Electrocatalysts for fuel cells

International Nuclear Information System (INIS)

Garcia C, M. A.; Fernandez V, S. M.; Vargas G, J. R.

2008-01-01

It was investigated the oxygen reduction reaction (fundamental reaction in fuel cells) on electrocatalysts of Pt, Co, Ni and their alloys CoNi, PtCo, PtNi, PtCoNi in H 2 SO 4 0.5 M and KOH 0.5 M as electrolyte. The electrocatalysts were synthesized using mechanical alloying processes and chemical vapor deposition. The electrocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray spectroscopy. The evaluation was performed using electrocatalytic technique of rotating disk electrode and kinetic parameters were determined for each electro catalyst. We report the performance of all synthesized electrocatalysts in acid and alkaline means. (Author)

Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

Science.gov (United States)

Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

2018-05-01

Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

Science.gov (United States)

Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

2017-09-19

As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

Enhanced Hydrogen Evolution Reactions on Nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS) Electrocatalyst

Energy Technology Data Exchange (ETDEWEB)

Digraskar, Renuka V.; Mulik, Balaji B. [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India); Walke, Pravin S. [National Centre for Nanosciences and Nanotechnology, University of Mumbai, Mumbai 400098, MH (India); Ghule, Anil V. [Department of Chemistry, Shivaji University, Kolhapur, 416004, MH (India); Sathe, Bhaskar R., E-mail: bhaskarsathe@gmail.com [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India)

2017-08-01

Graphical abstract: CZTS nano-electrocatalyst (2.6 ± 0.4 nm) for HER is synthesized by one step sonochemical method with uniform size distribution, which shows promisingly lower onset potential with higher current density and longer stability. - Highlights: • The nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS; ∼3 nm) based electrocatalytic systems were developed by facile sonochemical method. • The novel Cu{sub 2}ZnSnS{sub 4} based nanoclustered cathode improves the electrocatalytic performance toward hydrogen generation reaction (HER). • The electrocatalytic result exhibits lower Tafel slope, higher exchange current density, excellent current stability and lower charge transfer resistance. • The high activity due to synergetic effect of Cu, Zn, Sn and S from their internal cooperative supports. - Abstract: A novel and facile one-step sonochemical method is used to synthesize Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer−Emmett−Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density −130 mA/cm{sup 2}, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm{sup 2}, excellent

Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

Science.gov (United States)

Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

2010-12-14

Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

Performance of Nafion-TiO2 hybrid membranes and PtSn/C electrocatalysts in PEM type fuel cells fed with ethanol and H2/CO at high temperature

International Nuclear Information System (INIS)

Isidoro, Roberta Alvarenga

2010-01-01

In this work, Nafion-TiO 2 hybrid electrolytes and PtSn/C electrocatalysts were synthesized for the application in direct ethanol fuel cell operating at high temperature (130 degree C). For this purpose, TiO 2 particles were incorporated in commercial Nafion membranes by an 'in situ' sol gel route. The resulting materials were characterized by gravimetric analysis, water uptake, DSC, XRD and EDX. Electrocatalysts based on carbon dispersed platinum-tin (PtSn/C), with different composition, were produced by alcohol-reduction method and were employed as anodic electrode. The electrocatalysts were characterized by XRD, EDX, XPS and transmission electronic spectroscopy. The electrochemical characterization was conducted by cyclic voltametry, carbon monoxide linear anodic voltammetry (CO stripping), and chronoamperometry. Membrane-electrodes assembly (MEAs) were formed with PtSn/C anodes, Pt/C cathodes and Nafion-TiO 2 hybrids. The performance of these MEA was evaluated in single-cell fed with H2/CO mixture or ethanol solution at the anode and oxygen at the cathode in the temperature range of 80-130 degree C. The analysis showed that the hybrid membranes improved the DEFC performance due to crossover suppression and that PtSn/C 70:30 electrocatalysts, prepared by an alcohol reduction process, showed better performance in ethanol oxidation. (author)

High performance platinum single atom electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-07-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

l-cysteine desulfhydrase-related H2 S production is involved in OsSE5-promoted ammonium tolerance in roots of Oryza sativa.

Science.gov (United States)

Guo, Hongming; Zhou, Heng; Zhang, Jing; Guan, Wenxue; Xu, Sheng; Shen, Wenbiao; Xu, Guohua; Xie, Yanjie; Foyer, Christine Helen

2017-09-01

Previous studies revealed that rice heme oxygenase PHOTOPERIOD SENSITIVITY 5 (OsSE5) is involved in the regulation of tolerance to excess ammonium by enhancing antioxidant defence. In this study, the relationship between OsSE5 and hydrogen sulfide (H 2 S), a well-known signalling molecule, was investigated. Results showed that NH 4 Cl triggered the induction of l-cysteine desulfhydrase (l-DES)-related H 2 S production in rice seedling roots. A H 2 S donor not only alleviated the excess ammonium-triggered inhibition of root growth but also reduced endogenous ammonium, both of which were aggravated by hypotaurine (HT, a H 2 S scavenger) or dl-propargylglycine (PAG, a l-DES inhibitor). Nitrogen metabolism-related enzymes were activated by H 2 S, thus resulting in the induction of amino acid synthesis and total nitrogen content. Interestingly, the activity of l-DES, as well as the enzymes involved in nitrogen metabolism, was significantly increased in the OsSE5-overexpression line (35S:OsSE5), whereas it impaired in the OsSE5-knockdown mutant (OsSE5-RNAi). The application of the HT/PAG or H 2 S donor could differentially block or rescue NH 4 Cl-hyposensitivity or hypersensitivity phenotypes in 35S:OsSE5-1 or OsSE5-RNAi-1 plants, with a concomitant modulation of nitrogen assimilation. Taken together, these results illustrated that H 2 S function as an indispensable positive regulator participated in OsSE5-promoted ammonium tolerance, in which nitrogen metabolism was facilitated. © 2017 John Wiley & Sons Ltd.

Performance PtSnRh electrocatalysts supported on carbon-Sb2O5.SbO2 for the electro-oxidation of ethanol, prepared by an alcohol-reduction process

International Nuclear Information System (INIS)

Castro, Jose Carlos

2013-01-01

PtSnRh electrocatalysts supported on carbon-Sb 2 O 5 .SnO 2 , with metal loading of 20 wt%, were prepared by an alcohol-reduction process, using H 2 PtCl 6 .6H 2 O (Aldrich), RhCl 3 .xH 2 O (Aldrich) and SnCl 2 .2H 2 O (Aldrich), as source of metals; Sb 2 O 5 .SnO 2 (ATO) and carbon Vulcan XC72, as support; and ethylene glycol as reducing agent. The electrocatalysts obtained were characterized physically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms showed which PtSnRh/C-ATO electrocatalysts had FCC structure of Pt and Pt alloys, besides several peaks associated with SnO 2 and ATO. The average sizes of crystallites were between 2 and 4 nm. TEM micrographs showed a good distribution of the nanoparticles on the support. The average sizes of particles were between 2 and 3 nm, with good agreement for the average size of the crystallites. The performances of the electrocatalysts were analyzed by electrochemical techniques and in real conditions of operation using single direct ethanol fuel cell. In the chronoamperometry at 50 deg C, the electrocatalysts with carbon (85 wt%) and ATO (15 wt%) support, showed the best activity, and the atomic proportions which achieved the best results were PtSnRh(70:25:05) e (90:05:05). PtSnRh(70:25:05)/85C+15ATO electrocatalysts showed the best performance in a direct ethanol fuel cell. (author)

Adoptive transfer of transplantation tolerance in the H-2 compatible mouse system CBA/C3H

International Nuclear Information System (INIS)

Siegl, E.; Brock, J.; Schulze, H.A.

1985-01-01

Transfer of neonatally induced tolerance in the H-2 compatible CBA/C3H strain combination is possible with different efficiency by injection of adherent and non-adherent spleen cells, unseparated spleen cells and lymph node cells from C3H-tolerant CBA mice into sublethal irradiated CBA mice. The most efficient cell populations are adherent spleen cells and lymph node cells. Successfull transfer of transplantation tolerance is not possible to non-irradiated mice. The adherent fraction of spleen cells and lymph node cells contains a suppressor cell population responsible for transplantation tolerance against non-H-2 antigens. The induced transplantation tolerance is not due to a chimeric state of C3H-tolerant CBA mice. (author)

Carbon-supported iron complexes as electrocatalysts for the cogeneration of hydroxylamine and electricity in a NO-H2 fuel cell: A combined electrochemical and density functional theory study

Science.gov (United States)

Sheng, Xia; Alvarez-Gallego, Yolanda; Dominguez-Benetton, Xochitl; Baert, Kitty; Hubin, Annick; Zhao, Hailiang; Mihaylov, Tzvetan T.; Pierloot, Kristine; Vankelecom, Ivo F. J.; Pescarmona, Paolo P.

2018-06-01

Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely bis(salicylidene)ethylenediimine (Salen) and phthalocyanine (Pc), supported on activated carbon or graphite were prepared and evaluated as electrocatalysts, either without further treatment or after pyrolysis at 700 °C. The performance in the reduction of NO of gas diffusion cathodes based on these electrocatalysts was investigated in an electrochemical half cell (3-electrode configuration) using linear sweep voltammetry (LSV). The most promising electrocatalysts were studied further by chronoamperometric experiments in a H2-NO fuel cell, which allowed comparison in terms of power output and hydroxylamine production. Depending on the concentration of the NO feed (6 or 18%), the best electrocatalytic performance was delivered either by FePc or FeSalen. The gas diffusion electrode based on FeSalen supported on activated carbon with 0.3 wt% Fe-loading provided the highest current density (86 A/m2) and the best current efficiency (43%) towards the desired NH2OH when operating at the higher NO concentration (18%). Moreover, FeSalen offers the advantage of being cheaper than FePc. The experimental work was complemented by density functional theory (DFT) calculations, which allowed to shed more light on the reaction mechanism for the reduction of nitric oxide at the atomistic level.

3D structured Mo-doped Ni3S2 nanosheets as efficient dual-electrocatalyst for overall water splitting

Science.gov (United States)

Wu, Chengrong; Liu, Bitao; Wang, Jun; Su, Yongyao; Yan, Hengqing; Ng, Chuntan; Li, Cheng; Wei, Jumeng

2018-05-01

Searching for a cost-effective, high efficient and stable bifunctional electrocatalyst for overall water-splitting is critical to renewable energy systems. In this study, three-dimensional (3D) curved nanosheets of Mo-doped Ni3S2 grown on nickel foam were successfully synthesized via a one-step hydrothermal process. The hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) in alkaline environment of this 3D catalyst are investigated in detail. The results show that it possesses lower overpotential, high current densities and small Tafel slopes both in OER and HER. For HER, the catalysts show excellent electrochemical performance, demonstrating a low over-potential of 212 mV at 10 mA cm-2 with a large decrease of 127 mV compared to the undoped Ni3S2. And it also shows a lower overpotential of 260 mV at 10 mA cm-2 which decreases 30 mV for OER. In addition, it is only need 1.67 V for the overall water splitting at 10 mA cm-2 which is 70 mV. It found that the Mo element would change the morphology of Ni3S2 and induce much more active sites for HER and OER. The as-prepared Mo-doped Ni3S2 bi-functional electrocatalyst could act as the promising electrode materials for water splitting.

Synthesis and electrochemical characterization of highly tolerant Pd electrocatalysts as cathodes in direct ethylene glycol fuel cells (DEGFC)

Energy Technology Data Exchange (ETDEWEB)

Rodriguez Varela, F.J.; Fraire Luna, S. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila (Mexico)] e-mail: javier.varela@cinvestav.edu.mx; Savadogo, O. [Laboratoire d' Electrochimie et de Materiaux Energetiques, Ecole Polytechnique de Montreal, Montreal, QC (Canada)

2009-09-15

Highly selective Pd electrocatalysts were synthesized by the formic acid method and evaluated as cathodes for DEGFC applications. In rotating disc measurements in acid medium, the Pd/C cathode showed important catalytic activity for the Oxygen Reduction Reaction (ORR). In the presence of ethylene glycol (EG, C{sub 2}H{sub 6}O{sub 2}), Pd/C exhibited an excellent electrochemical behavior and full tolerance to the organic molecule. No current density peaks associated to the EG oxidation reaction emerged and the shift in onset potential for the ORR (Eonset) toward more negative potentials was negligible on this cathode. Moreover, the evaluation of Pd/C in a DEGFC operating at 80 degrees Celsius demonstrated its high performance as cathode. As a comparison, commercial Pt/C was tested under the same conditions showing a limited selectivity for the ORR. The detrimental effect of EG on the Pt electrocatalysts resulted in high intensity current density peaks due to the oxidation of EG and a significant shift in Eonset. Given these results, it is expected that highly efficient Pd-based cathodes can find application in DEGFCs. [Spanish] Se sintetizaron electrocatalizadores altamente selectivos mediante el metodo de acido formico y se evaluaron como catodos en aplicaciones de CCGED. En mediciones de disco rotatorio en medio acido, el catodo Pd/C mostro importante actividad catalitica en la reaccion de reduccion de oxigeno (RRO). En la presencia de glicol de etileno (GE, C{sub 2}H{sub 6}O{sub 2}), Pd/C exhibio un excelente comportamiento electromecanico y tolerancia total a la molecula organica. No surgieron picos de densidad de corriente asociados con la reaccion de oxidacion de GE y el corrimiento en el potencial de inicio para la RRO (Einicio) hacia potenciales mas negativos fue despreciable en este catodo. Como comparacion, se probo un Pt/C bajo las mismas condiciones y se observo una selectividad limitada para el RRO. El efecto perjudicial de GE en el electrocatalizador

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Oxygen reduction reaction on a highly-alloyed Pt-Ni supported carbon electrocatalyst in acid solution

CSIR Research Space (South Africa)

Zheng, H

2010-08-31

Full Text Available Alloyed electrocatalysts such as PtNi/C[1-2], PtCo/C[3], PtCr/C[4], PtFe/C [5-6], and non-alloyed Pt-TiO2/C were reportedly investigated for methanol tolerance during Oxygen reduction reaction (ORR). The high methanol tolerance...

Hollow TiO2@Co9S8 Core-Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production.

Science.gov (United States)

Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang; Wang, Yadong; Wang, Xiuli; Lu, Xihong; Xia, Xinhui; Tu, Jiangping

2018-03-01

Designing ever more efficient and cost-effective bifunctional electrocatalysts for oxygen/hydrogen evolution reactions (OER/HER) is greatly vital and challenging. Here, a new type of binder-free hollow TiO 2 @Co 9 S 8 core-branch arrays is developed as highly active OER and HER electrocatalysts for stable overall water splitting. Hollow core-branch arrays of TiO 2 @Co 9 S 8 are readily realized by the rational combination of crosslinked Co 9 S 8 nanoflakes on TiO 2 core via a facile and powerful sulfurization strategy. Arising from larger active surface area, richer/shorter transfer channels for ions/electrons, and reinforced structural stability, the as-obtained TiO 2 @Co 9 S 8 core-branch arrays show noticeable exceptional electrocatalytic performance, with low overpotentials of 240 and 139 mV at 10 mA cm -2 as well as low Tafel slopes of 55 and 65 mV Dec -1 for OER and HER in alkaline medium, respectively. Impressively, the electrolysis cell based on the TiO 2 @Co 9 S 8 arrays as both cathode and anode exhibits a remarkably low water splitting voltage of 1.56 V at 10 mA cm -2 and long-term durability with no decay after 10 d. The versatile fabrication protocol and smart branch-core design provide a new way to construct other advanced metal sulfides for energy conversion and storage.

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Science.gov (United States)

Pan, Zhong-Hua; Tao, Yun-Wen; He, Quan-Feng; Wu, Qiao-Yu; Cheng, Li-Ping; Wei, Zhan-Hua; Wu, Ji-Huai; Lin, Jin-Qing; Sun, Di; Zhang, Qi-Chun; Tian, Dan; Luo, Geng-Geng

2018-06-12

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H 2 evolution turnover frequency (TOF) of 7838 s -1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s -1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H 2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O 2 and H 2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalysts for fuel cells; Electrocatalizadores para celdas de combustible

Energy Technology Data Exchange (ETDEWEB)

Garcia C, M. A.; Fernandez V, S. M. [ININ, Depto. de Quimica, Apdo. Postal 18-1027, Col. Escandon, Mexico 11801, D. F. (Mexico); Vargas G, J. R. [IPN, Depto. de Ingenieria Metalurgica, Mexico 07300, D. F. (Mexico)

2008-07-01

It was investigated the oxygen reduction reaction (fundamental reaction in fuel cells) on electrocatalysts of Pt, Co, Ni and their alloys CoNi, PtCo, PtNi, PtCoNi in H{sub 2}SO{sub 4} 0.5 M and KOH 0.5 M as electrolyte. The electrocatalysts were synthesized using mechanical alloying processes and chemical vapor deposition. The electrocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray spectroscopy. The evaluation was performed using electrocatalytic technique of rotating disk electrode and kinetic parameters were determined for each electro catalyst. We report the performance of all synthesized electrocatalysts in acid and alkaline means. (Author)

Pt-Ru nanoparticles supported on functionalized carbon as electrocatalysts for the methanol oxidation

International Nuclear Information System (INIS)

Salgado, J.R.C.; Fernandes, J.C.S.; Botelho do Rego, A.M.; Ferraria, A.M.; Duarte, R.G.; Ferreira, M.G.S.

2011-01-01

Highlights: → The functionalized carbon using acid solutions contains surface oxygenated groups. → Uniform dispersion of PtRu nanoparticles on the carbon surface was achieved. → Physical analysis showed the formation of PtRu alloy catalysts on functionalized carbon. → PtRu alloy catalysts on functionalized carbon enhanced the methanol oxidation rate. - Abstract: Platinum-ruthenium alloy electrocatalysts, for methanol oxidation reaction, were prepared on carbons thermally treated in helium atmosphere or chemically functionalized in H 2 O 2 , or in HNO 3 + H 2 SO 4 or in HNO 3 solutions. The functionalized carbon that is produced using acid solutions contains more surface oxygenated functional groups than carbon treated with H 2 O 2 solution or HeTT. The XRD/HR-TEM analysis have showed the existence of a higher alloying degree for Pt-Ru electrocatalysts supported on functionalized carbon, which present superior electrocatalytic performance, assessed by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy, as compared to electrocatalysts on unfunctionalized carbon. It also was found that Pt-Ru alloy electrocatalysts on functionalized carbon improve the reaction rate compared to Pt-Ru on carbons treated with H 2 O 2 solution and thermally. A mechanism is discussed, where oxygenated groups generated from acid functionalization of carbon and adsorbed on Pt-Ru electrocatalysts are considered to enhance the electrocatalytic activity of the methanol oxidation reaction.

Methanol resistant ruthenium electrocatalysts for oxygen reduction synthesized by pyrolysis of Ru{sub 3}(CO){sub 12} in different atmospheres

Energy Technology Data Exchange (ETDEWEB)

Altamirano-Gutierrez, A.; Jimenez-Sandoval, O.; Uribe-Godinez, J.; Borja-Arco, E. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro, Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Castellanos, R.H. [Universidad del Papaloapan, Campus Tuxtepec, Circuito Central No. 200, Col. Parque Industrial, Tuxtepec, Oax. 68301 (Mexico); Olivares-Ramirez, J.M. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

2009-10-15

Novel ruthenium electrocatalysts for the oxygen reduction reaction (ORR) were prepared by pyrolysis of Ru{sub 3}(CO){sub 12} in three atmospheres: neutral (N{sub 2}), partially oxidative (air) and partially reductive (70:30 N{sub 2}/H{sub 2}), at temperatures in the 80-700 C range. The materials were characterized by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy. A thermogravimetric analysis of the Ru{sub 3}(CO){sub 12} precursor in the three atmospheres was also performed. The electrocatalytic properties of the materials were evaluated by rotating disk electrode measurements in 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The kinetic parameters, such as the Tafel slope, exchange current density and charge transfer coefficient, are reported. The catalysts prepared in N{sub 2} and N{sub 2}/H{sub 2}, in general, show a higher performance than those synthesized in air. In the two nitrogen containing atmospheres, a pyrolysis temperature of 360 C seems to lead to better electrocatalytic properties for the ORR. The new electrocatalysts are also tolerant to methanol concentrations as high as 2.0 mol L{sup -1}. (author)

A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

2017-12-01

Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

Investigation of Novel Electrocatalysts for Metal Supported Solid Oxide Fuel Cells - Ru:GDC

DEFF Research Database (Denmark)

Sudireddy, Bhaskar Reddy; Nielsen, Jimmi; Thydén, Karl Tor Sune

2015-01-01

Even though solid oxide fuel cells (SOFCs) have a high potential with respect to efficiency and fuel flexibility they are not yet competitive in terms of cost and durability with conventional chemical energy conversion technologies. The potential cost reduction can be achieved through...... in tolerating the vibrations, transient loads, thermal and redox cycling [1-2]. The DTU MS-SOFC design based on ferritic stainless steel requires incorporation of electrocatalyst into the anode functional layer by infiltration methods [3]. Previously, the preferred electrocatalyst has been gadolinium doped...... and microstructure of the infiltrated electrocatalyst layer was characterized using high-resolution electron microscopy. The electrochemical characterization involved polarization curves and electrochemical impedance spectroscopy (EIS) in the temperature range of 650-750ºC. The polarization curve for Ru...

Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

KAUST Repository

Alsabban, Merfat M.; Min, Shixiong; Hedhili, Mohamed N.; Ming, Jun; Li, Lain-Jong; Huang, Kuo-Wei

2016-01-01

Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

Editors' Choice Growth of Layered WS2Electrocatalysts for Highly Efficient Hydrogen Production Reaction

KAUST Repository

Alsabban, Merfat M.

2016-08-18

Seeking more economical alternative electrocatalysts without sacrificing much in performance to replace precious metal Pt is one of the major research topics in hydrogen evolution reactions (HER). Tungsten disulfide (WS2) has been recognized as a promising substitute for Pt owing to its high efficiency and low-cost. Since most existing works adopt solution-synthesized WS2 crystallites for HER, direct growth of WS2 layered materials on conducting substrates should offer new opportunities. The growth of WS2 by the thermolysis of ammonium tetrathiotungstate (NH4)(2)WS4 was examined under various gaseous environments. Structural analysis and electrochemical studies show that the H2S environment leads to the WS2 catalysts with superior HER performance with an extremely low overpotential (eta(10) = 184 mV). (C) The Author(s) 2016. Published by ECS. All rights reserved.

NiCo2S4 nanowires array as an efficient bifunctional electrocatalyst for full water splitting with superior activity

Science.gov (United States)

Liu, Danni; Lu, Qun; Luo, Yonglan; Sun, Xuping; Asiri, Abdullah M.

2015-09-01

The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability.The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability. Electronic supplementary information (ESI) available: Experimental section and ESI Figures. See DOI: 10.1039/c5nr04064g

Highly effective and CO-tolerant PtRu electrocatalysts supported on poly(ethyleneimine) functionalized carbon nanotubes for direct methanol fuel cells

International Nuclear Information System (INIS)

Cheng, Yi; Jiang, San Ping

2013-01-01

A highly efficient and CO tolerant PtRu electrocatalysts supported on amino-rich, cationic poly(ethyleneimine) polyelectrolyte functionalized multi-walled carbon nanotubes (PtRu/PEI-MWCNTs) has been developed. The catalysts were characterized by thermogravimetric analysis, Raman spectroscopy, cyclic voltammograms, CO stripping, chronoamperometry, transmission electron microscopy (TEM) and X-ray diffraction (XRD). The PtRu particles with average size ∼2.5 nm are well dispersed on PEI-MWCNTs. The peak current for the methanol oxidation reaction on 40% PtRu/PEI-MWCNTs is 636mAmg Pt −1 , 5.7 times higher than 112mA mg Pt −1 measured on the 40% PtRu supported on acid treated MWCNTs (PtRu/AO-MWCNTs) under identical conditions. PtRu/PEI-MWCNTs catalysts exhibit a superior electrocatalytic activity and stability for the methanol oxidation reaction due to its high tolerance toward CO poisoning as compared with PtRu/AO-MWCNTs for direct methanol fuel cells

Room-Temperature Wet Chemical Synthesis of Au NPs/TiH2/Nanocarved Ti Self-Supported Electrocatalysts for Highly Efficient H2 Generation.

Science.gov (United States)

Amin, Mohammed A; Fadlallah, Sahar A; Alosaimi, Ghaida S; Ahmed, Emad M; Mostafa, Nasser Y; Roussel, Pascal; Szunerits, Sabine; Boukherroub, Rabah

2017-09-06

Self-supported electrocatalysts are a new class of materials exhibiting high catalytic performance for various electrochemical processes and can be directly equipped in energy conversion devices. We present here, for the first time, sparse Au NPs self-supported on etched Ti (nanocarved Ti substrate self-supported with TiH 2 ) as promising catalysts for the electrochemical generation of hydrogen (H 2 ) in KOH solutions. Cleaned, as-polished Ti substrates were etched in highly concentrated sulfuric acid solutions without and with 0.1 M NH 4 F at room temperature for 15 min. These two etching processes yielded a thin layer of TiH 2 (the corrosion product of the etching process) self-supported on nanocarved Ti substrates with different morphologies. While F - -free etching process led to formation of parallel channels (average width: 200 nm), where each channel consists of an array of rounded cavities (average width: 150 nm), etching in the presence of F - yielded Ti surface carved with nanogrooves (average width: 100 nm) in parallel orientation. Au NPs were then grown in situ (self-supported) on such etched surfaces via immersion in a standard gold solution at room temperature without using stabilizers or reducing agents, producing Au NPs/TiH 2 /nanostructured Ti catalysts. These materials were characterized by scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS), grazing incidence X-ray diffraction (GIXRD), and X-ray photoelectron spectroscopy (XPS). GIXRD confirmed the formation of Au 2 Ti phase, thus referring to strong chemical interaction between the supported Au NPs and the substrate surface (also evidenced from XPS) as well as a titanium hydride phase of chemical composition TiH 2 . Electrochemical measurements in 0.1 M KOH solution revealed outstanding hydrogen evolution reaction (HER) electrocatalytic activity for our synthesized catalysts, with Au NPs/TiH 2 /nanogrooved Ti catalyst being the best one among them. It exhibited fast kinetics

Spherical α-MnO2 Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al–Air Battery

Directory of Open Access Journals (Sweden)

Kui Chen

2018-04-01

Full Text Available Traditional noble metal platinum (Pt is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO2 and nitrogen-doped Ketjenblack (N-KB (denoted as MnO2-SM150-0.5 is examined as a potential electrocatalyst in oxygen reduction reactions (ORR and oxygen evolution reactions (OER. This α-MnO2 is prepared by redox reaction between K2S2O8 and MnSO4 in acid conditions with a facile hydrothermal process (named the SM method. As a result, MnO2-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V at a discharge density of 50 mA cm−2 in homemade Al–air batteries that is higher than commercial 20% Pt/C (~1.19 V. The superior electrocatalytic performance of MnO2-SM150-0.5 could be attributed to its higher Mn3+/Mn4+ ratio and the synergistic effect between MnO2 and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO2-based composite electrocatalyst.

Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

Science.gov (United States)

Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

2015-09-01

The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Symmetrical synergy of hybrid Co9S8-MoSx electrocatalysts for hydrogen evolution reaction

KAUST Repository

Zhou, Xiaofeng

2017-01-07

There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered as several promising HER candidates. Here, a highly active and stable hybrid electrocatalyst 3D flower-like hierarchical Co9S8 nanosheets incorporated with MoSx has been developed via a one-step sulfurization method. Since the amounts of Co9S8 and MoSx are easily adjustable, we verify that small amounts of MoSx promotes the HER activity of Co9S8, and vise versa. In other words, we validate that symmetric synergy for HER in the Co- and Mo-based sulfide hybrid catalysts, a long-standing question requiring clear experimental proofs. Meanwhile, the best electrocatalyst Co9S8-30@MoSx/CC in this study exhibits excellent HER performance with an overpotential of −98 mV at −10 mA/cm2, a small Tafel slope of 64.8 mV/dec, and prominent electrochemical stability.

Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2.

Science.gov (United States)

Kowal, A; Li, M; Shao, M; Sasaki, K; Vukmirovic, M B; Zhang, J; Marinkovic, N S; Liu, P; Frenkel, A I; Adzic, R R

2009-04-01

Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol's slow, inefficient oxidation even at the best electrocatalysts. We synthesized a ternary PtRhSnO(2)/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C-C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO(2), which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst's activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt-Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C-C bond splitting in other catalytic processes.

Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

KAUST Repository

Joya, Khurram Saleem

2014-03-10

Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

KAUST Repository

Joya, Khurram Saleem; Joya, Yasir F.; De Groot, Huub J M

2014-01-01

Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of MoS2 and MoO2 for their applications in H2 generation and lithium ion batteries: a review

International Nuclear Information System (INIS)

Zhao Yufei; Zhang Yuxia; Yang Zhiyu; Yan Yiming; Sun Kening

2013-01-01

Scientists increasingly witness the applications of MoS 2 and MoO 2 in the field of energy conversion and energy storage. On the one hand, MoS 2 and MoO 2 have been widely utilized as promising catalysts for electrocatalytic or photocatalytic hydrogen evolution in aqueous solution. On the other hand, MoS 2 and MoO 2 have also been verified as efficient electrode material for lithium ion batteries. In this review, the synthesis, structure and properties of MoS 2 and MoO 2 are briefly summarized according to their applications for H 2 generation and lithium ion batteries. Firstly, we overview the recent advancements in the morphology control of MoS 2 and MoO 2 and their applications as electrocatalysts for hydrogen evolution reactions. Secondly, we focus on the photo-induced water splitting for H 2 generation, in which MoS 2 acts as an important co-catalyst when combined with other semiconductor catalysts. The newly reported research results of the significant functions of MoS 2 nanocomposites in photo-induced water splitting are presented. Thirdly, we introduce the advantages of MoS 2 and MoO 2 for their enhanced cyclic performance and high capacity as electrode materials of lithium ion batteries. Recent key achievements in MoS 2 - and MoO 2 -based lithium ion batteries are highlighted. Finally, we discuss the future scope and the important challenges emerging from these fascinating materials. (review)

Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction

International Nuclear Information System (INIS)

Garcia C, M. A.

2008-01-01

In this research, the molecular oxygen reduction reaction (ORR) was investigated on electrocatalysts of Co, Ni, Pt and their alloys CoNi, PtCo, PtNi and PtCoNi by using H 2 SO 4 0.5 and KOH 0.5 M solutions as electrolytes. The electrocatalysts were synthesized by Mechanical Alloying (MA) and Chemical Vapor Deposition (CVD) processes. For MA, metallic powders were processed during 20 h of milling in a high energy SPEX 8000 mill. For CVD, a hot-wall reactor was utilized and Co, Ni and Pt acetilactetonates were used as precursors. Films were deposited at a total pressure of 1 torr and temperatures of 400-450 C. Electrocatalysts were characterized by X-Ray Diffraction (XRD). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Electrocatalysts prepared by mechanical alloying showed a homogeneously dispersed agglomeration of particles with nano metric size. Electrocatalysts obtained by CVD showed, in some cases, non uniform films, with particles of nano metric size, as well. The electrocatalytic performance was evaluated by using the Rotating Disk Electrode technique (RDE). Electrocatalysts prepared by MA showed higher activity than those obtained by CVD. All electrocatalysts were evaluated in alkaline media. Only electrocatalysts containing Pt were evaluated in acid media, because those materials with Co, Ni and their alloys showed instability in acidic media. Most electrocatalysts followed a mechanism for the ORR producing a certain proportion of H 2 O 2 . All electrocatalysts, exhibited a fair or good electrocatalytic activity in comparison with other similar reported materials. It was found that MA and CVD are appropriate processes to prepare electrocatalysts for the ORR with particles of nano metric size and performing with an acceptable catalytic activity. PtCoNi 70-23-7% by MA and PtCoNi-CVD electrocatalysts showed the highest activity in alkaline media, while in acidic electrolyte PtCoNi 70

Transgenic Centipedegrass (Eremochloa ophiuroides [Munro] Hack. Overexpressing S-Adenosylmethionine Decarboxylase (SAMDC Gene for Improved Cold Tolerance Through Involvement of H2O2 and NO Signaling

Directory of Open Access Journals (Sweden)

Jianhao Luo

2017-09-01

Full Text Available Centipedegrass (Eremochloa ophiuroides [Munro] Hack. is an important warm-season turfgrass species. Transgenic centipedgrass plants overexpressing S-adenosylmethionine decarboxylase from bermudagrass (CdSAMDC1 that was induced in response to cold were generated in this study. Higher levels of CdSAMDC1 transcript and sperimidine (Spd and spermin (Spm concentrations and enhanced freezing and chilling tolerance were observed in transgenic plants as compared with the wild type (WT. Transgenic plants had higher levels of polyamine oxidase (PAO activity and H2O2 than WT, which were blocked by pretreatment with methylglyoxal bis (guanylhydrazone or MGBG, inhibitor of SAMDC, indicating that the increased PAO and H2O2 were a result of expression of CdSAMDC1. In addition, transgenic plants had higher levels of nitrate reductase (NR activity and nitric oxide (NO concentration. The increased NR activity were blocked by pretreatment with MGBG and ascorbic acid (AsA, scavenger of H2O2, while the increased NO level was blocked by MGBG, AsA, and inhibitors of NR, indicating that the enhanced NR-derived NO was dependent upon H2O2, as a result of expression CdSAMDC1. Elevated superoxide dismutase (SOD and catalase (CAT activities were observed in transgenic plants than in WT, which were blocked by pretreatment with MGBG, AsA, inhibitors of NR and scavenger of NO, indicating that the increased activities of SOD and CAT depends on expression of CdSAMDC1, H2O2, and NR-derived NO. Our results suggest that the elevated cold tolerance was associated with PAO catalyzed production of H2O2, which in turn led to NR-derived NO production and induced antioxidant enzyme activities in transgenic plants.

