation of 290 bp DNA fragments is successfully demonstrated with in situ real-time UV spectroscopic characterization. Electrophoretic analysis confirms that the denaturation and renaturation processes are reversible without degradation of the DNA. The serial electrolytic cell based electrochemical pH alteration method presented in this work would promote investigations of a wide variety of potential-dependent processes and techniques.

Stress corrosion cracking of titanium alloys

NASA Technical Reports Server (NTRS)

May, R. C.; Beck, F. H.; Fontana, M. G.

1971-01-01

Experiments were conducted to study (1) the basic electrochemical behavior of titanium in acid chloride solutions and (2) the response of the metal to dynamic straining in the same evironment. The aim of this group of experiments was to simulate, as nearly as possible, the actual conditions which exist at the tip of a crack. One of the foremost theories proposed to explain the propagation of stress corrosion cracks is a hydrogen embrittlement theory involving the precipitation of embrittling titanium hydrides inside the metal near the crack tip. An initial survey of the basic electrochemical literature indicated that surface hydrides play a critical role in the electrochemistry of titanium in acid solutions. A comprehensive analysis of the effect of surface films, particularly hydrides, on the electrochemical behavior of titanium in these solution is presented.

Electrochemical, H2O2-Boosted Catalytic Oxidation System

NASA Technical Reports Server (NTRS)

Akse, James R.; Thompson, John O.; Schussel, Leonard J.

2004-01-01

An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples

PubMed Central

Madhu, Rajesh; Veeramani, Vediyappan; Chen, Shen-Ming

2014-01-01

For the first time, high-surface-area (approximately 1465 m2 g−1), highly porous and heteroatom-enriched activated carbon (HAC) was prepared from banana stems (Musa paradisiaca, Family: Musaceae) at different carbonization temperatures of 700, 800 and 900°C (HAC) using a simple and eco-friendly method. The amounts of carbon, hydrogen, nitrogen and sulfur in the HAC are 61.12, 2.567, 0.4315, and 0.349%, respectively. Using X-ray diffraction (XRD), CHNS elemental analysis, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, the prepared activated carbon appears amorphous and disordered in nature. Here, we used HAC for an electrochemical application of nitrite (NO2−) sensor to control the environmental pollution. In addition, HAC exhibits noteworthy performance for the highly sensitive determination of nitrite. The limit of detection (LODs) of the nitrite sensor at HAC-modified GCE is 0.07 μM. In addition, the proposed method was applied to determine nitrite in various water samples with acceptable results. PMID:24755990

Effect of Boron Microalloying Element on Susceptibility to Hydrogen Embrittlement in High Strength Mooring Chain Steel

NASA Astrophysics Data System (ADS)

Li, H.; Cheng, X. Y.; Shen, H. P.; Su, L. C.; Zhang, S. Y.

The susceptibility to hydrogen embrittlement in high strength mooring chain steel with different boron content (0, 0.003 %, 0.008 %) were investigated by electrochemical hydrogen charging technique and tensile test. The results revealed that appropriate boron content can effectively depress hydrogen induced embrittlement. Precharged with a low current density, this effect seemed to be unobvious. It gradually became clearly with the increasing current density. The increase of resistance to the hydrogen embrittlement for 3B and 8B after adding appropriate boron was attributed to three facts. The first was that the segregation of boron atoms along grain boundaries reduced the grain boundary segregation of phosphorus, which prohibited hydrogen concentration at the grain boundaries, depressing the possibility of the intergranular fracture due to H. The second was that the segregation of boron increased intergranular cohesion, enhanced grain boundary strength, and refined the final microstructure. The third was that the addition of boron changed the state of hydrogen traps, leading to the small amount of diffusible hydrogen. That is to say, hydrogen transferred to these defects by dislocations was accordingly decreased, which led to the low sensitive of hydrogen induced cracking.

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

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

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

Electrochemical Hydrogen Peroxide Generator

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K.; Singh, Waheguru; Anderson, Kelvin C.

2010-01-01

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

EPA Science Inventory

Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

High-performance hydrogen fuel cell using nitrate reduction reaction on a non-precious catalyst.

PubMed

Han, Sang-Beom; Song, You-Jung; Lee, Young-Woo; Ko, A-Ra; Oh, Jae-Kyung; Park, Kyung-Won

2011-03-28

The H(2)-NO(3)(-) electrochemical cell using nitrate reduction on a non-precious cathode catalyst shows much improved efficiency despite ∼75% reduction of Pt metal loading as compared to typical PEMFCs using typical ORR on precious catalysts.

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

DOE PAGES

Gao, Min -Rui; Chan, Maria K. Y.; Sun, Yugang

2015-07-03

In this study, layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of -103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10 -3more » mA cm -2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance.« less

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

PubMed Central

Gao, Min-Rui; Chan, Maria K.Y.; Sun, Yugang

2015-01-01

Layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of −103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10−3 mA cm−2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance. PMID:26138031

Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide

DOE PAGES

Chen, Shucheng; Chen, Zhihua; Siahrostami, Samira; ...

2017-10-30

Hydrogen peroxide (H 2O 2), an important industrial chemical, is currently produced through an energy-intensive anthraquinone process that is limited to large-scale facilities. Small-scale decentralized electrochemical production of H 2O 2 via a two-electron oxygen reduction reaction (ORR) offers unique opportunities for sanitization applications and the purification of drinking water. The development of inexpensive, efficient, and selective catalysts for this reaction remains a challenge. Here in this paper, we examine two different porous carbon-based electrocatalysts and show that they exhibit high selectivity for H 2O 2 under alkaline conditions. By rationally varying synthetic methods, we explore the effect of poremore » size on electrocatalytic performance. Furthermore, by means of density functional calculations, we point out the critical role of carbon defects. Our theory results show that the majority of defects in graphene are naturally selective for the two-electron reduction of O 2 to H 2O 2, and we identify the types of defects with high activity.« less

Catalyst supports for polymer electrolyte fuel cells.

PubMed

Subban, Chinmayee; Zhou, Qin; Leonard, Brian; Ranjan, Chinmoy; Edvenson, Heather M; Disalvo, F J; Munie, Semeret; Hunting, Janet

2010-07-28

A major challenge in obtaining long-term durability in fuel cells is to discover catalyst supports that do not corrode, or corrode much more slowly than the current carbon blacks used in today's polymer electrolyte membrane fuel cells. Such materials must be sufficiently stable at low pH (acidic conditions) and high potential, in contact with the polymer membrane and under exposure to hydrogen gas and oxygen at temperatures up to perhaps 120 degrees C. Here, we report the initial discovery of a promising class of doped oxide materials for this purpose: Ti(1-x)M(x)O(2), where M=a variety of transition metals. Specifically, we show that Ti(0.7)W(0.3)O(2) is electrochemically inert over the appropriate potential range. Although the process is not yet optimized, when Pt nanoparticles are deposited on this oxide, electrochemical experiments show that hydrogen is oxidized and oxygen reduced at rates comparable to those seen using a commercial Pt on carbon black support.

Scalable and efficient separation of hydrogen isotopes using graphene-based electrochemical pumping

NASA Astrophysics Data System (ADS)

Lozada-Hidalgo, M.; Zhang, S.; Hu, S.; Esfandiar, A.; Grigorieva, I. V.; Geim, A. K.

2017-05-01

Thousands of tons of isotopic mixtures are processed annually for heavy-water production and tritium decontamination. The existing technologies remain extremely energy intensive and require large capital investments. New approaches are needed to reduce the industry's footprint. Recently, micrometre-size crystals of graphene are shown to act as efficient sieves for hydrogen isotopes pumped through graphene electrochemically. Here we report a fully-scalable approach, using graphene obtained by chemical vapour deposition, which allows a proton-deuteron separation factor of around 8, despite cracks and imperfections. The energy consumption is projected to be orders of magnitude smaller with respect to existing technologies. A membrane based on 30 m2 of graphene, a readily accessible amount, could provide a heavy-water output comparable to that of modern plants. Even higher efficiency is expected for tritium separation. With no fundamental obstacles for scaling up, the technology's simplicity, efficiency and green credentials call for consideration by the nuclear and related industries.

Nanoporous platinum-cobalt alloy for electrochemical sensing for ethanol, hydrogen peroxide, and glucose.

PubMed

Xu, Caixia; Sun, Fenglei; Gao, Hua; Wang, Jinping

2013-05-30

Nanoporous platinum-cobalt (NP-PtCo) alloy with hierarchical nanostructure is straightforwardly fabricated by dealloying PtCoAl alloy in a mild alkaline solution. Selectively etching Al resulted in a hierarchical three-dimensional network nanostructure with a narrow size distribution at 3 nm. The as-prepared NP-PtCo alloy shows superior performance toward ethanol and hydrogen peroxide (H2O2) with highly sensitive response due to its unique electrocatalytic activity. In addition, NP-PtCo also exhibits excellent amperometric durability and long-term stability for H2O2 as well as a good anti-interference toward ascorbic acid, uric acid, and dopamine. The hierarchical nanoporous architecture in PtCo alloy is also highly active for glucose sensing electrooxidation and sensing in a wide linear range. The NP-PtCo alloy holds great application potential for electrochemical sensing with simple preparation, unique catalytic activity, and high structure stability. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys

DOEpatents

Ovshinsky, Stanford R.; Fetcenko, Michael A.

1996-01-01

An electrochemical hydrogen storage material comprising: (Base Alloy).sub.a M.sub.b where, Base Alloy is an alloy of Mg and Ni in a ratio of from about 1:2 to about 2:1, preferably 1:1; M represents at least one modifier element chosen from the group consisting of Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, and Ca; b is greater than 0.5, preferably 2.5, atomic percent and less than 30 atomic percent; and a+b=100 atomic percent. Preferably, the at least one modifier is chosen from the group consisting of Co, Mn, Al, Fe, and Cu and the total mass of the at least one modifier element is less than 25 atomic percent of the final composition. Most preferably, the total mass of said at least one modifier element is less than 20 atomic percent of the final composition.

A non-enzymatic sensor for hydrogen peroxide based on polyaniline, multiwalled carbon nanotubes and gold nanoparticles modified Au electrode.