Transgenic Centipedegrass (Eremochloa ophiuroides [Munro] Hack.) Overexpressing S-Adenosylmethionine Decarboxylase (SAMDC) Gene for Improved Cold Tolerance Through Involvement of H2O2 and NO Signaling.

Science.gov (United States)

Luo, Jianhao; Liu, Mingxi; Zhang, Chendong; Zhang, Peipei; Chen, Jingjing; Guo, Zhenfei; Lu, Shaoyun

2017-01-01

Centipedegrass ( Eremochloa ophiuroides [Munro] Hack.) is an important warm-season turfgrass species. Transgenic centipedgrass plants overexpressing S-adenosylmethionine decarboxylase from bermudagrass ( CdSAMDC1 ) that was induced in response to cold were generated in this study. Higher levels of CdSAMDC1 transcript and sperimidine (Spd) and spermin (Spm) concentrations and enhanced freezing and chilling tolerance were observed in transgenic plants as compared with the wild type (WT). Transgenic plants had higher levels of polyamine oxidase (PAO) activity and H 2 O 2 than WT, which were blocked by pretreatment with methylglyoxal bis (guanylhydrazone) or MGBG, inhibitor of SAMDC, indicating that the increased PAO and H 2 O 2 were a result of expression of CdSAMDC1 . In addition, transgenic plants had higher levels of nitrate reductase (NR) activity and nitric oxide (NO) concentration. The increased NR activity were blocked by pretreatment with MGBG and ascorbic acid (AsA), scavenger of H 2 O 2 , while the increased NO level was blocked by MGBG, AsA, and inhibitors of NR, indicating that the enhanced NR-derived NO was dependent upon H 2 O 2 , as a result of expression CdSAMDC1 . Elevated superoxide dismutase (SOD) and catalase (CAT) activities were observed in transgenic plants than in WT, which were blocked by pretreatment with MGBG, AsA, inhibitors of NR and scavenger of NO, indicating that the increased activities of SOD and CAT depends on expression of CdSAMDC1 , H 2 O 2 , and NR-derived NO. Our results suggest that the elevated cold tolerance was associated with PAO catalyzed production of H 2 O 2 , which in turn led to NR-derived NO production and induced antioxidant enzyme activities in transgenic plants.

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

Energy Technology Data Exchange (ETDEWEB)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: brandalise@usp.br, E-mail: mmtusi@usp.br, E-mail: rmpiasen@ipen.br, E-mail: ovcorrea@ipen.br, E-mail: mlinardi@ipen.br, E-mail: espinace@ipen.br, E-mail: aolivei@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2009-07-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H{sub 2}PtCl{sub 6.6}H{sub 2}O, RuCl{sub 3.x}H{sub 2}O and Bi(NO{sub 3}){sub 3.5}H{sub 2}O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

PtRu/C and PtRuBi/C electrocatalysts prepared by two different methodologies of borohydride reduction process for ethanol electro-oxidation

International Nuclear Information System (INIS)

Brandalise, Michele; Tusi, Marcelo Marques; Piasentin, Ricardo Marcelo; Correa, Olandir Vercino; Linardi, Marcelo; Spinace, Estevam Vitorio; Oliveira Neto, Almir

2009-01-01

PtRu/C (50:50) and PtRuBi/C (50:40:10) electrocatalysts were prepared by borohydride reduction using H 2 PtCl 6.6 H 2 O, RuCl 3.x H 2 O and Bi(NO 3 ) 3.5 H 2 O as metals sources and Vulcan XC72 as support. The borohydride solution was added in two different ways: drop by drop and rapid addition of all the solution. The obtained electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of ethanol was studied by cyclic voltammetry and chronoamperometry at room temperature and on a single cell of a direct ethanol fuel cell (DEFC) at 100 deg C. PtRuBi/C electrocatalysts showed superior performance for ethanol electro-oxidation than PtRu/C electrocatalysts prepared in a similar way. However, PtRuBi/C electrocatalyst prepared by rapid addition of the borohydride solution showed superior performance for ethanol electro oxidation at room temperature, while PtRuBi/C electrocatalyst prepared by addition drop by drop of borohydride solution showed superior performance on DEFC at 100 deg C. (author)

Activity and Selectivity for O-2 Reduction to H2O2 on Transition Metal Surfaces

DEFF Research Database (Denmark)

Siahrostami, Samira; Verdaguer Casadevall, Arnau; Karamad, Mohammadreza

2013-01-01

Industrially viable electrochemical production of H2O2 requires active, selective and stable electrocatalyst materials to catalyse the oxygen reduction reaction to H2O2. On the basis of density functional theory calculations, we explain why single site catalysts such as Pd/Au show improved...

Preparation and characterization of PT-rare earth/C electrocatalysts for PEM fuel cells

International Nuclear Information System (INIS)

Santoro, Thais Aranha de Barros

2009-01-01

Pt-rare earth/C electrocatalysts (rare earth = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) were prepared (20 wt.% and Pt-to-RE atomic ratio of 50:50) by an alcohol reduction process using H 2 PtCl 6 .6H 2 O (Aldrich) and rare earth (III) chlorides (Aldrich) as metal sources, ethylene glycol as solvent and reducing agent, and Vulcan XC72 as support. The electrocatalysts were characterized by Energy Dispersive X-ray Spectroscopy (EDX), X-Ray Diffractometry (XRD) and Transmission Electron Microscopy (TEM). The energy dispersive x-ray spectroscopy analysis showed that the Pt-Rare Earth atomic ratios obtained for all electrocatalysts were similar to those used in the preparations. In all diffractograms, it was observed a broad peak at about 25 degree which was associated to the Vulcan XC72 support material and four peaks at approximately 28=40 degree, 47 degree, 67 degree and 82 degree, which were associated to the (111), (200), (220), (311), and (222) planes, respectively, of the face-centered cubic (fcc) structure characteristic of platinum and platinum alloys. For the Pt-Rare Earth/C electrocatalysts, it was also observed peaks related to the rare earth oxides on the X ray diffractograms. PtLa/C electrocatalysts were prepared at different atomic ratio. Transmission electronic microscopy micrographs of electrocatalysts showed a reasonable distribution of the Pt particles on the carbon support with some agglomerations, which is in agreement with x-ray diffractometry result. The performance for CO, methanol and ethanol oxidation was investigated by cyclic voltammetry, chronoamperometry and Fourier transform infrared spectroscopy spectroscopy. The electrocatalytic activity of the Pt-Rare Earth/C electro catalyst, specially PtLa/C, were higher than that of the Pt/C electrocatalyst. Fourier transform infrared spectroscopy studies for ethanol oxidation on Pt-Rare Earth/C electrocatalyst showed that acetaldehyde and acetic acid were the main products. The PtLa/C (30

Manganese dioxide-supported silver bismuthate as an efficient electrocatalyst for oxygen reduction reaction in zinc-oxygen batteries

International Nuclear Information System (INIS)

Sun, Yanzhi; Yang, Meng; Pan, Junqing; Wang, Pingyuan; Li, Wei; Wan, Pingyu

2016-01-01

In this paper, we present a new efficient composite electrocatalyst, manganese dioxide-supported silver bismuthate (Ag 4 Bi 2 O 5 /MnO 2 ), for oxygen reduction reaction (ORR) in alkaline media. The new electrocatalyst was characterized with scanning electron microscope (SEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements indicate that the Ag 4 Bi 2 O 5 /MnO 2 composite is a very efficient electrocatalyst for ORR in alkaline media. The physical and electrochemical characterization results suggest that the high activity is ascribed to the support effects from MnO 2 and the synergetic effects among Ag 4 Bi 2 O 5 and MnO 2 . The analysis of rotating disk electrode (RDE) results shows that the ORR occurs via a four-electron pathway on the surface of the Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst. This electrocatalyst was further tested in a designed zinc–oxygen (Zn–O 2 ) battery. This battery can offer a discharge time of 225 h at 120 mA cm −2 , increasing by more than 492% as compared with pure MnO 2 electrocatalyst. It demonstrates that this inexpensive Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst is a viable alternative to platinum electrocatalyst for energy conversion devices.

Co-tolerant anode electrocatalysts for impure hydrogen oxidation in solid polymer fuel cells

Energy Technology Data Exchange (ETDEWEB)

Cooper, S J; Thompsett, D [Johnson Matthey Technology Centre, Sonning Common (United Kingdom); Tseung, A C.C.; Chen, K Y [Essex Univ., Colchester (United Kingdom)

1997-09-01

Recent work by the Chemical Energy Research Centre (CERC) at the University of Essex under the direction of Professor A.C.C. Tseung has investigated the combination of tungsten trioxide (WO{sub 3}) with carbon supported platinum (Pt) and platinum ruthenium (PtRu) catalysts for carbon monoxide (CO) tolerance for application in low temperature fuel cells. In particular, a catalyst combining Pt, Ru and WO{sub 3} gave a significantly improved tolerance to the effect of CO on H{sub 2} oxidation, at 80{sup o}C using fuel of 100 ppm CO in H{sub 2} and 0.5 M sulphuric acid (H{sub 2}SO{sub 4}) electrolyte. The aim of this project was to make a direct comparison between the catalyst technology developed at the University of Essex with the current Johnson Matthey PtRu catalyst technology as used in Proton Exchange Fuel Cells (PEMFC). (Author)

Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution

Directory of Open Access Journals (Sweden)

Lei Yang

2017-09-01

Full Text Available Recently, transition metal dichalcogenides (TMDs, represented by MoS2, have been proven to be a fascinating new class of electrocatalysts in hydrogen evolution reaction (HER. The rich chemical activities, combined with several strategies to regulate its morphologies and electronic properties, make MoS2 very attractive for understanding the fundamentals of electrocatalysis. In this review, recent developments in using MoS2 as electrocatalysts for the HER with high activity are presented. The effects of edges on HER activities of MoS2 are briefly discussed. Then we demonstrate strategies to further enhance the catalytic performance of MoS2 by improving its conductivity or engineering its structure. Finally, the key challenges to the industrial application of MoS2 in electrocatalytic hydrogen evolution are also pointed out.

MnO2/MCMB electrocatalyst for all solid-state alkaline zinc-air cells

International Nuclear Information System (INIS)

Zhang, G.Q.; Zhang, X.G.

2004-01-01

Nanostructured MnO 2 /mesocarbon microbeads (MCMB) composite has been prepared successfully for use in zinc-air cell as electrocatalyst for oxygen reaction. The scanning electron microscope (SEM) images showed that the MnO 2 nanorods were formed and covered on the surface of MCMB in bird's nest morphology. X-ray diffraction (XRD) pattern indicated that the MnO 2 has the hollandite structure with a composition approximating KMn 8 O 16 . By the cathodic polarization curve tests, the nanostructured material demonstrated excellent electrocatalytic activity as a kind of oxygen electrode electrocatalyst compared with electrolytic MnO 2 . An all solid-state zinc-air cell has been fabricated with this material as electrocatalyst for oxygen electrode and potassium salt of cross-linked poly(acrylic acid) as an alkaline polymer gel electrolyte. The cell has good discharge characteristics at room temperature

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

Science.gov (United States)

Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

2016-05-01

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CuZn Alloy- Based Electrocatalyst for CO2 Reduction

KAUST Repository

Alazmi, Amira

2014-06-01

ABSTRACT CuZn Alloy- Based Electrocatalyst for CO2 Reduction Amira Alazmi Carbon dioxide (CO2) is one of the major greenhouse gases and its emission is a significant threat to global economy and sustainability. Efficient CO2 conversion leads to utilization of CO2 as a carbon feedstock, but activating the most stable carbon-based molecule, CO2, is a challenging task. Electrochemical conversion of CO2 is considered to be the beneficial approach to generate carbon-containing fuels directly from CO2, especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys with heat treatments at different temperatures have been evaluated as electrocatalysts for CO2 reduction. It was found that the catalytic activity of these electrodes was strongly dependent on the thermal oxidation temperature before their use for electrochemical measurements. The polycrystalline CuZn electrode without thermal treatment shows the Faradaic efficiency for CO formation of only 30% at applied potential ~−1.0 V vs. RHE with current density of ~−2.55 mA cm−2. In contrast, the reduction of oxide-based CuZn alloy electrode exhibits 65% Faradaic efficiency for CO at lower applied potential about −1.0 V vs. RHE with current density of −2.55 mA cm−2. Furthermore, stable activity was achieved over several hours of the reduction reaction at the modified electrodes. Based on electrokinetic studies, this improvement could be attributed to further stabilization of the CO2•− on the oxide-based Cu-Zn alloy surface.

Performance PtSnRh electrocatalysts supported on carbon-Sb{sub 2}O{sub 5}.SbO{sub 2} for the electro-oxidation of ethanol, prepared by an alcohol-reduction process; Desempenho de eletrocatalisadores PtSnRh suportados em carbono-Sb{sub 2}O{sub 5}.SnO{sub 2} para a oxidacao eletroquimica do etanol, preparados pelo metodo de reducao por alcool

Energy Technology Data Exchange (ETDEWEB)

Castro, Jose Carlos

2013-07-01

PtSnRh electrocatalysts supported on carbon-Sb{sub 2}O{sub 5}.SnO{sub 2}, with metal loading of 20 wt%, were prepared by an alcohol-reduction process, using H{sub 2}PtCl{sub 6}.6H{sub 2}O (Aldrich), RhCl{sub 3}.xH{sub 2}O (Aldrich) and SnCl{sub 2}.2H{sub 2}O (Aldrich), as source of metals; Sb{sub 2}O{sub 5}.SnO{sub 2} (ATO) and carbon Vulcan XC72, as support; and ethylene glycol as reducing agent. The electrocatalysts obtained were characterized physically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms showed which PtSnRh/C-ATO electrocatalysts had FCC structure of Pt and Pt alloys, besides several peaks associated with SnO{sub 2} and ATO. The average sizes of crystallites were between 2 and 4 nm. TEM micrographs showed a good distribution of the nanoparticles on the support. The average sizes of particles were between 2 and 3 nm, with good agreement for the average size of the crystallites. The performances of the electrocatalysts were analyzed by electrochemical techniques and in real conditions of operation using single direct ethanol fuel cell. In the chronoamperometry at 50 deg C, the electrocatalysts with carbon (85 wt%) and ATO (15 wt%) support, showed the best activity, and the atomic proportions which achieved the best results were PtSnRh(70:25:05) e (90:05:05). PtSnRh(70:25:05)/85C+15ATO electrocatalysts showed the best performance in a direct ethanol fuel cell. (author)

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

Energy Technology Data Exchange (ETDEWEB)

Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

2007-02-01

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability

Science.gov (United States)

Ling, Ying; Yang, Zehui; Yang, Jun; Zhang, Yunfeng; Zhang, Quan; Yu, Xinxin; Cai, Weiwei

2018-02-01

As is well known, the lower durability and sluggish methanol oxidation reaction (MOR) of PtRu alloy electrocatalyst blocks the commercialization of direct methanol fuel cells (DMFCs). Here, we design a new PtRu electrocatalyst, with highly stable CO tolerance and durability, in which the PtRu nanoparticles are embedded in nitrogen doped carbon layers derived from carbonization of poly(vinyl pyrrolidone). The newly fabricated electrocatalyst exhibits no loss in electrochemical surface area (ECSA) and MOR activity after potential cycling from 0.6-1.0 V versus reversible hydrogen electrode, while commercial CB/PtRu retains only 50% of its initial ECSA. Meanwhile, due to the same protective layers, the Ru dissolution is decelerated, resulting in stable CO tolerance. Methanol oxidation reaction (MOR) testing indicates that the activity of newly fabricated electrocatalyst is two times higher than that of commercial CB/PtRu, and the fuel cell performance of the embedded PtRu electrocatalyst was comparable to that of commercial CB/PtRu. The embedded PtRu electrocatalyst is applicable in real DMFC operation. This study offers important and useful information for the design and fabrication of durable and CO tolerant electrocatalysts.

Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

Science.gov (United States)

Sun, Shichen; Awadallah, Osama; Cheng, Zhe

2018-02-01

It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

High-throughput synthesis of mixed-metal electrocatalysts for CO2 reduction

International Nuclear Information System (INIS)

He, Jingfu; Dettelbach, Kevan E.; Li, Tengfei; Salvatore, Danielle A.; Berlinguette, Curtis P.

2017-01-01

The utilization of CO 2 as a feedstock requires fundamental breakthroughs in catalyst design. The efficiencies and activities of pure metal electrodes towards the CO 2 reduction reaction are established, but the corresponding data on mixed-metal systems are not as well developed. In this study we show that the near-infrared driven decomposition (NIRDD) of solution-deposited films of metal salts and subsequent electrochemical reduction offers the unique opportunity to form an array of mixed-metal electrocatalyst coatings with excellent control of the metal stoichiometries. This synthetic method enabled us to develop an empirical structure-property correlation to help inform the development of optimized CO 2 catalyst compositions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes.

Science.gov (United States)

Berber, Mohamed R; Hafez, Inas H; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-11-23

Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm(2) (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs.

CuZn Alloy- Based Electrocatalyst for CO2 Reduction

KAUST Repository

Alazmi, Amira

2014-01-01

, especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys

2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

Science.gov (United States)

Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

2016-08-01

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell

Energy Technology Data Exchange (ETDEWEB)

Imran Jafri, Razack; Sujatha, N.; Ramaprabhu, S. [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai (India); Rajalakshmi, N. [Center for Fuel Cell Technology (ARCI), Madavakkam, Chennai (India)

2009-08-15

Bi-functional catalysts based on Au supported on oxide based nanomaterials for use in fuel cells were evaluated by electrochemical methods for oxygen reduction reaction (ORR) in Polymer Electrolyte Membrane Fuel Cell (PEMFC). Metal oxide coated multi walled carbon nanotubes (MWNTs) (MnO{sub 2}/MWNT and ZnO/MWNT) were prepared by reduction of potassium permanganate and oxidation of Zn powder on MWNT surface respectively. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT were prepared by chemical reduction of chloroauric acid on MnO{sub 2}/MWNT and ZnO/MWNT. The samples were characterized and linear sweep voltammetric studies were performed in N{sub 2} saturated, O{sub 2} saturated and methanol containing 1 M KOH solution and the results have been discussed. A single fuel cell was also constructed using Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as ORR electrocatalysts. A maximum power density of 45 mW/cm{sup 2} and 56 mW/cm{sup 2} was obtained with Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT respectively. Additionally, the methanol tolerance of these electrocatalysts has been investigated and results have been discussed. (author)

Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

Science.gov (United States)

Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

2017-12-01

Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation

International Nuclear Information System (INIS)

Crisafulli, Rudy

2013-01-01

PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H 2 PtCl 6 .6H 2 O, SnCl 2 .2H 2 O and CuCl 2 .2H 2 O as metal sources, NaBH 4 and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of PtSnCu/C (50:40:10) AR/ED > PtSnCu/C (50:10:40) BR/CD. PtSn/C (50:50) BR/CD, PtSnCu/C (50:10:40) BR/CD, PtSnCu/C (50:40:10) AR/CD electrocatalysts and Pt/C BASF, PtSn/C (75:25) BASF commercial electrocatalysts were tested in single Direct Ethanol Fuel Cell. The results showed the following performance for ethanol electro-oxidation: PtSn/C (50:50) BR/CD > PtSnCu/C (50:40:10) AR/CD > PtSnCu/C > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) BR/CD > Pt/C BASF. (author)

Specific IgE to peanut 2S albumin Ara h 7 has a discriminative ability comparable to Ara h 2 and 6.

Science.gov (United States)

Blankestijn, M A; Otten, H G; Suer, W; Weimann, A; Knol, E F; Knulst, A C

2018-01-01

Little is known on the clinical relevance of peanut 2S albumin Ara h 7. To investigate the discriminative ability of Ara h 7 in peanut allergy and assess the role of cross-reactivity between Ara h 2, 6 and Ara h 7 isoforms. Sensitization to recombinant peanut storage proteins Ara h 1, 2, 3, 6, and 7 was assessed using a line blot in sera from 40 peanut-tolerant and 40 peanut-allergic patients, based on food challenge outcome. A dose-dependent ELISA inhibition experiment was performed with recombinant Ara h 2, 6 and Ara h 7 isoforms. For Ara h 7.0201, an area under the ROC curve was found of 0.83, comparable to Ara h 2 (AUC 0.81) and Ara h 6 (AUC 0.85). Ara h 7 intensity values strongly correlated with those from Ara h 2 and 6 (r s = 0.81). Of all patients sensitized to 2S albumins Ara h 2, 6, or 7, the majority was co-sensitized to all three (n = 24, 68%), although mono-sensitization to either 2S albumin was also observed in selected patients (Ara h 2: n = 6, 17%; Ara h 6: n = 2, 6%; Ara h 7: n = 2, 6%). Binding to Ara h 7.0101 could be strongly inhibited by Ara h 7.0201, but not the other way around. Specific IgE against Ara h 7.0201 has a predictive ability for peanut allergy similar to Ara h 2 and 6 and possesses unique IgE epitopes as well as epitopes shared between the other Ara h 7 isoform and Ara h 2 and 6. While co-sensitization to all three 2S albumins is most common, mono-sensitization to either Ara h 2, 6, or 7 occurs in selected patients, leading to a risk of misdiagnosis when testing for a single 2S albumin. © 2017 John Wiley & Sons Ltd.

High-throughput synthesis of mixed-metal electrocatalysts for CO{sub 2} reduction

Energy Technology Data Exchange (ETDEWEB)

He, Jingfu; Dettelbach, Kevan E.; Li, Tengfei [Department of Chemistry, The University of British Columbia, Vancouver, BC (Canada); Salvatore, Danielle A. [Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada); Berlinguette, Curtis P. [Department of Chemistry, The University of British Columbia, Vancouver, BC (Canada); Department of Chemical and Biological Engineering, The University of British Columbia, Vancouver, BC (Canada)

2017-05-22

The utilization of CO{sub 2} as a feedstock requires fundamental breakthroughs in catalyst design. The efficiencies and activities of pure metal electrodes towards the CO{sub 2} reduction reaction are established, but the corresponding data on mixed-metal systems are not as well developed. In this study we show that the near-infrared driven decomposition (NIRDD) of solution-deposited films of metal salts and subsequent electrochemical reduction offers the unique opportunity to form an array of mixed-metal electrocatalyst coatings with excellent control of the metal stoichiometries. This synthetic method enabled us to develop an empirical structure-property correlation to help inform the development of optimized CO{sub 2} catalyst compositions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

Science.gov (United States)

Wu, Tianli; Pi, Mingyu; Wang, Xiaodeng; Guo, Weimeng; Zhang, Dingke; Chen, Shijian

2018-01-01

Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of -69 mV and -118 mV with a small Tafel slope of 51 mV dec-1 to obtain current densities of 10 mA cm-2 and 50 mA cm-2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.

Seawater splitting for high-efficiency hydrogen evolution by alloyed PtNix electrocatalysts

Science.gov (United States)

Zheng, Jingjing

2017-08-01

Robust electrocatalyst is a prerequisite to realize high-efficiency hydrogen evolution by water splitting. Expensive platinum (Pt) is a preferred electrode catalyst for state-of-the-art hydrogen evolution reaction (HER). We present here a category of alloyed PtNix electrocatalysts by a facile green chemical reduction method, which are used to catalyze HER during seawater splitting. The catalytic performances are optimized by tuning stoichiometric Pt/Ni ratio, yielding a maximized catalytic behavior for PtNi5 electrode. The minimized onset potential is as low as -0.38 V and the corresponding Tafel slope is 119 mV dec-1. Moreover, the launched alloy electrodes have remarkable stability at -1.2 V over 12 h. The high efficiency as well as good durability demonstrates the PtNix electrocatalysts to be promising in practical applications.

Design Principles for Covalent Organic Frameworks as Efficient Electrocatalysts in Clean Energy Conversion and Green Oxidizer Production.

Science.gov (United States)

Lin, Chun-Yu; Zhang, Lipeng; Zhao, Zhenghang; Xia, Zhenhai

2017-05-01

Covalent organic frameworks (COFs), an emerging class of framework materials linked by covalent bonds, hold potential for various applications such as efficient electrocatalysts, photovoltaics, and sensors. To rationally design COF-based electrocatalysts for oxygen reduction and evolution reactions in fuel cells and metal-air batteries, activity descriptors, derived from orbital energy and bonding structures, are identified with the first-principle calculations for the COFs, which correlate COF structures with their catalytic activities. The calculations also predict that alkaline-earth metal-porphyrin COFs could catalyze the direct production of H 2 O 2 , a green oxidizer and an energy carrier. These predictions are supported by experimental data, and the design principles derived from the descriptors provide an approach for rational design of new electrocatalysts for both clean energy conversion and green oxidizer production. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

Science.gov (United States)

Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

2017-11-01

Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H2SO4 0.5M

International Nuclear Information System (INIS)

Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

2007-01-01

Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H 2 SO 4 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

The microbe-secreted isopeptide poly-γ-glutamic acid induces stress tolerance in Brassica napus L. seedlings by activating crosstalk between H2O2 and Ca2+

Science.gov (United States)

Lei, Peng; Pang, Xiao; Feng, Xiaohai; Li, Sha; Chi, Bo; Wang, Rui; Xu, Zongqi; Xu, Hong

2017-01-01

Poly-γ-glutamic acid (γ-PGA) is a microbe-secreted isopeptide that has been shown to promote growth and enhance stress tolerance in crops. However, its site of action and downstream signaling pathways are still unknown. In this study, we investigated γ-PGA-induced tolerance to salt and cold stresses in Brassica napus L. seedlings. Fluorescent labeling of γ-PGA was used to locate the site of its activity in root protoplasts. The relationship between γ-PGA-induced stress tolerance and two signal molecules, H2O2 and Ca2+, as well as the γ-PGA-elicited signaling pathway at the whole plant level, were explored. Fluorescent labeling showed that γ-PGA did not enter the cytoplasm but instead attached to the surface of root protoplasm. Here, it triggered a burst of H2O2 in roots by enhancing the transcription of RbohD and RbohF, and the elicited H2O2 further activated an influx of Ca2+ into root cells. Ca2+ signaling was transmitted via the stem from roots to leaves, where it elicited a fresh burst of H2O2, thus promoting plant growth and enhancing stress tolerance. On the basis of these observation, we propose that γ-PGA mediates stress tolerance in Brassica napus seedlings by activating an H2O2 burst and subsequent crosstalk between H2O2 and Ca2+ signaling. PMID:28198821

Self-Driven Photoelectrochemical Splitting of H2S for S and H2 Recovery and Simultaneous Electricity Generation.

Science.gov (United States)

Luo, Tao; Bai, Jing; Li, Jinhua; Zeng, Qingyi; Ji, Youzhi; Qiao, Li; Li, Xiaoyan; Zhou, Baoxue

2017-11-07

A novel, facile self-driven photoelectrocatalytic (PEC) system was established for highly selective and efficient recovery of H 2 S and simultaneous electricity production. The key ideas were the self-bias function between a WO 3 photoanode and a Si/PVC photocathode due to their mismatched Fermi levels and the special cyclic redox reaction mechanism of I - /I 3 - . Under solar light, the system facilitated the separation of holes in the photoanode and electrons in the photocathode, which then generated electricity. Cyclic redox reactions were produced in the photoanode region as follows: I - was transformed into I 3 - by photoholes or hydroxyl radicals, H 2 S was oxidized to S by I 3 - , and I 3 - was then reduced to I - . Meanwhile, H + was efficiently converted to H 2 in the photocathode region. In the system, H 2 S was uniquely oxidized to sulfur but not to polysulfide (S x n- ) because of the mild oxidation capacity of I 3 - . High recovery rates for S and H 2 were obtained up to ∼1.04 mg h -1 cm -1 and ∼0.75 mL h -1 cm -1 , respectively, suggesting that H 2 S was completely converted into H 2 and S. In addition, the output power density of the system reached ∼0.11 mW cm -2 . The proposed PEC-H 2 S system provides a self-sustaining, energy-saving method for simultaneous H 2 S treatment and energy recovery.

High-Performance Rh ₂ P Electrocatalyst for Efficient Water Splitting

Energy Technology Data Exchange (ETDEWEB)

Duan, Haohong [Department; Chemistry; Li, Dongguo [Materials; Tang, Yan [Department; amp, Molecular; He, Yang [Department; Ji, Shufang [Department; Wang, Rongyue [Materials; Lv, Haifeng [Materials; Lopes, Pietro P. [Materials; Paulikas, Arvydas P. [Materials; Li, Haoyi [Department; amp, Molecular; Mao, Scott X. [Department; Wang, Chongmin [Environmental; Markovic, Nenad M. [Materials; Li, Jun [Department; amp, Molecular; Stamenkovic, Vojislav R. [Materials; Li, Yadong [Department

2017-04-05

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

Fe/N/C hollow nanospheres by Fe(iii)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction

Science.gov (United States)

Zhou, Dan; Yang, Liping; Yu, Linghui; Kong, Junhua; Yao, Xiayin; Liu, Wanshuang; Xu, Zhichuan; Lu, Xuehong

2015-01-01

In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O. Moreover, it displays better electrochemical durability and tolerance to methanol crossover effect in an alkaline medium than the Pt/C. The excellent catalytic performance of Fe/N/C HNSs-750 towards ORR can be ascribed to their high specific surface area, mesoporous morphology, homogeneous distribution of abundant active sites, high pyridinic nitrogen content, graphitic nitrogen and graphitic carbon, as well as the synergistic effect of nitrogen and iron species for catalyzing ORR.In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O

Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

Science.gov (United States)

Gacutan, E. M.; Climaco, M. I.; Telan, G. J.; Malijan, F.; Hsu, H. Y.; Garcia, J.; Fulo, H.; Tongol, B. J.

2012-12-01

The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm-2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H2SO4:HNO3. The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0-15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd-NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst.

Stable and efficient nitrogen-containing-carbon based electrocatalysts for reactions in energy conversion systems.

Science.gov (United States)

Wang, Sicong; Teng, Zhenyuan; Wang, Chengyin; Wang, Guoxiu

2018-05-17

High activity and stability are crucial for practical electrocatalysts used for reactions in fuel cells, metal-air batteries and water electrolysis including ORR, HER, OER and oxidation reactions of formic acid and alcohols. N-C based electrocatalysts have shown promising prospects for catalyzing these reactions, however, there is no systematic review for strategies toward engineering active and stable N-C based electrocatalysts reported by far. Herein, a comprehensive comparison of recently reported N-C based electrocatalysts regarding both electrocatalytic activity and long-term stability is presented. In the first part of this review, relationships between electrocatalytic reactions and element selections for modifying N-C based materials are discussed. Afterwards, synthesis methods for N-C based electrocatalysts are summarized, and synthetic strategies for highly stable N-C based electrocatalysts are presented. Multiple tables containing data on crucial parameters for both electrocatalytic activity and stability are displayed in this review. Finally, constructing M-Nx moieties is proposed as the most promising engineering strategy for stable N-C based electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bridgehead isomer effects in bis(phosphido)-bridged diiron hexacarbonyl proton reduction electrocatalysts.

Science.gov (United States)

Rahaman, Ahibur; Gimbert-Suriñach, Carolina; Ficks, Arne; Ball, Graham E; Bhadbhade, Mohan; Haukka, Matti; Higham, Lee; Nordlander, Ebbe; Colbran, Stephen B

2017-03-07

The influence of the substitution, orientation and structure of the phosphido bridges in [Fe 2 (CO) 6 (μ-PR 2 ) 2 ] electrocatalysts of proton reduction has been studied. The isomers e,a-[Fe 2 (CO) 6 {μ-P(Ar)H} 2 ] (1a(Ar): Ar = Ph, 2'-methoxy-1,1'-binaphthyl (bn')), e,e-[Fe 2 (CO) 6 {μ-P(Ar)H} 2 ] (1b(Ar): Ar = Ph, bn') were isolated from reactions of iron pentacarbonyl and the corresponding primary phosphine, syntheses that also afforded the phosphinidene-capped tri-iron clusters, [Fe 3 (CO) 9 (μ-CO)(μ 3 -Pbn')] (2) and [Fe 3 (CO) 9 (μ 3 -PAr) 2 ] (3(Ar), Ar = Ph, bn'). A ferrocenyl (Fc)-substituted dimer [Fe 2 (CO) 6 {μ:μ'-1,2-(P(CH 2 Fc)CH 2 ) 2 C 6 H 4 }] (4), in which the two phosphido bridges are linked by an o-xylyl group, was also prepared. The molecular structures of complexes 1a(Ph), 1b(Ph), 1b(bn'), 2 and 4 were established by X-ray crystallography. All complexes have been examined as electrocatalysts for proton reduction using p-toluene sulfonic acid in tetrahydrofuran. Cyclic voltammograms of the dimers with acid exhibit two catalysis waves for proton reduction. The first wave, which appears at the potential of the primary reduction, reaches maximum current (turnover) at moderate acid concentrations and is rapidly overtaken by the second wave, which appears at more negative potential. Both of these reductive waves show an initial first order dependence on acid. The electrochemistry and electrocatalyses of the [Fe 2 (CO) 6 (μ-PR 2 ) 2 ] dimers show subtle variations with the nature of the bridging phosphido group(s), including the orientation of bridgehead hydrogen atoms.

Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium

International Nuclear Information System (INIS)

Feng Yongjun; Alonso-Vante, Nicolas

2012-01-01

Highlights: ► Cubic CoSe 2 a non-precious metal electrocatalyst for oxygen reduction in KOH. ► The catalyst shows four-electron transfer pathway in overall reaction. ► Catalyst has higher methanol tolerance than commercial Pt/C catalyst. - Abstract: A Carbon-supported CoSe 2 nanocatalyst has been developed as an alternative non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in alkaline medium. The catalyst was prepared via a surfactant-free route and its electrocatalytic activity for the ORR has been investigated in detail in 0.1 M KOH electrolyte at 25 °C using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The prepared catalyst showed promising catalytic activity towards ORR in a four-electron transfer pathway and higher tolerance to methanol compared to commercial Pt/C catalyst in 0.1 M KOH. To some extent, the increase of CoSe 2 loading on the electrode favors a faster reduction of H 2 O 2 intermediate to H 2 O.

Exfoliated MoS2 nanosheets as efficient catalysts for electrochemical hydrogen evolution

International Nuclear Information System (INIS)

Ji, Shanshan; Yang, Zhe; Zhang, Chao; Liu, Zhenyan; Tjiu, Weng Weei; Phang, In Yee; Zhang, Zheng; Pan, Jisheng; Liu, Tianxi

2013-01-01

Graphical abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on exfoliation of bulk MoS 2 crystals via a direct dispersion and ultrasonication method. Drop-casting method is used to fabricate the exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings. The E-MoS 2 /GCE with electrode loading of 48 μg cm −1 exhibits high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV). -- Highlights: • Two-dimensional MoS 2 nanosheets have been obtained by exfoliation of bulk MoS 2 crystals. • Exfoliated MoS 2 nanosheets show high electrocatalytic activity for H 2 production. • This study provides a new approach for renewable and economic H 2 production. -- Abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on liquid exfoliation of bulk MoS 2 via a direct dispersion and ultrasonication method. Transmission electron microscopy and atomic force microscopy measurements show that the exfoliated MoS 2 consists of two-dimensional nanosheets. The exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings is fabricated via a drop-casting method. The electrocatalytic activity of E-MoS 2 /GCE toward hydrogen evolution reaction is examined using linear sweep voltammetry. It is shown that the E-MoS 2 /GCE with an electrode loading of 48 μg cm −2 exhibits a high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV)

Topotactic Conversion of Copper(I) Phosphide Nanowires for Sensitive Electrochemical Detection of H2O2 Release from Living Cells.

Science.gov (United States)

Li, Zhenzhen; Xin, Yanmei; Wu, Wenlong; Fu, Baihe; Zhang, Zhonghai

2016-08-02

In this work, we clearly demonstrate for the first time the use of transition-metal phosphides to set up a new cathodic analysis platform for sensitive and selective electrochemical nonenzymatic detection of H2O2. With the help of a facile topotactic conversion method, the noble metal-free electrocatalyst of copper(I) phosphide nanowires on three-dimensional porous copper foam (Cu3P NWs/CF) is fabricated with electrochemical anodized Cu(OH)2 NWs as precursor. The Cu3P NWs/CF-based sensor presents excellent electrocatalytic activity for H2O2 reduction with a detection limit of 2 nM, the lowest detection limit achieved by noble-metal free electrocatalyst, which guarantees the possibility of sensitive and reliable detection of H2O2 release from living tumorigenic cells, thus showing the potential application as a sensitive cancer cell detection probe.

Pt and PtRu nanoparticles supported on N-doped carbons as electrocatalysts for methanol electro oxidation

Energy Technology Data Exchange (ETDEWEB)

Pereira, Viviane Santos; Silva, Julio Cesar Martins; Oliveira Neto, Almir; Spinace, Estevam Vitorio, E-mail: viviane_sp_saopaulo@yahoo.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2016-07-01

Full text: Methanol is a liquid transportation fuel that can be produced from fossil or renewable resources. Fuel cells employing methanol directly as fuel (Direct Methanol Fuel Cell - DMFC) are very attractive as power source for portable, mobile and stationary applications [1]. PtRu/C electrocatalyst has been considered the best electrocatalyst for methanol electro-oxidation, however, its performance is strongly dependent on the method of preparation and on the characteristics of the carbon support. N-doped carbons with different N contents (1, 2 and 5 wt%) were prepared by thermal treatment of carbon with urea at 800 deg C. Pt and PtRu nanoparticles were supported on N-doped carbons by coreduction of Pt(IV) and Ru(III) ions using an alcohol-reduction process [2]. The obtained materials were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction, Transmission electron microscopy and Cyclic Voltammetry. Pt and PtRu nanoparticles supported on N-doped carbons showed superior performance for methanol electro-oxidation when compared to the materials supported on non-modified carbon and to Pt/C and PtRu/C commercial electrocatalysts. Pt/C and PtRu/C prepared with the carbon modified with 2.5 wt% of N content showed the best activities. (author) [1] Y. Zhou, K. Neyerlin, T.S. Olson, S. Pylypenko, J. Bult, H.N. Dinh, T. Gennett, Z. Shao and R. O'Hayre, Energy Environ. Sci. 3, 1437 (2010); [2] E.V. Spinace, A.Oliveira Neto, T.R.R. Vasconcellos, M. Linardi, J. Power Sources 137, 17 (2004)

The CdS/CdSe/ZnS Photoanode Cosensitized Solar Cells Basedon Pt, CuS, Cu2S, and PbS Counter Electrodes

Directory of Open Access Journals (Sweden)

Tung Ha Thanh

2014-01-01

Full Text Available Highly ordered mesoporous TiO2 modified by CdS, CdSe, and ZnS quantum dots (QDs was fabricated by successive ionic layer adsorption and reaction (SILAR method. The quantity of material deposition seems to be affected not only by the employed deposition method but also and mainly by the nature of the underlying layer. The CdS, CdSe, and ZnS QDs modification expands the photoresponse range of mesoporous TiO2 from ultraviolet region to visible range, as confirmed by UV-Vis spectrum. Optimized anode electrodes led to solar cells producing high current densities. Pt, CuS, PbS, and Cu2S have been used as electrocatalysts on counter electrodes. The maximum solar conversion efficiency reached in this work was 1.52% and was obtained by using Pt electrocatalyst. CuS, PbS, and Cu2S gave high currents and this was in line with the low charge transfer resistances recorded in their case.

A Co3O4-CDots-C3N4 three component electrocatalyst design concept for efficient and tunable CO2 reduction to syngas.

Science.gov (United States)

Guo, Sijie; Zhao, Siqi; Wu, Xiuqin; Li, Hao; Zhou, Yunjie; Zhu, Cheng; Yang, Nianjun; Jiang, Xin; Gao, Jin; Bai, Liang; Liu, Yang; Lifshitz, Yeshayahu; Lee, Shuit-Tong; Kang, Zhenhui

2017-11-28

Syngas, a CO and H 2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO 2 and H + /H 2 O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C 3 N 4 composite (a CO 2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co 3 O 4 , MoS 2 , Au and Pt serve as the HER component. The Co 3 O 4 -CDots-C 3 N 4 electrocatalyst is found to be the most efficient among the combinations studied. The H 2 /CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100 h) with no other products besides CO and H 2 . Insight into the mechanisms balancing between CO 2 reduction and H 2 evolution when applying the HER-CDots-C 3 N 4 catalyst concept is provided.

Low Pt content of carbon supported Pt-Ni-TiO2 nanotube electrocatalysts for direct methanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Jiang, Q.Z; Wu, X.; Ma, Z.F. [Shanghai Jiao Tong Univ., Shanghai, (China). Dept. of Chemical Engineering

2008-07-01

Interest in titanium oxide (TiO2) nanomaterial is growing due to their special characteristics for optics, catalysis, and photoelectricity conversion. In this study, the anatase/rutile crystalline of TiO2 nanoparticles was synthesized by co-deposition. TiO2 nanotubes were then obtained by microwave irradiations. This paper described the mechanism to fabricate TiO2 nanotubes. The conditions for preparing TiO2 nanotubes by microwave irradiation were optimized. Electrocatalysts were then prepared on the basis of the synthesized TiO2 nanotube. Their performances were investigated by the electro-oxidation of methanol. When Pt electrocatalysts were doped with a certain content of TiO2 nanotubes, they had more electrocatalytic activity for methanol electro-oxidation, particularly if the second transition metal, such as Ni, was added into the electrocatalyst. The electrocatalysts contained 5 and 10 wt per cent of Pt and Ni respectively. The 10 wt per cent TiO2 nanotubes showed better activities than any other catalysts for methanol electro-oxidation. According to XRD and TEM results, the size of nanoparticles of Pt became smaller after adding TiO2 nanotubes into the catalysts. It was concluded that here might be some interactions between Pt, Ni, and TiO2 nanotubes.

Covalent Organic Framework Electrocatalysts for Clean Energy Conversion.

Science.gov (United States)

Lin, Chun-Yu; Zhang, Detao; Zhao, Zhenghang; Xia, Zhenhai

2018-02-01

Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas storage, adsorption, optoelectricity, etc. owning to the unprecedented combination of large surface area, high crystallinity, tunable pore size, and unique molecular architecture. Although COFs are in their initial research stage, progress has been made in the design and synthesis of COF-based electrocatalysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and CO 2 reduction in energy conversion and fuel generation. Design principles are also established for some of the COF materials toward rational design and rapid screening of the best electrocatalysts for a specific application. Herein, the recent advances in the design and synthesis of COF-based catalysts for clean energy conversion and storage are presented. Future research directions and perspectives are also being discussed for the development of efficient COF-based electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Rh ₂ P Electrocatalyst for Efficient Water Splitting

Energy Technology Data Exchange (ETDEWEB)

Duan, Haohong; Li, Dongguo; Tang, Yan; He, Yang; Ji, Shufang; Wang, Rongyue; Lv, Haifeng; Lopes, Pietro P.; Paulikas, Arvydas P.; Li, Haoyi; Mao, Scott X.; Wang, Chongmin; Markovic, Nenad M.; Li, Jun; Stamenkovic, Vojislav R.; Li, Yadong

2017-04-05

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

Enhanced electro-oxidation of ethanol using PtSn/CeO{sub 2}-C electrocatalyst prepared by an alcohol-reduction process

Energy Technology Data Exchange (ETDEWEB)

Neto, Almir Oliveira; Farias, Luciana A.; Dias, Ricardo R.; Brandalise, Michelle; Linardi, Marcelo; Spinace, Estevam V. [Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 - Cidade Universitaria, CEP 05508-900 Sao Paulo-SP (Brazil)

2008-09-15

PtSn/CeO{sub 2}-C electrocatalysts were prepared by an alcohol-reduction process using ethylene glycol as solvent and reduction agent and CeO{sub 2} and Vulcan Carbon XC72 as supports. The electrocatalysts were characterized by EDX and XRD. The electro-oxidation of ethanol was studied at room temperature by chronoamperometry. PtSn/CeO{sub 2}-C electrocatalyst with 15 wt% of CeO{sub 2} showed a significant increase of performance for ethanol oxidation compared to PtSn/C catalyst. Preliminary tests at 100C on a single cell of a direct ethanol fuel cell (DEFC) also confirm the results obtained by chronoamperometry. (author)

Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

International Nuclear Information System (INIS)

Gacutan, E M; Tongol, B J; Climaco, M I; Telan, G J; Malijan, F; Hsu, H Y; Garcia, J; Fulo, H

2012-01-01

The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm −2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H 2 SO 4 :HNO 3 . The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0–15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd–NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst. (paper)

An in situ vapour phase hydrothermal surface doping approach for fabrication of high performance Co3O4 electrocatalysts with an exceptionally high S-doped active surface.

Science.gov (United States)

Tan, Zhijin; Liu, Porun; Zhang, Haimin; Wang, Yun; Al-Mamun, Mohammad; Yang, Hua Gui; Wang, Dan; Tang, Zhiyong; Zhao, Huijun

2015-04-04

A facile in situ vapour phase hydrothermal (VPH) surface doping approach has been developed for fabrication of high performance S-doped Co3O4 electrocatalysts with an unprecedentedly high surface S content (>47%). The demonstrated VPH doping approach could be useful for enrichment of surface active sites for other metal oxide electrocatalysts.

Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

Science.gov (United States)

Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

2018-03-01

Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts

Energy Technology Data Exchange (ETDEWEB)

Digby Macdonald

2005-04-15

The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

Highly active dealloyed Cu@Pt core-shell electrocatalyst towards 2-propanol electrooxidation in acidic solution

Energy Technology Data Exchange (ETDEWEB)

Poochai, Chatwarin, E-mail: p_chatwarin@yahoo.com

2017-02-28

Highlights: • This is the first report on electrooxidation of 2-propanol in acidic media on dealloyed Cu@Pt/CP core-shell electrocatalyst. • The dealloyed Cu@Pt/CP is prepared using cyclic co-electrodeposition and selective Cu dealloying (CCEd-sCuD). • The structure of dealloyed Cu@Pt/CP is core-shell structure with Cu-rich core and Pt-rich surface. • The dealloyed Cu@Pt/CP shows high activity and great stability towards 2-propanol electrooxidation in acidic media. - Abstract: Dealloyed Cu@Pt core-shell electrocatalyst was fabricated by cyclic co-electrodeposition and selective Cu dealloying (CCEd-sCuD) on carbon paper (CP), namely Cu@Pt/CP. The Cu@Pt/CP exhibited a core-shell structure comprising with a Cu-rich core and a Pt-rich shell. The crystalline phases of Pt/CP and Cu@Pt/CP were a face-centered cubic (fcc). The compressive lattice strain approximately 0.85% was found in the Cu@Pt/CP owing to a lattice mismatch between a core and a shell region. In the core-region, Cu was formed Pt-Cu alloy as major and copper oxide and also metallic copper as minor. The morphology and grain size of the Cu@Pt/CP displayed a porous spherical shape with 100 nm in diameter, while those of Pt/CP seemed to be a cubic shape with smaller diameter of 40 nm. In electrochemical and catalytic activity, the surface of Cu@Pt/CP had a larger electrochemical active surface area (ECSA) than that of Pt/CP due to a porous formation caused by Cu dealloying. It is not surprising that the Cu@Pt/CP showed higher catalytic activity and greater stability towards 0.5 M 2-propanol electrooxidation in 0.5 M H{sub 2}SO{sub 4} in terms of peak current density (j{sub p}), peak potential (E{sub p}), onset potential (E{sub onset}), diffusion coefficient (D), and charge transfer resistance (R{sub ct}) which were caused by electronic structure modification, higher compressive lattice strain, and larger ECSA, compared with Pt/CP.

A novel H2S/H2O2 fuel cell operating at the room temperature

Energy Technology Data Exchange (ETDEWEB)

Sanli, Ayse Elif [Gazi University (Turkey)], email: aecsanli@gmail.com; Aytac, Aylin [Department of Chemistry, Faculty of Science, Gazi University, Teknikokullar (Turkey)], email: aytaca@gazi.edu.tr

2011-07-01

This study concerns the oxidation mechanism of hydrogen sulfide and a fuel cell; acidic peroxide is used as the oxidant and basic hydrogen sulfide is the fuel. A solid state H2S/H2O2 stable fuel cell was produced at room temperature. A cell potential of 0.85 V was reached; this is quite remarkable in comparison to the H2S/O2 fuel cell potential of 0.85 V obtained at 850-1000 degree celsius. The hydrogen sulfide goes through an oxidation reaction in the alkaline fuel cell (H2S/H2O2 fuel cell) which opens up the possibility of using the cheaper nickel as a catalyst. As a result, the fuel cell becomes a potentially low cost technology. A further benefit from using H2S as the alkaline liquid H2S/H2O2 fuel cell, is that sulfide ions are oxidized at the anode, releasing electrons. Sulfur produced reacts with the other sulfide ions and forms disulfide and polysulfide ions in basic electrolytes (such as Black Sea water).

Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

Science.gov (United States)

Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

2017-05-01

Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

Studies of a series of [Ni(P(R)2N(Ph)2)2(CH3CN)]2+ complexes as electrocatalysts for H2 production: substituent variation at the phosphorus atom of the P2N2 ligand.

Science.gov (United States)

Kilgore, Uriah J; Stewart, Michael P; Helm, Monte L; Dougherty, William G; Kassel, W Scott; DuBois, Mary Rakowski; DuBois, Daniel L; Bullock, R Morris

2011-11-07

A series of [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes containing the cyclic diphosphine ligands [P(R)(2)N(Ph)(2) = 1,5-diaza-3,7-diphosphacyclooctane; R = benzyl (Bn), n-butyl (n-Bu), 2-phenylethyl (PE), 2,4,4-trimethylpentyl (TP), and cyclohexyl (Cy)] have been synthesized and characterized. X-ray diffraction studies reveal that the cations of [Ni(P(Bn)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) and [Ni(P(n-Bu)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) have distorted trigonal bipyramidal geometries. The Ni(0) complex [Ni(P(Bn)(2)N(Ph)(2))(2)] was also synthesized and characterized by X-ray diffraction studies and shown to have a distorted tetrahedral structure. These complexes, with the exception of [Ni(P(Cy)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2), all exhibit reversible electron transfer processes for both the Ni(II/I) and Ni(I/0) couples and are electrocatalysts for the production of H(2) in acidic acetonitrile solutions. The heterolytic cleavage of H(2) by [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes in the presence of p-anisidine or p-bromoaniline was used to determine the hydride donor abilities of the corresponding [HNi(P(R)(2)N(Ph)(2))(2)](BF(4)) complexes. However, for the catalysts with the most bulky R groups, the turnover frequencies do not parallel the driving force for elimination of H(2), suggesting that steric interactions between the alkyl substituents on phosphorus and the nitrogen atom of the pendant amines play an important role in determining the overall catalytic rate. © 2011 American Chemical Society

The performance and degradation of Pt electrocatalysts on novel carbon carriers for PEMFC applications

Energy Technology Data Exchange (ETDEWEB)

Mamat, M.S.; Grant, D.M.; Walker, G.S. [Energy and Sustainability Research Division, Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD (United Kingdom); Grigoriev, S.A.; Dzhus, K.A. [Hydrogen Energy and Plasma Technology Institute, Russian Research Center ' ' Kurchatov Institute' ' , Kurchatov sq. 1, 123182 Moscow (Russian Federation)

2010-07-15

Electrocatalyst stability is an important factor influencing the performance of polymer electrolyte membrane (PEM) fuel cells and is essential in maintaining the cell output. The aim of this work was to elucidate factors which influence the stability of platinum supported onto graphitic nanofibres (Pt/GNFs) and to compare the performance of these materials with the commonly used Pt/Vulcan electrocatalyst. Platinum nanoparticles (average diameter of 6.9 nm) were supported on GNFs which were prepared by chemical vapour deposition over an unsupported nickel oxide (NiO) catalyst precursor. The performance of Pt/GNFs based electrodes were studied by cyclic voltammetry and a single-cell fuel cell test and were compared with a commercially available carbon nanostructure, Vulcan XC-72, which was also impregnated with Pt nanoparticles. Characterisation of the pre- and post-operation of the Pt/GNFs by XRD and TEM showed that structural changes of the Pt had occurred during testing. It was found that the average diameter of each grain and the degree of agglomeration among particles was increased, creating elongated clusters of Pt along the carbon fibre. Analysis of electrocatalyst post-operation also identified that the sulphate from the Nafion membrane was reacting with the Pt surface forming platinum sulphide (PtS). These phases were confirmed by the presence of low intensity, but sharp XRD peaks, attributed to a few large diameter particles (49 nm). These two factors resulted in current density dropping from 0.2 A/cm{sup 2} to 0.1 A/cm{sup 2} (at 0.70 V) over a 25 h test period. (author)

Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry.

Science.gov (United States)

Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie

2008-09-14

PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

A first principle Comparative study of electronic and optical properties of 1H –MoS2 and 2H –MoS2

International Nuclear Information System (INIS)

Kumar, Ashok; Ahluwalia, P.K.

2012-01-01

First principle calculations of electronic and optical properties of monolayer MoS 2 , so called 1H –MoS 2 , is performed which has emerged as a new direct band gap semiconductor. Before calculations of the properties of 1H –MoS 2 , we have calculated structural parameters, electronic properties (electronic band structure and electronic density of states) and frequency dependent optical response (real and imaginary part of dielectric function, energy loss function, absorption and reflectance spectra) of 2H –MoS 2 and compared with existing experimental results and found that our calculated results are in very good agreements with experimental results. To compare the dielectric functions of bulk (2H –MoS 2 ) and monolayer (1H –MoS 2 ) phases we have further extended these calculations to the single layer MoS 2 (1H –MoS 2 ) which is analogous to graphene. Structural parameters of 1H –MoS 2 are found very close to its bulk 2H –MoS 2 . We find direct electronic band gap at ‘K’ high symmetry point as compared to indirect band gap in its bulk 2H – MoS2. Our calculated dielectric function for 1H – MoS2 shows structure at nearly same energy positions as compared to 2H – MoS2 with additional structure at 3.8 eV. Also additional well defined energy loss peaks revealing the plasmonic resonances at 15.7 eV and 16.0 eV for E vector perpendicular and parallel to c axis respectively for 1H – MoS2 have been found, which are the signatures of surface plasmons at these energies. -- Highlights: ► Structural parameters of 2H-MoS2 and 1H-MoS2 are nearly identical. ► States around the Fermi energy are mainly due to the metal d states. ► Strong hybridization between Mo-d and S-p states below the Fermi energy has been found. ► Optical spectra of 2H-MoS2 finds very good agreements with experimental optical spectra. ► The band gap is found to be direct for 1H-MoS2 as compared to indirect for 2H-MoS2.

A Pt-Co3O4-CD electrocatalyst with enhanced electrocatalytic performance and resistance to CO poisoning achieved by carbon dots and Co3O4 for direct methanol fuel cells.

Science.gov (United States)

Sun, Yue; Zhou, Yunjie; Zhu, Cheng; Hu, Lulu; Han, Mumei; Wang, Aoqi; Huang, Hui; Liu, Yang; Kang, Zhenhui

2017-05-04

Highly efficient electrocatalysts remain huge challenges in direct methanol fuel cells (DMFCs). Here, a Pt-Co 3 O 4 -CDs/C composite was fabricated as an anode electrocatalyst with low Pt content (12 wt%) by using carbon dots (CDs) and Co 3 O 4 nanoparticles as building blocks. The Pt-Co 3 O 4 -CDs/C composite catalyst shows a significantly enhanced electrocatalytic activity (1393.3 mA mg -1 Pt), durability (over 4000 s) and CO-poisoning tolerance. The superior catalytic activity should be attributed to the synergistic effect of CDs, Pt and Co 3 O 4 . Furthermore, the Pt-Co 3 O 4 -CDs/C catalyst was integrated into a single cell, which exhibits a maximum power density of 45.6 mW cm -2 , 1.7 times the cell based on the commercial 20 wt% Pt/C catalyst.

H₂ production through electro-oxidation of SO₂

DEFF Research Database (Denmark)

Kriek, Roelof J.; Rossmeisl, Jan; Siahrostami, Samira

2014-01-01

one volt lower than that of a regular water electrolyser. In taking this technology forward the greatest improvement to be made is in developing a suitable electrocatalyst, which is also the 'lowest hanging fruit' in that very limited research and development has been conducted on the electrocatalyst....... The electrolysis of aqueous solutions of dissolved SO2 holds huge environmental potential in that SO2 is converted to sulphuric acid (H2SO4) and at the same time hydrogen gas is produced. A further benefit or incentive is that a sulphur depolarised electrolyser (SDE) operates at an applied potential that is about...... are found to scale with the surface reactivity (measured as the adsorption of OH). Irrespective of the pathway water needs to be activated and reduction of SO2 to elemental sulphur must be avoided. This requirement alone calls for an electrode potential of at least 0.7-0.8 V for all the investigated...

Electrocatalysts using porous polymers and method of preparation

Energy Technology Data Exchange (ETDEWEB)

Liu, Di-Jia; Yuan, Shengwen; Goenaga, Gabriel A.

2016-08-02

A method of producing an electrocatalyst article using porous polymers. The method creates a porous polymer designed to receive transition metal groups disposed at ligation sites and activating the transition metals to form an electrocatalyst which can be used in a fuel cell. Electrocatalysts prepared by this method are also provided. A fuel cell which includes the electrocatalyst is also provided.

Electrocatalysts using porous polymers and method of preparation

Energy Technology Data Exchange (ETDEWEB)

Liu, Di-Jia; Yuan, Shengwen; Goenaga, Gabriel A.

2015-04-21

A method of producing an electrocatalyst article using porous polymers. The method creates a porous polymer designed to receive transition metal groups disposed at ligation sites and activating the transition metals to form an electrocatalyst which can be used in a fuel cell. Electrocatalysts prepared by this method are also provided. A fuel cell which includes the electrocatalyst is also provided.

N- and S-doped high surface area carbon derived from soya chunks as scalable and efficient electrocatalysts for oxygen reduction

Science.gov (United States)

Rana, Moumita; Arora, Gunjan; Gautam, Ujjal K.

2015-02-01

Highly stable, cost-effective electrocatalysts facilitating oxygen reduction are crucial for the commercialization of membrane-based fuel cell and battery technologies. Herein, we demonstrate that protein-rich soya chunks with a high content of N, S and P atoms are an excellent precursor for heteroatom-doped highly graphitized carbon materials. The materials are nanoporous, with a surface area exceeding 1000 m2 g-1, and they are tunable in doping quantities. These materials exhibit highly efficient catalytic performance toward oxygen reduction reaction (ORR) with an onset potential of -0.045 V and a half-wave potential of -0.211 V (versus a saturated calomel electrode) in a basic medium, which is comparable to commercial Pt catalysts and is better than other recently developed metal-free carbon-based catalysts. These exhibit complete methanol tolerance and a performance degradation of merely ˜5% as compared to ˜14% for a commercial Pt/C catalyst after continuous use for 3000 s at the highest reduction current. We found that the fraction of graphitic N increases at a higher graphitization temperature, leading to the near complete reduction of oxygen. It is believed that due to the easy availability of the precursor and the possibility of genetic engineering to homogeneously control the heteroatom distribution, the synthetic strategy is easily scalable, with further improvement in performance.

A Pt-free Electrocatalyst Based on Pyrolized Vinazene-Carbon Composite for Oxygen Reduction Reaction

International Nuclear Information System (INIS)

Akinpelu, Akeem; Merzougui, Belabbes; Bukola, Saheed; Azad, Abdul-Majeed; Basheer, Rafil A.; Swain, Greg M.; Chang, Qiaowan; Shao, Minhua

2015-01-01

The 2-vinyl-4, 5-dicyanoimidazole (Vinazene) was used as a nitrogen precursor to synthesize a promising non-precious metal (NPM) catalyst for oxygen reduction reaction (ORR). Vinazene together with an iron source was impregnated into a carbon matrix and pyrolyzed at 900 °C in N 2 atmosphere. The structure of the resulting Fe–N–C nanocomposite was analyzed by X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction. Both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) experiments showed excellent ORR activity for the obtained catalyst with low H 2 O 2 formation (∼3.0%) in 0.1 M KOH. The catalyst was found to be rich in mesoporous structure along with high percentage of pyrrolic-N function with surface area of about 673 m 2 g −1 and pore size of 4.2 nm. In addition to its excellent ORR activity, the catalyst showed remarkable tolerance towards methanol oxidation and demonstrates good stability over 10,000 potential cycles (0.6–1.0 V Vs RHE). We believe that this N-rich Vinazene molecule will be beneficial to further development of nitrogen doped carbon electrocatalysts

A neural network potential energy surface for the NaH2 system and dynamics studies on the H(2S) + NaH(X1Σ+) → Na(2S) + H2(X1Σg+) reaction.

Science.gov (United States)

Wang, Shufen; Yuan, Jiuchuang; Li, Huixing; Chen, Maodu

2017-08-02

In order to study the dynamics of the reaction H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), a new potential energy surface (PES) for the ground state of the NaH 2 system is constructed based on 35 730 ab initio energy points. Using basis sets of quadruple zeta quality, multireference configuration interaction calculations with Davidson correction were carried out to obtain the ab initio energy points. The neural network method is used to fit the PES, and the root mean square error is very small (0.00639 eV). The bond lengths, dissociation energies, zero-point energies and spectroscopic constants of H 2 (X 1 Σ g + ) and NaH(X 1 Σ + ) obtained on the new NaH 2 PES are in good agreement with the experiment data. On the new PES, the reactant coordinate-based time-dependent wave packet method is applied to study the reaction dynamics of H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), and the reaction probabilities, integral cross-sections (ICSs) and differential cross-sections (DCSs) are obtained. There is no threshold in the reaction due to the absence of an energy barrier on the minimum energy path. When the collision energy increases, the ICSs decrease from a high value at low collision energy. The DCS results show that the angular distribution of the product molecules tends to the forward direction. Compared with the LiH 2 system, the NaH 2 system has a larger mass and the PES has a larger well at the H-NaH configuration, which leads to a higher ICS value in the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction. Because the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction releases more energy, the product molecules can be excited to a higher vibrational state.

Facile preparation of efficient electrocatalysts for oxygen reduction reaction: One-dimensional meso/macroporous cobalt and nitrogen Co-doped carbon nanofibers

Science.gov (United States)

Yoon, Ki Ro; Choi, Jinho; Cho, Su-Ho; Jung, Ji-Won; Kim, Chanhoon; Cheong, Jun Young; Kim, Il-Doo

2018-03-01

Efficient electrocatalyst for oxygen reduction reaction (ORR) is an essential component for stable operation of various sustainable energy conversion and storage systems such as fuel cells and metal-air batteries. Herein, we report a facile preparation of meso/macroporous Co and N co-doped carbon nanofibers (Co-Nx@CNFs) as a high performance and cost-effective electrocatalyst toward ORR. Co-Nx@CNFs are simply obtained from electrospinning of Co precursor and bicomponent polymers (PVP/PAN) followed by temperature controlled carbonization and further activation step. The prepared Co-Nx@CNF catalyst carbonized at 700 °C (Co-Nx@CNF700) shows outstanding ORR performance, i.e., a low onset potential (0.941 V) and half wave potential (0.814 V) with almost four-electron transfer pathways (n= 3.9). In addition, Co-Nx@CNF700 exhibits a superior methanol tolerance and higher stability (>70 h) in Zn-air battery in comparison with Pt/C catalyst (∼30 h). The outstanding performance of Co-Nx@CNF700 catalysts is attributed to i) enlarged surface area with bimodal porosity achieved by leaching of inactive species, ii) increase of exposed ORR active Co-Nx moieties and graphitic edge sites, and iii) enhanced electrical conductivity and corrosion resistance due to the existence of numerous graphitic flakes in carbon matrix.

H(2 enhances arabidopsis salt tolerance by manipulating ZAT10/12-mediated antioxidant defence and controlling sodium exclusion.

Directory of Open Access Journals (Sweden)

Yanjie Xie

Full Text Available BACKGROUND: The metabolism of hydrogen gas (H(2 in bacteria and algae has been extensively studied for the interesting of developing H(2-based fuel. Recently, H(2 is recognized as a therapeutic antioxidant and activates several signalling pathways in clinical trials. However, underlying physiological roles and mechanisms of H(2 in plants as well as its signalling cascade remain unknown. METHODOLOGY/PRINCIPAL FINDINGS: In this report, histochemical, molecular, immunological and genetic approaches were applied to characterize the participation of H(2 in enhancing Arabidopsis salt tolerance. An increase of endogenous H(2 release was observed 6 hr after exposure to 150 mM NaCl. Arabidopsis pretreated with 50% H(2-saturated liquid medium, mimicking the induction of endogenous H(2 release when subsequently exposed to NaCl, effectively decreased salinity-induced growth inhibition. Further results showed that H(2 pretreatment modulated genes/proteins of zinc-finger transcription factor ZAT10/12 and related antioxidant defence enzymes, thus significantly counteracting the NaCl-induced reactive oxygen species (ROS overproduction and lipid peroxidation. Additionally, H(2 pretreatment maintained ion homeostasis by regulating the antiporters and H(+ pump responsible for Na(+ exclusion (in particular and compartmentation. Genetic evidence suggested that SOS1 and cAPX1 might be the target genes of H(2 signalling. CONCLUSIONS: Overall, our findings indicate that H(2 acts as a novel and cytoprotective regulator in coupling ZAT10/12-mediated antioxidant defence and maintenance of ion homeostasis in the improvement of Arabidopsis salt tolerance.