PubMed

Narang, Jagriti; Chauhan, Nidhi; Pundir, C S

2011-11-07

We describe the construction of a polyaniline (PANI), multiwalled carbon nanotubes (MWCNTs) and gold nanoparticles (AuNPs) modified Au electrode for determination of hydrogen peroxide without using peroxidase (HRP). The AuNPs/MWCNT/PANI composite film deposited on Au electrode was characterized by Scanning Electron Microscopy (SEM) and electrochemical methods. Cyclic voltammetric (CV) studies of the electrode at different stages of construction demonstrated that the modified electrode had enhanced electrochemical oxidation of H(2)O(2), which offers a number of attractive features to develop amperometric sensors based on split of H(2)O(2). The amperometric response to H(2)O(2) showed a linear relationship in the range from 3.0 μM to 600.0 μM with a detection limit of 0.3 μM (S/N = 3) and with high sensitivity of 3.3 mA μM(-1). The sensor gave accurate and satisfactory results, when employed for determination of H(2)O(2) in milk and urine.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution.

PubMed

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Gadolinium nanoparticle based switchable mirrors: quenching of hydrogenation-dehydrogenation hysteresis.

PubMed

Aruna, I; Mehta, B R; Malhotra, L K

2007-06-01

A continuous and reversible 'structural, optical, and electronic' transition between the reflecting metallic dihydride and transparent semiconducting trihydride states observed in rare earth metals on hydrogenation make these materials and their hydrides suitable for switchable mirror, sensing, and other technological applications. Recently Pd capped Gd nanoparticle based 'new generation' switchable mirrors have been fabricated with extended color neutrality, better optical contrast, and faster kinetics in comparison to the polycrystalline, epitaxial, alloy, and multilayer films. The present report aims at investigating the effect of nanoparticle nature on the hydrogenation-dehydrogenation hysteresis in switchable mirrors by carrying out in situ measurement of optical transmittance and electrode potentials during electrochemical hydrogen loading-deloading of Gd nanoparticle samples. Interestingly, Gd nanoparticle samples were observed to exhibit quenched hysteresis. The quenching of hysteresis in hydrogen-induced properties has been attributed to the absence of structural transition upon hydrogenation, reduction in topographical interlocking of the grains and elimination of lateral clamping of the slack nanoparticle layer to the substrate.

Description and field test of an in situ coliform monitoring system

NASA Technical Reports Server (NTRS)

Grana, D. C.; Wilkins, J. R.

1979-01-01

A prototype in situ system for monitoring the levels of fecal coliforms in shallow water bodies was developed and evaluated. This system was based on the known relationship between the concentration of the coliform bacteria and the amount of hydrogen they produce during growth in a complex organic media. The prototype system consists of a sampler platform, which sits on the bottom; a surface buoy, which transmits sampler-generated data; and a shore station, which receives, displays the data, and controls the sampler. The concept of remote monitoring of fecal coliform concentrations by utilizing a system based on the electrochemical method was verified during the evaluation of the prototype.

Oxide and hydrogen capped ultrasmall blue luminescent Si nanoparticles

NASA Astrophysics Data System (ADS)

Belomoin, Gennadiy; Therrien, Joel; Nayfeh, Munir

2000-08-01

We dispersed electrochemical etched silicon into a colloid of ultrasmall ultrabright Si nanoparticles. Direct imaging using transmission electron microscopy shows particles of ˜1 nm in diameter, and infrared and electron photospectroscopy show that they are passivated with hydrogen. Under 350 nm excitation, the luminescence is dominated by an extremely strong blue band at 390 nm. We replace hydrogen by a high-quality ultrathin surface oxide cap by self-limiting oxidation in H2O2. Upon capping, the excitation efficiency drops, but only by a factor of 2, to an efficiency still two-fold larger than that of fluorescein. Although of slightly lower brightness, capped Si particles have superior biocompatability, an important property for biosensing applications.

Kinetics of Hydrogen Diffusion in LaNi(sub 5-x)Sn(sub x) Alloys

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Hightower, A.; Witham, C.; Bowman, R. C.; Fultz, B.

1996-01-01

Solid-state diffusion of hydrogen in metal hydride (MH) alloys is recognized as the rate determining step in the discharge of MH alloys in alkaline Ni-MH rechargeable cells. In our pursuit of new ternary solutes in LaNi(sub 5) for extended cycle lifetimes, we have observed noticeable improvement in the cycle life with small substitutions of Sn and Ge for Ni. Furthermore, these substituents also facilitate enhanced charge transfer kinetics for hydriding-dehydriding process. In this paper, we report our studies on the kinetics of hydrogen diffusion in LaNi(sub 5-x) Sn(sub x) alloys by electrochemical pulse techniques, chronoamperometry and chronocoulometry.

Atomic cobalt on nitrogen-doped graphene for hydrogen generation

PubMed Central

Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L.G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

2015-01-01

Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

Hydrogenated TiO2 nanotube arrays for supercapacitors.

PubMed

Lu, Xihong; Wang, Gongming; Zhai, Teng; Yu, Minghao; Gan, Jiayong; Tong, Yexiang; Li, Yat

2012-03-14

We report a new and general strategy for improving the capacitive properties of TiO(2) materials for supercapacitors, involving the synthesis of hydrogenated TiO(2) nanotube arrays (NTAs). The hydrogenated TiO(2) (denoted as H-TiO(2)) were obtained by calcination of anodized TiO(2) NTAs in hydrogen atmosphere in a range of temperatures between 300 to 600 °C. The H-TiO(2) NTAs prepared at 400 °C yields the largest specific capacitance of 3.24 mF cm(-2) at a scan rate of 100 mV s(-1), which is 40 times higher than the capacitance obtained from air-annealed TiO(2) NTAs at the same conditions. Importantly, H-TiO(2) NTAs also show remarkable rate capability with 68% areal capacitance retained when the scan rate increase from 10 to 1000 mV s(-1), as well as outstanding long-term cycling stability with only 3.1% reduction of initial specific capacitance after 10,000 cycles. The prominent electrochemical capacitive properties of H-TiO(2) are attributed to the enhanced carrier density and increased density of hydroxyl group on TiO(2) surface, as a result of hydrogenation. Furthermore, we demonstrate that H-TiO(2) NTAs is a good scaffold to support MnO(2) nanoparticles. The capacitor electrodes made by electrochemical deposition of MnO(2) nanoparticles on H-TiO(2) NTAs achieve a remarkable specific capacitance of 912 F g(-1) at a scan rate of 10 mV s(-1) (based on the mass of MnO(2)). The ability to improve the capacitive properties of TiO(2) electrode materials should open up new opportunities for high-performance supercapacitors. © 2012 American Chemical Society

Icosahedral quasicrystalline (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx alloys: Synthesis, structure and their application in Ni-MH batteries

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

Hu, Wen; State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun 130022, Jilin; Yi, Jianhong

2013-06-01

Thanks to the revolutionary discovery of 5-fold symmetry contributed by Shechtman, quasicrystal is now recognized as another solid-state existing form. As the second largest class of quasicrystals, titanium-based icosahedral quasicrystals are very promising for hydrogen storage applications owing to their inherent abundant interstitial sites and favorable hydrogen-metal chemistry. In this context, (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx (x=0.5–6) quaternary icosahedral quasicrystals have been successfully synthesized via arc-melting and subsequent melt-spinning techniques, and then their electrochemical performance toward hydrogen is explored. When the molar ratio of Sc addition is under 1%, a maximum discharge capacity of about 270 mA h g⁻¹ can be delivered. With furthermore » increasing Sc amount to 6%, good cycling stability as well as significantly retarded self-discharge rate (capacity retention 94% after 24 h relaxation) is observed. But meanwhile, the discharge capacities fall into 250-240 mA h g⁻¹, and the electrocatalytic activity improvement is highly demanded. - Graphical abstract: Quasicrystalline Ti–V–Ni–Sc hydrogen storage materials: Sc addition into Ti₁.₆V₀.₄Ni alloy forms the icosahedral phase (see picture). With optimal Sc dosage, the anodic cycling stability and self-discharge property are greatly enhanced. - Highlights: • Crystalline disallowed 5-fold symmetry is present in (Ti₁.₆V₀.₄Ni)₁₀₀₋xScx alloys. • Ti-based metastable quasicrystalline alloys can store hydrogen electrochemically. • A maximum discharge capacity of 270 mA h g⁻¹ can be delivered. • Advantageous cycle stability and self-discharge property benefit from Sc addition. • Ti and V dissolution is suppressed by an oxide layer resulting from Sc corrosion.« less

CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

NASA Astrophysics Data System (ADS)

Janardhanan, Vinod M.; Deutschmann, Olaf

Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH 4 (3% H 2 O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary.

Removal of arsenic, phosphates and ammonia from well water using electrochemical/chemical methods and advanced oxidation: a pilot plant approach.

PubMed

Orescanin, Visnja; Kollar, Robert; Nad, Karlo; Halkijevic, Ivan; Kuspilic, Marin; Findri Gustek, Stefica

2014-01-01

The purpose of this work was to develop a pilot plant purification system and apply it to groundwater used for human consumption, containing high concentrations of arsenic and increased levels of phosphates, ammonia, mercury and color. The groundwater used was obtained from the production well in the Vinkovci County (Eastern Croatia). Due to a complex composition of the treated water, the purification system involved a combined electrochemical treatment, using iron and aluminum electrode plates with simultaneous ozonation, followed by a post-treatment with UV, ozone and hydrogen peroxide. The removal of the contaminant with the waste sludge collected during the electrochemical treatment was also tested. The combined electrochemical and advanced oxidation treatment resulted in the complete removal of arsenic, phosphates, color, turbidity, suspended solids and ammonia, while the removal of other contaminants of interest was up to 96.7%. Comparable removal efficiencies were obtained by using waste sludge as a coagulant.

Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact.

PubMed

Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

2018-01-12

Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from 'electrochemical' to 'mechanical', which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

Electrocatalytic oxidation of hydrogen peroxide on a platinum electrode in the imitation of oxidative drug metabolism of lidocaine.