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

Science.gov (United States)

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-03-01

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions

Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

KAUST Repository

Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

2014-01-01

Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

KAUST Repository

Bukola, Saheed

2014-11-01

Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

Polysulfides and products of H2S/S-nitrosoglutathione in comparison to H2S, glutathione and antioxidant Trolox are potent scavengers of superoxide anion radical and produce hydroxyl radical by decomposition of H2O2.

Science.gov (United States)

Misak, Anton; Grman, Marian; Bacova, Zuzana; Rezuchova, Ingeborg; Hudecova, Sona; Ondriasova, Elena; Krizanova, Olga; Brezova, Vlasta; Chovanec, Miroslav; Ondrias, Karol

2018-06-01

Exogenous and endogenously produced sulfide derivatives, such as H 2 S/HS - /S 2- , polysulfides and products of the H 2 S/S-nitrosoglutathione interaction (S/GSNO), affect numerous biological processes in which superoxide anion (O 2 - ) and hydroxyl (OH) radicals play an important role. Their cytoprotective-antioxidant and contrasting pro-oxidant-toxic effects have been reported. Therefore, the aim of our work was to contribute to resolving this apparent inconsistency by studying sulfide derivatives/free radical interactions and their consequent biological effects compared to the antioxidants glutathione (GSH) and Trolox. Using the electron paramagnetic resonance (EPR) spin trapping technique and O 2 - , we found that a polysulfide (Na 2 S 4 ) and S/GSNO were potent scavengers of O 2 - and cPTIO radicals compared to H 2 S (Na 2 S), GSH and Trolox, and S/GSNO scavenged the DEPMPO-OH radical. As detected by the EPR spectra of DEPMPO-OH, the formation of OH in physiological solution by S/GSNO was suggested. All the studied sulfide derivatives, but not Trolox or GSH, had a bell-shaped potency to decompose H 2 O 2 and produced OH in the following order: S/GSNO > Na 2 S 4  ≥ Na 2 S > GSH = Trolox = 0, but they scavenged OH at higher concentrations. In studies of the biological consequences of these sulfide derivatives/H 2 O 2 properties, we found the following: (i) S/GSNO alone and all sulfide derivatives in the presence of H 2 O 2 cleaved plasmid DNA; (ii) S/GSNO interfered with viral replication and consequently decreased the infectivity of viruses; (iii) the sulfide derivatives induced apoptosis in A2780 cells but inhibited apoptosis induced by H 2 O 2 ; and (iv) Na 2 S 4 modulated intracellular calcium in A87MG cells, which depended on the order of Na 2 S 4 /H 2 O 2 application. We suggest that the apparent inconsistency of the cytoprotective-antioxidant and contrasting pro-oxidant-toxic biological effects of sulfide derivatives results from their time

Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction; Electrocatalizadores a base de platino, cobalto y niquel preparados por aleado mecanico y CVD para la reaccion de reduccion de oxigeno

Energy Technology Data Exchange (ETDEWEB)

Garcia C, M A [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)

2008-07-01

In this research, the molecular oxygen reduction reaction (ORR) was investigated on electrocatalysts of Co, Ni, Pt and their alloys CoNi, PtCo, PtNi and PtCoNi by using H{sub 2}SO{sub 4} 0.5 and KOH 0.5 M solutions as electrolytes. The electrocatalysts were synthesized by Mechanical Alloying (MA) and Chemical Vapor Deposition (CVD) processes. For MA, metallic powders were processed during 20 h of milling in a high energy SPEX 8000 mill. For CVD, a hot-wall reactor was utilized and Co, Ni and Pt acetilactetonates were used as precursors. Films were deposited at a total pressure of 1 torr and temperatures of 400-450 C. Electrocatalysts were characterized by X-Ray Diffraction (XRD). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Electrocatalysts prepared by mechanical alloying showed a homogeneously dispersed agglomeration of particles with nano metric size. Electrocatalysts obtained by CVD showed, in some cases, non uniform films, with particles of nano metric size, as well. The electrocatalytic performance was evaluated by using the Rotating Disk Electrode technique (RDE). Electrocatalysts prepared by MA showed higher activity than those obtained by CVD. All electrocatalysts were evaluated in alkaline media. Only electrocatalysts containing Pt were evaluated in acid media, because those materials with Co, Ni and their alloys showed instability in acidic media. Most electrocatalysts followed a mechanism for the ORR producing a certain proportion of H{sub 2}O{sub 2}. All electrocatalysts, exhibited a fair or good electrocatalytic activity in comparison with other similar reported materials. It was found that MA and CVD are appropriate processes to prepare electrocatalysts for the ORR with particles of nano metric size and performing with an acceptable catalytic activity. PtCoNi 70-23-7% by MA and PtCoNi-CVD electrocatalysts showed the highest activity in alkaline media, while in acidic

Method for heavy-water production by H2S--H2O chemical exchange process

International Nuclear Information System (INIS)

Strathdee, G.G.

1978-01-01

The invention discloses a heavy water production stage in a bithermal H 2 S gas H 2 O liquid exchange plant wherein the cold tower is operated under temperature and pressure conditions such that H 2 S in the liquid phase is formed and is maintained in the separation units (sieve trays or plates) of the cold tower. It has been found that the presence of liquid H 2 S acts as an efficient anti-foaming agent

Charge transfer in H2+-H(1s) collisions

International Nuclear Information System (INIS)

Errea, L.F.; Macias, A.; Mendez, L.; Rabadan, I.; Riera, A.

2005-01-01

We present an ab initio study of H 2 + +H(1s) collisions at H 2 + impact energies between 0.4 and 50keV. Cross sections are obtained within the sudden approximation for rotation and vibration of the diatomic molecule. We have found that anisotropy effects are crucial to correctly describe this system in this energy range

Electron capture, electron loss, and deexcitation of fast H(2 2S) and H(1 2S) atoms in collisions with molecular hydrogen and inert gases

International Nuclear Information System (INIS)

Roussel, F.; Pradel, P.; Spiess, G.

1977-01-01

Collisions of ground-state (1 2 S) and metastable (2 2 S) hydrogen atoms with rare gases and molecular hydrogen have been studied in the energy range 0.5--3.0 keV. For an acceptance angle of 55 mrad, the electron loss and the electron-capture cross sections of both H(1 2 S) and H(2 2 S) have been measured and compared with previous experimental values. The deexcitation cross section for H(2 2 S) has been deduced with the help of previously measured total-quenching cross sections for H(2 2 S). The ratio of the electron-capture cross sections for H(2 2 S) relative to H(1 2 S) is found to be very large for argon at low energies. The effects of large-angle scattering and of highly excited states of H are discussed

One- or two-electron water oxidation, hydroxyl radical, or H_2O_2 evolution

International Nuclear Information System (INIS)

Siahrostami, Samira; Li, Guo-Ling; Viswanathan, Venkatasubramanian; Nørskov, Jens K.

2017-01-01

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H_2O_2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O_2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H_2O_2, and O_2.

Study of fluorine doped (Nb,Ir)O_2 solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

International Nuclear Information System (INIS)

Kadakia, Karan Sandeep; Jampani, Prashanth H.; Velikokhatnyi, Oleg I.; Datta, Moni Kanchan; Patel, Prasad; Chung, Sung Jae; Park, Sung Kyoo; Poston, James A.; Manivannan, Ayyakkannu; Kumta, Prashant N.

2016-01-01

Graphical abstract: High surface area (∼300 m"2/g) nanostructured powders of nominal composition (Nb_1_−_xIr_x)O_2 and (Nb_1_−_xIr_x)O_2:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb_1_−_xIr_x)O_2 with an optimal composition (Nb_0_._7_5Ir_0_._2_5)O_2:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO_2 and nanostructured in-house chemically synthesized IrO_2. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb_1_−_xIr_x)O_2:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb_0_._7_5Ir_0_._2_5)O_2:10F exhibits superior electrochemical activity than pure IrO_2. • Stability of the (Nb,Ir)O_2:10F nanomaterials is comparable to pure (Nb,Ir)O_2. • High surface area F doped (Nb,Ir)O_2 are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m"2/g) nanostructured powders of (Nb_1_−_xIr_x)O_2 and (Nb_1_−_xIr_x)O_2:10F (∼100 m"2/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb_2O_5 and 10 wt.% F doped Nb_2O_5 powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O_2 and 10 wt.% F doped (Nb,Ir)O_2 [(NbIr)O_2:10F] electro-catalysts by soaking in IrCl_4 followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb_0_._7_5Ir_0_._2_5)O_2:10F with ∼75 at.% reduction in noble metal content exhibited comparable OER activity to commercial hydrated IrO_2 and nanostructured in-house chemically synthesized IrO_2

Differential cross sections for transfer into the 2S state of hydrogen: H+ + H2, H+ + D2

International Nuclear Information System (INIS)

Williams, D.G.; Lee, A.R.; Butcher, E.C.

1986-01-01

Differential cross sections for electron capture into the 2S state of hydrogen are presented for the reactions H + + H 2 and H + + D 2 . The results are for laboratory collision energies between 3.3 and 24 keV and scattering angles between 30 and 90'. The measurements expand on the results previously presented. (author)

Evaluation of the performance degradation at PAFC investigation of dealloying process of electrocatalysts with in-situ XRD

Energy Technology Data Exchange (ETDEWEB)

Nakajima, Noriyuki; Uchida, Hiroyuki; Watanabe, Masahiro [Yamanashi Univ., Kofu (Japan)] [and others

1996-12-31

As a complementary research project to the demonstration project of 5MW and 1 MW PAFC plants, the mechanism and rate of deterioration of the cells and stacks have been studied from 1995 FY, with the objective of establishing an estimation method for the service life-time of the cell stacks. This work has been performed in the Basic Research Project, as part of that project on PAFC`s, selecting four subjects (Electrocatalysts degradation, Electrolyte fill-level, Cell material corrosion, Electrolyte loss) as the essential factors relating to the life-time. In this study, the effect of temperature and potential on the dealloying process of electrocatalysts was examined in H{sub 3}PO{sub 4} electrolyte with X-ray diffraction measurement.

The effect of low platinum loading on the efficiency of PEMFC’s electrocatalysts supported on TiO2–Nb, and SnO2–Nb: An experimental comparison between active and stable conditions

International Nuclear Information System (INIS)

Shahgaldi, Samaneh; Hamelin, Jean

2015-01-01

Highlights: • SnO 2 –Nb, and TiO 2 –Nb thin films synthesized via sputtering. • SnO 2 –Nb, and TiO 2 –Nb thin films applied as a Pt support in PEMFC. • Low amount of Pt sputtered on supports as catalyst in cathode side. • Fabricate a single cell and plot I–V curves. - Abstract: Electrocatalyst supports have been demonstrated to strongly influence the cost, performance and durability of PEMFC systems, which have been among the heated research topics in the course of the past decades. However, the present support materials used in fuel cell stack are not adequately durable for commercialization. Development of active electrocatalyst with cost effectiveness and high durability is one of the main challenges. In this paper, titania and tin oxide nanoparticles doped nobidium were selected as thermo chemically stable and carbonless electrocatalyst supports. Low Pt loading (0.05 mg/cm 2 ) is deposited on supports through sputtering method, and the structure, the distribution of nanoparticles, and the electrical resistivity were systematically analyzed. To make the studies of oxygen reduction reaction activity, catalytic stability and performance of PEMFC more precise, rotation disk electrode (RDE), cyclic voltammetry (CV), and single cell test were utilized. The data analysis of this study highlighted that SnO 2 –Nb–Pt depicted higher stability and better fuel cell performance in comparison with TiO 2 –Nb–Pt

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

International Nuclear Information System (INIS)

Garcia, Amanda C.; Paganin, Valdecir A.; Ticianelli, Edson A.

2008-01-01

The performance of H 2 /O 2 proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and 'in situ' X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO 2 at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H 2 + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm -2 , with the cell presenting potential losses below 200 mV at 1 A cm -2 , with respect to the system fed with pure H 2 . For the PdPt/C catalysts no CO 2 formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H 2 electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO 2 in the PEMFC anode outlet

Oxygen reduction reaction of (C-PCTNB@CNTs): A nitrogen and phosphorus dual-doped carbon electro-catalyst derived from polyphosphazenes

Science.gov (United States)

Dar, Sami Ullah; Ud Din, Muhammad Aizaz; Hameed, Muhammad Usman; Ali, Shafqat; Akram, Raheel; Wu, Zhanpeng; Wu, Dezhen

2018-01-01

This research describes the synthesis of a novel type of poly [cyclotriphosphazene-co-1,3,5-triol nitrobenzene] (PCTNB) microspheres with uniform size and diameter of more than 2 μm having well characterization. These microspheres are further used to wrap the CNTs by a facile route using template based non-covalent method to form PCTNB@CNTs composite. This composite is further well analyzed before it is subjected to pyrolysis. The direct carbonization of the PCTNB@CNTs is performed at 600 °C at a rate of 5 °C/min under N2 atmosphere to render the N, P, O doped carbonized PCTNB@CNTs having enhanced electronic features to be applied as an ORR electrocatalysts in fuel cells accompanied by TEM, XPS, Raman, FT-IR, TGA and BET analyses. Here, we have designed a metal-free, N, P, O doped (C-PCTNB@CNTs) electro-catalyst which exhibit significantly high ORR performance in acidic PEM cells showing much higher onset potential of (0.94 V) and half-wave potential of (0.85 V) with electron transfer number (n) 3.9 at 0.4-0.7 V as compared to other non-metallic electro-catalysts. Thus, (C-PCTNB@CNTs) is a metal-free, methanol tolerant carbon-based ORR catalyst, and it opens up new avenues for clean energy generation for affordable and durable fuel cells.

A banana NAC transcription factor (MusaSNAC1) impart drought tolerance by modulating stomatal closure and H2O2 content.

Science.gov (United States)

Negi, Sanjana; Tak, Himanshu; Ganapathi, T R

2018-03-01

MusaSNAC1 function in H 2 O 2 mediated stomatal closure and promote drought tolerance by directly binding to CGT[A/G] motif in regulatory region of multiple stress-related genes. Drought is a abiotic stress-condition, causing reduced plant growth and diminished crop yield. Guard cells of the stomata control photosynthesis and transpiration by regulating CO 2 exchange and water loss, thus affecting growth and crop yield. Roles of NAC (NAM, ATAF1/2 and CUC2) protein in regulation of stress-conditions has been well documented however, their control over stomatal aperture is largely unknown. In this study we report a banana NAC protein, MusaSNAC1 which induced stomatal closure by elevating H 2 O 2 content in guard cells during drought stress. Overexpression of MusaSNAC1 in banana resulted in higher number of stomata closure causing reduced water loss and thus elevated drought-tolerance. During drought, expression of GUS (β-glucuronidase) under P MusaSNAC1 was remarkably elevated in guard cells of stomata which correlated with its function as a transcription factor regulating stomatal aperture closing. MusaSNAC1 is a transcriptional activator belonging to SNAC subgroup and its 5'-upstream region contain multiple Dof1 elements as well as stress-associated cis-elements. Moreover, MusaSNAC1 also regulate multiple stress-related genes by binding to core site of NAC-proteins CGT[A/G] in their 5'-upstream region. Results indicated an interesting mechanism of drought tolerance through stomatal closure by H 2 O 2 generation in guard cells, regulated by a NAC-protein in banana.

Investigation of H2S separation from H2S/CH4 mixtures using functionalized and non-functionalized vertically aligned carbon nanotube membranes

Science.gov (United States)

Gilani, Neda; Towfighi, Jafar; Rashidi, Alimorad; Mohammadi, Toraj; Omidkhah, Mohammad Reza; Sadeghian, Ahmad

2013-04-01

Separation of H2S from binary mixtures of H2S/CH4 using vertically aligned carbon nanotube membranes fabricated in anodic aluminum oxide (AAO) template was studied experimentally. Carbon nanotubes (CNTs) were grown in five AAO templates with different pore diameters using chemical vapor deposition, and CNT/AAO membranes with tubular carbon nanotube structure and open caps were selected for separation of H2S. For this, two tubular CNT/AAO membranes were fabricated with the CNT inner diameters of 23 and 8 nm. It was found that permeability and selectivity of the membrane with inner diameter of 23 nm for CNT were independent of upstream feed pressure and H2S feed concentration unlike that of CNT having an inner diameter of 8 nm. Selectivity of these membranes for separation of H2S was obtained in the ranges of 1.36-1.58 and 2.11-2.86, for CNTs with internal diameters of 23 and 8 nm, respectively. In order to enhance the separation of H2S from H2S/CH4 mixtures, dodecylamine was used to functionalize the CNT/AAO membrane with higher selectivity. The results showed that for amido-functionalized membrane, both upstream feed pressure and H2S partial pressure in the feed significantly increased H2S permeability, and selectivity for H2S being in the range of 3.0-5.57 respectively.

Pr0.6Sr0.4CoO3-δ electrocatalyst for solid oxide fuel cell cathode introduced via infiltration

International Nuclear Information System (INIS)

Lee, Shiwoo; Miller, Nicholas; Staruch, Margo; Gerdes, Kirk; Jain, Menka; Manivannan, Ayyakkannu

2011-01-01

Highlights: → High electrocatalytic activity of Sr-doped PrCoO 3 for oxygen reduction reaction has been demonstrated. → 35-38% of power density enhancement has been achieved for a commercial cell by introducing Sr-doped PrCoO 3 via infiltration. → Fuel cells modified with nano-sized electrocatalyst have shown relatively stable performance for 200 h. → Reliable performance comparison has been realized by utilizing a parallel cell testing system. - Abstract: Effects of infiltrated Pr 0.6 Sr 0.4 CoO 3-δ (PSCo) electrocatalyst on SOFC cathode performance have been studied. Nano-sized particulate catalysts, deposited on surfaces of a composite cathode of Sm 2 O 3 doped CeO 2 (SDC) and La 1-x Sr x Co 1-y Fe y O 3-δ (LSCF), are assumed to effectively widen active sites, or triple phase boundaries, for the oxygen reduction reaction. Area specific resistance of commercially available cells has been decreased by 36-40% with the addition of 23 wt% PSCo electrocatalyst on cathode. Analysis of the impedance spectra demonstrates that PSCo electrocatalyst plays a significant role in dissociation of oxygen molecules and adsorption of oxygen atoms into the cathode. A total of 200 h operation of the cells demonstrated that catalytic activity of PSCo has not been significantly degraded. Simultaneous operations of multiple cells using a parallel-cell testing system have made it possible to compare the performance of several cells with high reliability.

Molten carbonate fuel cells fed with biogas: combating H(2)S.

Science.gov (United States)

Ciccoli, R; Cigolotti, V; Lo Presti, R; Massi, E; McPhail, S J; Monteleone, G; Moreno, A; Naticchioni, V; Paoletti, C; Simonetti, E; Zaza, F

2010-06-01

The use of biomass and waste to produce alternative fuels, due to environmental and energy security reasons, is a high-quality solution especially when integrated with high efficiency fuel cell applications. In this article we look into the coupling of an anaerobic digestion process of organic residues to electrochemical conversion to electricity and heat through a molten carbonate fuel cell (MCFC). In particular the pathway of the exceedingly harmful compound hydrogen sulphide (H(2)S) in these phases is analysed. Hydrogen sulphide production in the biogas is strongly interrelated with methane and/or hydrogen yield, as well as with operating conditions like temperature and pH. When present in the produced biogas, this compound has multiple negative effects on the performance and durability of an MCFC. Therefore, there are important issues of integration to be solved. Three general approaches to solve the sulphur problem in the MCFC are possible. The first is to prevent the formation of hydrogen sulphide at the source: favouring conditions that inhibit its production during fermentation. Secondly, to identify the sulphur tolerance levels of the fuel cell components currently in use and develop sulphur-tolerant components that show long-term electrochemical performance and corrosion stability. The third approach is to remove the generated sulphur species to very low levels before the gas enters the fuel cell. Copyright 2010 Elsevier Ltd. All rights reserved.

Metal- and Carbon-Based Materials as Heterogeneous Electrocatalysts for CO₂ Reduction.

Science.gov (United States)

Khan, Azam; Ullah, Haseeb; Nasir, Jamal Abdul; Shuda, Suzanne; Chen, Wei; Khan, M Abdullah

2018-05-01

Climate change caused by continuous rising level of CO2 and the depletion of fossil fuels reserves has made it highly desirable to electrochemically convert CO2 into fuels and commodity chemicals. Implementing this approach will close the carbon cycle by recycling CO2 providing a sustainable way to store energy in the chemical bonds of portable molecular fuels. In order to make the process commercially viable, the challenge of slow kinetics of CO2 electroreduction and low energy efficiency of the process need to be addressed. To this end, this review summarizes the progress made in the past few years in the development of heterogeneous electrocatalysts with a focus on nanostructured material for CO2 reduction to CO, HCOOH/HCOO-, CH2O, CH4, H2C2O4/HC2O-4, C2H4, CH3OH, CH3CH2OH, etc. The electrocatalysts presented here are classified into metals, metal alloys, metal oxides, metal chalcogenides and carbon based materials on the basis of their elemental composition, whose performance is discussed in light of catalyst activity, product selectivity, Faradaic efficiency (FE), catalytic durability and in selected cases mechanism of CO2 electroreduction. The effect of particle size, morphology and solution-electrolyte type and composition on the catalyst property/activity is also discussed and finally some strategies are proposed for the development of CO2 electroreduction catalysts. The aim of this article is to review the recent advances in the field of CO2 electroreduction in order to further facilitate research and development in this area.

PEM-fuel cells for mobile application. Sub task: development of electrocatalysts. Final report; PEM-Brennstoffzelle fuer mobile Anwendung. Teilprojekt: Katalysatorenentwicklung. Abschlussbericht

Energy Technology Data Exchange (ETDEWEB)

Starz, K A

1999-01-01

PEM fuel cells are gaining increasing importance for use in automotive application. The goal of the research program reported here was to develop the basic technology and components for PEMFC stacks for use in transport applications. The sub-task of Degussa was to develop improved electrocatalysts for PEMFC single cells and stacks. The technical objectives of the research project were met. Electrocatalysts, characterized by a high Pt-dispersion, high surface area and excellent activity, were developed. With this material, considerable progress was made to reduce the total platinum loading of PEMFC cells and stacks to about 0,5 mgPt/cm{sup 2}. With this value, the goal of the program (<0,8 mg/cm{sup 2}) was significantly surpassed. Additionally, higher power densities of >0.4 W/cm{sup 2} were achieved at Degussa for hydrogen/air and reformate/air operation of the PEMFC. A CO-tolerant anode electrocatalyst, exhibiting a CO-tolerance of up to 100 ppm CO, enables the operation of PEMFC stacks with on-board generated methanol reformate. The performance of the new electrocatalyst materials was verified by DaimlerChrysler in a PEMFC demonstration stack at the end of the program. (orig.) [Deutsch] PEM-Brennstoffzellen gewinnen fuer die mobile Anwendung immer mehr an Bedeutung. Im Rahmen des hier beschriebenen Leitprojektes sollten die Basistechnologien fuer den Einsatz der PEM-Brennstoffzelle im mobilen Bereich (Elektrotraktion) entwickelt werden. Das Teilprojekt der Degussa befasst sich mit der Entwicklung von verbesserten Elektrokatalysatoren fuer PEM-Brennstoffzellenstacks. Die technischen Arbeitsziele des Vorhabens wurden erreicht. So konnten Elektrokatalysatoren bereitgestellt werden, die sich durch eine hohe Pt-Dispersion, eine grosse Pt-Oberflaeche sowie eine sehr gute Aktivitaet auszeichnen. Mit diesen Elektrokatalysatoren gelang es, die Platinbeladung der PEM-Elektroden (Anode und Kathode) erheblich abzusenken. Mit einer Gesamtplatinbeladung von 0,5 mg/cm{sup 2

First report of vertically aligned (Sn,Ir)O2:F solid solution nanotubes: Highly efficient and robust oxygen evolution electrocatalysts for proton exchange membrane based water electrolysis

Science.gov (United States)

Ghadge, Shrinath Dattatray; Patel, Prasad P.; Datta, Moni K.; Velikokhatnyi, Oleg I.; Shanthi, Pavithra M.; Kumta, Prashant N.

2018-07-01

One dimensional (1D) vertically aligned nanotubes (VANTs) of (Sn0.8Ir0.2)O2:10F are synthesized for the first time by a sacrificial template assisted approach. The aim is to enhance the electrocatalytic activity of F doped (Sn,Ir)O2 solid solution electrocatalyst for oxygen evolution reaction (OER) in proton exchange membrane (PEM) based water electrolysis by generating (Sn0.8Ir0.2)O2:10F nanotubes (NTs). The 1D vertical channels and the high electrochemically active surface area (ECSA ∼38.46 m2g-1) provide for facile electron transport. This results in low surface charge transfer resistance (4.2 Ω cm2), low Tafel slope (58.8 mV dec-1) and excellent electrochemical OER performance with ∼2.3 and ∼2.6 fold higher electrocatalytic activity than 2D thin films of (Sn0.8Ir0.2)O2:10F and benchmark IrO2 electrocatalysts, respectively. Furthermore, (Sn0.8Ir0.2)O2:10F NTs exhibit excellent mass activity (21.67 A g-1), specific activity (0.0056 mAcm-2) and TOF (0.016 s-1), which is ∼2-2.6 fold higher than thin film electrocatalysts at an overpotential of 270 mV, with a total mass loading of 0.3 mg cm-2. In addition, (Sn0.8Ir0.2)O2:10F NTs demonstrate remarkable electrochemical durability - comparable to thin films of (Sn0.8Ir0.2)O2:10F and pure IrO2, operated under identical testing conditions in PEM water electrolysis. These results therefore indicate promise of (Sn0.8Ir0.2)O2:10F NTs as OER electrocatalysts for efficient and sustainable hydrogen production.

Relative importance of H2 and H2S as energy sources for primary production in geothermal springs.

Science.gov (United States)

D'Imperio, Seth; Lehr, Corinne R; Oduro, Harry; Druschel, Greg; Kühl, Michael; McDermott, Timothy R

2008-09-01

Geothermal waters contain numerous potential electron donors capable of supporting chemolithotrophy-based primary production. Thermodynamic predictions of energy yields for specific electron donor and acceptor pairs in such systems are available, although direct assessments of these predictions are rare. This study assessed the relative importance of dissolved H(2) and H(2)S as energy sources for the support of chemolithotrophic metabolism in an acidic geothermal spring in Yellowstone National Park. H(2)S and H(2) concentration gradients were observed in the outflow channel, and vertical H(2)S and O(2) gradients were evident within the microbial mat. H(2)S levels and microbial consumption rates were approximately three orders of magnitude greater than those of H(2). Hydrogenobaculum-like organisms dominated the bacterial component of the microbial community, and isolates representing three distinct 16S rRNA gene phylotypes (phylotype = 100% identity) were isolated and characterized. Within a phylotype, O(2) requirements varied, as did energy source utilization: some isolates could grow only with H(2)S, some only with H(2), while others could utilize either as an energy source. These metabolic phenotypes were consistent with in situ geochemical conditions measured using aqueous chemical analysis and in-field measurements made by using gas chromatography and microelectrodes. Pure-culture experiments with an isolate that could utilize H(2)S and H(2) and that represented the dominant phylotype (70% of the PCR clones) showed that H(2)S and H(2) were used simultaneously, without evidence of induction or catabolite repression, and at relative rate differences comparable to those measured in ex situ field assays. Under in situ-relevant concentrations, growth of this isolate with H(2)S was better than that with H(2). The major conclusions drawn from this study are that phylogeny may not necessarily be reliable for predicting physiology and that H(2)S can dominate over H(2

pH tolerance in freshwater bacterioplankton: trait variation of the community as measured by leucine incorporation.

Science.gov (United States)

Bååth, Erland; Kritzberg, Emma

2015-11-01

pH is an important factor determining bacterial community composition in soil and water. We have directly determined the community tolerance (trait variation) to pH in communities from 22 lakes and streams ranging in pH from 4 to 9 using a growth-based method not relying on distinguishing between individual populations. The pH in the water samples was altered to up to 16 pH values, covering in situ pH ± 2.5 U, and the tolerance was assessed by measuring bacterial growth (Leu incorporation) instantaneously after pH adjustment. The resulting unimodal response curves, reflecting community tolerance to pH, were well modeled with a double logistic equation (mean R(2) = 0.97). The optimal pH for growth (pHopt) among the bacterial communities was closely correlated with in situ pH, with a slope (0.89 ± 0.099) close to unity. The pH interval, in which growth was ≥90% of that at pHopt, was 1.1 to 3 pH units wide (mean 2.0 pH units). Tolerance response curves of communities originating from circum-neutral pH were symmetrical, whereas in high-pH (8.9) and especially in low-pH (pH waters, decreasing pH was more detrimental for bacterial growth than increasing pH, with a tendency for the opposite for high-pH waters. A pH tolerance index, using the ratio of growth at only two pH values (pH 4 and 8), was closely related to pHopt (R(2) = 0.83), allowing for easy determination of pH tolerance during rapid changes in pH. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Preparation and characterization of Pt–CeO{sub 2}/C and Pt–TiO{sub 2}/C electrocatalysts with improved electrocatalytic activity for methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Hameed, R.M. Abdel [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Amin, R.S. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt); El-Khatib, K.M., E-mail: Kamelced@hotmail.com [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt); Fetohi, Amani E. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)

2016-03-30

Graphical abstract: - Highlights: • Adding TiO{sub 2} or CeO{sub 2} to Pt/C reduced its Pt particle size. • Methanol oxidation current density decreased as Pt–CeO{sub 2}/C > Pt–TiO{sub 2}/C > Pt/C. • Decreased R{sub ct} values were observed at Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C. - Abstract: Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C electrocatalysts were synthesized by solid state reaction of TiO{sub 2}/C and CeO{sub 2}/C powders using intermittent microwave heating, followed by chemical reduction of platinum ions using mixed reducing agents of ethylene glycol and sodium borohydride. The crystal structure, surface morphology and chemical composition of prepared electrocatalysts were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX). The phase angle values of different Pt diffraction planes in Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C were shifted in the positive direction relative to those in Pt/C. Pt particles with diameter values of 3.06 and 2.78 nm were formed in Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C, respectively. The electrochemical performance of prepared electrocatalysts was examined using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Pt–CeO{sub 2}/C showed an enhanced oxidation current density when compared to Pt/C. Long time oxidation test at Pt–TiO{sub 2}/C and Pt–CeO{sub 2}/C revealed their improved stability. Lower charge transfer resistance values were estimated at Pt–metal oxide/C electrocatalysts.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

Preparation of PtRu/C anode electrocatalysts using gamma radiation for methanol electro-oxidation

International Nuclear Information System (INIS)

Silva, Dionisio Fortunato da

2006-01-01

Pt Ru/C (carbon-supported Pt Ru nanoparticles) anode electrocatalysts were prepared using radiolytic process (gamma radiation) and tested for methanol electro-oxidation. In this process, water/2-propanol and water/ethylene glycol solutions containing the metallic ions and the carbon support were submitted to gamma radiation under stirring. The water/alcohol ratio (v/v) and the total dose (kGy) were studied. A nominal Pt Ru atomic ratio of 50:50 were used in all experiments. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). The electro-oxidation of methanol was studied by cyclic voltammetry using the thin porous coating technique. The electrocatalysts prepared in water/2-propanol showed crystallite size in the range of 3-5 nm and Pt Ru atomic ratio of 50:50. The electrocatalysts prepared in water/ethylene glycol showed crystallite size (2-3 nm) smaller than the ones obtained in water/2-propanol, however, the Pt Ru atomic ratios obtained were approximately 80:20, showing that only part of ruthenium ions were reduced. For methanol oxidation the electrocatalytic activity depends on the water/2-propanol and water/ethylene glycol ratio used in the reaction medium. The electrocatalysts prepared in water/2-propanol showed inferior performance to the ones prepared in water/ethylene glycol, which showed similar or superior performances (amperes per gram of platinum) to the commercial electrocatalyst from E-TEK. (author)

Homogeneously Dispersed Co9S8 Anchored on Nitrogen and Sulfur Co-Doped Carbon Derived from Soybean as Bifunctional Oxygen Electrocatalysts and Supercapacitors.

Science.gov (United States)

Xiao, Zhen; Xiao, Guozheng; Shi, Minhao; Zhu, Ying

2018-05-16

Developing low-cost and highly active multifunctional electrocatalysts to replace noble metal catalysts is crucial for the commercialization of future clean energy technology. Herein, homogeneous Co 9 S 8 nanoparticles anchored on nitrogen and sulfur co-doped porous carbon nanomaterials (CoS@NSCs) are fabricated by pyrolysis of natural soybean treated with cobalt nitrate. The unique porous structures of the soybean are utilized to provide space for the oxidation and complexation reactions for cobalt compounds, thus leading to in situ generation of homogenously dispersed cobalt sulfide nanoparticles that anchored on the N,S co-doped carbon framework. Because of the coupling effect of cobalt sulfide and doping heteroatoms, CoS@NSC-800 not only displays excellent electrocatalytic performances with low overpotential and high current density toward both oxygen reduction reaction and oxygen evolution reaction comparable to the commercial Pt/C catalyst and IrO 2 catalyst, but also might be a promising candidate for high-performance supercapacitors. The method for the preparation of the multifunctional hybrids is simple but effective for the formation of uniformly distributed metal sulfide nanoparticles anchored on carbon materials, therefore providing a new perspective for the design and synthesis of multifunctional electrocatalysts for electrochemical energy conversion and storage at a large scale.

WS_2 nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

International Nuclear Information System (INIS)

Han, Guan-Qun; Liu, Yan-Ru; Hu, Wen-Hui; Dong, Bin; Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi; Liu, Chen-Guang

2015-01-01

WS_2 nanosheets (WS_2 NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS_2 (E-WS_2). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS_2 consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS_2, with a low overpotential of 80 mV and high current density (10 mA cm"−"2, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS_2 for HER. • E-WS_2 shows the better electrocatalytic activity than bulk WS_2. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

Large-area MoS2 grown using H2S as the sulphur source

International Nuclear Information System (INIS)

Dumcenco, Dumitru; Ovchinnikov, Dmitry; Lopez Sanchez, Oriol; Kis, Andras; Gillet, Philippe; Alexander, Duncan T L; Lazar, Sorin; Radenovic, Aleksandra

2015-01-01

We report on the growth of molybdenum disulphide (MoS 2 ) using H 2 S as a gas-phase sulfur precursor that allows controlling the domain growth direction of domains in both vertical (perpendicular to the substrate plane) and horizontal (within the substrate plane), depending on the H 2 S:H 2 ratio in the reaction gas mixture and temperature at which they are introduced during growth. Optical and atomic force microscopy measurements on horizontal MoS 2 demonstrate the formation of monolayer triangular-shape domains that merge into a continuous film. Scanning transmission electron microscopy of monolayer MoS 2 shows a regular atomic structure with a hexagonal symmetry. Raman and photoluminescence spectra confirm the monolayer thickness of the material. Field-effect transistors fabricated on MoS 2 domains that are transferred onto Si/SiO 2 substrates show a mobility similar to previously reported exfoliated and chemical vapor deposition-grown materials. (paper)

Molybdenum sulphides on carbon supports as electrocatalysts for hydrogen evolution in acidic industrial wastewater

International Nuclear Information System (INIS)

Kokko, M.; Bayerköhler, F.; Erben, J.; Zengerle, R.; Kurz, Ph.; Kerzenmacher, S.

2017-01-01

Highlights: • MoS_x is an efficient and durable catalyst for H_2 evolution in acidic wastewater. • MoS_x outperformed Pt as H_2-catalyst in long term in acidic wastewater. • Improved activity over time was likely due to changes in MoS_x structure. - Abstract: Microbial electrolysis cells (MECs) are an attractive future alternative technology to generate renewable hydrogen and simultaneously treat wastewaters. The thermodynamics of hydrogen evolution in MECs can be greatly improved by operating the cathode at acidic pH in combination with a neutral pH microbial anode. This can easily be achieved with acidic industrial wastewaters that have to be neutralised before discharge. For the hydrogen evolution reaction (HER) in acidic wastewater, efficient and inexpensive catalysts are required that are compatible with the often complex chemical composition of wastewaters. In this study, molybdenum sulphides (MoS_x) on different carbon supports were successfully used for hydrogen evolution in different acidic media. At first, the cathodes were screened by linear sweep voltammetry in sulphuric acid (pH 0) or phosphate buffer (pH 2.2). After this, the overpotentials for H_2 production of the best cathodes and their long term performances (⩾1 week) were determined in acidic industrial wastewater (pH 2.4) obtained from a plant mainly producing cellulose acetate. For the most promising MoS_x cathodes, the overpotentials for HER (at 3 mA cm"−"2) were only ∼40 mV higher than for a platinum electrode. Most importantly, the catalytic efficiency of the MoS_x electrodes improved in the wastewater over time (7–17 days), while Pt electrodes were found to be slowly deactivated. Thus, MoS_x emerges as an affordable, efficient and especially durable electrocatalyst for HER in real acidic wastewaters and this could be an important contribution to take energy production from wastewaters in the form of hydrogen towards practical applications.

A permselective CeO{sub x} coating to improve the stability of oxygen evolution electrocatalysts

Energy Technology Data Exchange (ETDEWEB)

Obata, Keisuke; Takanabe, Kazuhiro [King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Division PSE, Thuwal (Saudi Arabia)

2018-02-05

Highly active NiFeO{sub x} electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time owing to the loss of Fe species from the active sites into solution during catalysis. The anodic deposition of a CeO{sub x} layer prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeO{sub x} layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH{sup -} and O{sub 2} through while preventing the diffusion of redox ions through the layer to function as a selective O{sub 2}-evolving electrode. The use of such a permselective protective layer provides a new strategy for improving the durability of electrocatalysts. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

A new method to synthesize sulfur-doped graphene as effective metal-free electrocatalyst for oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Zhai, Chunyang; Sun, Mingjuan [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Zhu, Mingshan, E-mail: mingshanzhu@yahoo.com [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Song, Shaoqing [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China); Jiang, Shujuan, E-mail: sjjiang@ecit.edu.cn [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China)

2017-06-15

Highlights: • S doped graphene was facile synthesized by one-pot solvothermal method. • DMSO acted as S source as well as reaction solvent. • S-RGO worked as an efficient metal-free electrocatalyst for ORR. • S-RGO acted as a promising candidate instead of Pt-based catalyst. - Abstract: The exploration of a metal-free catalyst with highly efficient yet low-cost for the oxygen-reduction reaction (ORR) is under wide spread investigation. In this paper, by using dimethyl sulfoxide (DMSO) as S source as well as solvent, we report a new, low-cost, and facile solvothermal route to synthesize S-doped reduced graphene oxide (S-RGO). The existence of S element in the framework of RGO was solidly confirmed by energy-dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized S-RGO can be worked as an efficient metal-free electrocatalyst for ORR. Moreover, compared to commercial Pt/C electrocatalyst, the S-RGO displays superior resistance to crossover effect and stability by evaluating the addition of methanol and CO poisoning experiment. This result not only shows S-RGO as a promising candidate instead of Pt-based catalyst for ORR, but also provides a new approach for the preparation of metal-free electrocatalyst in future.

When NiO@Ni Meets WS2 Nanosheet Array: A Highly Efficient and Ultrastable Electrocatalyst for Overall Water Splitting.

Science.gov (United States)

Wang, Dewen; Li, Qun; Han, Ce; Xing, Zhicai; Yang, Xiurong

2018-01-24

The development of low-cost, high-efficiency, and stable bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance for large-scale water splitting. Here, we develop a new strategy for the first design and synthesis of a NiO@Ni decorated WS 2 nanosheet array on carbon cloth (NiO@Ni/WS 2 /CC) composite. This composite serves as a unique three-dimensional (3D) synergistic electrocatalyst that not only combines the intrinsic properties of individual NiO@Ni and WS 2 , but also exhibits significantly improved HER and OER activities when compared to that of pure NiO@Ni and WS 2 . This electrocatalyst possesses Pt-like activity for HER and exhibits better OER performance than that for commercial RuO 2 , as well as demonstrating superior long-term durability in alkaline media. Furthermore, it enables an alkaline electrolyzer with a current density of 10 mA cm -2 at a cell voltage as 1.42 V, which is the lowest one among all reported values to date. The excellent performance is mainly attributed to the unique 3D configuration and multicomponent synergies among NiO, Ni, and WS 2 . Our findings provide a new idea to design advanced bifunctional catalysts for water splitting.

Hydrogen Dynamics in Cyanobacteria Dominated Microbial Mats Measured by Novel Combined H2/H2S and H2/O2 Microsensors

Directory of Open Access Journals (Sweden)

Karen Maegaard

2017-10-01

Full Text Available Hydrogen may accumulate to micromolar concentrations in cyanobacterial mat communities from various environments, but the governing factors for this accumulation are poorly described. We used newly developed sensors allowing for simultaneous measurement of H2S and H2 or O2 and H2 within the same point to elucidate the interactions between oxygen, sulfate reducing bacteria, and H2 producing microbes. After onset of darkness and subsequent change from oxic to anoxic conditions within the uppermost ∼1 mm of the mat, H2 accumulated to concentrations of up to 40 μmol L-1 in the formerly oxic layer, but with high variability among sites and sampling dates. The immediate onset of H2 production after darkening points to fermentation as the main H2 producing process in this mat. The measured profiles indicate that a gradual disappearance of the H2 peak was mainly due to the activity of sulfate reducing bacteria that invaded the formerly oxic surface layer from below, or persisted in an inactive state in the oxic mat during illumination. The absence of significant H2 consumption in the formerly oxic mat during the first ∼30 min after onset of anoxic conditions indicated absence of active sulfate reducers in this layer during the oxic period. Addition of the methanogenesis inhibitor BES led to increase in H2, indicating that methanogens contributed to the consumption of H2. Both H2 formation and consumption seemed unaffected by the presence/absence of H2S.

Non-platinum electrocatalysts for PEM fuel cells

Energy Technology Data Exchange (ETDEWEB)

Lee, K.; Zhang, L.; Shi, Z.; Hui, R.; Zhang, J. [National Research Council of Canada, Vancouver, BC (Canada). Inst. For Fuel Cell Innovation

2008-07-01

High cost, low reliability and durability are the main barriers preventing widespread commercialization of fuel cells. In particular, the platinum (Pt)-based electrocatalysts used in proton exchange membrane (PEM) fuel cells, including direct methanol fuel cells (DMFCs) are major contributors to the high cost of PEM fuel cells. The Institute for Fuel Cell Innovation at the National Research Council of Canada has developed several new non-Pt electrocatalysts for PEM fuel cell applications. This paper presented the research results on these catalysts, including transition metal macrocycles, chalcogenides, and Ir- or Pd-based alloys. It also described catalyst structure modes via theoretical density functional theory (DFT) calculations. Research activities on these electrocatalysts was summarized in terms of catalytic activity and the oxygen reduction reaction (ORR). Typical catalysts such as cobalt(Co)-polypyrrole (PPy) and the chalcogenides show promising results in terms of catalytic activity and a 4-electron reaction mechanism. Efforts are underway to modify both catalyst structure and synthesis methods in order to further improve catalyst performance. 4 refs., 2 figs.

Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: pjampani@pitt.edu [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)

2016-10-15

Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

A role for H2S in the microcirculation of newborns: the major metabolite of H2S (thiosulphate is increased in preterm infants.

Directory of Open Access Journals (Sweden)

Rebecca M Dyson

Full Text Available Excessive vasodilatation during the perinatal period is associated with cardiorespiratory instability in preterm neonates. Little evidence of the mechanisms controlling microvascular tone during circulatory transition exists. We hypothesised that hydrogen sulphide (H2S, an important regulator of microvascular reactivity and central cardiac function in adults and animal models, may contribute to the vasodilatation observed in preterm newborns. Term and preterm neonates (24-43 weeks gestational age were studied. Peripheral microvascular blood flow was assessed by laser Doppler. Thiosulphate, a urinary metabolite of H2S, was determined by high performance liquid chromatography as a measure of 24 hr total body H2S turnover for the first 3 days of postnatal life. H2S turnover was greatest in very preterm infants and decreased with increasing gestational age (p = 0.0001. H2S turnover was stable across the first 72 hrs of life in older neonates. In very preterm neonates, H2S turnover increased significantly from day 1 to 3 (p =0.0001; and males had higher H2S turnover than females (p = 0.04. A significant relationship between microvascular blood flow and H2S turnover was observed on day 2 of postnatal life (p = 0.0004. H2S may play a role in maintaining microvascular tone in the perinatal period. Neonates at the greatest risk of microvascular dysfunction characterised by inappropriate peripheral vasodilatation--very preterm male neonates--are also the neonates with highest levels of total body H2S turnover suggesting that overproduction of this gasotransmitter may contribute to microvascular dysfunction in preterms. Potentially, H2S is a target to selectively control microvascular tone in the circulation of newborns.

Large-area snow-like MoSe2 monolayers: synthesis, growth mechanism, and efficient electrocatalyst application.

Science.gov (United States)

Huang, Jingwen; Liu, Huiqiang; Jin, Bo; Liu, Min; Zhang, Qingchun; Luo, Liqiong; Chu, Shijin; Chu, Sheng; Peng, Rufang

2017-07-07

This study explores the large-area synthesis of controllable morphology, uniform, and high-quality monolayer. MoSe 2 is essential for its potential application in optoelectronics, photocatalysis, and renewable energy sources. In this study, we successfully synthesized snow-like MoSe 2 monolayers using a simple chemical vapor deposition method. Results reveal that snow-like MoSe 2 is a single crystal with a hexagonal structure, a thickness of ∼0.9 nm, and a lateral dimension of up to 20 μm. The peak position of the photoluminescence spectra is ∼1.52 eV corresponding to MoSe 2 monolayer. The growth mechanism of the snow-like MoSe 2 monolayer was investigated and comprised a four-step process during growth. Finally, we demonstrate that the snow-like MoSe 2 monolayers are ideal electrocatalysts for hydrogen evolution reactions (HERs), reflected by a low Tafel slope of ∼68 mV/decade. Compared with the triangular-shaped MoSe 2 monolayer, the hexangular snow-like shape with plentiful edges is superior for perfect electrocatalysts for HERs or transmission devices of optoelectronic signals.

Evaluation of plasma H2S levels and H2S synthesis in streptozotocin induced Type-2 diabetes-an experimental study based on Swietenia macrophylla seeds

Directory of Open Access Journals (Sweden)

Moumita Dutta

2014-05-01

Conclusions: Although considering a small sample size, it can conclude that the fasting blood glucose levels are inversely related to plasma H2S levels as well as H2S synthesis activity in plasma and the extract of S. macrophylla is associated with increased plasma H2S levels with effective lowering of blood glucose in streptozotocin induced diabetic rats.

A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

KAUST Repository

Rasul, Shahid

2014-12-23

The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous CO2 conversion. A non-noble metal electrocatalyst based on a copper-indium (Cu-In) alloy that selectively converts CO2 to CO with a low overpotential is reported. The electrochemical deposition of In on rough Cu surfaces led to Cu-In alloy surfaces. DFT calculations showed that the In preferentially located on the edge sites rather than on the corner or flat sites and that the d-electron nature of Cu remained almost intact, but adsorption properties of neighboring Cu was perturbed by the presence of In. This preparation of non-noble metal alloy electrodes for the reduction of CO2 provides guidelines for further improving electrocatalysis.

A Highly Active and Alcohol-Tolerant Cathode Electrocatalyst Containing Ag Nanoparticles Supported on Graphene

International Nuclear Information System (INIS)

Jiang, Rongzhong; Moton, Elizabeth; McClure, Joshua P.; Bowers, Zachary

2014-01-01

A highly active oxygen reduction reaction (ORR) catalyst was synthesized by supporting Ag nano-particles on graphene nano platelets (Ag/GNP) via ultrasound treatment. The Ag/GNP catalyzes the O 2 molecule through a 4-electron reduction to water in 0.1 M KOH electrolyte. The half-wave potential for the ORR on Ag/GNP is similar to a Pt black coated electrode (i.e -0.27 V at Ag/GNP, and -0.18 V at 40% Pt/C vs.SCE). The kinetic rate for the ORR on Ag/GNP is 3.16 × 10 −2 cm · s −1 at -0.4 V vs. SCE. The effect of alcohols and other impurities on the ORR catalytic activity for Ag/GNP was examined and found to be highly tolerant to methanol, ethanol and ethylene glycol. The Ag/GNP catalyst is also tolerant to tetraalkyl ammonium hydroxides; i.e. functional groups related to the chemical structure of common alkaline electrolyte membranes

Functionalization of liquid-exfoliated two-dimensional 2H-MoS2.

Science.gov (United States)

Backes, Claudia; Berner, Nina C; Chen, Xin; Lafargue, Paul; LaPlace, Pierre; Freeley, Mark; Duesberg, Georg S; Coleman, Jonathan N; McDonald, Aidan R

2015-02-23

Layered two-dimensional (2D) inorganic transition-metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2 . We found that the reaction of liquid-exfoliated 2D MoS2 , with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2 -M(OAc)2 materials. Importantly, this method furnished the 2H-polytype of MoS2 which is a semiconductor. X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H-MoS2 allows for its dispersion/processing in more conventional laboratory solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical absorption of H2S for biogas purification

Directory of Open Access Journals (Sweden)

Horikawa M.S.

2004-01-01

Full Text Available This work presents an experimental study of purification of a biogas by removal of its hydrogen sulphide (H2S content. The H2S was removed by means of chemical absorption in an iron-chelated solution catalyzed by Fe/EDTA, which converts H2S into elemental sulphur (S. Preparation of the catalyst solution and the results of biogas component absorption in the catalyst solution (0.2 mol/L are presented. These results are compared with those for physical absorption into pure water under similar conditions. Experimental results demonstrate that, under the same experimental conditions, a higher percentage of H2S can be removed in the catalytic solution than in water. In a continuous counter current using adequate flow-rate phases contact at room temperature and low gas pressure, the results demonstrate that is possible to totally remove the H2S from the biogas with the prepared catalytic solution.

When NiO@Ni Meets WS2 Nanosheet Array: A Highly Efficient and Ultrastable Electrocatalyst for Overall Water Splitting

Directory of Open Access Journals (Sweden)

Dewen Wang

2017-12-01

Full Text Available The development of low-cost, high-efficiency, and stable bifunctional electrocatalysts toward the hydrogen evolution reaction (HER and oxygen evolution reaction (OER is of paramount importance for large-scale water splitting. Here, we develop a new strategy for the first design and synthesis of a NiO@Ni decorated WS2 nanosheet array on carbon cloth (NiO@Ni/WS2/CC composite. This composite serves as a unique three-dimensional (3D synergistic electrocatalyst that not only combines the intrinsic properties of individual NiO@Ni and WS2, but also exhibits significantly improved HER and OER activities when compared to that of pure NiO@Ni and WS2. This electrocatalyst possesses Pt-like activity for HER and exhibits better OER performance than that for commercial RuO2, as well as demonstrating superior long-term durability in alkaline media. Furthermore, it enables an alkaline electrolyzer with a current density of 10 mA cm–2 at a cell voltage as 1.42 V, which is the lowest one among all reported values to date. The excellent performance is mainly attributed to the unique 3D configuration and multicomponent synergies among NiO, Ni, and WS2. Our findings provide a new idea to design advanced bifunctional catalysts for water splitting.

H2S and polysulfide metabolism: Conventional and unconventional pathways.

Science.gov (United States)

Olson, Kenneth R

2018-03-01

It is now well established that hydrogen sulfide (H 2 S) is an effector of a wide variety of physiological processes. It is also clear that many of the effects of H 2 S are mediated through reactions with cysteine sulfur on regulatory proteins and most of these are not mediated directly by H 2 S but require prior oxidation of H 2 S and the formation of per- and polysulfides (H 2 S n , n = 2-8). Attendant with understanding the regulatory functions of H 2 S and H 2 S n is an appreciation of the mechanisms that control, i.e., both increase and decrease, their production and catabolism. Although a number of standard "conventional" pathways have been described and well characterized, novel "unconventional" pathways are continuously being identified. This review summarizes our current knowledge of both the conventional and unconventional. Copyright © 2017 Elsevier Inc. All rights reserved.

The solubility of gold in H 2 O-H 2 S vapour at elevated temperature and pressure

Science.gov (United States)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2011-09-01

This experimental study sheds light on the complexation of gold in reduced sulphur-bearing vapour, specifically, in H 2O-H 2S gas mixtures. The solubility of gold was determined in experiments at temperatures of 300, 350 and 365 °C and reached 2.2, 6.6 and 6.3 μg/kg, respectively. The density of the vapour varied from 0.02 to 0.22 g/cm 3, the mole fraction of H 2S varied from 0.03 to 0.96, and the pressure in the cell reached 263 bar. Statistically significant correlations of the amount of gold dissolved in the fluid with the fugacity of H 2O and H 2S permit the experimental data to be fitted to a solvation/hydration model. According to this model, the solubility of gold in H 2O-H 2S gas mixtures is controlled by the formation of sulphide or bisulphide species solvated by H 2S or H 2O molecules. Formation of gold sulphide species is favoured statistically over gold bisulphide species and thus the gold is interpreted to dissolve according to reactions of the form: Au(s)+(n+1)HS(g)=AuS·(HS)n(g)+H(g) Au(s)+HS(g)+mHO(g)=AuS·(HO)m(g)+H(g) Equilibrium constants for Reaction (A1) and the corresponding solvation numbers ( K A1 and n) were evaluated from the study of Zezin et al. (2007). The equilibrium constants as well as the hydration numbers for Reaction (A2) ( K A2 and m) were adjusted simultaneously by a custom-designed optimization algorithm and were tested statistically. The resulting values of log K A2 and m are -15.3 and 2.3 at 300 and 350 °C and -15.1 and 2.2 at 365 °C, respectively. Using the calculated stoichiometry and stability of Reactions (A1) and (A2), it is now possible to quantitatively evaluate the contribution of reduced sulphur species to the transport of gold in aqueous vapour at temperatures up to 365 °C. This information will find application in modelling gold ore-forming processes in vapour-bearing magmatic hydrothermal systems, notably those of epithermal environments.

Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

Science.gov (United States)

Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

2016-08-01

Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

Synthesis and evaluation of Pt-alloys supported on MWCNTS as ethylene glycol-tolerant ORR cathodes

Energy Technology Data Exchange (ETDEWEB)

Morales-Acosta, D.; Arriaga, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico); Alvarez-Contreras, L. [Centro de Investigacion en Materiales Avanzados S. C., Chihuahua, Chihuahua (Mexico); Fraire Luna, S.; Rodriguez Varela, F.J. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila (Mexico)]. E-mail: javier.varela@cinvestav.edu.mx

2009-09-15

In this work, a Pt-Co/MWCNT alloy (atomic ratio 70:30) was synthesized and evaluated as oxygen reduction reaction (ORR) cathode for Direct Ethylene Glycol Fuel Cells (DEGFC) applications. The alloy showed good performance for the ORR in acid medium, while in the presence of 0.125M EG (C{sub 2}H{sub 6}O{sub 2}) the MWCNTs-supported electrocatalyst showed a very high selectivity for the cathodic reaction and a high degree of tolerance to the organic fuel, i.e., a very small shift in the onset potential for the ORR, Eonset, and no peak current densities associated to the oxidation of EG, a detrimental effect of organic fuels normally observed in the case of Pt-alone electrocatalysts. [Spanish] En este trabajo, se sintetizo y evaluo una aleacion Pt-Co/NTCMP (razon atomica 70/30) como catodo de reaccion de reduccion de oxigeno (RRO) para aplicaciones de celdas de combustible de glicol de etileno directo (CCGED). La aleacion mostro buen desempeno para la RRO en medio acido, en tanto que la presencia de 0.125M de GE (C{sub 2}H{sub 6}O{sub 2}) del electrocatalizador soportado por NTCMP mostro una muy alta selectividad para la reaccion catodica y un alto grado de tolerancia al combustible organico, es decir, un corrimiento muy pequeno del potencial de inicio para la RRO, Einicio, y no densidades de corriente asociadas a la oxidacion del GE, efecto perjudicial de los combustibles organicos que se observa en el caso del electrocatalizadores solo de Pt.

WS{sub 2} nanosheets based on liquid exfoliation as effective electrocatalysts for hydrogen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Han, Guan-Qun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yan-Ru; Hu, Wen-Hui [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Chai, Yong-Ming; Liu, Yun-Qi [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

2015-11-01

WS{sub 2} nanosheets (WS{sub 2} NSs) as electrocatalysts for hydrogen evolution reaction (HER) have been prepared based on liquid exfoliation in dimethyl-formamide (DMF) via a direct dispersion and ultrasonication method. X-ray diffraction (XRD) shows the decreasing crystalline of the exfoliated WS{sub 2} (E-WS{sub 2}). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the as prepared E-WS{sub 2} consists of a few two-dimensional nanosheets, with large wrinkles on the surface. Electrochemical measurements show an excellent activity and stability of the E-WS{sub 2}, with a low overpotential of 80 mV and high current density (10 mA cm{sup −2}, at η = 205 mV), which indicates that through the process of exfoliation in DMF, both the dispersion and the amount of active sites have been improved greatly. Therefore, DMF is a promising alternative for exfoliating two-dimensional nanomaterials for highly efficient HER electrocatalysts. - Highlights: • A facile exfoliation process in DMF has been used to prepare E-WS{sub 2} for HER. • E-WS{sub 2} shows the better electrocatalytic activity than bulk WS{sub 2}. • DMF provides a promising alternative for enhancing exfoliation of 2D materials.

Endogenous mitigation of H2S inside of the landfills.

Science.gov (United States)

Fang, Yuan; Zhong, Zhong; Shen, Dongsheng; Du, Yao; Xu, Jing; Long, Yuyang

2016-02-01

Vast quantities of hydrogen sulfide (H2S) emitted from landfill sites require urgent disposal. The current study focused on source control and examined the migration and conversion behavior of sulfur compounds in two lab-scale simulated landfills with different operation modes. It aimed to explore the possible strategies and mechanisms for H2S endogenous mitigation inside of landfills during decomposition. It was found that the strength of H2S emissions from the landfill sites was dependent on the municipal solid waste (MSW) degradation speed and vertical distribution of sulfide. Leachate recirculation can shorten both the H2S influence period and pollution risk to the surrounding environment. H2S endogenous mitigation may be achieved by chemical oxidation, biological oxidation, adsorption, and/or precipitation in different stages. Migration and conversion mainly affected H2S release behavior during the initial stabilization phase in the landfill. Microbial activities related to sulfur, nitrogen, and iron can further promote H2S endogenous mitigation during the high reducing phase. Thus, H2S endogenous mitigation can be effectively enhanced via control of the aforementioned processes.

Emission of Lyman α radiation in H2 + H*(2s) collisions at thermal energies

International Nuclear Information System (INIS)

Stern, B.

1991-01-01

A previously-published study of the thermal-energy collision between H 2 and metastable H*(2s), which could lead to the emission of Lyman α radiation, is reconsidered to take into account possible polarization effects. The total was function of the system is expanded in terms of the molecular states of the intermediate complex H 2 * , which constitute the minimal basis of the four adiabatic states dissociating into H 2 + H*(n=2) where they are normally degenerate in energy. The results of the calculation show the existence, between three of those states, of average values of the separation distance R (R ≅ 10 atomic units) of long range (ΔR ≅ 2 au) electronic interactions which depend on the geometric form of the H 2 * molecule. From the molecular data the hypothesis of no longer considering H 2 with H*(2s) as a rigid rotator is postulated and justified, after a purely quantum mechanical treatment of the radial equations. The mean ratio of the (oscillating) polarization angular differential cross sections tot he elastic ones is found important (> ∼ 1/10). The inelastic phenomena are anticipated to be more marked in the ortho than in the para hydrogen at a low collision energy (75 meV). (15 refs., 2 tabs., 9 figs.)

Development of PdM (M = Ni, Cu, Ag) electrocatalysts for oxygen reduction reaction in alkaline medium in the absence and presence of alcohol

International Nuclear Information System (INIS)

Isidoro, Roberta Alvarenga

2015-01-01

Pd/C, Pd Cu/C, Pd Ni/C and Pd Ag/C electrocatalysts were produced by microwave method to be used as cathode in alkaline fuel cell in the absence and presence of alcohol. This method showed to be effective for the materials production, the particles exhibited good dispersion in carbon support and it produced electrocatalysts with a particle size of about 3.5 nm, according to XRD and TEM analysis. In cyclic voltammetry is observed that Pd Cu/C and Pd Ni/C electrocatalysts has higher active area with higher amount of Cu and Ni, respectively. Rotating ring disk analysis in the electrocatalysts showed that the amount of peroxide produced was at most 4%. This data is similar to Koutecky-Levich analysis, once for both the ORR occurs via 4 electrons. Materials stability analysis showed that they kept or improve performance in ORR, comparing the data before and after 1000 voltammetric cycles. Tolerance tests in methanol and ethanol were performed in a half cell in all electrocatalysts compositions. In presence of methanol and ethanol the compositions 50:50, to all materials studied, showed less influence in the presence of alcohol in ORR linear scan. In alkaline fuel cell Pd Ag/C 70:30 showed better performance for ORR in presence of methanol and Pd Ni/C 70:30 showed better performance for ORR in ethanol presence. (author)

Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

Energy Technology Data Exchange (ETDEWEB)

Wen, Xiao-Ping; Dai, Hong-Bin, E-mail: mshbdai@scut.edu.cn; Wu, Lin-Song; Wang, Ping, E-mail: mspwang@scut.edu.cn

2017-07-01

Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N{sub 2}H{sub 4} electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N{sub 2}H{sub 4} as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

International Nuclear Information System (INIS)

Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

2017-01-01

Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N_2H_4 electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N_2H_4 as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

H2S-induced S-sulfhydration of pyruvate carboxylase contributes to gluconeogenesis in liver cells.

Science.gov (United States)

Ju, YoungJun; Untereiner, Ashley; Wu, Lingyun; Yang, Guangdong

2015-11-01

Cystathionine gamma-lyase (CSE)-derived hydrogen sulfide (H(2)S) possesses diverse roles in the liver, affecting lipoprotein synthesis, insulin sensitivity, and mitochondrial biogenesis. H(2)S S-sulfhydration is now proposed as a major mechanism for H(2)S-mediated signaling. Pyruvate carboxylase (PC) is an important enzyme for gluconeogenesis. S-sulfhydration regulation of PC by H(2)S and its implication in gluconeogenesis in the liver have been unknown. Gene expressions were analyzed by real-time PCR and western blotting, and protein S-sulfhydration was assessed by both modified biotin switch assay and tag switch assay. Glucose production and PC activity was measured with coupled enzyme assays, respectively. Exogenously applied H(2)S stimulates PC activity and gluconeogenesis in both HepG2 cells and mouse primary liver cells. CSE overexpression enhanced but CSE knockout reduced PC activity and gluconeogenesis in liver cells, and blockage of PC activity abolished H(2)S-induced gluconeogenesis. H(2)S had no effect on the expressions of PC mRNA and protein, while H(2)S S-sulfhydrated PC in a dithiothreitol-sensitive way. PC S-sulfhydration was significantly strengthened by CSE overexpression but attenuated by CSE knockout, suggesting that H(2)S enhances glucose production through S-sulfhydrating PC. Mutation of cysteine 265 in human PC diminished H(2)S-induced PC S-sulfhydration and activity. In addition, high-fat diet feeding of mice decreased both CSE expression and PC S-sulfhydration in the liver, while glucose deprivation of HepG2 cells stimulated CSE expression. CSE/H(2)S pathway plays an important role in the regulation of glucose production through S-sulfhydrating PC in the liver. Tissue-specific regulation of CSE/H(2)S pathway might be a promising therapeutic target of diabetes and other metabolic syndromes. Copyright © 2015 Elsevier B.V. All rights reserved.

Highly dispersed TaOx nanoparticles prepared by electrodeposition as oxygen reduction electrocatalysts for polymer electrolyte fuel cells

KAUST Repository

Seo, Jeongsuk

2013-06-06

Based on the chemical stability of group IV and V elements in acidic solutions, TaOx nanoparticles prepared by electrodeposition in an ethanol-based Ta plating bath at room temperature were investigated as novel nonplatinum electrocatalysts for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs). Electrodeposition conditions of Ta complexes and subsequent various heat treatments for the deposited TaOx were examined for the best performance of the ORR. TaOx particles on carbon black (CB), electrodeposited at a constant potential of -0.5 V Ag/AgCl for 10 s and then heat-treated by pure H2 flow at 523 K for 1 h, showed excellent catalytic activity with an onset potential of 0.93 VRHE (for 2 μA cm-2) for the ORR. Surface characterizations of the catalysts were performed by scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). The loading amounts of the electrodeposited material on the CB were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). All the physical results suggested that high dispersion of TaOx particles on the CB surface with 2-3 nm size was critical and key for high activity. The chemical identity and modified surface structure for the deposited TaOx catalysts before and after H 2 heat treatment were analyzed by X-ray photoelectron spectroscopy (XPS). The formation of more exposed active sites on the electrode surface and enhanced electroconductivity of the tantalum oxide promoted from the H 2 treatment greatly improved the ORR performance of the electrodeposited TaOx nanoparticles on CB. Finally, the highly retained ORR activity after an accelerated durability test in an acidic solution confirmed and proved the chemical stability of the oxide nanoparticles. The high utilization of the electrodeposited TaOx nanoparticles uniformly dispersed on CB for the ORR was comparable to that of commercial Pt/CB catalysts

Evaluation of Saccharomyces cerevisiae GAS1 with respect to its involvement in tolerance to low pH and salt stress.