PubMed

Nouri-Nigjeh, Eslam; Bruins, Andries P; Bischoff, Rainer; Permentier, Hjalmar P

2012-10-21

Electrochemistry in combination with mass spectrometry has shown promise as a versatile technique not only in the analytical assessment of oxidative drug metabolism, but also for small-scale synthesis of drug metabolites. However, electrochemistry is generally limited to reactions initiated by direct electron transfer. In the case of substituted-aromatic compounds, oxidation proceeds through a Wheland-type intermediate where resonance stabilization of the positive charge determines the regioselectivity of the anodic substitution reaction, and hence limits the extent of generating drug metabolites in comparison with in vivo oxygen insertion reactions. In this study, we show that the electrocatalytic oxidation of hydrogen peroxide on a platinum electrode generates reactive oxygen species, presumably surface-bound platinum-oxo species, which are capable of oxygen insertion reactions in analogy to oxo-ferryl radical cations in the active site of Cytochrome P450. Electrochemical oxidation of lidocaine at constant potential in the presence of hydrogen peroxide produces both 3- and 4-hydroxylidocaine, suggesting reaction via an arene oxide rather than a Wheland-type intermediate. No benzylic hydroxylation was observed, thus freely diffusing radicals do not appear to be present. The results of the present study extend the possibilities of electrochemical imitation of oxidative drug metabolism to oxygen insertion reactions.

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

Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

NASA Astrophysics Data System (ADS)

Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

2018-03-01

Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

The Influence of MgH2 on the Assessment of Electrochemical Data to Predict the Degradation Rate of Mg and Mg Alloys

PubMed Central

Mueller, Wolf-Dieter; Hornberger, Helga

2014-01-01

Mg and Mg alloys are becoming more and more of interest for several applications. In the case of biomaterial applications, a special interest exists due to the fact that a predictable degradation should be given. Various investigations were made to characterize and predict the corrosion behavior in vitro and in vivo. Mostly, the simple oxidation of Mg to Mg2+ ions connected with adequate hydrogen development is assumed, and the negative difference effect (NDE) is attributed to various mechanisms and electrochemical results. The aim of this paper is to compare the different views on the corrosion pathway of Mg or Mg alloys and to present a neglected pathway based on thermodynamic data as a guideline for possible reactions combined with experimental observations of a delay of visible hydrogen evolution during cyclic voltammetry. Various reaction pathways are considered and discussed to explain these results, like the stability of the Mg+ intermediate state, the stability of MgH2 and the role of hydrogen overpotential. Finally, the impact of MgH2 formation is shown as an appropriate base for the prediction of the degradation behavior and calculation of the corrosion rate of Mg and Mg alloys. PMID:24972140

Metal | polypyrrole battery with the air regenerated positive electrode

NASA Astrophysics Data System (ADS)

Grgur, Branimir N.

2014-12-01

Recharge characteristics of the battery based on the electrochemically synthesized polypyrrole cathode and aluminum, zinc, or magnesium anode in 2 M NH4Cl are investigated. It is shown that polypyrrole electrode can be regenerated by the reoxidation with the dissolved oxygen from the air. Using the polypyrrole synthesized on high surface graphite-felt electrode under modest discharge conditions, stable discharge voltage of 1.1 V is obtained. Such behavior is explained by the complex interaction of polypyrrole and hydrogen peroxide produced by the oxygen reduction reaction. The electrochemical characteristics are compared with the zinc-manganese dioxide and zinc-air systems.

Surface-Charge-Mediated Formation of H-TiO2 @Ni(OH)2 Heterostructures for High-Performance Supercapacitors.

PubMed

Ke, Qingqing; Guan, Cao; Zhang, Xiao; Zheng, Minrui; Zhang, Yong-Wei; Cai, Yongqing; Zhang, Hua; Wang, John

2017-02-01

An electrochemically favorable Ni(OH) 2 with porously hierarchical structure and ultrathin nanosheets in a core-shell structure H-TiO 2 @Ni(OH) 2 is achieved through modulating the surface chemical activity of TiO 2 by hydrogenation, which creates a defect-rich surface of TiO 2 , thereby facilitating the subsequent nucleation and growth of Ni(OH) 2 . These configuration-tailored H-TiO 2 @Ni(OH) 2 core-shell nanowires exhibit a superior electrochemical performance and good flexibility. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical incineration of wastes

NASA Technical Reports Server (NTRS)

Kaba, L.; Hitchens, G. D.; Bockris, J. O'M.

1989-01-01

A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

Graphene Based Electrochemical Sensors and Biosensors: A Review

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

Shao, Yuyan; Wang, Jun; Wu, Hong

2010-05-01

Graphene, emerging as a true 2-dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene-based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphene-based enzyme biosensors have been summarized in more detail; Graphene-based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.

Diamond surface functionalization with biomimicry - Amine surface tether and thiol moiety for electrochemical sensors

NASA Astrophysics Data System (ADS)

Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

2014-05-01

The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen-oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

Redox Chemistry of Molybdenum Trioxide for Ultrafast Hydrogen-Ion Storage.

PubMed

Wang, Xianfu; Xie, Yiming; Tang, Kai; Wang, Chao; Yan, Chenglin

2018-05-11

Hydrogen ions are ideal charge carriers for rechargeable batteries due to their small ionic radius and wide availability. However, little attention has been paid to hydrogen-ion storage devices because they generally deliver relatively low Coulombic efficiency as a result of the hydrogen evolution reaction that occurs in an aqueous electrolyte. Herein, we successfully demonstrate that hydrogen ions can be electrochemically stored in an inorganic molybdenum trioxide (MoO 3 ) electrode with high Coulombic efficiency and stability. The as-obtained electrode exhibits ultrafast hydrogen-ion storage properties with a specific capacity of 88 mA hg -1 at an ultrahigh rate of 100 C. The redox reaction mechanism of the MoO 3 electrode in the hydrogen-ion cell was investigated in detail. The results reveal a conversion reaction of the MoO 3 electrode into H 0.88 MoO 3 during the first hydrogen-ion insertion process and reversible intercalation/deintercalation of hydrogen ions between H 0.88 MoO 3 and H 0.12 MoO 3 during the following cycles. This study reveals new opportunities for the development of high-power energy storage devices with lightweight elements. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Constant-load delayed fracture test of atmospherically corroded high strength steels

NASA Astrophysics Data System (ADS)

Akiyama, Eiji; Matsukado, Katsuhiro; Li, Songjie; Tsuzaki, Kaneaki

2011-07-01

Constant load tests of circumferentially notched round bar specimens of high strength steels after cyclic corrosion test and outdoor exposure have been performed to demonstrate that delayed fracture occurs when the hydrogen content from the environment, H E, exceeds the critical hydrogen content for delayed fracture, H C. During the constant load tests the humidity around the specimen was increased in stepwise manner to increase hydrogen entry. After fracture the specimen was kept at the humidity long enough to homogenize hydrogen in the specimen and to obtain more quantitative hydrogen content by thermal desorption analysis. H E of the fractured specimens was higher than H C, and H E of the specimens not fractured was lower than H C. This result confirms that the balance between H C and H E determines the occurrence of delayed fracture and that hydrogen-content-based evaluation of susceptibility to delayed fracture is reasonable. To certify the increase of H E with increase in humidity, electrochemical hydrogen permeation test was carried out. The hydrogen permeation current density was increased especially at 98%RH. Enhancement of hydrogen entry with increase in CCT number was also shown by the test.

Fuel Cells | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion, Electrochimica Acta (2016) Suppression of Oxygen Reduction Reaction Activity on Pt-Based Electrocatalysts from Ionomer Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction, Journal of the Electrochemical Society

Improvement on the Repair Effect of Electrochemical Chloride Extraction Using a Modified Electrode Configuration

PubMed Central

Feng, Wei; Xu, Jinxia; Jiang, Linhua; Song, Yingbin; Cao, Yalong; Tan, Qiping

2018-01-01

To improve the repair effect of electrochemical chloride extraction, a modified electrode configuration is applied in this investigation. In this configuration, two auxiliary electrodes placed in the anodic and cathodic electrolytes were used as the anode and cathode, respectively. Besides this, the steel in the mortar was grounded to protect it from corrosion. By a comparative experiment, the potential evolution, various ions concentrations (Cl−, OH−, Na+, and K+) in different mortar depths, the corrosion potential, and the current density of the steel were measured. The results indicate that compared to electrochemical chloride extraction with the traditional electrode configuration, this electrochemical chloride extraction method with a modified electrode configuration has a similar chloride removal ratio. Besides this, potential of steel is just about 800 mV for a saturated calomel electrode (SCE) during the treatment, which did not reach the hydrogen evolution potential. The phenomenon of the accumulation of OH−, Na+, and K+ did not occur when the modified electrode configuration is applied. Additionally, higher corrosion potentials and lower corrosion current rates were measured after performing electrochemical chloride extraction with the modified electrode configuration. Additionally, it is a short period of time for the steel to go from activation to passivation. On this basis, the modified electrode configuration may overcome the drawbacks of electrochemical chloride extraction. PMID:29389855

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide

NASA Astrophysics Data System (ADS)

Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.; Thomas, Joseph G.; Ding, Qi; Chang, Hung-Chih; Tsai, Meng-Lin; He-Hau, Jr.; Jin, Song

2015-12-01

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm-2 at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n+-p-p+ silicon micropyramids achieved photocurrents up to 35 mA cm-2 at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Electrode structures and surfaces for Li batteries

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho; Balasubramanian, Mahalingam; Croy, Jason

2017-03-14

This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

LEED-AES-Thin Layer Electrochemical Studies of Hydrogen Adsorption on Platinum Single Crystals.

DTIC Science & Technology

1982-08-01

of the voltametry sweep and has been observed in HF but not H2SO4 as the electrolyte (1). This anomalous behavior is not easily explained by any...Fig. 3. Cyclic linear sweep voltametry curve for Pt(3ll) in 0.1 N WF. Sveep rate: 50 uV/s. Solid line: secoad cycle 0.05 to 0.5 V; dotted line: fourth...Without such cycling, the hydrogen region of the voltametry curves usually does not yield well defined peaks in either polycrystalline or single crystal

Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases

PubMed Central

Wilson, Aaron D.; Shoemaker, R. K.; Miedaner, A.; Muckerman, J. T.; DuBois, Daniel L.; DuBois, M. Rakowski

2007-01-01

Studies of the role of proton relays in molecular catalysts for the electrocatalytic production and oxidation of H2 have been carried out. The electrochemical production of hydrogen from protonated DMF solutions catalyzed by [Ni(P2PhN2Ph)2(CH3CN)](BF4)2, 3a (where P2PhN2Ph is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane), permits a limiting value of the H2 production rate to be determined. The turnover frequency of 350 s−1 establishes that the rate of H2 production for the mononuclear nickel catalyst 3a is comparable to those observed for Ni-Fe hydrogenase enzymes. In the electrochemical oxidation of hydrogen catalyzed by [Ni(P2CyN2Bz)2](BF4)2, 3b (where Cy is cyclohexyl and Bz is benzyl), the initial step is the reversible addition of hydrogen to 3b (Keq = 190 atm−1 at 25°C). The hydrogen addition product exists as three nearly isoenergetic isomers 4A–4C, which have been identified by a combination of one- and two-dimensional 1H, 31P, and 15N NMR spectroscopies as Ni(0) complexes with a protonated amine in each cyclic ligand. The nature of the isomers, together with calculations, suggests a mode of hydrogen activation that involves a symmetrical interaction of a nickel dihydrogen ligand with two amine bases in the diphosphine ligands. Single deprotonation of 4 by an external base results in a rearrangement to [HNi(P2CyN2Bz)2](BF4), 5, and this reaction is reversed by the addition of a proton to the nickel hydride complex. The small energy differences associated with significantly different distributions in electron density and protons within these molecules may contribute to their high catalytic activity. PMID:17360385

System level electrochemical principles

NASA Technical Reports Server (NTRS)

Thaller, L. H.

1985-01-01

The traditional electrochemical storage concepts are difficult to translate into high power, high voltage multikilowatt storage systems. The increased use of electronics, and the use of electrochemical couples that minimize the difficulties associated with the corrective measures to reduce the cell to cell capacity dispersion were adopted by battery technology. Actively cooled bipolar concepts are described which represent some attractive alternative system concepts. They are projected to have higher energy densities lower volumes than current concepts. They should be easier to scale from one capacity to another and have a closer cell to cell capacity balance. These newer storage system concepts are easier to manage since they are designed to be a fully integrated battery. These ideas are referred to as system level electrochemistry. The hydrogen-oxygen regenerative fuel cells (RFC) is probably the best example of the integrated use of these principles.

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

The use of pyro-polymeric catalysts and a new cylindrical cell design in oxygen-aluminum generators

NASA Astrophysics Data System (ADS)

Kiseleva, E. A.; Zhuk, A. Z.; Kleymenov, B. V.; Oudaltsov, V. G.

2018-01-01

The increase in energy consumption, the economic crisis, the development of certain areas of engineering and energy, as well as the related deterioration of the environmental situation, require the development of new electrochemical current sources with high specific characteristics. In the field of creating air-hydrogen fuel cells, the problems of safety and mobile storage of hydrogen have not been completely solved, stagnation in the development of lithium-ion, lithium-air and lithium-sulfur batteries has been outlined. All this requires searching for new technological solutions, ways to increase the energy and resource characteristics of electrochemical current sources (ECS), reducing their cost [1-2]. The use of metals (aluminum, zinc, magnesium) as an energy carrier is due to their high energy intensity (in combination with the lack of transport, storage and on-board storage problems) of the relatively low cost of metals, their availability, storage safety and the absence of harmful emissions when used. As in the chemical and electrochemical use of metals, safe products (oxides, hydroxides) are formed, which are reduced to metals within the framework of traditional production technologies. Thus, a closed cycle of energy use is organized. The task of this paper is to evaluate the possibility of reducing the cost and increasing the specific power of ECS using oxygen depolarization. The goal is achieved by using non-platinum catalysts and optimizing the design of the current source.

Electrochemical latent redox ratiometric probes for real-time tracking and quantification of endogenous hydrogen sulfide production in living cells.

PubMed

Manibalan, Kesavan; Mani, Veerappan; Chang, Pu-Chieh; Huang, Chih-Hung; Huang, Sheng-Tung; Marchlewicz, Kasper; Neethirajan, Suresh

2017-10-15

Hydrogen sulfide (H 2 S) was discovered as a third gasotransmitter in biological systems and recent years have seen a growing interest to understand its physiological and pathological functions. However, one major limiting factor is the lack of robust sensors to quantitatively track its production in real-time. We described a facile electrochemical assay based on latent redox probe approach for highly specific and sensitive quantification in living cells. Two chemical probes, Azido Benzyl ferrocene carbamate (ABFC) and N-alkyl Azido Benzyl ferrocene carbamate (NABFC) composed of azide trigger group were designed. H 2 S molecules specifically triggered the release of reporters from probes and the current response was monitored using graphene oxide film modified electrode as transducer. The detection limits are 0.32µM (ABFC) and 0.076µM (NABFC) which are comparable to those of current sensitive methods. The probes are successful in the determination of H 2 S spiked in whole human blood, fetal bovine serum, and E. coli. The continuous monitoring and quantification of endogenous H 2 S production in E. coli were successfully accomplished. This work lays first step stone towards real-time electrochemical quantification of endogenous H 2 S in living cells, thus hold great promise in the analytical aspects of H 2 S. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrogen bubble dynamic template fabrication of nanoporous Cu film supported by graphene nanaosheets: A highly sensitive sensor for detection of nitrite.

PubMed

Majidi, Mir Reza; Ghaderi, Seyran

2017-12-01

High surface area nanoporous Cu film (NPCF) has been successfully synthesized using a hydrogen bubble dynamic template on the graphene nanosheets (GNs) modified glassy carbon electrode (GCE). The effect of different synthesis conditions such as applied potential and deposition time on the NPCF morphology was investigated. The structure and constituent of the NPCF-GNs/GCE were characterized by scanning electron microscopy (SEM), energy-dispersive x-ray (EDX), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and electrochemical methods. The study on electrocatalytic performance of the NPCF-GNs/GCE demonstrated that this electrode has excellent catalytic activity toward nitrite oxidation. The quantitative measurement of nitrite by amperometric method showed a wide concentration range (0.1-100µmolL -1 ) with a detection limit and a sensitivity of 8.87 × 10 -8 molL -1 and 3.1 AL/molcm 2 , respectively. The excellent electrochemical response and high sensitivity of the proposed electrode were attributed to the 3D structure of NPCF and the synergic effect of NPCF and GNs. Furthermore, this electrode showed some other advantages including good repeatability, high reproducibility, long-term stability and anti-interference performance toward nitrite sensing. The applicability of the proposed electrode was proved by successful determination of nitrite in real samples (tap water, river water and sausage samples). Copyright © 2017 Elsevier B.V. All rights reserved.

Electrodeposition of flower-like platinum on electrophoretically grown nitrogen-doped graphene as a highly sensitive electrochemical non-enzymatic biosensor for hydrogen peroxide detection

NASA Astrophysics Data System (ADS)

Tajabadi, M. T.; Sookhakian, M.; Zalnezhad, E.; Yoon, G. H.; Hamouda, A. M. S.; Azarang, Majid; Basirun, W. J.; Alias, Y.

2016-11-01

An efficient non-enzymatic biosensor electrode consisting of nitrogen-doped graphene (N-graphene) and platinum nanoflower (Pt NF) with different N-graphene loadings were fabricated on indium tin oxide (ITO) glass using a simple layer-by-layer electrophoretic and electrochemical sequential deposition approach. N-graphene was synthesized by annealing graphene oxide with urea at 900 °C. The structure and morphology of the as-fabricated non-enzymatic biosensor electrodes were determined using X-ray diffraction, field emission electron microscopy, transmission electron microscopy, Raman and X-ray photoelectron spectra. The as-fabricated Pt NF-N-graphene-modified ITO electrodes with different N-graphene loadings were utilized as a non-enzymatic biosensor electrode for the detection of hydrogen peroxide (H2O2). The behaviors of the hybrid electrodes towards H2O2 reduction were assessed using chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy analysis. The Pt NF-N-graphene-modified ITO electrode with a 0.05 mg ml-1 N-graphene loading exhibited the lowest detection limit, fastest amperometric sensing, a wide linear response range, excellent stability and reproducibility for the non-enzymatic H2O2 detection, due to the synergistic effect between the electrocatalytic activity of the Pt NF and the high conductivity and large surface area of N-graphene.

Catalysis in high-temperature fuel cells.

PubMed

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

The 1975 GSFC Battery Workshop

NASA Technical Reports Server (NTRS)

1975-01-01

The proceedings of the 1975 Goddard Space Flight Center Battery Workshop are presented. The major topics of discussion were nickel cadmium batteries and, to a lesser extent, nickel hydrogen batteries. Battery design, manufacturing techniques, testing programs, and electrochemical characteristics were considered. The utilization of these batteries for spacecraft power supplies was given particular attention.

A high energy-density nickel-hydrogen battery design

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

Miller, L.

1982-09-01

A light-weight Ni-H/sub 2/ battery design concept (projected energy-density 46.7 Whr/Kg or 21.2 Whr/Lb) suitable for immediate or near-term spacecraft integration is described. The proposed design does not violate proven and qualified design concepts, or critical electrochemical component designs or functions.

Beyond graphene: Electrochemical sensors and biosensors for biomarkers detection.