Science.gov (United States)

Matsushika, Akinori; Suzuki, Toshihiro; Goshima, Tetsuya; Hoshino, Tamotsu

2017-08-01

We previously showed that overexpression of IoGAS1, which was isolated from the multiple stress-tolerant yeast Issatchenkia orientalis, endows Saccharomyces cerevisiae cells with the ability to grow and ferment under acidic and high-salt conditions. The deduced amino acid sequence of the IoGAS1 gene product exhibits 60% identity with the S. cerevisiae Gas1 protein, a glycosylphosphatidylinositol-anchored protein essential for maintaining cell wall integrity. However, the functional roles of ScGAS1 in stress tolerance and pH regulation remain unclear. In the present study, we characterized ScGAS1 regarding its roles in tolerance to low pH and high salt concentrations. Transcriptional analysis indicated that, as for the IoGAS1 gene, ScGAS1 expression was pH dependent, with maximum expression at pH 3.0; the presence of salt increased endogenous expression of both GAS1 genes at almost all pH levels. These results suggested that ScGAS1, like IoGAS1, is involved in a novel acid- and salt-stress adaptation mechanism in S. cerevisiae. Overexpression of ScGAS1 in S. cerevisiae improved growth and ethanol production from glucose under acid stress without added salt, although the stress tolerance of the ScGAS1-overexpressing strain was inferior to that of the IoGAS1-overexpressing strain. However, overexpression of ScGAS1 did not result in increased tolerance of S. cerevisiae to combined acid and salt stress, even though ScGAS1 appears to be a salt-responsive gene. Thus, ScGAS1 is directly implicated in tolerance to low pH but does not confer salinity tolerance, supporting the view that ScGAS1 and IoGAS1 have overlapping yet distinct roles in stress tolerance in yeast. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Plasmas pour la destruction de l'H2S et des mercaptans Plasmas for Destruction of H2s and Mercaptans

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Czernichowski A.

2006-12-01

Full Text Available Cet article passe en revue l'utilisation des plasmas comme milieu activateurs d'une oxydation de H2S ou CH3SH dilués dans l'air, le CO2 ou la vapeur d'eau, à fins de conversion en SO, moins malodorant. Le produit peut être ensuite utilisé comme réactif dans un processus similaire à celui de Claus, en présence d'eau, ce qui permet de convertir deux fois plus de polluants initiaux en soufre élémentaire. Une attention particulière est portée aux décharges électriques glissantes (GlidArc. Ces décharges puissantes produisent un plasma non thermique qui active des réactions oxydatrices. La plupart des expériences ont été réalisées en utilisant les réacteurs GlidArc-I à un ou à quatre étages. Les sulfures dilués dans l'air dans des concentrations initiales atteignant jusqu'à 1 %( H2S ou 0,1 % (CH3SH ont été traités sous des flux jusqu'à 70 m3(n/h d'air pollué et sous une puissance de 5 kW. Les essais ont été réalisés sous 1 atm. Une dépollution jusqu'à 100 % a été obtenue moyennant un coût énergétique assez bas dépendant de la concentration initiale du polluant : environ 1000 kWh par kilogramme de soufre extrait pour 100 ppm de H2S et seulement 10 kWh/kg pour 1 % initial d'H2S dans l'air. Pratiquement les mêmes coûts ont été observés dans le cas de mélanges CH3SH-air. En utilisant une très simple douche en recirculation d'eau qui lave les gaz sortants (l'eau se sature avec le SO2 et capture ainsi l'H2S non traité nous avons divisé ces coûts d'énergie par trois, en évitant également l'émission de SO2, et en obtenant du soufre non toxique. Un nouveau principe (et réacteur GlidArc-II est ensuite présenté ; il s'agit d'une brosseà décharges électriques. Nos premiers tests sont très prometteurs car dès à présent, nous divisons déjà la dépense énergétique par deux par rapport au GlidArc-I. L'échelle industrielle peut par conséquent être envisagée. Plasmas are reviewed as activation

A new global analytical potential energy surface of NaH2+ system and dynamical calculation for H(2S) + NaH+(X2Σ+) → Na+(1S) + H2(X1Σg+) reaction

Science.gov (United States)

Yuan, Meiling; Li, Wentao; Yuan, Jiuchuang

2018-05-01

A new global potential energy surface (PES) of the NaH2+ system is constructed by fitting 27,621 ab initio energy points with the neural network method. The root mean square error of the new PES is only 4.1609 × 10-4 eV. Based on the new PES, dynamical calculations have been performed using the time-dependent quantum wave packet method. These results are then compared with the H(2S) + LiH+(X2Σ+) → Li+(1S) + H2(X1Σg+) reaction. The direct abstract mechanism is found to play an important role in the reaction because only forward scattering signals on the differential cross section results for all calculated collision energies.

Electrocatalyst advances for hydrogen oxidation in phosphoric acid fuel cells

Science.gov (United States)

Stonehart, P.

1984-01-01

The important considerations that presently exist for achieving commercial acceptance of fuel cells are centered on cost (which translates to efficiency) and lifetime. This paper addresses the questions of electrocatalyst utilization within porous electrode structures and the preparation of low-cost noble metal electrocatalyst combinations with extreme dispersions of the metal. Now that electrocatalyst particles can be prepared with dimensions of 10 A, either singly or in alloy combinations, a very large percentage of the noble metal atoms in a crystallite are available for reaction. The cost savings for such electrocatalysts in the present commercially driven environment are considerable.

Preparation of PtSn/C, PtRu/C, PtRh/C, PtRuRh/C and PtSnRh/C electrocatalysts using an alcohol-reduction process for methanol and ethanol oxidation

International Nuclear Information System (INIS)

Dias, Ricardo Rodrigues

2009-01-01

In this work, Pt/C, PtRh (90:10), PtRh/C (50:50), PtSn/C (50:50), PtRu (50:50)/C, PtRuRh/C (50:40:10) and PtSnRh/C (50:40:10) were prepared by an alcohol-reduction process with metal loading of 20 wt.% using H 2 PtCl 6 .6H 2 O (Aldrich), SnCl 2 .2H 2 O (Aldrich),and RhCl 2 .XH 2 O (Aldrich) as metals sources and Vulcan XC72 as support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry (CV). The electro-oxidation of ethanol was studied by CV, chronoamperomety at room temperature in acid medium and tests at 100 deg C on a single cell of a direct methanol or ethanol fuel cell. The EDX analysis showed that the metal atomic ratios of the obtained electrocatalysts were similar to the nominal atomic ratios used in the preparation. The diffractograms of electrocatalysts prepared showed four peaks at approximately 2θ = 40 0 , 47 0 , 67 0 and 82 0 , which are associated with the (111), (200), (220) and (311) planes, respectively, of a face cubic-centered (fcc) structure characteristic of platinum and platinum alloys. The average crystallite sizes using the Scherrer equation and the calculated values were in the range of 2–3 nm. For PtSn/C and PtSnRh/C two additional peaks were observed at 2θ = 34 0 and 52 0 that were identified as a SnO 2 phase. PtSn/C (50:50) and PtSnRh/C (50:40:10) electrocatalyst showed the best performance for ethanol oxidation at room temperature. For methanol oxidation at room temperature PtRu/C, PtSn/C and PtRuRh/C electrocatalysts showed the best performance. Tests at 100 deg C on a single cell of a direct ethanol fuel cell PtSnRh/C showed the best performance, for methanol oxidation PtRuRh/C showed the best performance. (author)

The novel sRNA s015 improves nisin yield by increasing acid tolerance of Lactococcus lactis F44.

Science.gov (United States)

Qi, Jiakun; Caiyin, Qinggele; Wu, Hao; Tian, Kairen; Wang, Binbin; Li, Yanni; Qiao, Jianjun

2017-08-01

Nisin, a polycyclic antibacterial peptide produced by Lactococcus lactis, is stable at low pH. Improving the acid tolerance of L. lactis could thus enhance nisin yield. Small non-coding RNAs (sRNAs) play essential roles in acid tolerance by regulating their target mRNAs at the post-transcriptional level. In this study, a novel sRNA, s015, was identified in L. lactis F44 via the use of RNA sequencing, qRT-PCR analysis, and Northern blotting. s015 improved the acid tolerance of L. lactis and boosted nisin yield at low pH. In silico predictions enabled us to construct a library of possible s015 target mRNAs. Statistical analysis and validation suggested that s015 contains a highly conserved region (5'-GAAAAAAAC-3') that likely encompasses the regulatory core of the sRNA. atpG, busAB, cysD, ilvB, tcsR, ung, yudD, and ywdA were verified as direct targets of s015, and the interactions between s015 and its target genes were elucidated. This work provided new insight into the adaptation mechanism of L. lactis under acid stress.

Highly Stable and Active Pt/Nb-TiO2 Carbon-Free Electrocatalyst for Proton Exchange Membrane Fuel Cells

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Shuhui Sun

2012-01-01

Full Text Available The current materials used in proton exchange membrane fuel cells (PEMFCs are not sufficiently durable for commercial deployment. One of the major challenges lies in the development of an inexpensive, efficient, and highly durable and active electrocatalyst. Here a new type of carbon-free Pt/Nb-TiO2 electrocatalyst has been reported. Mesoporous Nb-TiO2 hollow spheres were synthesized by the sol-gel method using polystyrene (PS sphere templates. Pt nanoparticles (NPs were then deposited onto mesoporous Nb-TiO2 hollow spheres via a simple wet-chemical route in aqueous solution, without the need for surfactants or potentiostats. The growth densities of Pt NPs on Nb-TiO2 supports could be easily modulated by simply adjusting the experimental parameters. Electrochemical studies of Pt/Nb-TiO2 show much enhanced activity and stability than commercial E-TEK Pt/C catalyst. PtNP/Nb-TiO2 is a promising new cathode catalyst for PEMFC applications.

Degradation kinetics of monoethanolamine during CO2 and H2 S absorption from biogas

Directory of Open Access Journals (Sweden)

Preecha Kasikamphaiboon

2015-02-01

Full Text Available The rate of degradation of MEA during CO2 and H2 S absorption in the biogas upgrading process was examined in four degradation systems, i.e., MEA-CO2 , MEA-CO2 -O2 , MEA-CO2 -H2 S and MEA-CO2 -O2 -H2 S. Degradation experiments were performed in a 800-ml stainless steel autoclave reactor, using MEA concentrations of 3 and 5 mol/L, CO2 loadings of 0.4 and 0.5 mol CO2 /mol MEA, O2 pressure of 200 kPa, and H2 S concentrations of 84 and 87 mg/L at temperatures of 120 and 140C. The results showed that, for the MEA-CO2 system, an increase in temperature or MEA concentration resulted in a higher rate of MEA degradation. In contrast, an increase in CO2 loading in the MEA-CO2 -O2 system led to a reduction of MEA degradation. The degradation rate of the system with O2 was with 8.3 times as high as that of the system without O2 . The presence of H2 S did not appear to affect the rate of degradation in the MEA-CO2 -H2 S system. However, for the system in which both H2 S and O2 were present, the MEA degradation was additionally induced by H2 S, thus, resulting in higher degradation rates than those of the system with O2 only. The extent of degradation under the same period of time increased in the order MEA-CO2 , MEA-CO2 -H2 S < MEA-CO2 -O2 < MEA-CO2 -O2 -H2 S.

[3H]-labelling of hydroxyethyl groups - synthesis of S-(2-hydroxy [2-3H] ethyl) glutathione and of [3H]-melphalan

International Nuclear Information System (INIS)

Verny, M.; Nicolas, C.

1988-01-01

The easy preparation of 2-bromo [1- 3 H] ethanol allows the tritium labelling of molecules bearing S- or N-hydroxyethyl groups. Thus S-(2-hydroxy [2- 3 H] ethyl) glutathione and [ 3 H]-Melphalan were synthesised with specific radioactivities of around 10 mCi/mmol (370 MBq/mmol). These values could be theoretically raised to 10 Ci/mmol (370 GBq/mmol), according to the specific activity of the labelling precursor, sodium [ 3 H] borohydride. (author)

Raman spectrum of predissociating H/sub 2/S

International Nuclear Information System (INIS)

Kleinermanns, K.; Suntz, R.; Schneider, R.

1986-01-01

Emission spectroscopy of photodissociating molecules provides interesting insights into the short-time dynamics of bond raptures. The authors report here a resolved H/sub 2/S photoemission spectrum after excitation at 193 nm, although its electronic spectrum in this wavelength region is diffuse. The electronic spectrum of H/sub 2/S between 250 and 170 nm is nearly continuous probably due to predissociation

SOFT X-RAY IRRADIATION OF H{sub 2}S ICE AND THE PRESENCE OF S{sub 2} IN COMETS

Energy Technology Data Exchange (ETDEWEB)

Jimenez-Escobar, A.; Munoz Caro, G. M. [Centro de Astrobiologia (CSIC-INTA), Carretera de Ajalvir, km 4, Torrejon de Ardoz, 28850 Madrid (Spain); Ciaravella, A.; Candia, R.; Micela, G. [INAF-Osservatorio Astronomico di Palermo, P.za Parlamento 1, 90134 Palermo (Italy); Cecchi-Pestellini, C., E-mail: munozcg@cab.inta-csic.es [INAF-Osservatorio Astronomico di Cagliari, Strada n.54, Loc. Poggio dei Pini, I-09012 Capoterra (Canada) (Italy)

2012-06-01

Little is known about the effects of X-rays in interstellar ices. To understand the sulfur depletion in dense clouds and the presence of S{sub 2} in comets, we simulated experimentally the soft X-ray processing (0.3 keV) of H{sub 2}S ice for the first time. Experiments were performed under ultrahigh vacuum conditions at 8 K using infrared and quadrupole mass spectrometry to monitor the solid and gas phases, respectively. A UV irradiation experiment using a similar dose was made for comparison. After X-ray irradiation, an infrared absorption appears near 4.0 {mu}m which is attributed to H{sub 2}S{sub 2} formation in the ice. This identification is also supported by the desorption at 133 K of m/z 66, 65, 64, corresponding to the mass fragments of H{sub 2}S{sub 2}. The H{sub 2}S{sub 2} species is expected to be present in interstellar and cometary ices that were processed by X-rays. Further irradiation leads to dissociation of this molecule forming S{sub 2} and larger S-molecules up to S{sub 8}, which may explain the depletion of sulfur in dense clouds. CS{sub 2} was so far the parent molecule proposed for S{sub 2} formation in comets. But the abundance of H{sub 2}S{sub 2}, formed by irradiation of pure H{sub 2}S or H{sub 2}S in an H{sub 2}O-ice matrix, should be larger than that of CS{sub 2} in the ice, the latter requiring a carbon source for its formation. Based on our experimental results, we propose that S{sub 2} in comets could be formed by dissociation of H{sub 2}S{sub 2} in the ice.

Evaluation of Pd Nanoparticle-Decorated CeO2-MWCNT Nanocomposite as an Electrocatalyst for Formic Acid Fuel Cells

Science.gov (United States)

Saleem, Junaid; Safdar Hossain, SK.; Al-Ahmed, Amir; Rahman, Ateequr; McKay, Gordon; Hossain, Mohammed M.

2018-04-01

In this work, CeO2-modified Pd/CeO2-carbon nanotube (CNT) electrocatalyst for the electro-oxidation of formic acid has been investigated. The support CNT was first modified with different amounts (5-30 wt.%) of CeO2 using a precipitation-deposition method. The electrocatalysts were developed by dispersing Pd on the CeO2-CNT supports using the borohydride reduction method. The synthesized electrocatalysts were analyzed for composition, morphology and electronic structure using x-ray diffraction (XRD), scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) techniques. The formation of Pd nanoparticles on the CeO2-CNT support was confirmed using TEM. The activity of Pd/CeO2-CNT and of Pd-CNT samples upon oxidation of formic acid was evaluated by using carbon monoxide stripping voltammetry, cyclic voltammetry, and chronoamperometry. The addition of moderate amounts of cerium oxide (up to 10 wt.%) significantly improved the activity of Pd/CeO2-CNT compared to the unmodified Pd-CNT. Pd/10 wt.% CeO2-CNT showed a current density of 2 A mg-1, which is ten times higher than that of the unmodified Pd-CNT (0.2 A mg-1). Similarly, the power density obtained for Pd/10 wt.% CeO2-CNT in an air-breathing formic acid fuel cell was 6.8 mW/cm2 which is two times higher than Pd-CNT (3.2 mW/cm2), thus exhibiting the promotional effects of CeO2 to Pd/CeO2-CNT. A plausible justification for the improved catalytic performance and stability is provided in the light of the physical characterization results.

Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

KAUST Repository

Ohnishi, R.

2013-03-12

Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

KAUST Repository

Ohnishi, R.; Katayama, M.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

2013-01-01

Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

High-Temperature Corrosion of T92 Steel in N{sub 2}/H{sub 2}O/H{sub 2}S-Mixed Gas

Energy Technology Data Exchange (ETDEWEB)

Shi, Yuke; Kim, Min Jung; Park, Soon Yong; Abro, M. Ali; Yadav, Poonam; Lee, Dong Bok [Sungkyunkwan University, Suwon (Korea, Republic of)

2016-06-15

The ASTM T92 steel was corroded at 600 ℃ and 800 ℃ at 1 atm of N{sub 2}/3.1%H{sub 2}O/2.42%H{sub 2}S-mixed gas. The formed scales were thick and fragile. They consisted primarily of the outer FeS scale and the inner (FeS, FeCr{sub 2}S{sub 4})-mixed scale containing a small amount of the Cr{sub 2}O{sub 3} scale. This indicated that corrosion occurred mainly via sulfidation rather than oxidation due to the H{sub 2}S gas. Since FeS was present throughout the whole scale, T92 steel was non-protective, displaying high corrosion rates.

Evaluation of Pt−Au/MWCNT (Multiwalled Carbon Nanotubes) electrocatalyst performance as cathode of a proton exchange membrane fuel cell

International Nuclear Information System (INIS)

Beltrán-Gastélum, M.; Salazar-Gastélum, M.I.; Félix-Navarro, R.M.; Pérez-Sicairos, S.; Reynoso-Soto, E.A.; Lin, S.W.; Flores-Hernández, J.R.; Romero-Castañón, T.; Albarrán-Sánchez, I.L.; Paraguay-Delgado, F.

2016-01-01

A comparative study between Pt−Au/MWCNT and Pt/C (commercial) as cathodic electrocatalyst of H_2/O_2 fuel cell is performed. Pt−Au/MWCNT is synthesized using the reverse microemulsion method and this procedure is scaled-up in order to prepare membrane-electrode assemblies for fuel cells with an active area of 9 cm"2. Those electrocatalysts are characterized by both physicochemical techniques and electrochemical measurements to evaluate their catalytic activity for ORR (Oxygen Reduction Reaction). In the half-cell study, Pt−Au/MWCNT show higher kinetic current density as cathodic electrocatalyst compared with Pt/C. Likewise, in a fuel cell hardware the maximum power density is significantly higher for Pt−Au/MWCNT cathode (625 mW cm"−"2 at 0.426 V) when compared with Pt/C anode (355 mW cm"−"2 at 0.499 V). - Highlights: • Pt−Au/MWCNT was synthesized by reverse microemulsión method. • Pt−Au/MWCNT and Pt/C were characterized by microscopic and spectroscopic techniques. • Both materials were studied as catalysts for ORR by electrochemical techniques. • Catalysts were used to prepare MEA's, the performance in fuel cell was evaluated. • Maximum power densities were 625 mW cm"−"2 for Pt−Au/MWCNT and 355 mW cm"−"2 for Pt/C.

Emission of hydrogen sulfide (H2S) at a waterfall in a sewer: study of main factors affecting H2S emission and modeling approaches.

Science.gov (United States)

Jung, Daniel; Hatrait, Laetitia; Gouello, Julien; Ponthieux, Arnaud; Parez, Vincent; Renner, Christophe

2017-11-01

Hydrogen sulfide (H 2 S) represents one of the main odorant gases emitted from sewer networks. A mathematical model can be a fast and low-cost tool for estimating its emission. This study investigates two approaches to modeling H 2 S gas transfer at a waterfall in a discharge manhole. The first approach is based on an adaptation of oxygen models for H 2 S emission at a waterfall and the second consists of a new model. An experimental set-up and a statistical data analysis allowed the main factors affecting H 2 S emission to be studied. A new model of the emission kinetics was developed using linear regression and taking into account H 2 S liquid concentration, waterfall height and fluid velocity at the outlet pipe of a rising main. Its prediction interval was estimated by the residual standard deviation (15.6%) up to a rate of 2.3 g H 2 S·h -1 . Finally, data coming from four sampling campaigns on sewer networks were used to perform simulations and compare predictions of all developed models.

Calculations of H+ + Cs→H(2s or 2p) + Cs+ reaction cross sections

International Nuclear Information System (INIS)

Valance, A.; Spiess, G.

1975-01-01

The H(2s) and H(2p) atom production cross-sections are calculated and compared with experimental results in the incident proton energy range 250-2400eV. The calculation method used involves a perturbation of the stationary molecular states, these adiabatic potentials being obtained from a pseudo-potential describing the core of cesium [fr

Glycerol electro-oxidation in alkaline medium using Pd/C and PdSn/C electrocatalysts prepared by electron beam irradiation

International Nuclear Information System (INIS)

Geraldes, Adriana Napoleao; Silva, Dionisio Fortunato da; Pino, Eddy Segura; Spinace, Estevan Vitorio; Oliveira Neto, Almir; Linardi, Marcelo; Santos, Mauro Coelhos dos

2013-01-01

Carbon-supported metal nanoparticles were prepared for fuel cell applications by radiation-induced reduction of metal ions precursors. Pd/C and PdSn/C electrocatalysts (Pd:Sn atomic ratio 90:10), prepared by using electron beam irradiation, were tested for glycerol electro-oxidation in single alkaline direct glycerol fuel cell (ADGFC). EDX analysis showed that the Pd:Sn atomic ratio is very similar to the nominal one. X-ray diffractograms of PdSn/C electrocatalyst showed the presence of Pd (fcc) phase. Cyclic voltammetry (CV) indicated that Pd/C and PdSn/C electrocatalysts have good activity for glycerol electro-oxidation, at room temperature. Experiments with single ADGFC were carried out from 60 to 90 deg C, using Pd/C and PdSn/C electrocatalysts and glycerol 2.0 mol.L -1 , as fuel. The best performance was obtained at 85 deg C, for both electrocatalysts. The Pd/C and PdSn/C electrocatalysts showed similar performance (34 mW cm -2 ), at 85 deg C. (author)

Ethanol electro-oxidation in alkaline medium using Pd/c and PdRh/C electrocatalysts prepared by electron beam irradiation

International Nuclear Information System (INIS)

Silva, Dionisio Furtunato da; Geraldes, Adriana Napoleao; Pino, Eddy Segura; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Linardi, Marcelo

2013-01-01

In this study, carbon-supported Pd (Pd/C) and bimetallic PdRh (Pd:Rh 90:10 atomic ratio) (PdRh/C) electrocatalysts were prepared using electron beam irradiation. The morphology and composition of the obtained materials were characterized by Cyclic voltammetry (VC), Chronoamperometry (CA), Energy dispersive X-ray (EDX), X-ray Diffraction (XRD) and Thermo-gravimetric analysis (TGA). The catalytic activities of the electrocatalysts toward the ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC), in a range temperature of 50 to 85 deg C. The best performances were obtained at 85 deg C (25 mW.cm -2 ) and 75 deg C (38 mW.cm -2 ) for Pd/C and PdRh/C electrocatalysts, respectively. The XRD of the PdRh/C electrocatalyst showed the presence of Pd-rich (fcc) phase. CV and CA experiments showed that PdRh/C electrocatalyst demonstrated superior activity toward ethanol electro-oxidation at room temperature, compared to Pd/C electrocatalyst. (author)

Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction

Science.gov (United States)

Yan, Kai-Li; Shang, Xiao; Li, Zhen; Dong, Bin; Li, Xiao; Gao, Wen-Kun; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

2017-09-01

Designing mixed metal oxides with unique nanostructures as efficient electrocatalysts for water electrolysis has been an attractive approach for the storage of renewable energies. The ternary mixed metal spinel oxides FexNi1-xCo2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, 1) have been synthesized by a facile hydrothermal approach and calcination treatment using nickel foam as substrate. Fe/Ni ratios have been proved to affect the nanostructures of FexNi1-xCo2O, which imply different intrinsic activity for oxygen evolution reaction (OER). SEM images show that Fe0.5Ni0.5Co2O4 has the uniform nanowires morphology with about 30 nm of the diameter and 200-300 nm of the length. The OER measurements show that Fe0.5Ni0.5Co2O4 exhibits the better electrocatalytic performances with lower overpotential of 350 mV at J = 10 mA cm-2. In addition, the smaller Tafel slope of 27 mV dec-1 than other samples with different Fe/Ni ratios for Fe0.5Ni0.5Co2O4 is obtained. The improved OER activity of Fe0.5Ni0.5Co2O4 may be attributed to the synergistic effects from ternary mixed metals especially Fe-doping and the uniform nanowires supported on NF. Therefore, synthesizing Fe-doped multi-metal oxides with novel nanostructures may be a promising strategy for excellent OER electrocatalysts and it also provides a facile way for the fabrication of high-activity ternary mixed metal oxides electrocatalysts.

Investigation of nano Pt and Pt-based alloys electrocatalysts for direct methanol fuel cells and their properties

Directory of Open Access Journals (Sweden)

Chunguang Suo

2014-03-01

Full Text Available The electrocatalysts used in micro direct methanol fuel cell (μDMFC, such as Pt/C and Pt alloy/C, prepared by liquid-phase NaBH4 reduction method have been investigated. XC-72 (Cobalt corp. Company, U.S.A is chosen as the activated carrier for the electrocatalysts to keep the catalysts powder in the range of several nanometers. The XRD, SEM, EDX analyses indicated that the catalysts had small particle size in several nanometers, in excellent dispersed phase and the molar ratio of the precious metals was found to be optimal. The performances of the DMFCs using cathodic catalyst with Pt percentage of 30wt% and different anodic catalysts (Pt-Ru, Pt-Ru-Mo were tested. The polarization curves and power density curves of the cells were measured to determine the optimal alloy composition and condition for the electrocatalysts. The results showed that the micro direct methanol fuel cell with 30wt% Pt/C as the cathodic catalyst and n(Pt:n(Ru:n(Mo = 3:2:2 PtRuMo/C as the anodic catalyst at room temperature using 2.0mol/L methanol solution has the best performances.

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electrooxidation; Preparacao de eletrocatalisadores PtSnCu/C e PtSn/C e ativacao por processos de dealloying para aplicacao na oxidacao eletroquuimica do etanol

Energy Technology Data Exchange (ETDEWEB)

Crisafulli, Rudy

2013-06-01

PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H{sub 2}PtCl{sub 6}.6H{sub 2}O, SnCl{sub 2}.2H{sub 2}O and CuCl{sub 2}.2H{sub 2}O as metal sources, NaBH{sub 4} and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, Xray diffraction, transmission electron microscopy, line scan energy dispersive Xray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic effluents were analysed by gas chromatography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the assynthesized electrocatalysts were in the range of <=2 nm to 3 nm and after dealloying there were no significant variations in sizes. The energy dispersive Xray analysis of the as-synthesized electrocatalysts showed a Pt:Sn and Pt:Sn:Cu atomic ratios similar to the nominal values. After chemical and electrochemical dealloying of the electrocatalysts the ranged Pt:Sn and Pt:Sn:Cu atomic ratios showed that Cu and Sn atoms were removed. However, chemical dealloying process proved to be more efficient for removing Cu and electrochemical dealloying for removing Sn. The line scan energy dispersive X-ray analysis showed that acid and electrochemical treatments were efficient to dealloying Cu and/or Sn superficial atoms of

Effect of H{sub 2}S on the thermodynamic stability and electrochemical performance of Ni cermet-type of anodes for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Venkateswara Rao, M.

2006-11-15

For SOFCs to be main means of power generation, they should be able to exploit wide variety of fuels. Among Ni-cermets, Ni-YSZ is the state-of-the-art materials for SOFC-anode which is the fuel electrode. But sulphur impurity present in different gaseous fuels (e.g Biogas), depending on its concentration, is highly poisonous to the stability and electrochemical performance of the Ni catalyst in the cermet anodes. Thus in this study the microstructural stability of Ni-YSZ, Ni-CGO and Ni-LSGM cermets in H{sub 2}S-containing hydrogen gas is studied in the intermediate temperature range of SOFC operation. Thermodynamic modelling of Ni-S-O-H quaternary system was performed for the calculation of thermodynamic stability and sulphur-tolerance limit of Ni in the gaseous atmosphere made up of H, O and S. The effect of presence H{sub 2}S in fuel gas, in the concentrations well below the thermodynamic tolerance limit, on the electrochemical performance of the anodes is studied by using model Ni-patterned electrodes on YSZ and LSGM. Thermodynamic modelling of the Ni-S-O-H quaternary was performed by employing CALPHAD methodology. The modelling of Ni-S binary phase diagram was performed by using sublattice models for the non-stoichiometric phases. The optimised binaries of Ni-O, and Ni-H were taken from the literature. The Ni-O-S and Ni-O-H ternaries were extrapolated from the lower order binaries. In Ni-O-S ternary, NiSO{sub 4} is the only ternary compound present. The ternary compounds, Ni(OH){sub 2} and NiOOH in the Ni-O-H ternary were considered as stoichiometric line compounds. The model parameters of the ternary compounds were optimised using the experimental data. The Ni-S-O-H quaternary was calculated by extrapolation method as employed in the CALPHAD methodology. Inorder to understand the H{sub 2}-oxidation mechanism and the role played by the electrolyte in the reaction mechanism, symmetrical cells of Ni-patterned YSZ single crystals with different crystallographic

Hydrogen sulfide enhances nitric oxide-induced tolerance of hypoxia in maize (Zea mays L.).

Science.gov (United States)

Peng, Renyi; Bian, Zhiyuan; Zhou, Lina; Cheng, Wei; Hai, Na; Yang, Changquan; Yang, Tao; Wang, Xinyu; Wang, Chongying

2016-11-01

Our data present H 2 S in a new role, serving as a multi-faceted transducer to different response mechanisms during NO-induced acquisition of tolerance to flooding-induced hypoxia in maize seedling roots. Nitric oxide (NO), serving as a secondary messenger, modulates physiological processes in plants. Recently, hydrogen sulfide (H 2 S) has been demonstrated to have similar signaling functions. This study focused on the effects of treatment with H 2 S on NO-induced hypoxia tolerance in maize seedlings. The results showed that treatment with the NO donor sodium nitroprusside (SNP) enhanced survival rate of submerged maize roots through induced accumulation of endogenous H 2 S. The induced H 2 S then enhanced endogenous Ca 2+ levels as well as the Ca 2+ -dependent activity of alcohol dehydrogenase (ADH), improving the capacity for antioxidant defense and, ultimately, the hypoxia tolerance in maize seedlings. In addition, NO induced the activities of key enzymes in H 2 S biosynthesis, such as L-cysteine desulfhydrases (L-CDs), O-acetyl-L-serine (thiol)lyase (OAS-TL), and β-Cyanoalanine Synthase (CAS). SNP-induced hypoxia tolerance was enhanced by the application of NaHS, but was eliminated by the H 2 S-synthesis inhibitor hydroxylamine (HA) and the H 2 S-scavenger hypotaurine (HT). H 2 S concurrently enhanced the transcriptional levels of relative hypoxia-induced genes. Together, our findings indicated that H 2 S serves as a multi-faceted transducer that enhances the nitric oxide-induced hypoxia tolerance in maize (Zea mays L.).

Electron capture from H(2s) by H+ at low energies

International Nuclear Information System (INIS)

Blanco, S.A.; Falcon, C.A.; Piacentini, R.D.

1986-01-01

Total cross sections for resonant electron capture by protons from metastable H(2s) targets have been computed in a six-state molecular close-coupling formalism. Transitions between degenerate sublevels of the L shell of the target occurring at large internuclear distances have been taken into account in the impact parameter approximation. Cross sections are presented for impact velocities between 0.05 and 0.3 au. The results are compared with theoretical calculations for capture from H(2s) by Li 3+ , C 6+ and N 7+ . (author)

Freezing and desiccation tolerance in entomopathogenic nematodes: diversity and correlation of traits.