PubMed

Bollella, Paolo; Fusco, Giovanni; Tortolini, Cristina; Sanzò, Gabriella; Favero, Gabriele; Gorton, Lo; Antiochia, Riccarda

2017-03-15

Graphene's success has stimulated great interest and research in the synthesis and characterization of graphene-like 2D materials, single and few-atom-thick layers of van der Waals materials, which show fascinating and technologically useful properties. This review presents an overview of recent electrochemical sensors and biosensors based on graphene and on graphene-like 2D materials for biomarkers detection. Initially, we will outline different electrochemical sensors and biosensors based on chemically derived graphene, including graphene oxide and reduced graphene oxide, properly functionalized for improved performances and we will discuss the various strategies to prepare graphene modified electrodes. Successively, we present electrochemical sensors and biosensors based on graphene-like 2D materials, such as boron nitride (BN), graphite-carbon nitride (g-C 3 N 4 ), transition metal dichalcogenides (TMDs), transition metal oxides and graphane, outlining how the new modified 2D nanomaterials will improve the electrochemical performances. Finally, we will compare the results obtained with different sensors and biosensors for the detection of important biomarkers such as glucose, hydrogen peroxide and cancer biomarkers and highlight the advantages and disadvantages of the use of graphene and graphene-like 2D materials in different sensing platforms. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Lawal, Abdulazeez T., E-mail: abdul.lawal@yahoo.com

Graphical abstract: Carbon nanotubes. - Highlights: • This review discusses synthesis and applications of carbon nanotubes sensors. • The review summarizes contributions of carbon nanotube to electrochemical biosensor. • Good electrical conductivity makes carbon nanotubes a good material for biosensors. • Carbon nanotubes promotes electron transfer that aids biosensing of biomolecules. - Abstract: This review summarizes the most recent contributions in the fabrication of carbon nanotubes-based electrochemical biosensors in recent years. It discusses the synthesis and application of carbon nanotubes to the assembly of carbon nanotube-based electrochemical sensors, its analytical performance and future expectations. An increasing number of reviews andmore » publications involving carbon nanotubes sensors have been reported ever since the first design of carbon nanotube electrochemical biosensors. The large surface area and good electrical conductivity of carbon nanotubes allow them to act as “electron wire” between the redox center of an enzyme or protein and an electrode's surface, which make them very excellent material for the design of electrochemical biosensors. Carbon nanotubes promote the different rapid electron transfers that facilitate accurate and selective detection of cytochrome-c, β-nicotinamide adenine dinucleotide, hemoglobin and biomolecules, such as glucose, cholesterol, ascorbic acid, uric acid, dopamine pesticides, metals ions and hydrogen peroxide.« less

Facile one-step electrochemical deposition of copper nanoparticles and reduced graphene oxide as nonenzymatic hydrogen peroxide sensor

NASA Astrophysics Data System (ADS)

Moozarm Nia, Pooria; Woi, Pei Meng; Alias, Yatimah

2017-08-01

For several decades, hydrogen peroxide has exhibited to be an extremely significant analyte as an intermediate in several biological devices as well as in many industrial systems. A straightforward and novel one-step technique was employed to develop a sensitive non-enzymatic hydrogen peroxide (H2O2) sensor by simultaneous electrodeposition of copper nanoparticles (CuNPs) and reduced graphene oxide (rGO). The electroreduction performance of the CuNPs-rGO for hydrogen peroxide detection was studied by cyclic voltammetry (CV) and chronoamperometry (AMP) methods The CuNPs-rGO showed a synergistic effect of reduced graphene oxide and copper nanoparticles towards the electroreduction of hydrogen peroxide, indicating high reduction current. At detection potential of -0.2 V, the CuNPs-rGO sensor demonstrated a wide linear range up to 18 mM with a detection limit of 0.601 mM (S/N = 3). Furthermore, with addition of hydrogen peroxide, the sensor responded very quickly (<3 s). The CuNPs-rGO presents high selectivity, sensitivity, stability and fast amperometric sensing towards hydrogen peroxide which makes it favorable for the development of non-enzymatic hydrogen peroxide sensor.

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most successful hydrogen pumping catalysts, comparable to a commercial Pt/C catalyst. Synthesized Pt/C materials were also used as PEMFC catalysts. We found the ALD catalysts with lower platinum loading to be competitive with a commercial fuel cell catalyst, especially when exhibiting similar platinum particle characteristics. The functionalized carbon helped produce smaller and more dispersed platinum particles; however, it encouraged carbon corrosion within an electrode, severing electrical connections and lowering energy production. The most suitable chemistry for competitive Pt/C catalysts was produced by platinum ALD on unmodified carbon using hydrogen as a reactant. ALD is a promising method for fabricating electrocatalysts, which could help fuel cells become an economically viable alternative to fossil fuels.

Development of a Hydrogen Peroxide Sensor Based on Screen-Printed Electrodes Modified with Inkjet-Printed Prussian Blue Nanoparticles

PubMed Central

Cinti, Stefano; Arduini, Fabiana; Moscone, Danila; Palleschi, Giuseppe; Killard, Anthony J.

2014-01-01

A sensor for the simple and sensitive measurement of hydrogen peroxide has been developed which is based on screen printed electrodes (SPEs) modified with Prussian blue nanoparticles (PBNPs) deposited using piezoelectric inkjet printing. PBNP-modified SPEs were characterized using physical and electrochemical techniques to optimize the PBNP layer thickness and electroanalytical conditions for optimum measurement of hydrogen peroxide. Sensor optimization resulted in a limit of detection of 2 × 10−7 M, a linear range from 0 to 4.5 mM and a sensitivity of 762 μA·mM−1·cm−2 which was achieved using 20 layers of printed PBNPs. Sensors also demonstrated excellent reproducibility (<5% rsd). PMID:25093348

A Review of Hydrogen/Halogen Flow Cells

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

Cho, Kyu Taek; Tucker, Michael C.; Weber, Adam Z.

Flow batteries provide an energy-storage solution for various grid-related stability and service issues that arise as renewable-energy-generation technologies are adopted. Among the most promising flow-battery systems are those using hydrogen/halogen redox couples, which promise the possibility of meeting the cost target of the US Department of Energy (DOE), due to their fast and reversible kinetics and low materials cost. However, significant critical issues and barriers for their adoption remain. In this review of halogen/hydrogen systems, technical and performance issues, and research and development progress are reviewed. The information in this review can be used as a technical guide for researchmore » and development of related redox-flow-battery systems and other electrochemical technologies.« less

A Review of Hydrogen/Halogen Flow Cells

DOE PAGES

Cho, Kyu Taek; Tucker, Michael C.; Weber, Adam Z.

2016-05-17

Flow batteries provide an energy-storage solution for various grid-related stability and service issues that arise as renewable-energy-generation technologies are adopted. Among the most promising flow-battery systems are those using hydrogen/halogen redox couples, which promise the possibility of meeting the cost target of the US Department of Energy (DOE), due to their fast and reversible kinetics and low materials cost. However, significant critical issues and barriers for their adoption remain. In this review of halogen/hydrogen systems, technical and performance issues, and research and development progress are reviewed. The information in this review can be used as a technical guide for researchmore » and development of related redox-flow-battery systems and other electrochemical technologies.« less

Sponge-like silver obtained by decomposition of silver nitrate hexamethylenetetramine complex

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

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

2016-07-15

Silver nitrate hexamethylenetetramine [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] coordination compound has been prepared via aqueous route and characterized by chemical analysis, XRD and electron microscopy. Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] under hydrogen and under inert has been studied by thermal analysis and mass spectrometry. Thermal decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] proceeds in the range 200–250 °C as a self-propagating rapid redox process accompanied with the release of multiple gases. The decomposition leads to formation of sponge-like silver having hierarchical open pore system with pore size spanning from 10 µm to 10 nm. The as-obtained silver spongesmore » exhibited favorable activity toward H{sub 2}O{sub 2} electrochemical reduction, making them potentially interesting as non-enzyme hydrogen peroxide sensors. - Graphical abstract: Thermal decomposition of silver nitrate hexamethylenetetramine coordination compound [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to sponge like silver that possesses open porous structure and demonstrates interesting properties as an electrochemical hydrogen peroxide sensor. Display Omitted - Highlights: • [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] orthorhombic phase prepared and characterized. • Decomposition of [Ag(NO{sub 3})·N{sub 4}(CH{sub 2}){sub 6}] leads to metallic silver sponge with opened porosity. • Ag sponge showed promising properties as a material for hydrogen peroxide sensors.« less

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.

Nickel-hydrogen. [metal hydrides, electrochemical corrosion, and structural design

NASA Technical Reports Server (NTRS)

Mchenry, E. J.

1977-01-01

Because of the disintegration of LaNi5 as the lattice expands on absorbing hydrogen, a nickel hydrogen cell similar to a nickel cadmium cell was designed. The positive electrode is wrapped in a microporous separator and the leads are insulated. A negative conducting grid is inserted and welded to the top of the can into an open ended container which is then turned upside down and filled so that LiNa5 powder occupies all the space not used by the rest of the components. The bottom of the can is then welded on. A fill tube is located either on the bottom or on the top of the can. When welded shut, the cell is put into a pressure bomb and the lanthanum nickel is activated at about 1,000 pounds of hydrogen. Electrolytes are added to the cell as well as whatever amount of hydrogen precharge desired, and the cell is sealed. Advantages and disadvantages of the cell are discussed.

Diffusion coefficient of hydrogen in a cast gamma titanium aluminide

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

Sundaram, P.A.; Wessel, E.; Ennis, P.J.

1999-06-04

Gamma titanium aluminides have the potential for high temperature applications because of their high specific strength and specific modulus. Their oxidation resistance is good, especially at intermediate temperatures and with suitable alloying additions, good oxidation resistance can be obtained up to 800 C. One critical area of application is in combustion engines in aero-space vehicles such as hypersonic airplanes and high speed civil transport airplanes. This entails the use of hydrogen as a fuel component and hence the effect of hydrogen on the mechanical properties of gamma titanium aluminides is of significant scientific and technological utility. The purpose of thismore » short investigation is to use an electrochemical method under galvanostatic conditions to determine the diffusion coefficient of hydrogen in a cast gamma titanium aluminide, a typical technical alloy with potential application in gas turbines under creep conditions. This result will be then compared with that obtained by microhardness profiling of electrolytically hydrogen precharged material.« less

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

A metal-organic cage incorporating multiple light harvesting and catalytic centres for photochemical hydrogen production

NASA Astrophysics Data System (ADS)

Chen, Sha; Li, Kang; Zhao, Fang; Zhang, Lei; Pan, Mei; Fan, Yan-Zhong; Guo, Jing; Shi, Jianying; Su, Cheng-Yong

2016-11-01

Photocatalytic water splitting is a natural but challenging chemical way of harnessing renewable solar power to generate clean hydrogen energy. Here we report a potential hydrogen-evolving photochemical molecular device based on a self-assembled ruthenium-palladium heterometallic coordination cage, incorporating multiple photo- and catalytic metal centres. The photophysical properties are investigated by absorption/emission spectroscopy, electrochemical measurements and preliminary DFT calculations and the stepwise electron transfer processes from ruthenium-photocentres to catalytic palladium-centres is probed by ultrafast transient absorption spectroscopy. The photocatalytic hydrogen production assessments reveal an initial reaction rate of 380 μmol h-1 and a turnover number of 635 after 48 h. The efficient hydrogen production may derive from the directional electron transfers through multiple channels owing to proper organization of the photo- and catalytic multi-units within the octahedral cage, which may open a new door to design photochemical molecular devices with well-organized metallosupramolecules for homogenous photocatalytic applications.

Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

PubMed

Tamburri, Emanuela; Cassani, Maria Cristina; Ballarin, Barbara; Tomellini, Massimo; Femoni, Cristina; Mignani, Adriana; Terranova, Maria Letizia; Orlanducci, Silvia

2016-05-23

Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

DOE PAGES

Alfonso, Dominic R.; Kauffman, Douglas R.