Science.gov (United States)

Shapiro-Ilan, David I; Brown, Ian; Lewis, Edwin E

2014-03-01

The ability of entomopathogenic nematodes to tolerate environmental stress such as desiccating or freezing conditions, can contribute significantly to biocontrol efficacy. Thus, in selecting which nematode to use in a particular biocontrol program, it is important to be able to predict which strain or species to use in target areas where environmental stress is expected. Our objectives were to (i) compare inter- and intraspecific variation in freeze and desiccation tolerance among a broad array of entomopathogenic nematodes, and (ii) determine if freeze and desiccation tolerance are correlated. In laboratory studies we compared nematodes at two levels of relative humidity (RH) (97% and 85%) and exposure periods (24 and 48 h), and nematodes were exposed to freezing temperatures (-2°C) for 6 or 24 h. To assess interspecific variation, we compared ten species including seven that are of current or recent commercial interest: Heterorhabditis bacteriophora (VS), H. floridensis, H. georgiana, (Kesha), H. indica (HOM1), H. megidis (UK211), Steinernema carpocapsae (All), S. feltiae (SN), S. glaseri (VS), S. rarum (17C&E), and S. riobrave (355). To assess intraspecific variation we compared five strains of H. bacteriophora (Baine, Fl1-1, Hb, Oswego, and VS) and four strains of S. carpocapsae (All, Cxrd, DD136, and Sal), and S. riobrave (355, 38b, 7-12, and TP). S. carpocapsae exhibited the highest level of desiccation tolerance among species followed by S. feltiae and S. rarum; the heterorhabditid species exhibited the least desiccation tolerance and S. riobrave and S. glaseri were intermediate. No intraspecific variation was observed in desiccation tolerance; S. carpocapsae strains showed higher tolerance than all H. bacteriophora or S. riobrave strains yet there was no difference detected within species. In interspecies comparisons, poor freeze tolerance was observed in H. indica, and S. glaseri, S. rarum, and S. riobrave whereas H. georgiana and S. feltiae exhibited the

The Arabidopsis cax3 mutants display altered salt tolerance, pH sensitivity and reduced plasma membrane H+-ATPase activity.

Science.gov (United States)

Zhao, Jian; Barkla, Bronwyn J; Marshall, Joy; Pittman, Jon K; Hirschi, Kendal D

2008-02-01

Perturbing CAX1, an Arabidopsis vacuolar H+/Ca2+ antiporter, and the related vacuolar transporter CAX3, has been previously shown to cause severe growth defects; however, the specific function of CAX3 has remained elusive. Here, we describe plant phenotypes that are shared among cax1 and cax3 including an increased sensitivity to both abscisic acid (ABA) and sugar during germination, and an increased tolerance to ethylene during early seedling development. We have also identified phenotypes unique to cax3, namely salt, lithium and low pH sensitivity. We used biochemical measurements to ascribe these cax3 sensitivities to a reduction in vacuolar H+/Ca2+ transport during salt stress and decreased plasma membrane H+-ATPase activity. These findings catalog an array of CAX phenotypes and assign a specific role for CAX3 in response to salt tolerance.

Computational study on the mechanisms and energetics of trimethylindium reactions with H2O and H2S.

Science.gov (United States)

Raghunath, P; Lin, M C

2007-07-19

The reactions of trimethylindium (TMIn) with H2O and H2S are relevant to the chemical vapor deposition of indium oxide and indium sulfide thin films. The mechanisms and energetics of these reactions in the gas phase have been investigated by density functional theory and ab initio calculations using the CCSD(T)/[6-31G(d,p)+Lanl2dz]//B3LYP/[6-31G(d,p)+Lanl2dz] and CCSD(T)/[6-31G(d,p)+Lanl2dz] //MP2/[6-31G(d,p)+Lanl2dz] methods. The results of both methods are in good agreement for the optimized geometries and relative energies. When TMIn reacts with H2O and H2S, initial molecular complexes [(CH3)3In:OH2 (R1)] and [(CH3)3In:SH2 (R2)] are formed with 12.6 and 3.9 kcal/mol binding energies. Elimination of a CH4 molecule from each complex occurs with a similar energy barrier at TS1 (19.9 kcal/mol) and at TS3 (22.1 kcal/mol), respectively, giving stable intermediates (CH3)2InOH and (CH3)2InSH. The elimination of the second CH4 molecule from these intermediate products, however, has to overcome very high and much different barriers of 66.1 and 53.2 kcal/mol, respectively. In the case of DMIn with H2O and H2S reactions, formation of both InO and InS is exothermic by 3.1 and 30.8 kcal/mol respectively. On the basis of the predicted heats of formation of R1 and R2 at 0 K and -20.1 and 43.6 kcal/mol, the heats of formation of (CH3)2InOH, (CH3)2InSH, CH3InO, CH3InS, InO, and InS are estimated to be -20.6, 31.8, and 29.0 and 48.4, 35.5, and 58.5 kcal/mol, respectively. The values for InO and InS are in good agreement with available experimental data. A similar study on the reactions of (CH3)2In with H2O and H2S has been carried out; in these reactions CH3InOH and CH3InSH were found to be the key intermediate products.

Impact of Weak Agostic Interactions in Nickel Electrocatalysts for Hydrogen Oxidation

Energy Technology Data Exchange (ETDEWEB)

Klug, Christina M. [Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K2-57, Richland, Washington 99352, United States; O’Hagan, Molly [Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K2-57, Richland, Washington 99352, United States; Bullock, R. Morris [Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K2-57, Richland, Washington 99352, United States; Appel, Aaron M. [Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K2-57, Richland, Washington 99352, United States; Wiedner, Eric S. [Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K2-57, Richland, Washington 99352, United States

2017-06-08

To understand how H2 binding and oxidation is influenced by [Ni(PR2NR'2)2]2+ PR2NR'2 catalysts with H2 binding energies close to thermoneutral, two [Ni(PPh2NR'2)2]2+ (R = Me or C14H29) complexes with phenyl substituents on phosphorous and varying alkyl chain lengths on the pendant amine were studied. In the solid state, [Ni(PPh2NMe2)2]2+ exhibits an anagostic interaction between the Ni(II) center and the α-CH3 of the pendant amine, and DFT and variable-temperature 31P NMR experiments suggest than the anagostic interaction persists in solution. The equilibrium constants for H2 addition to these complexes was measured by 31P NMR spectroscopy, affording free energies of H2 addition (ΔG°H2) of –0.8 kcal mol–1 in benzonitrile and –1.6 to –2.3 kcal mol–1 in THF. The anagostic interaction contributes to the low driving force for H2 binding by stabilizing the four-coordinate Ni(II) species prior to binding of H2. The pseudo-first order rate constants for H2 addition at 1 atm were measured by variable scan rate cyclic voltammetry, and were found to be similar for both complexes, less than 0.2 s–1 in benzonitrile and 3 –6 s–1 in THF. In the presence of exogenous base and H2 , turnover frequencies of electrocatalytic H2 oxidation were measured to be less than 0.2 s–1 in benzonitrile and 4 –9 s–1 in THF. These complexes are slower electrocatalysts for H2 oxidation than previously studied [Ni(PR2NR'2)2]2+ complexes due to a competition between H2 binding and formation of the anagostic interaction. However, the decrease in catalytic rate is accompanied by a beneficial 130 mV decrease in overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Computational resources were provided at the National Energy Research Scientific Computing Center (NERSC) at Lawrence

Synthesis and characterization of MoS{sub 2} cocatalysts for H{sub 2}-generation; Darstellung und Charakterisierung von MoS{sub 2} Cokatalysatoren fuer die H{sub 2}-Entwicklung

Energy Technology Data Exchange (ETDEWEB)

Djamil, John

2015-10-05

As a suitable alternative to fossil fuels and nuclear energy light induced generation of H{sub 2} represents a trend-setting research area in the field of regenerative energy. Therefore photocatalysts, which provide surface sites for light driven reduction of protons to H{sub 2}, are being investigated and developed. Enhancement of photocatalytic systems can be achieved by the usage of cocatalysts, which simplify charge separation and provide additional catalytic active sites as well. In the present work cocatalysts based on MoS{sub 2} were synthesized, characterized and investigated for photocatalytic H{sub 2} generation. MoS{sub 2} cocatalysts were synthesized by thermal decomposition of tetraalkyl ammonium thiomolybdates with varying carbon content in the organic cation and by mechanical treatment of bulk MoS{sub 2} respectively. Hence, samples with differing chemical composition as well as structural properties were obtained. Based on these findings relations between chemical composition, microstructural properties and photocatalytic activity were supposed to reveal. Nanoparticulate molybdenum sulfides resulted in both synthetic routes. Thermal decomposition of tetraalkyl ammonium thiomolybdates yielded in carbon containing molybdenum sulfide nanocomposites, in which carbon and sulfur content and the crystallite size as well varied with the carbon amount in the precursor. Additionally a composite with a significant enlarged interlayer distance between the MoS{sub 2} layers was obtained by thermal decomposition of (Ph{sub 4}P){sub 2}MoS{sub 4}. Such interlayer expansion could be explained by an insertion of in situ generated Ph{sub 3}PS- and (Ph{sub 4}P){sub 2}S-molecules between the MoS{sub 2} layers. While Ph{sub 3}PS-molecules were bonded through Mo-S-bonds to the MoS{sub 2} layers, (Ph{sub 4}P){sub 2}S-molecules remained free in rotation between MoS{sub 2} sheets. The mechanical treatment of bulk MoS{sub 2} resulted in different-sized MoS{sub 2

Two-Dimensional N,S-Codoped Carbon/Co ₉ S ₈ Catalysts Derived from Co(OH) ₂ Nanosheets for Oxygen Reduction Reaction

Energy Technology Data Exchange (ETDEWEB)

Fu, Shaofang [School of Mechanical; Zhu, Chengzhou [School of Mechanical; Song, Junhua [School of Mechanical; Feng, Shuo [School of Mechanical; Du, Dan [School of Mechanical; Key Laboratory of Pesticide and Chemical; Engelhard, Mark H. [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Xiao, Dongdong [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Li, Dongsheng [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Lin, Yuehe [School of Mechanical

2017-10-12

Investigation of highly active and cost-efficient electrocatalysts for oxygen reduction reaction is of great importance in a wide range of clean energy devices, including fuel cells and metal-air batteries. Herein, the simultaneous formation of Co9S8 and N,S-codoped carbon was achieved in a dual templates system. First, Co(OH)2 nanosheets and tetraethyl orthosilicate were utilized to direct the formation of two-dimensional carbon precursors, which were then dispersed into thiourea solution. After subsequent pyrolysis and templates removal, N/S-codoped porous carbon sheets confined Co9S8 catalysts (Co9S8/NSC) were obtained. Owing to the morphological and compositional advantages as well as the synergistic effects, the resultant Co9S8/NSC catalysts with modified doping level and pyrolysis degree exhibit superior ORR catalytic activity and long-term stability compared with the state-of-the-art Pt/C catalyst in alkaline media. Remarkably, the as-prepared carbon composites also reveal exceptional tolerance of methanol, indicating their potential applications in fuel cells.

H2S: a universal defense against antibiotics in bacteria.

Science.gov (United States)

Shatalin, Konstantin; Shatalina, Elena; Mironov, Alexander; Nudler, Evgeny

2011-11-18

Many prokaryotic species generate hydrogen sulfide (H(2)S) in their natural environments. However, the biochemistry and physiological role of this gas in nonsulfur bacteria remain largely unknown. Here we demonstrate that inactivation of putative cystathionine β-synthase, cystathionine γ-lyase, or 3-mercaptopyruvate sulfurtransferase in Bacillus anthracis, Pseudomonas aeruginosa, Staphylococcus aureus, and Escherichia coli suppresses H(2)S production, rendering these pathogens highly sensitive to a multitude of antibiotics. Exogenous H(2)S suppresses this effect. Moreover, in bacteria that normally produce H(2)S and nitric oxide, these two gases act synergistically to sustain growth. The mechanism of gas-mediated antibiotic resistance relies on mitigation of oxidative stress imposed by antibiotics.

The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

Energy Technology Data Exchange (ETDEWEB)

Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

2015-08-01

In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

Ethanol electro-oxidation in alkaline medium using Pd/c and PdRh/C electrocatalysts prepared by electron beam irradiation

Energy Technology Data Exchange (ETDEWEB)

Silva, Dionisio Furtunato da; Geraldes, Adriana Napoleao; Pino, Eddy Segura; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Linardi, Marcelo, E-mail: dfsilva@ipen.br, E-mail: drinager@ig.com.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2013-07-01

In this study, carbon-supported Pd (Pd/C) and bimetallic PdRh (Pd:Rh 90:10 atomic ratio) (PdRh/C) electrocatalysts were prepared using electron beam irradiation. The morphology and composition of the obtained materials were characterized by Cyclic voltammetry (VC), Chronoamperometry (CA), Energy dispersive X-ray (EDX), X-ray Diffraction (XRD) and Thermo-gravimetric analysis (TGA). The catalytic activities of the electrocatalysts toward the ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC), in a range temperature of 50 to 85 deg C. The best performances were obtained at 85 deg C (25 mW.cm{sup -2}) and 75 deg C (38 mW.cm{sup -2}) for Pd/C and PdRh/C electrocatalysts, respectively. The XRD of the PdRh/C electrocatalyst showed the presence of Pd-rich (fcc) phase. CV and CA experiments showed that PdRh/C electrocatalyst demonstrated superior activity toward ethanol electro-oxidation at room temperature, compared to Pd/C electrocatalyst. (author)

Correlating microstructure and activity for polysulfide reduction and oxidation at WS₂ electrocatalysts

DEFF Research Database (Denmark)

Stephens, Ifan E.L.; Ducati, Caterina; Fray, Derek J.

2013-01-01

The polysulfide reduction and oxidation activity of WS2 electrocatalysts was studied. This was undertaken with a specific view to improve the efficiency of the polysulfide-bromine redox flow battery, for large scale energy storage. Using data from the literature, it is estimated that the catalysts.......47 and 1 M NaOH, simulating the operating conditions of a half-charged polysulfide-bromine redox flow battery. The catalyst activity increased in the following order: IF-WS2

Preparation of Pt Ru/C electrocatalysts using gamma radiation for application as anode in direct methanol fuel cell

International Nuclear Information System (INIS)

Spinace, Estevam V.; Silva, Dionisio F. da; Cruz, Victor A. da; Oliveira Neto, Almir; Machado, Luci D.B.; Pino, Eddy S.; Linardi, Marcelo

2005-01-01

PtRu nanoparticles supported on carbon (PtRu/C electrocatalysts) were prepared submitting a water/2-propanol mixture containing the metal ions and the carbon support to gamma radiation. The water/2-propanol (v/v) and the total dose (kGy) were studied. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The methanol electro-oxidation was studied by cyclic voltammetry using the thin porous coating. In the studied conditions, the electrocatalytic activity of the prepared electrocatalysts depend on the water/2-propanol ratio used in the reaction medium. (author)

Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

Science.gov (United States)

Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

2010-07-20

Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

Effect of copper oxide electrocatalyst on CO2 reduction using Co3O4 as anode

Directory of Open Access Journals (Sweden)

V.S.K. Yadav

2016-09-01

Full Text Available The reduction of carbon dioxide (CO2 to products electrochemically (RCPE in 0.5 M NaHCO3 and Na2CO3 liquid phase electrolyte solutions was investigated. Cobalt oxide (Co3O4 as anode and cuprous oxide (Cu2O as the cathode were considered, respectively. The impacts of applied potential with time of reaction during reduction of CO2 to products were studied. The anode and cathode were prepared by depositing electrocatalysts on the graphite plate. Ultra-fast liquid chromatography (UFLC was used to analyze the products obtained from the reduction of CO2. The feasible way of reduction by applying voltages with current densities was clearly correlated. The results illustrate the capability of electrocatalyst successfully to remove atmospheric CO2 in the form of valuable chemicals. Maximum Faradaic efficiency of ethanol was 98.1% at 2 V and for formic acid (36.6% at 1.5 V was observed in NaHCO3. On the other hand, in Na2CO3 electrolyte solution maximum efficiency for ethanol was 55.21% at 1.5 V and 25.1% for formic acid at 2 V. In both electrolytes other end products like methanol, propanol, formaldehyde and acetic acid were formed at various applied voltage and output current densities.

Tolerance to LSD and DOB induced shaking behaviour: differential adaptations of frontocortical 5-HT(2A) and glutamate receptor binding sites.

Science.gov (United States)

Buchborn, Tobias; Schröder, Helmut; Dieterich, Daniela C; Grecksch, Gisela; Höllt, Volker

2015-03-15

Serotonergic hallucinogens, such as lysergic acid diethylamide (LSD) and dimethoxy-bromoamphetamine (DOB), provoke stereotype-like shaking behaviour in rodents, which is hypothesised to engage frontocortical glutamate receptor activation secondary to serotonin2A (5-HT2A) related glutamate release. Challenging this hypothesis, we here investigate whether tolerance to LSD and DOB correlates with frontocortical adaptations of 5-HT2A and/or overall-glutamate binding sites. LSD and DOB (0.025 and 0.25 mg/kg, i.p.) induce a ketanserin-sensitive (0.5 mg/kg, i.p., 30-min pretreatment) increase in shaking behaviour (including head twitches and wet dog shakes), which with repeated application (7× in 4 ds) is undermined by tolerance. Tolerance to DOB, as indexed by DOB-sensitive [(3)H]spiroperidol and DOB induced [(35)S]GTP-gamma-S binding, is accompanied by a frontocortical decrease in 5-HT2A binding sites and 5-HT2 signalling, respectively; glutamate-sensitive [(3)H]glutamate binding sites, in contrast, remain unchanged. As to LSD, 5-HT2 signalling and 5-HT2A binding, respectively, are not or only marginally affected, yet [(3)H]glutamate binding is significantly decreased. Correlation analysis interrelates tolerance to DOB to the reduced 5-HT2A (r=.80) as well as the unchanged [(3)H]glutamate binding sites (r=.84); tolerance to LSD, as opposed, shares variance with the reduction in [(3)H]glutamate binding sites only (r=.86). Given that DOB and LSD both induce tolerance, one correlating with 5-HT2A, the other with glutamate receptor adaptations, it might be inferred that tolerance can arise at either level. That is, if a hallucinogen (like LSD in our study) fails to induce 5-HT2A (down-)regulation, glutamate receptors (activated postsynaptic to 5-HT2A related glutamate release) might instead adapt and thus prevent further overstimulation of the cortex. Copyright © 2014 Elsevier B.V. All rights reserved.

pH Tolerance in Freshwater Bacterioplankton: Trait Variation of the Community as Measured by Leucine Incorporation

OpenAIRE

Bååth, Erland; Kritzberg, Emma

2015-01-01

pH is an important factor determining bacterial community composition in soil and water. We have directly determined the community tolerance (trait variation) to pH in communities from 22 lakes and streams ranging in pH from 4 to 9 using a growth-based method not relying on distinguishing between individual populations. The pH in the water samples was altered to up to 16 pH values, covering in situ pH ± 2.5 U, and the tolerance was assessed by measuring bacterial growth (Leu incorporation) in...

H2S-mediated thermal and photochemical methane activation.

Science.gov (United States)

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric V

2013-12-02

Sustainable, low-temperature methods for natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) mixed with methane, deemed altogether as sub-quality or "sour" gas. We propose a unique method of activation to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3 , and an energy carrier such as H2. For this purpose, we investigated the H2S-mediated methane activation to form a reactive CH3SH species by means of direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4 + H2S complex resulted in a barrierless relaxation by a conical intersection to form a ground-state CH3SH + H2 complex. The resulting CH3SH could further be coupled over acidic catalysts to form higher hydrocarbons, and the resulting H2 used as a fuel. This process is very different from conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced control over the conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the current industrial steam methane reforming (SMR). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward highly stable electrocatalysts via nanoparticle pore confinement.

Science.gov (United States)

Galeano, Carolina; Meier, Josef C; Peinecke, Volker; Bongard, Hans; Katsounaros, Ioannis; Topalov, Angel A; Lu, Anhui; Mayrhofer, Karl J J; Schüth, Ferdi

2012-12-19

The durability of electrode materials is a limiting parameter for many electrochemical energy conversion systems. In particular, electrocatalysts for the essential oxygen reduction reaction (ORR) present some of the most challenging instability issues shortening their practical lifetime. Here, we report a mesostructured graphitic carbon support, Hollow Graphitic Spheres (HGS) with a specific surface area exceeding 1000 m(2) g(-1) and precisely controlled pore structure, that was specifically developed to overcome the long-term catalyst degradation, while still sustaining high activity. The synthetic pathway leads to platinum nanoparticles of approximately 3 to 4 nm size encapsulated in the HGS pore structure that are stable at 850 °C and, more importantly, during simulated accelerated electrochemical aging. Moreover, the high stability of the cathode electrocatalyst is also retained in a fully assembled polymer electrolyte membrane fuel cell (PEMFC). Identical location scanning and scanning transmission electron microscopy (IL-SEM and IL-STEM) conclusively proved that during electrochemical cycling the encapsulation significantly suppresses detachment and agglomeration of Pt nanoparticles, two of the major degradation mechanisms in fuel cell catalysts of this particle size. Thus, beyond providing an improved electrocatalyst, this study describes the blueprint for targeted improvement of fuel cell catalysts by design of the carbon support.

Dynamics and tolerances for the CERN interdigital H LINAC

International Nuclear Information System (INIS)

Valero, S.; Ratzinger, U.

1992-01-01

A three tank interdigital H structure has been chosen for the 0.25 to 4.2 MeV/u part of the CERN heavy-ion injector linac. The complete design has been developed by GSI, in particular the longitudinal dimensions have been determined and multi-particle studies have been made using the program LORAS. Some RF tolerance studies have also be made at CERN using this program. For more general approach to the dynamics, the program DYNAC is being used at CERN especially where statistical analyses are essential i.e for determining emittance growth, tolerances on accelerator parameters and alignment. The approaches and results of these two programs are compared for this novel type of accelerator

Synthesis and spectroscopic stereospecificity assay of the deuterated quinolizidine alkaloids (2S)-[2H]- and (2R)-[2H]-sparteine

International Nuclear Information System (INIS)

Ebner, T.; Meese, C.O.; Rebell, J.

1989-01-01

Borohydride reduction of the (+)-1,2-dehydrosparteinium salts proceeds almost exclusively from the Si side, yielding, respectively, the stereoselectively (2S)(β)-deuterated (-)-sparteine and the (2R)(α)-deuterated (-)-sparteine. Stereo-chemistry and isotopic purity of the deuterium label (≥98%) are established unequivocally by 1 H, 2 H and 13 C NMR spectroscopy. (author)

Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN nanosheet

Science.gov (United States)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh

2018-05-01

We have investigated the electronic properties, adsorptions strength and charge transfer using first principles calculations using density functional theory (DFT). The hexagonal boron nitride (h-BN) substrate shows metallic behavior, which helps to enhance the absorption process. The adsorption of three different orientations (S, D and T) of the H2S gas molecules to analyze the maximum adsorption strength from them onto a copper cluster (Cu4) based on h-BN nanosheet. The maximum adsorption energy of the H2S gas molecule is -1.50 eV for the S orientation and for D and U, it is -0.71 eV and -0.78 eV, respectively. The results show that Cu4 cluster helps to capture H2S gas from the environment and results are useful for the cleaning environment from the toxic gases.

CoPd x oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

International Nuclear Information System (INIS)

Mustain, William E.; Kepler, Keith; Prakash, Jai

2007-01-01

The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm 2 single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 deg. C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd 3 , exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd 3 has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd 3 catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd 3 catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells

International Nuclear Information System (INIS)

Hsu, Ryan S; Higgins, Drew; Chen Zhongwei

2010-01-01

Novel tin-oxide (SnO 2 )-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO 2 -coated SWNT (SnO 2 -SWNT) bundles were synthesized by a simple chemical-solution route. SnO 2 -SWNT bundles supporting Pt (Pt/SnO 2 -SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO 2 -SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO 2 loading of Pt/SnO 2 -SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

Science.gov (United States)

Hsu, Ryan S; Higgins, Drew; Chen, Zhongwei

2010-04-23

Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

Ethanol Electro-oxidation on Novel Electrocatalyst PtVSnO2/C in Acidic Media

International Nuclear Information System (INIS)

Jin, Biyao; Sun, Hongyan; Huang, Minghui; Zhao, Lianhua

2014-01-01

Graphical abstract: - Highlights: • Novel electrocatalyst PtVSnO 2 /C is synthesized by a modified Bönnemann method. • Adding Sn and V changes the geometric and electronic structure of Pt. • PtVSnO 2 /C improved catalytic activity and the ability of resisting CO poisoning. - Abstract: A novel carbon-supported Pt-V-SnO 2 catalyst is prepared by a modified Bönnemann method. Pt/C, PtV/C, and PtSnO 2 /C are used for comparative analysis to study PtVSnO 2 /C in terms of its structure and electrocatalytic activity for the ethanol oxidation reaction (EOR). Characterization of its structural properties by X-ray diffraction (XRD) and transmission electron microscopy (TEM) is described. It is shown that the Pt lattice parameter decreases with the addition of V but increases with the addition of Sn in the PtVSn/C catalyst. TEM analysis reveals that the prepared catalyst particles are in the nanosize range (2-4 nm). EDS confirms the atomic compositions of the synthesized catalysts to be similar to the nominal values. The electrocatalytic activities are characterized by cyclic voltammetry (CV) and amperometric i-t curve measurement (i-t) techniques. The incorporation of a small amount of V in the PtSnO 2 /C electrocatalyst leads to higher activity for the ethanol oxidation reaction at room temperature. According to the Arrhenius equation, the apparent activation energy of PtVSnO 2 /C (3:1:3) for EOR is the lowest among the studied catalysts, which may be attributed to a synergistic effect between Sn and V

Ionic Liquid-Assisted Synthesis of Nanoscale (MoS2)x(SnO2)1-x on Reduced Graphene Oxide for the Electrocatalytic Hydrogen Evolution Reaction.

Science.gov (United States)

Ravula, Sudhir; Zhang, Chi; Essner, Jeremy B; Robertson, J David; Lin, Jian; Baker, Gary A

2017-03-08

Layered transition metal dichalcogenides (TMDs) have attracted increased attention due to their enhanced hydrogen evolution reaction (HER) performance. More specifically, ternary TMD nanohybrids, such as MoS 2(1-x) Se 2x or bimetallic sulfides, have arisen as promising electrocatalysts compared to MoS 2 and MoSe 2 due to their electronic, morphologic, and size tunabilities. Herein, we report the successful synthesis of few-layered MoS 2 /rGO, SnS 2 /rGO, and (MoS 2 ) x (SnO 2 ) 1-x /rGO nanohybrids anchored on reduced graphene oxide (rGO) through a facile hydrothermal reaction in the presence of ionic liquids as stabilizing, delayering agents. Spectroscopic and microscopic techniques (electron microscopy, X-ray diffraction, Raman spectroscopy, neutron activation analysis, and UV-vis spectrophotometry) are used to validate the hierarchical properties, phase identity, and the smooth compositional tunability of the (MoS 2 ) x (SnO 2 ) 1-x /rGO nanohybrids. Linear sweep voltammetry measurements reveal that incorporation of Sn into the ternary nanohybrids (as a discrete SnO 2 phase) greatly reduces the overpotential by 90-130 mV relative to the MoS 2 electrocatalyst. Significantly, the (MoS 2 ) 0.6 (SnO 2 ) 0.4 /rGO nanohybrid displays superior catalytic performance over MoS 2 alone, exhibiting a low overpotential (η 10 ) of 263 ± 5 mV and a small Tafel slope of 50.8 mV dec -1 . The hybrid catalyst shows high stability for the HER in acidic solutions, with negligible activity loss after 1000 cycles. The hierarchical structures and large surface areas possessing exposed, active edge sites make few-layered (MoS 2 ) x (SnO 2 ) 1-x /rGO nanohybrids promising nonprecious metal electrocatalysts for the HER.

Raman Spectroscopy and Electrochemical Investigations of Pt Electrocatalyst Supported on Carbon Prepared through Plasma Pyrolysis of Natural Gas

Directory of Open Access Journals (Sweden)

Tereza Cristina Santos Evangelista

2015-01-01

Full Text Available Physicochemical and electrochemical characterisations of Pt-based electrocatalysts supported on carbon (Vulcan carbon, C1, and carbon produced by plasma pyrolysis of natural gas, C2 toward ethanol electrooxidation were investigated. The Pt20/C180 and Pt20/C280 electrocatalysts were prepared by thermal decomposition of polymeric precursors at 350°C. The electrochemical and physicochemical characterisations of the electrocatalysts were performed by means of X-ray diffraction (XRD, transmission electron microscope (TEM, Raman scattering, cyclic voltammetry, and chronoamperometry tests. The XRD results show that the Pt-based electrocatalysts present platinum metallic which is face-centered cubic structure. The results indicate that the Pt20/C180 electrocatalyst has a smaller particle size (10.1–6.9 nm compared with the Pt20/C280 electrocatalyst; however, the Pt20/C280 particle sizes are similar (12.8–10.4 nm and almost independent of the reflection planes, which suggests that the Pt crystallites grow with a radial shape. Raman results reveal that both Vulcan carbon and plasma carbon are graphite-like materials consisting mostly of sp2 carbon. Cyclic voltammetry and chronoamperometry data obtained in this study indicate that the deposition of Pt on plasma carbon increases its electrocatalytic activity toward ethanol oxidation reaction.

Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

International Nuclear Information System (INIS)

Marx, D.

1959-11-01

We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of H2S with Calcium Permeable Channels and Transporters

Directory of Open Access Journals (Sweden)

Weihua Zhang

2015-01-01

Full Text Available A growing amount of evidence has suggested that hydrogen sulfide (H2S, as a gasotransmitter, is involved in intensive physiological and pathological processes. More and more research groups have found that H2S mediates diverse cellular biological functions related to regulating intracellular calcium concentration. These groups have demonstrated the reciprocal interaction between H2S and calcium ion channels and transporters, such as L-type calcium channels (LTCC, T-type calcium channels (TTCC, sodium/calcium exchangers (NCX, transient receptor potential (TRP channels, β-adrenergic receptors, and N-methyl-D-aspartate receptors (NMDAR in different cells. However, the understanding of the molecular targets and mechanisms is incomplete. Recently, some research groups demonstrated that H2S modulates the activity of calcium ion channels through protein S-sulfhydration and polysulfide reactions. In this review, we elucidate that H2S controls intracellular calcium homeostasis and the underlying mechanisms.

AOI [3] High-Temperature Nano-Derived Micro-H₂ and - H₂S Sensors

Energy Technology Data Exchange (ETDEWEB)

Sabolsky, Edward M. [West Virginia Univ., Morgantown, WV (United States)

2014-08-01

The emissions from coal-fired power plants remain a significant concern for air quality. This environmental challenge must be overcome by controlling the emission of sulfur dioxide (SO₂) and hydrogen sulfide (H₂S) throughout the entire coal combustion process. One of the processes which could specifically benefit from robust, low cost, and high temperature compatible gas sensors is the coal gasification process which converts coal and/or biomass into syngas. Hydrogen (H₂), carbon monoxide (CO) and sulfur compounds make up 33%, 43% and 2% of syngas, respectively. Therefore, development of a high temperature (>500°C) chemical sensor for in-situ monitoring of H₂, H₂S and SO2₂ levels during coal gasification is strongly desired. The selective detection of SO₂/H₂S in the presence of H₂, is a formidable task for a sensor designer. In order to ensure effective operation of these chemical sensors, the sensor system must inexpensively function within harsh temperature and chemical environment. Currently available sensing approaches, which are based on gas chromatography, electrochemistry, and IR-spectroscopy, do not satisfy the required cost and performance targets. This work focused on the development microsensors that can be applied to this application. In order to develop the high- temperature compatible microsensor, this work addressed various issues related to sensor stability, selectivity, and miniaturization. In the research project entitled “High-Temperature Nano-Derived Micro-H₂ and -H₂S Sensors”, the team worked to develop micro-scale, chemical sensors and sensor arrays composed of nano-derived, metal-oxide composite materials to detect gases like H₂, SO₂, and H₂S within high-temperature environments (>500°C). The research was completed in collaboration with NexTech Materials, Ltd. (Lewis Center, Ohio). Nex

Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H{sub 2}SO{sub 4} 0.5M; Electrocatalizadores de Platino, Cobalto y Niquel preparados por Aleado Mecanico para la reaccion de reduccion de oxigeno en H{sub 2}SO{sub 4} 0.5M

Energy Technology Data Exchange (ETDEWEB)

Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R. [lNIN, Depto. de Quimica, 52750 La Marquesa, Estado de Mexico (Mexico)

2007-07-01

Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H{sub 2}SO{sub 4} 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

Confinement dependence of electro-catalysts for hydrogen evolution from water splitting

Directory of Open Access Journals (Sweden)

Mikaela Lindgren

2014-02-01

Full Text Available Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE, where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.

Human organic cation transporter 2 (hOCT2): Inhibitor studies using S2-hOCT2 cells

International Nuclear Information System (INIS)

Chiba, Shoetsu; Ikawa, Toru; Takeshita, Hiroshi; Kanno, Sanae; Nagai, Tomonori; Takada, Meri; Mukai, Toshiji; Wempe, Michael F.