2017-08-14

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Fast electrochemical deposition of Ni(OH)2 precursor involving water electrolysis for fabrication of NiO thin films

NASA Astrophysics Data System (ADS)

Koyama, Miki; Ichimura, Masaya

2018-05-01

Ni(OH)2 precursor films were deposited by galvanostatic electrochemical deposition (ECD), and NiO thin films were fabricated by annealing in air. The effects of the deposition current densities were studied in a range that included current densities high enough to electrolyze water and generate hydrogen bubbles. The films fabricated by ECD involving water electrolysis had higher transparency and smoother surface morphology than those deposited with lower current densities. In addition, the annealed NiO films clearly had preferred (111) orientation when the deposition was accompanied by water electrolysis. p-type conduction was confirmed for the annealed films.

Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

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

Alfonso, Dominic R.; Kauffman, Douglas R.

Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

Integrated carbon fiber electrodes within hollow polymer microneedles for transdermal electrochemical sensing

PubMed Central

Miller, Philip R.; Gittard, Shaun D.; Edwards, Thayne L.; Lopez, DeAnna M.; Xiao, Xiaoyin; Wheeler, David R.; Monteiro-Riviere, Nancy A.; Brozik, Susan M.; Polsky, Ronen; Narayan, Roger J.

2011-01-01

In this study, carbon fiber electrodes were incorporated within a hollow microneedle array, which was fabricated using a digital micromirror device-based stereolithography instrument. Cell proliferation on the acrylate-based polymer used in microneedle fabrication was examined with human dermal fibroblasts and neonatal human epidermal keratinocytes. Studies involving full-thickness cadaveric porcine skin and trypan blue dye demonstrated that the hollow microneedles remained intact after puncturing the outermost layer of cadaveric porcine skin. The carbon fibers underwent chemical modification in order to enable detection of hydrogen peroxide and ascorbic acid; electrochemical measurements were demonstrated using integrated electrode-hollow microneedle devices. PMID:21522504

The Electrochemical Fluorination of Organosilicon Compounds

NASA Technical Reports Server (NTRS)

Seaver, Robert E.

1961-01-01

The electrochemical fluorination of tetramethylsilane, hexamethyl-disiloxane, diethyldichlorosilane, amyltrichlorosilane, and phenyltri-chlorosilane was conducted in an Inconel cell equipped with nickel electrodes. A potential of approximately 5.0 volts and a current of approximately 1.0 ampere were used for the electrolysis reaction. In all cases the fluorinations resulted in considerable scission of the carbon-silicon bonds yielding hydrogen and the various fluorinated decomposition products; no fluoroorganosilicon compounds were identified. The main decomposition products were silicon tetrafluoride, the corresponding fluorinated carbon compounds, and the various organofluorosilanes. It is suggested that this is due to the nucleophilic attack of the fluoride ion (or complex fluoride ion) on the carbon-silicon bond.

Square-wave adsorptive stripping voltammetric determination of nanomolar levels of bezafibrate using a glassy carbon electrode modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film.

PubMed

Ardila, Jorge Armando; Oliveira, Geiser Gabriel; Medeiros, Roberta Antigo; Fatibello-Filho, Orlando

2014-04-07

A highly sensitive method for bezafibrate determination using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes within a dihexadecyl hydrogen phosphate film based on square-wave adsorptive stripping voltammetry (SWAdSV) is proposed. The electrochemical behaviour of bezafibrate has been studied by cyclic voltammetry, showing an irreversible anodic peak at a potential of 1.09 V in 0.1 mol L(-1) phosphate buffer solution (pH 2.0). A study of the scan rate showed that the oxidation of bezafibrate is an adsorptive-controlled process, involving the transfer of two electrons and two protons per molecule. The analytical curve was linear over a bezafibrate concentration range from 50 to 910 nmol L(-1), with a detection limit of 16 nmol L(-1). This analytical method was successfully applied for benzafibrate determination in pharmaceutical formulations, with results showing good agreement with those obtained using a comparative spectrophotometric method, and has the potential for field application.

Microbial electrolysis cells for high yield hydrogen gas production from organic matter.

PubMed

Logan, Bruce E; Call, Douglas; Cheng, Shaoan; Hamelers, Hubertus V M; Sleutels, Tom H J A; Jeremiasse, Adriaan W; Rozendal, René A

2008-12-01

The use of electrochemically active bacteria to break down organic matter, combined with the addition of a small voltage (> 0.2 V in practice) in specially designed microbial electrolysis cells (MECs), can result in a high yield of hydrogen gas. While microbial electrolysis was invented only a few years ago, rapid developments have led to hydrogen yields approaching 100%, energy yields based on electrical energy input many times greater than that possible by water electrolysis, and increased gas production rates. MECs used to make hydrogen gas are similar in design to microbial fuel cells (MFCs) that produce electricity, but there are important differences in architecture and analytical methods used to evaluate performance. We review here the materials, architectures, performance, and energy efficiencies of these MEC systems that show promise as a method for renewable and sustainable energy production, and wastewater treatment.

An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions.

PubMed

Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping

2017-08-08

It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.

Regenerative Fuel Cell Test Rig Completed and Operational at Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.

2004-01-01

The NASA Glenn Research Center has completed construction of its first closed-cycle hydrogen-oxygen regenerative fuel cell (RFC). The RFC is an electrochemical system that collects and stores solar energy during the day then releases that energy at night, thus making the Sun's energy available all 24 hours. It consists of a dedicated hydrogen-oxygen fuel cell stack and an electrolyzer stack, the interconnecting plumbing and valves, cooling pumps, water transfer pumps, gas recirculation pumps, phase separators, storage tanks for oxygen (O2) and hydrogen (H2), heat exchangers, isolation valves, pressure regulators, nitrogen purge provisions, instrumentation, and other components. It includes all the equipment required to (1) absorb electrical power from an outside source and store it as pressurized hydrogen and oxygen and (2) make electrical power from the stored gases, saving the product water for reuse during the next cycle.

One man electrochemical air revitalization system

NASA Technical Reports Server (NTRS)

Huddleston, J. C.; Aylward, J. R.

1975-01-01

An integrated water vapor electrolysis (WVE) hydrogen depolarized CO2 concentrator (HDC) system sized for one man support over a wide range of inlet air conditions was designed, fabricated, and tested. Data obtained during 110 days of testing verified that this system can provide the necessary oxygen, CO2 removal, and partial humidity control to support one man (without exceeding a cabin partial pressure of 3.0 mmHg for CO2 and while maintaining a 20% oxygen level), when operated at a WVE current of 50 amperes and an HDC current of 18 amperes. An evaluation to determine the physical properties of tetramethylammonium bicarbonate (TMAC) and hydroxide was made. This provides the necessary electrolyte information for designing an HDC cell using TMAC.

Carbon Nanotubes (CNTs) for the Development of Electrochemical Biosensors

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

Lin, Yuehe; Yantasee, Wassana; Wang, Joseph

2005-01-01

Carbon nanotube (CNT) is a very attractive material for the development of biosensors because of its capability to provide strong electrocatalytic activity and minimize surface fouling of the sensors. This article reviews our recent developments of oxidase- and dehydrogenase-amperometric biosensors based on the immobilization of CNTs, the co-immobilization of enzymes on the CNTs/Nafion or the CNT/Teflon composite materials, or the attachment of enzymes on the controlled-density aligned CNT-nanoelectrode arrays. The excellent electrocatalytic activities of the CNTs on the redox reactions of hydrogen peroxide, nicotinamide adenine dinucleotide (NADH), and homocysteine have been demonstrated. Successful applications of the CNT-based biosensors reviewed hereinmore » include the low-potential detections of glucose, organophosphorus compounds, and alcohol.« less

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

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« less

Hydrogen production profiles using furans in microbial electrolysis cells.

PubMed

Catal, Tunc; Gover, Tansu; Yaman, Bugra; Droguetti, Jessica; Yilancioglu, Kaan

2017-06-01

Microbial electrochemical cells including microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are novel biotechnological tools that can convert organic substances in wastewater or biomass into electricity or hydrogen. Electroactive microbial biofilms used in this technology have ability to transfer electrons from organic compounds to anodes. Evaluation of biofilm formation on anode is crucial for enhancing our understanding of hydrogen generation in terms of substrate utilization by microorganisms. In this study, furfural and hydroxymethylfurfural (HMF) were analyzed for hydrogen generation using single chamber membrane-free MECs (17 mL), and anode biofilms were also examined. MECs were inoculated with mixed bacterial culture enriched using chloroethane sulphonate. Hydrogen was succesfully produced in the presence of HMF, but not furfural. MECs generated similar current densities (5.9 and 6 mA/cm 2 furfural and HMF, respectively). Biofilm samples obtained on the 24th and 40th day of cultivation using aromatic compounds were evaluated by using epi-fluorescent microscope. Our results show a correlation between biofilm density and hydrogen generation in single chamber MECs.

Hydrogen Embrittlement of Automotive Advanced High-Strength Steels

NASA Astrophysics Data System (ADS)

Lovicu, Gianfranco; Bottazzi, Mauro; D'Aiuto, Fabio; De Sanctis, Massimo; Dimatteo, Antonella; Santus, Ciro; Valentini, Renzo

2012-11-01

Advanced high-strength steels (AHSS) have a better combination between strength and ductility than conventional HSS, and higher crash resistances are obtained in concomitance with weight reduction of car structural components. These steels have been developed in the last few decades, and their use is rapidly increasing. Notwithstanding, some of their important features have to be still understood and studied in order to completely characterize their service behavior. In particular, the high mechanical resistance of AHSS makes hydrogen-related problems a great concern for this steel grade. This article investigates the hydrogen embrittlement (HE) of four AHSS steels. The behavior of one transformation induced plasticity (TRIP), two martensitic with different strength levels, and one hot-stamping steels has been studied using slow strain rate tensile (SSRT) tests on electrochemically hydrogenated notched samples. The embrittlement susceptibility of these AHSS steels has been correlated mainly to their strength level and to their microstructural features. Finally, the hydrogen critical concentrations for HE, established by SSRT tests, have been compared to hydrogen contents absorbed during the painting process of a body in white (BIW) structure, experimentally determined during a real cycle in an industrial plant.

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

Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins.

PubMed

Dreyse, Paulina; Honores, Jessica; Quezada, Diego; Isaacs, Mauricio

2015-11-01

The electrochemical reduction of carbon dioxide is studied herein by using conducting polymers based on metallotetraruthenated porphyrins (MTRPs). The polymers on glassy carbon electrodes were obtained by electropolymerization processes of the monomeric MTRP. The linear sweep voltammetry technique resulted in polymeric films that showed electrocatalytic activity toward carbon dioxide reduction with an onset potential of -0.70 V. The reduction products obtained were hydrogen, formic acid, formaldehyde, and methanol, with a tendency for a high production of methanol with a maximum value of turnover frequency equal to 15.07 when using a zinc(II) polymeric surface. Studies of the morphology (AFM) and electrochemical impedance spectroscopy results provide an adequate background to explain that the electrochemical reduction is governed by the roughness of the polymer, for which the possible mechanism involves a series of one-electron reduction reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The fabrication and electrochemical properties of electrospun nanofibers of a multiwalled carbon nanotube grafted by chitosan

NASA Astrophysics Data System (ADS)

Feng, Wei; Wu, Zigang; Li, Yu; Feng, Yiyu; Yuan, Xiaoyan

2008-03-01

Multiwalled carbon nanotubes (MWCNTs) were grafted by chitosan (CS); the product could disperse well in poly(vinyl alcohol) (PVA) aqueous solution with 2% (v/v) acetic acid solution. Because this product has potential in several biological fields, it was electrospun so as to enlarge the surface area. Raman spectra indicated that the electrospinning process did not severely alter the electron hybridization of carbon atoms within the nanotube framework. Moreover and interestingly, these nanofibers showed a novel sheath-core structure; the outer and inner diameters of these sheath-core nanofibers were about 200 nm and 100 nm, respectively. These nanofibers' electrochemical properties were characterized by detection of hydrogen peroxide and voltammetric responses of potassium ferricyanide. The electrospun fibers' web displayed faster electron transfer kinetics and better electrochemical properties than its cast film, which justified further applications in biological areas.

Studies on the electrochemical behavior of thiazolidine and its applications using a flow-through chronoamperometric sensor based on a gold electrode.

PubMed

Wang, Lai-Hao; Li, Wen-Jie

2011-09-06

The electrochemical behaviors of thiazolidine (tetrahydrothiazole) on gold and platinum electrodes were investigated in a Britton-Robinson buffer (pH 2.77-11.61), acetate buffer (pH 4.31), phosphate buffer solutions (pH 2.11 and 6.38) and methanol or acetonitrile containing various supporting electrolytes. Detection was based on a gold wire electrochemical signal obtained with a supporting electrolyte containing 20% methanol-1.0 mM of phosphate buffer (pH 6.87, potassium dihydrogen phosphate and dipotassium hydrogen phosphate) as the mobile phase. Comparison with results obtained with a commercial amperometric detector shows good agreement. Using the chronoamperometric sensor with the current at a constant potential, and measurements with suitable experimental parameters, a linear concentration from 0.05 to 16 mg L-1 was found. The limit of quantification (LOQ) of the method for thiazolidine was found to be 1 ng.

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

Development of Ni-Ba(Zr,Y)O3 cermet anodes for direct ammonia-fueled solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Miyazaki, Kazunari; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

2017-10-01

In this study, the availability of Ni-Ba(Zr,Y)O3-δ (BZY) cermet for the anode of direct ammonia-fueled solid oxide fuel cells (SOFCs) is evaluated. In this device, the anodes need to be active for the catalytic ammonia decomposition as well as the electrochemical hydrogen oxidation. In the catalytic activity test, ammonia decomposes completely over Ni-BZY at ca. 600 °C, while higher temperature is required to accomplish the complete decomposition over the conventional SOFC anode of Ni-yttria-stabilized zirconia cermet. The high activity of Ni-BZY is attributed to the high basicity of BZY and the high resistance to hydrogen poisoning effect. The electrochemical property of Ni-BZY anode is also evaluated with the anode-supported cell of Ni-BZY|BZY|Pt at 600-700 °C with feeding ammonia or hydrogen as a fuel. Since the residence time of ammonia fuel in the thick Ni-BZY anode is long, the difference in the cell performance between two fuels is relatively small. Furthermore, it is proved that the steam concentration in the fuel strongly affects the cell performance. We find that this factor is important to satisfy the above mentioned requirements for the anode of direct ammonia-fueled SOFCs. Throughout this study, it is concluded that Ni-BZY cermet will be a promising anode.

A novel IrNi@PdIr/C core-shell electrocatalyst with enhanced activity and durability for the hydrogen oxidation reaction in alkaline anion exchange membrane fuel cells.

PubMed

Qin, Bowen; Yu, Hongmei; Jia, Jia; Jun, Chi; Gao, Xueqiang; Yao, Dewei; Sun, Xinye; Song, Wei; Yi, Baolian; Shao, Zhigang

2018-03-08

Herein, a novel non-platinum core-shell catalyst, namely, IrNi@PdIr/C was prepared via a galvanic replacement reaction; it exhibits enhanced hydrogen oxidation activity and excellent stability under alkaline conditions. Electrochemical experiments demonstrated that the mass and specific activities at 50 mV of IrNi@PdIr/C are 2.1 and 2.2 times that of commercial Pt/C in 0.1 M KOH at 298 K, respectively. Moreover, accelerated degradation tests have shown that the electrochemically active surface area (ECSA) of IrNi@PdIr/C reduces by only 5.1%, which is almost 4 times less than that of commercial Pt/C and the mass activity at 50 mV of IrNi@PdIr/C after 2000 potential cycles is still 1.8 times higher than that of aged Pt/C. XRD and XPS analysis suggest that the enhanced HOR activity is attributed to the weakening of the hydrogen binding to the PdIr overlayers induced by the IrNi core. The better stability to potential cycling can be associated with the PdIr shell, which inhibits oxide formation. These results suggest that IrNi@PdIr/C is a promising non-platinum anode catalyst for alkaline anion exchange membrane fuel cells.

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

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

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Microbial utilization of electrically reduced neutral red as the sole electron donor for growth and metabolite production

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

Park, D.H.; Laivenieks, M.; Guettler, M.V.

1999-07-01

Electrically reduced neutral red (NR) served as the sole source of reducing power for growth and metabolism of pure and mixed cultures of H[sub 2]-consuming bacteria in a novel electrochemical bioreactor system. NR was continuously reduced by the cathodic potential ([minus]1.5 V) generated from an electric current (0.3 to 1.0 mA), and it was subsequently oxidized by Actinobacillus succinogenes or by mixed methanogenic cultures. The A. succinogenes mutant strain FZ-6 did not grow on fumarate alone unless electrically reduced NR or hydrogen was present as the electron donor for succinate production. The mutant strain, unlike the wild type, lacked pyruvatemore » formate lyase and formate dehydrogenase. Electrically reduced NR also replaced hydrogen as the sole electron donor source for growth and production of methane from CO[sub 2]. These results show that both pure and mixed cultures can function as electrochemical devices when electrically generated reducing power can be used to drive metabolism. The potential utility of utilizing electrical reducing power in enhancing industrial fermentations or biotransformation processes is discussed.« less

Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

NASA Astrophysics Data System (ADS)

Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

2016-10-01

An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study.

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

PubMed

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

2015-04-21

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

Synthesis of fcc Mg-Ti-H alloys by high energy ball milling: Structure and electrochemical hydrogen storage properties

NASA Astrophysics Data System (ADS)

Rousselot, Steeve; Guay, Daniel; Roué, Lionel

Mg-Ti-H alloys were synthesized by high energy ball milling from equimolar mixtures of MgH 2 + TiH 2, MgH 2 + Ti and Mg + TiH 2 in the presence of 10 wt.% Pd. X-ray diffraction analyses combined with Rietveld refinement revealed that after 60 h of milling, all as-milled Mg-Ti-H alloys are made of two face-centered-cubic (fcc) phases, with lattice parameters ∼4.47 and ∼4.25 Å, in different proportions depending on the composition of the initial mixture. The Mg-Ti-H alloys displayed a similar electrochemical behavior, i.e. their hydrogen discharge capacity was highest during the first cycle and then decreased rapidly with cycling. The maximum discharge capacities of the 60 h-milled MgH 2 + TiH 2, MgH 2 + Ti and Mg + TiH 2 materials were 300, 443 and 454 mAh g -1, respectively. No apparent correlation could be established between the maximum discharge capacity of the Mg-Ti-H materials and the two fcc phase proportion.

Study of the Charge Transfer Process of LaNi5 Type Electrodes in Ni-MH Batteries

NASA Astrophysics Data System (ADS)

Le, Xuan Que; Nguyen, Phu Thuy

2002-12-01

As a result of the charge process of LaNi5 type electrode, hydrogen is reversibly absorbed on the electrode surface. The process consists two principal steps. During the both processes, the first reaction step occurs in the interface solid/liquid, negatively charged, with high static electric field, where the double layer structure became more compact. The transfer of charge under high electric field depends on many factors, principally on compositions of the electrode materials. Effects on that of Co, Fe, Mn substitutes, with different concentrations, have been comparatively studied using electrochemical technique. The analyse of interface C -.V study results has been realised, respecting Mott-Schottky relation. Optimal contents of some additives have been discussed. Some advantages of the applied electrochemical methods have been confirmed. The mechanism of the charges transfer and of the hydrogen reversible storage in the crystal structure in the batteries has been discussed. With the proposed mechanism, one can more explicitly understand the difference of the magnetic effect of the electrode materials before and after charge-discharge process can be explained.

Development method of Hybrid Energy Storage System, including PEM fuel cell and a battery

NASA Astrophysics Data System (ADS)

Ustinov, A.; Khayrullina, A.; Borzenko, V.; Khmelik, M.; Sveshnikova, A.

2016-09-01

Development of fuel cell (FC) and hydrogen metal-hydride storage (MH) technologies continuously demonstrate higher efficiency rates and higher safety, as hydrogen is stored at low pressures of about 2 bar in a bounded state. A combination of a FC/MH system with an electrolyser, powered with a renewable source, allows creation of an almost fully autonomous power system, which could potentially replace a diesel-generator as a back-up power supply. However, the system must be extended with an electro-chemical battery to start-up the FC and compensate the electric load when FC fails to deliver the necessary power. Present paper delivers the results of experimental and theoretical investigation of a hybrid energy system, including a proton exchange membrane (PEM) FC, MH- accumulator and an electro-chemical battery, development methodology for such systems and the modelling of different battery types, using hardware-in-the-loop approach. The economic efficiency of the proposed solution is discussed using an example of power supply of a real town of Batamai in Russia.

Computational materials design for energy applications

NASA Astrophysics Data System (ADS)

Ozolins, Vidvuds

2013-03-01

General adoption of sustainable energy technologies depends on the discovery and development of new high-performance materials. For instance, waste heat recovery and electricity generation via the solar thermal route require bulk thermoelectrics with a high figure of merit (ZT) and thermal stability at high-temperatures. Energy recovery applications (e.g., regenerative braking) call for the development of rapidly chargeable systems for electrical energy storage, such as electrochemical supercapacitors. Similarly, use of hydrogen as vehicular fuel depends on the ability to store hydrogen at high volumetric and gravimetric densities, as well as on the ability to extract it at ambient temperatures at sufficiently rapid rates. We will discuss how first-principles computational methods based on quantum mechanics and statistical physics can drive the understanding, improvement and prediction of new energy materials. We will cover prediction and experimental verification of new earth-abundant thermoelectrics, transition metal oxides for electrochemical supercapacitors, and kinetics of mass transport in complex metal hydrides. Research has been supported by the US Department of Energy under grant Nos. DE-SC0001342, DE-SC0001054, DE-FG02-07ER46433, and DE-FC36-08GO18136.

Construction of CuS/Au Heterostructure through a Simple Photoreduction Route for Enhanced Electrochemical Hydrogen Evolution and Photocatalysis

PubMed Central

Basu, Mrinmoyee; Nazir, Roshan; Fageria, Pragati; Pande, Surojit

2016-01-01

An efficient Hydrogen evolution catalyst has been developed by decorating Au nanoparticle on the surface of CuS nanostructure following a green and environmental friendly approach. CuS nanostructure is synthesized through a simple wet-chemical route. CuS being a visible light photocatalyst is introduced to function as an efficient reducing agent. Photogenerated electron is used to reduce Au(III) on the surface of CuS to prepare CuS/Au heterostructure. The as-obtained heterostructure shows excellent performance in electrochemical H2 evolution reaction with promising durability in acidic condition, which could work as an efficient alternative for novel metals. The most efficient CuS-Au heterostructure can generate 10 mA/cm2 current density upon application of 0.179 V vs. RHE. CuS-Au heterostructure can also perform as an efficient photocatalyst for the degradation of organic pollutant. This dual nature of CuS and CuS/Au both in electrocatalysis and photocatalysis has been unveiled in this study. PMID:27703212

2D Covalent Metals: A New Materials Domain of Electrochemical CO2 Conversion with Broken Scaling Relationship.

PubMed

Shin, Hyeyoung; Ha, Yoonhoo; Kim, Hyungjun

2016-10-04

Toward a sustainable carbon cycle, electrochemical conversion of CO 2 into valuable fuels has drawn much attention. However, sluggish kinetics and a substantial overpotential, originating from the strong correlation between the adsorption energies of intermediates and products, are key obstacles of electrochemical CO 2 conversion. Here we show that 2D covalent metals with a zero band gap can overcome the intrinsic limitation of conventional metals and metal alloys and thereby substantially decrease the overpotential for CO 2 reduction because of their covalent characteristics. From first-principles-based high-throughput screening results on 61 2D covalent metals, we find that the strong correlation between the adsorption energies of COOH and CO can be entirely broken. This leads to the computational design of CO 2 -to-CO and CO 2 -to-CH 4 conversion catalysts in addition to hydrogen-evolution-reaction catalysts. Toward efficient electrochemical catalysts for CO 2 reduction, this work suggests a new materials domain having two contradictory properties in a single material: covalent nature and electrical conductance.

Field-Assisted Splitting of Pure Water Based on Deep-Sub-Debye-Length Nanogap Electrochemical Cells.

PubMed

Wang, Yifei; Narayanan, S R; Wu, Wei

2017-08-22

Owing to the low conductivity of pure water, using an electrolyte is common for achieving efficient water electrolysis. In this paper, we have fundamentally broken through this common sense by using deep-sub-Debye-length nanogap electrochemical cells to achieve efficient electrolysis of pure water (without any added electrolyte) at room temperature. A field-assisted effect resulted from overlapped electrical double layers can greatly enhance water molecules ionization and mass transport, leading to electron-transfer limited reactions. We have named this process "virtual breakdown mechanism" (which is completely different from traditional mechanisms) that couples the two half-reactions together, greatly reducing the energy losses arising from ion transport. This fundamental discovery has been theoretically discussed in this paper and experimentally demonstrated in a group of electrochemical cells with nanogaps between two electrodes down to 37 nm. On the basis of our nanogap electrochemical cells, the electrolysis current density from pure water can be significantly larger than that from 1 mol/L sodium hydroxide solution, indicating the much better performance of pure water splitting as a potential for on-demand clean hydrogen production.

Carbon paste electrode with covalently immobilized thionine for electrochemical sensing of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Thenmozhi, K.; Sriman Narayanan, S.

2017-11-01

A water-soluble redox mediator, thionin was covalently immobilized to the functionalized graphite powder and a carbon paste electrode was fabricated from this modified graphite powder. The immobilization procedure proved to be effective in anchoring the thionin mediator in the graphite electrode setup without any leakage problem during the electrochemical studies. The covalent immobilization of the thionin mediator was studied with FT-IR and the electrochemical response of the thionin carbon paste electrode was optimized on varying the supporting electrolyte, pH and scan rate. The modified electrode exhibited well-defined electrocatalytic activity towards the reduction of H2O2 at a lower potential of -0.266 V with good sensitivity. The developed amperometric sensor was efficient towards H2O2 in the linear range from 2.46 × 10-5 M to 4.76 × 10-3 M, with a detection limit of 1.47 × 10-5 M respectively. Important advantages of this sensor are its excellent electrochemical performance, simple fabrication, easy renewability, reproducible analytical results, acceptable accuracy and good operational and long-term stability.

Corrosion-Indicating Pigment And Probes

NASA Technical Reports Server (NTRS)

Bar-Cohen, Yoseph; Bugga, Ratnakumar V.; Attia, Alan I.

1993-01-01

Proposed hydrogen-sensitive paint for metal structures changes color at onset of corrosion, involving emission of hydrogen as result of electrochemical reactions. Pigment of suitable paint includes rhodium compound RhCl(PPh3)3, known as Wilkinson's catalyst. As coating on critical parts of such structures as bridges and aircraft, paint gives early warning of corrosion, and parts thus repaired or replaced before failing catastrophically. Reveals corrosion before it becomes visible to eye. Inspection for changes in color not ordinarily necessitate removal of structure from service, and costs less than inspection by x-ray or thermal neutron radiography, ultrasonic, eddy-current, or acoustic-emission techniques.

Generation of a stable supramolecular hydrogen evolving photocatalyst by alteration of the catalytic center.

PubMed

Mengele, Alexander K; Kaufhold, Simon; Streb, Carsten; Rau, Sven

2016-04-21

A new dyad consisting of a Ru(II) chromophore, a tetrapyridophenazine bridging ligand and a Rh(Cp*)Cl catalytic center, [Ru(tbbpy)2(tpphz)Rh(Cp*)Cl]Cl(PF6)2, acts as durable photocatalyst for hydrogen production from water. Catalytic activity is observed for more than 650 hours. Electrochemical investigations reveal that up to two electrons can be transferred to the catalytic center by a thermodynamically favorable intramolecular process, which has so far not been reported for similar tpphz based supramolecular photocatalysts. Additionally, mercury poisoning tests indicate that the new dyad works as a homogeneous photocatalyst.

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hong; King, Glen C.; Watt, Gerald D.

2007-01-01

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Synergistic Enhancement of Electrocatalytic CO 2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes

DOE PAGES

Rogers, Cameron; Perkins, Wade S.; Veber, Gregory; ...

2017-02-24

Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here in this paper, we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO 2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO 2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrodemore » (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO 2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.« less

Large-area synthesis of monolayered MoS(2(1-x))Se(2x) with a tunable band gap and its enhanced electrochemical catalytic activity.

PubMed

Yang, Lei; Fu, Qi; Wang, Wenhui; Huang, Jian; Huang, Jianliu; Zhang, Jingyu; Xiang, Bin

2015-06-21

"Band gap engineering" in two-dimensional (2D) materials plays an important role in tailoring their physical and chemical properties. The tuning of the band gap is typically achieved by controlling the composition of the semiconductor alloys. However, large-area preparation of 2D alloys remains a major challenge. Here, we report the large-area synthesis of high-quality monolayered MoS2(1-x)Se2x with a size coverage of hundreds of microns using a chemical vapor deposition method. The photoluminescence (PL) spectroscopy results confirm the tunable band gap in MoS2(1-x)Se2x, which is modulated by varying the Se content. Atomic-scale analysis was performed and the chemical composition was characterized using high-resolution scanning transmission electron microscopy and X-ray photoemission spectroscopy. With the introduction of Se into monolayered MoS2, it leads to enhanced catalytic activity in an electrochemical reaction for hydrogen generation, compared to monolayered MoS2 and MoSe2. It is promising as a potential alternative to expensive noble metals.

Electrochemical biofilm control: a review.

PubMed

Sultana, Sujala T; Babauta, Jerome T; Beyenal, Haluk

2015-01-01

One of the methods of controlling biofilms that has widely been discussed in the literature is to apply a potential or electrical current to a metal surface on which the biofilm is growing. Although electrochemical biofilm control has been studied for decades, the literature is often conflicting, as is detailed in this review. The goals of this review are: (1) to present the current status of knowledge regarding electrochemical biofilm control; (2) to establish a basis for a fundamental definition of electrochemical biofilm control and requirements for studying it; (3) to discuss current proposed mechanisms; and (4) to introduce future directions in the field. It is expected that the review will provide researchers with guidelines on comparing datasets across the literature and generating comparable datasets. The authors believe that, with the correct design, electrochemical biofilm control has great potential for industrial use.

Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact

NASA Astrophysics Data System (ADS)

Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

2018-01-01

Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from ‘electrochemical’ to ‘mechanical’, which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.