2013-01-01

Highly expressed in kidney and located on the basolateral membrane, human organic cation transporter 2 (hOCT2) can transport various compounds (i.e. drugs and toxins) into the proximal tubular cell. Using cultured proximal tubule cells stably expressing hOCT2 (i.e. S2-hOCT2 cells), we sought to probe different compound classes (e.g. analgesics, anti-depressants, anti-psychotics, disinfectant, herbicides, insecticides, local anesthetic, muscarinic acetylcholine receptor antagonist, sedatives, steroid hormone, stimulants and toxins) for their ability to inhibit 14 C-TEA uptake, a prototypical OCT2 substrate. Aconitine, amitriptyline, atropine, chlorpyrifos, diazepam, fenitrothion, haloperidol, lidocaine, malathion, mianserin, nicotine and triazolam significantly inhibited 14 C-TEA uptake; IC 50 values were 59.2, 2.4, 2.0, 20.7, 32.3, 13.2, 32.5, 104.6, 71.1, 17.7, 52.8 and 65.5 μM, respectively. In addition, aconitine, amitriptyline, atropine, chlorpyrifos, fenitrothion, haloperidol, lidocaine, and nicotine displayed competitive inhibition with K i values of 145.6, 2.5, 2.4, 24.8, 16.9, 51.6, 86.8 and 57.7 μM, respectively. These in vitro data support the notion that compounds pertaining to a wide variety of different drug classes have the potential to decrease renal clearance of drugs transported via hOCT2. Consequently, these data warrant additional studies to probe hOCT2 and its role to influence drug pharmacokinetics

Women’s G Tolerance

Science.gov (United States)

1986-08-01

for the groups matched by age (70 pairs), weight sickness, uncomfortable feelings of distension in arms (26 pairs), and act~vity status (84 pairs...mass-spring-damper) s ,stem Straining G tolerance, being dpendent on skeletal having a resonant frequency above about I Hz. As muscular strength and...of the women’s G tolerance stud\\ scclic variations in muscular strength and endurance. was below 0.1 Hz (11), the production of any significant

H2S cracking resistance of type 420 stainless steel tubulars

International Nuclear Information System (INIS)

Klein, L.J.

1984-01-01

Type 420 stainless steel (13Cr) production tubing is being used successfully in deep sour gas wells in the Tuscaloosa Trend. Despite their reputation for poor H 2 S cracking resistance in laboratory tests, 12-13% Cr steels continue to perform well in sour environments. NACE Tensile Test and Shell bent beam test results indicate Type 420 is more resistant to H 2 S cracking than Type 410, but is not as resistant as carbon steel, at to 586-690 MPa (85-100 ksi) yield strength level. In addition to evaluating Type 420 stainless steel in the standard NACE Tensile and Shell bent beam tests, the effects on cracking tendency of chloride concentration, pH, and H 2 S gas concentration in the NACE Test solution were also examined. Type 420 appears to be more resistant to H 2 S cracking than is indicated by standard laboratory tests, at least in low H 2 S level sour environments

Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene

Science.gov (United States)

Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2016-05-01

Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade

H2S mediated thermal and photochemical methane activation

Science.gov (United States)

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric

2013-01-01

Sustainable, low temperature methods of natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) in mixture with methane, CH4, altogether deemed as sub-quality or “sour” gas. We propose a unique method for activating this “sour” gas to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier, such as H2. For this purpose, we computationally investigated H2S mediated methane activation to form a reactive CH3SH species via direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex results in a barrier-less relaxation via a conical intersection to form a ground state CH3SH+H2 complex. The resulting CH3SH can further be heterogeneously coupled over acidic catalysts to form higher hydrocarbons while the H2 can be used as a fuel. This process is very different from a conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced controllability over the process conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the currently industrially used methane steam reforming (SMR). PMID:24150813

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

Energy Technology Data Exchange (ETDEWEB)

Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

2017-08-17

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

The roles of H2S and H2O2 in regulating AsA-GSH cycle in the leaves of wheat seedlings under drought stress.

Science.gov (United States)

Shan, Changjuan; Zhang, Shengli; Ou, Xingqi

2018-01-25

This paper investigated the roles of hydrogen sulfide (H 2 S) and hydrogen peroxide (H 2 O 2 ) and the possible relationship between them in regulating the AsA-GSH cycle in wheat leaves under drought stress (DS). Results showed that DS markedly increased the production of H 2 S and H 2 O 2 , the transcript levels and activities of ascorbate peroxidase (APX), glutathione reductase (GR), monodehydroascorbate reductase (MDHAR), and dehydroascorbate reductase (DHAR); malondialdehyde (MDA) content; and electrolyte leakage (EL). Meanwhile, DS markedly reduced plant height and biomass. Above increases induced by drought stress except MDA content and EL were all suppressed by pretreatments with H 2 S synthesis inhibitor aminooxyaceticacid (AOA) and H 2 O 2 synthesis inhibitor diphenylene iodonium (DPI). Besides, pretreatments with AOA and DPI further significantly increased MDA content and EL and significantly reduced plant height and biomass under DS. DPI reduced the production of H 2 O 2 and H 2 S induced by DS. AOA also reduced the production of H 2 S and H 2 O 2 induced by DS. Pretreatments with NaHS + AOA and H 2 O 2 + DPI reversed above effects of AOA and DPI. Our results suggested that H 2 S and H 2 O 2 all participated in the up-regulation of AsA-GSH cycle in wheat leaves by DS and possibly affected each other.

Review of low pressure plasma processing of proton exchange membrane fuel cell electrocatalysts

OpenAIRE

Brault , Pascal

2016-01-01

Review article; International audience; The present review is describing recent advances in plasma deposition and treatment of low temperature proton exchange membrane fuel cells electrocatalysts. Interest of plasma processing for growth of platinum based, non-precious and metal free electrocatalysts is highlighted. Electrocatalysts properties are tentatively correlated to plasma parameters.

Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jie; Chen, Jinwei, E-mail: jwchen@scu.edu.cn; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin, E-mail: rl.wang@scu.edu.cn

2016-12-15

Graphical abstract: A hybrid catalyst was prepared via a quite green and simple method to achieve an one-pot synthesis of the N-doping carbon, tungsten carbides, and iron/cobalt carbides. It exhibited comparable electrocatalytic activity, higher durability and ability to methanol tolerance compared with commercial Pt/C to ORR. - Highlights: • A novel type of hybrid Fe/Co/WC@NC catalysts have been successfully synthesized. • The hybrid catalyst also exhibited better durability and methanol tolerance. • Multiple effective active sites of Fe{sub 3}C, Co{sub 3}C, WC, and NC help to improve catalytic performance. - Abstract: This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe{sub 3}C and Co{sub 3}C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe{sub 3}C, and Co{sub 3}C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

RuP{sub 2}-based catalysts with platinum-like activity and higher durability for the hydrogen evolution reaction at all pH values

Energy Technology Data Exchange (ETDEWEB)

Pu, Zonghua; Amiinu, Ibrahim Saana; Kou, Zongkui; Li, Wenqiang; Mu, Shichun [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology (China)

2017-09-11

Highly active, stable, and cheap Pt-free catalysts for the hydrogen evolution reaction (HER) are under increasing demand for future energy conversion systems. However, developing HER electrocatalysts with Pt-like activity that can function at all pH values still remains as a great challenge. Herein, based on our theoretical predictions, we design and synthesize a novel N,P dual-doped carbon-encapsulated ruthenium diphosphide (RuP{sub 2} rate at NPC) nanoparticle electrocatalyst for HER. Electrochemical tests reveal that, compared with the Pt/C catalyst, RuP{sub 2} rate at NPC not only has Pt-like HER activity with small overpotentials at 10 mA cm{sup -2} (38 mV in 0.5 m H{sub 2}SO{sub 4}, 57 mV in 1.0 m PBS and 52 mV in 1.0 m KOH), but demonstrates superior stability at all pH values, as well as 100 % Faradaic yields. Therefore, this work adds to the growing family of transition-metal phosphides/heteroatom-doped carbon heterostructures with advanced performance in HER. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

Science.gov (United States)

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-15

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

Biochars as Potential Adsorbers of CH4, CO2 and H2S

Directory of Open Access Journals (Sweden)

Sumathi Sethupathi

2017-01-01

Full Text Available Methane gas, as one of the major biogases, is a potential source of renewable energy for power production. Biochar can be readily used to purify biogas contaminants such as H2S and CO2. This study assessed the adsorption of CH4, H2S, and CO2 onto four different types of biochars. The adsorption dynamics of biochars were investigated in a fixed-bed column, by determining the breakthrough curves and adsorption capacities of biochars. The physicochemical properties of biochars were considered to justify the adsorption performance. The results showed that CH4 was not adsorbed well by the subjected biochars whereas CO2 and H2S were successfully captured. The H2S and CO2 breakthrough capacity were related to both the surface adsorption and chemical reaction. The adsorption capacity was in the following order: perilla > soybean stover > Korean oak > Japanese oak biochars. The simultaneous adsorption also leads to a competition of sorption sites. Biochars are a promising material for the biogas purification industry.

Dynamics and tolerances for the CERN Interdigital H linac

International Nuclear Information System (INIS)

Bylinsky, Y.; Ratzinger, U.; Valero, S.

1992-01-01

A three tank Interdigital H structure has been chosen for the 0.25 to 4.2 MeV/u part of the CERN heavy-ion injector linac. The complete design has been developed by GSI; in particular the longitudinal dimensions have been determined and multi-particle studies have been made using the program LORAS. Some RF tolerance studies have also been made at CERN using this program. For a more general approach to the dynamics, the program DYNAC is being used at CERN, especially where statistical analyses are essential; i.e. for determining emittance growth, tolerances on accelerator parameters and alignment. The approaches and results of these two programs are compared for this novel type of accelerator. (Author) 6 refs., 3 tabs., 3 figs

Microwave-irradiation polyol synthesis of PVP-protected Pt–Ni electrocatalysts for methanol oxidation reaction

CSIR Research Space (South Africa)

Mathe, Ntombizodwa R

2017-01-01

Full Text Available ://doi.org/10.1007/s12678-017-0441-3 Microwave-Irradiation Polyol Synthesis of PVP-Protected Pt–Ni Electrocatalysts for Methanol Oxidation Reaction Ntombizodwa R. Mathe Manfred R. Scriba Rirhandzu S. Rikhotso Neil J. Coville ABSTRACT: Bimetallic Pt...

Preparation of PtRu/C and PtSn/C electrocatalysts using electron beam irradiation for direct and ethanol fuel cell

International Nuclear Information System (INIS)

Silva, Dionisio Furtunato da

2009-01-01

PtRu/C and PtSn/C electrocatalysts were prepared using electron beam irradiation. The metal ions were dissolved in water/2-propanol and water/ethylene glycol solutions and the carbon support was added. The resulting mixtures were irradiated under stirring. The effect of water/ethylene glycol and water/2-propanol (v/v) ratio, Pt:Ru and Pt:Sn atomic ratios, the irradiation time and dose rate were studied. The obtained materials were characterized by Energy dispersive analysis of X-rays (EDX), X-ray diffraction (XRD), cyclic voltammetry (CV) and Moessbauer spectroscopy. The electro-oxidation of methanol and ethanol were studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. The electrocatalysts were also tested on the Direct Methanol and Ethanol Fuel Cells. PtRu/C electrocatalysts prepared in water/ethylene glycol showed Pt:Ru atomic ratios different from the nominal ones. The results suggested that part of the Ru(III) ions were not reduced. The obtained materials showed the face-centered cubic (fcc) structure of Pt and Pt alloys with crystallite sizes of 2-3 nm. PtRu/C electrocatalysts prepared in water/2-propanol showed Pt:Ru atomic ratios similar to the nominal ones. The obtained materials also showed the fcc structure of platinum and platinum alloys with crystallite sizes of 3-4 nm. PtSn/C electrocatalysts prepared in water/ethylene glycol and water/2-propanol showed Pt:Sn atomic ratios similar to the nominal ones. The obtained materials showed the platinum (fcc) phase with crystallite sizes in the range of 2 - 4 nm and a SnO 2 (cassiterite) phase. The obtained PtRu/C and PtSn/C electrocatalysts showed similar or superior performance for methanol and ethanol electro-oxidation compared to commercial PtRu/C (E-TEK) and PtSn/C (BASF) electrocatalysts. (author)

Two wheat glutathione peroxidase genes whose products are located in chloroplasts improve salt and H2O2 tolerances in Arabidopsis.

Directory of Open Access Journals (Sweden)

Chao-Zeng Zhai

Full Text Available Oxidative stress caused by accumulation of reactive oxygen species (ROS is capable of damaging effects on numerous cellular components. Glutathione peroxidases (GPXs, EC 1.11.1.9 are key enzymes of the antioxidant network in plants. In this study, W69 and W106, two putative GPX genes, were obtained by de novo transcriptome sequencing of salt-treated wheat (Triticum aestivum seedlings. The purified His-tag fusion proteins of W69 and W106 reduced H2O2 and t-butyl hydroperoxide (t-BHP using glutathione (GSH or thioredoxin (Trx as an electron donor in vitro, showing their peroxidase activity toward H2O2 and toxic organic hydroperoxide. GFP fluorescence assays revealed that W69 and W106 are localized in chloroplasts. Quantitative real-time PCR (Q-RT-PCR analysis showed that two GPXs were differentially responsive to salt, drought, H2O2, or ABA. Isolation of the W69 and W106 promoters revealed some cis-acting elements responding to abiotic stresses. Overexpression of W69 and W106 conferred strong tolerance to salt, H2O2, and ABA treatment in Arabidopsis. Moreover, the expression levels of key regulator genes (SOS1, RbohD and ABI1/ABI2 involved in salt, H2O2 and ABA signaling were altered in the transgenic plants. These findings suggest that W69 and W106 not only act as scavengers of H2O2 in controlling abiotic stress responses, but also play important roles in salt and ABA signaling.

Platinum monolayer electrocatalysts for oxygen reduction: effect of substrates, and long-term stability

Directory of Open Access Journals (Sweden)

J. ZHANG

2005-03-01

Full Text Available We describe a novel concept for a Ptmonolayer electrocatalyst and present the results of our electrochemical, X-ray absorption spectroscopy, and scanning tunneling microscopy studies. The electrocatalysts were prepared by a new method for depositing Pt monolayers involving the galvanic displacement by Pt of an underpotentially deposited Cu monolayer on substrates of Au (111, Ir(111, Pd(111, Rh(111 and Ru(0001 single crylstals, and Pd nanoparticles. The kinetics of O2 reduction showed significant enhancement with Pt monolayers on Pd(111 and Pd nanoparticle surfaces in comparisonwith the reaction on Pt(111 and Pt nanoparticles, respectively. This increase in catalytic activity is attributed partly to the decreased formation of PtOH, as shown by in situ X-ray absorption spectroscopy. The results illustrate that placing a Pt monolayer on a suitable substrate of metal nanoparticles is an attractive way of designing better O2 reduction electrocatalysts with very low Pt contents.

Elevated 1-h post-challenge plasma glucose levels in subjects with normal glucose tolerance or impaired glucose tolerance are associated with whole blood viscosity.

Science.gov (United States)

Marini, Maria Adelaide; Fiorentino, Teresa Vanessa; Andreozzi, Francesco; Mannino, Gaia Chiara; Perticone, Maria; Sciacqua, Angela; Perticone, Francesco; Sesti, Giorgio

2017-08-01

It has been suggested that glucose levels ≥155 mg/dl at 1-h during an oral glucose tolerance test (OGTT) may predict development of type 2 diabetes and cardiovascular events among adults with normal glucose tolerance (NGT 1 h-high). Studies showed a link between increased blood viscosity and type 2 diabetes. However, whether blood viscosity is associated with dysglycemic conditions such as NGT 1 h-high, impaired glucose tolerance (IGT) or impaired fasting glucose (IFG) is unsettled. 1723 non-diabetic adults underwent biochemical evaluation and OGTT. A validated formula based on hematocrit and total plasma proteins was employed to estimate whole blood viscosity. Subjects were categorized into NGT with 1 h glucose h-low), NGT-1 h-high, IFG and/or IGT. Hematocrit and blood viscosity values appeared significantly higher in individuals with NGT 1 h-high, IFG and/or IGT as compared to NGT 1 h-low subjects. Blood viscosity was significantly correlated with age, waist circumference, blood pressure, HbA1c, fasting, 1- and 2-h post-challenge insulin levels, total cholesterol and low-density lipoprotein, triglycerides, fibrinogen, white blood cell, and inversely correlated with high-density lipoprotein and insulin sensitivity. Of the four glycemic parameters, 1-h post-challenge glucose showed the strongest correlation with blood viscosity (β = 0.158, P h post-challenge plasma glucose. They also suggest that a subgroup of NGT individuals with 1-h post-challenge plasma >155 mg/dl have increased blood viscosity comparable to that observed in subjects with IFG and/or IGT.

A molecular molybdenum–schiff base electro-catalyst for generating hydrogen from acetic acid or water

International Nuclear Information System (INIS)

Cao, Jie-Ping; Fang, Ting; Zhou, Ling-Ling; Fu, Ling-Zhi; Zhan, Shuzhong

2014-01-01

Highlights: • The reaction of ligand, H 2 L and MoCl 5 gives a Mo(VI) complex [MoL(O) 2 ] 1. • Complex 1 is capable of catalyzing hydrogen evolution from acetic acid and water. • TOF reaches a maximum of 68 (DMF) and 356 (buffer, pH 6) moles/h, respectively. • Sustained proton reduction catalysis occurs over a 69 h period and no decomposition of 1. - ABSTRACT: The reaction of 2-pyridylamino-N,N-bis(2-methylene-4-ethyl-6-tert-butylphenol) (H 2 L) and MoCl 5 gives a molybdenum(VI) complex [MoL(O) 2 ] 1, a new molecular electrocatalyst, which has been determined by X-ray crystallography. Electrochemical studies show that complex 1 can catalyze hydrogen evolution from acetic acid or aqueous buffer. Turnover frequency (TOF) reaches a maximum of 68 (in N,N-Dimethylformamide (DMF)) and 356 (in buffer, pH 6.0) moles of hydrogen per mole of catalyst per hour, respectively. Sustained proton reduction catalysis occurs at glassy carbon (GC) electrode to give H 2 over a 69 h electrolysis period and no observable decomposition of the catalyst

Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

Energy Technology Data Exchange (ETDEWEB)

Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir, E-mail: drinager@ig.com.br, E-mail: dfsilva@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Santos, Mauro Coelho dos [Universidade Federal do ABC (LEMN/CCNH/UFABC), Santo Andre, SP (Brazil)

2015-07-01

Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm{sup -2} and 31 mW.cm{sup -2} for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

Ethanol electro-oxidation in alkaline medium using Pd/MWCNT and PdAuSn/MWCNT electrocatalysts prepared by electron beam irradiation

International Nuclear Information System (INIS)

Geraldes, Adriana Napoleao; Silva, Dionisio Furtunato da; Andrade e Silva, Leonardo Gondin de; Spinace, Estevam Vitorio; Oliveira Neto, Almir; Santos, Mauro Coelho dos

2015-01-01

Environmental problems and the world growing demand for energy has mobilized the scientific community in finding of clean and renewable energy sources. In this context, fuel cells appear as appropriate technology for generating electricity through alcohols electro-oxidation. Multi Wall Carbon Nanotubes (MWCNT)-supported Pd and trimetallic PdAuSn (Pd:Au:Sn 50:10:40 atomic ratio) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by VC, Chronoamperometry, EDX, TEM and XRD. The catalytic activities of electrocatalysts toward ethanol electro-oxidation were evaluated in alkaline medium in a single alkaline direct ethanol fuel cell (ADEFC) in a range temperature 60 to 90 deg C. The best performances were obtained at 85 deg C: 33 mW.cm -2 and 31 mW.cm -2 for Pd/ MWCNT and PdAuSn/MWCNT electrocatalysts, respectively. X-ray diffractograms of electrocatalysts showed the presence of Pd-rich (fcc) and Au-rich (fcc) phases. Cyclic voltammetry and chronoamperometry experiments showed that PdAuSn/MWCNT electrocatalyst demonstrated similar activity toward ethanol electro-oxidation at room temperature, compared to electrocatalyst Pd/MWCNT. (author)

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Science.gov (United States)

Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

2014-11-21

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

The Role of Endogenous H(2)S in Cardiovascular Physiology

DEFF Research Database (Denmark)

Skovgaard, Nini; Gouliaev, Anja; Aalling, Mathilde

2011-01-01

Recent research has shown that the endogenous gas hydrogen sulphide (H(2)S) is a signalling molecule of considerable biological potential and has been suggested to be involved in a vast number of physiological processes. In the vascular system, H(2)S is synthesized from cysteine by cystathionine-...

Synthesis and characterization of PtRuMo/C nanoparticle electrocatalyst for direct ethanol fuel cell

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhen-Bo; Yin, Ge-Ping [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Lin, Yong-Ge [Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, San Juan, PR 00931 (United States)

2007-07-10

This research aims at enhancement of the performance of anodic catalysts for the direct ethanol fuel cell (DEFC). Two distinct DEFC nanoparticle electrocatalysts, PtRuMo/C and PtRu/C, were prepared and characterized, and one glassy carbon working electrode for each was employed to evaluate the catalytic performance. The cyclic-voltammetric, chronoamperometric, and amperometric current-time measurements were done in the solution 0.5 mol L{sup -1} CH{sub 3}CH{sub 2}OH and 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The composition, particle sizes, lattice parameters, morphology, and the oxidation states of the metals on nanoparticle catalyst surfaces were determined by energy dispersive analysis of X-ray (EDAX), X-ray diffraction (XRD), transmission electron micrographs (TEM) and X-ray photoelectron spectrometer (XPS), respectively. The results of XRD analysis showed that both PtRuMo/C and PtRu/C had a face-centered cubic (fcc) structure with smaller lattice parameters than that of pure platinum. The typical particle sizes were only about 2.5 nm. Both electrodes showed essentially the same onset potential as shown in the CV for ethanol electrooxidation. Despite their comparable active specific areas, PtRuMo/C was superior to PtRu/C in respect of the catalytic activity, durability and CO-tolerance. The effect of Mo in the PtRuMo/C nanoparticle catalyst was illustrated with a bifunctional mechanism, hydrogen-spillover effect and the modification on the Pt electronic states. (author)

Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

Science.gov (United States)

Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

2017-10-01

Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

Study of H/sub 2/S emissions from a salt water marsh

Energy Technology Data Exchange (ETDEWEB)

Goldberg, A B; Maroulis, P J; Wilner, L A; Bandy, A R

1981-01-01

A gas chromatographic method was developed for measuring background levels of atmospheric H/sub 2/S. A detectivity of 0.02 ppBV (S/N=2) was achieved with a frequency of one sample per 8 min. A reduction of the detectivity to 0.005 ppBV was predicted with modest optimization effort. The technique was applied in a study of H/sub 2/s emissions from a salt water marsh. Large diurnal variations of the H/sub 2/S levels were observed that were relatively repeatable under similar meteorological conditions. The area averaged emission rate of h2s for one evening in July was estimated to be between 3 and 16 g S/m/sup 2//y. The emission rate was estimated to have decreased by a factor of at least 10 between 22 July and 13 December 1978. Atlantic Ocean air was found to be very low in H/sub 2/S content, typically less than 30 ppTV.

Electrodeposition of a Pt-PrO{sub 2-x} electrocatalyst on diamond electrodes for the oxidation of methanol

Energy Technology Data Exchange (ETDEWEB)

Chen, Liang; Hu, Jingping; Foord, John S. [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA (United Kingdom)

2012-09-15

The electrodeposition of Pt-PrO{sub 2-x} nanostructures on boron-doped diamond electrodes was explored by decorating platinum nanoparticles with praseodymium oxide, for application as an electrocatalyst in the electrooxidation of methanol in direct methanol fuel cells. A high loading of platinum with good stability was deposited by adopting a two-stage protocol, which involved a stepped potential route and a chronoamperometric approach. Praseodymium oxide was then coated on the platinum particles from solutions containing praseodymium nitrate and hydrogen peroxide. The porous microstructure of the resulting catalyst was characterized by X-ray photoelectron spectroscopy and scanning electron microscope, along with electrochemical measurement. The addition of praseodymium oxide to the Pt resulted in a higher catalytic activity profile for methanol oxidation along with an improved resistance to poisoning effects caused by incompletely oxidized carbonaceous species. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Comparative study of SOS2 and a novel PMP3-1 gene expression in two sunflower (Helianthus annuus L.) lines differing in salt tolerance.

Science.gov (United States)

Saadia, Mubshara; Jamil, Amer; Ashraf, Muhammad; Akram, Nudrat Aisha

2013-06-01

Gene expression pattern of two important regulatory proteins, salt overly sensitive 2 (SOS2) and plasma membrane protein 3-1 (PMP3-1), involved in ion homeostasis, was analyzed in two salinity-contrasting sunflower (Helianthus annuus L.) lines, Hysun-38 (salt tolerant) and S-278 (moderately salt tolerant). The pattern was studied at selected time intervals (24 h) under 150 mM NaCl treatment. Using reverse transcription PCR, SOS2 gene fragment was obtained from young leaf and root tissues of opposing lines while that for PMP3-1 was obtained only from young root tissues. Both tolerant and moderately tolerant lines showed a gradual increase in SOS2 expression in sunflower root tissues. Leaf tissues showed the gradually increasing pattern of SOS2 expression in tolerant plants as compared to that for moderately tolerant ones that showed a relatively lower level of expression for this gene. We found the highest level of PMP 3-1 expression in the roots of tolerant sunflower line at 6 and 12 h postsalinity treatment. The moderately tolerant line showed higher expression of PMP3-1 at 12 and 24 h after salt treatment. Overall, the expression of genes for both the regulator proteins varied significantly in the two sunflower lines differing in salinity tolerance.

Testosterone 15β-hydroxylation by solvent tolerant Pseudomonas putida S12

NARCIS (Netherlands)

Ruijssenaars, H.J.; Sperling, E.M.G.M.; Wiegerinck, P.H.G.; Brands, F.T.L.; Wery, J.; Bont, J.A.M.de

2007-01-01

A steroid 15β-hydroxylating whole-cell solvent tolerant biocatalyst was constructed by expressing the Bacillus megaterium steroid hydroxylase CYP106A2 in the solvent tolerant Pseudomonas putida S12. Testosterone hydroxylation was improved by a factor 16 by co-expressing Fer, a putative Fe-S protein

A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

Science.gov (United States)

Feng, Yan; Liu, Hui; Yang, Jun

2017-06-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

Production of 34S-labeled gypsum (Ca34SO4.2H2O Produção de gesso (Ca34SO4.2H2O, marcado com 34S

Directory of Open Access Journals (Sweden)

Alexssandra Luiza Rodrigues Molina Rossete

2006-08-01

Full Text Available Agricultural gypsum (CaSO4.2H2O stands out as an effective source of calcium and sulfur, and to control aluminum saturation in the soil. Labeled as 34S it can elucidate important aspects of the sulfur cycle. Ca34SO4.2H2O was obtained by chemical reaction between Ca(OH2 and H2(34SO4, performed under slow agitation. The acid was produced by ion exchange chromatography using the Dowex 50WX8 cation exchange resin and a Na2(34SO4 eluting solution. After precipitation, the precipitate was separated and dried in a ventilated oven at 60ºC. From 2.2 L H2SO4 0.2 mol L-1 and 33.6 g Ca(OH2, 73.7 ± 0.6 g Ca34SO4.2H2O were produced on average in the tests, representing a mean yield of 94.6 ± 0.8%, with 98% purity. The 34SO2 gas was obtained from Ca34SO4.2H2O in the presence of NaPO3 in a high vacuum line and was used for the isotopic determination of S in an ATLAS-MAT model CH-4 mass spectrometer.O gesso agrícola (CaSO4.2H2O destaca-se como fonte eficiente de cálcio e enxofre e na redução da saturação de alumínio no solo. O 34S como traçador isotópico pode elucidar aspectos importantes no ciclo do enxofre. Para tanto o Ca34SO4.2H2O foi obtido por reação química entre o Ca(OH2 e solução de H2(34SO4, realizada sob agitação lenta. O ácido foi produzido por cromatografia de troca iônica, utilizando resina catiônica Dowex 50WX8 e solução eluente de Na2(34SO4. Após a precipitação foi separado o precipitado e realizada a secagem em estufa ventilada à temperatura de 60ºC. Nos testes, a partir de 2,2 L de H2SO4 0,2 mol L-1 e 33,6 g de Ca(OH2, foram produzidos em média 73,7 ± 0,6 g de Ca34SO4.2H2O representando um rendimento médio de 94,6 ± 0,8%, com pureza de 98%. A partir do Ca34SO4.2H2O na presença de NaPO3, em linha de alto vácuo, obteve-se o gás 34SO2 utilizado para a determinação isotópica do S no espectrômetro de massas ATLAS-MAT modelo CH-4.

Investigation of the chemistry of liquid H{sub 2}S scavengers

Energy Technology Data Exchange (ETDEWEB)

Buhaug, Janne Bjoerntvedt

2002-07-01

The production of natural gas in the North Sea is facing a growing problem: contamination of the natural gas with dihydrogen sulfide, H{sub 2}S. As a gas reservoir is emptied, seawater containing sulfates is pumped into it, and the sulfates are reduced to dihydrogen sulfide by sulfate-reducing bacteria. Dihydrogen sulfide is then pumped up along with the oil, gas and water from the reservoir, causing severe corrosion of pipelines and contamination of the final natural gas product. Dihydrogen sulfide is extremely toxic, and in fields with especially large concentrations of H{sub 2}S this is a severe health risk for the platform workers. Hence, it is desirable to remove the dihydrogen sulfide at the earliest stage possible. There are four main methods for removing H{sub 2}S from natural gas: (1) Liquid scavengers, (2) Solid scavengers, (3) Liquid redox processes, (4) Amine / Claus catalyst. Liquid scavengers are widely used in the natural gas industry, especially at sites with relatively low concentrations of H{sub 2}S. As a rule of thumb, liquid scavengers are economically favourable at sites with a removal of less than 50 kg/day of H{sub 2}S. This thesis is concerned with the cyclic amine 1,3,5 -tris(2-hydroxyethyl)-1,3,5-triazinane, often referred to as Triazine. This is used in fields with relatively low concentration of H{sub 2}S and dominates the liquid scavenger market.

Combinatorial investigation of Pt-Ru-Sn alloys as an anode electrocatalysts for direct alcohol fuel cells

Energy Technology Data Exchange (ETDEWEB)

Chu, Young Hwan [Department of New Energy.Resource Engineering, College of Science and Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si, Gangwon-Do 220-702 (Korea); Shul, Yong Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 134, Shinchon-Dong, Seodaemun-Gu, Seoul 120-749 (Korea)

2010-10-15

Low-temperature direct alcohol fuel cells fed with different kinds of alcohol (methanol, ethanol and 2-propanol) have been investigated by employing ternary electrocatalysts (Pt-Ru-Sn) as anode catalysts. Combinatorial chemistry has been applied to screen the 66-PtRuSn-anode arrays at the same time to reduce cost, time, and effort when we select the optimum composition of electrocatalysts for DAFCs (Direct Alcohol Fuel Cells). PtRuSn (80:20:0) showed the lowest onset potential for methanol electro-oxidation, PtRuSn (50:0:50) for ethanol, and PtRuSn (20:70:10) for 2-propanol in CV results respectively, and single cell performance test indicated that Ru is more suitable for direct methanol fuel cell system, Sn for direct ethanol fuel cell system, and 2-propanol could be applied as fuel with low platinum composition anode electrocatalyst. The single cell performance results and electrochemical results (CV) were well matched with the combinatorial electrochemical results. As a result, we could verify the availability of combinatorial chemistry by comparing the results of each extreme electrocatalysts compositions as follows: PtRuSn (80:20:0) for methanol, PtRuSn (50:0:50) for ethanol and PtRuSn (20:70:10) for 2-propanol. (author)

Osmopriming-induced salt tolerance during seed germination of alfalfa most likely mediates through H2O2 signaling and upregulation of heme oxygenase.

Science.gov (United States)

Amooaghaie, Rayhaneh; Tabatabaie, Fatemeh

2017-07-01

The present study showed that osmopriming or pretreatment with low H 2 O 2 doses (2 mM) for 6 h alleviated salt-reduced seed germination. The NADPH oxidase activity was the main source, and superoxide dismutase (SOD) activity might be a secondary source of H 2 O 2 generation during osmopriming or H 2 O 2 pretreatment. Hematin pretreatment similar to osmopriming improved salt-reduced seed germination that was coincident with the enhancement of heme oxygenase (HO) activity. The semi-quantitative RT-PCR confirmed that osmopriming or H 2 O 2 pretreatment was able to upregulate heme oxygenase HO-1 transcription, while the application of N,N-dimethyl thiourea (DMTU as trap of endogenous H 2 O 2 ) and diphenyleneiodonium (DPI as inhibitor of NADPHox) not only blocked the upregulation of HO but also reversed the osmopriming-induced salt attenuation. The addition of CO-saturated aqueous rescued the inhibitory effect of DMTU and DPI on seed germination and α-amylase activity during osmopriming or H 2 O 2 pretreatment, but H 2 O 2 could not reverse the inhibitory effect of ZnPPIX (as HO inhibitor) or Hb (as CO scavenger) that indicates that the CO acts downstream of H 2 O 2 in priming-driven salt acclimation. The antioxidant enzymes and proline synthesis were upregulated in roots of seedlings grown from primed seeds, and these responses were reversed by adding DMTU, ZnPPIX, and Hb during osmopriming. These findings for the first time suggest that H 2 O 2 signaling and upregulation of heme oxygenase play a crucial role in priming-driven salt tolerance.

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

Science.gov (United States)

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-01

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

The acid tolerance response and pH adaptation of Enterococcus faecalis in extract of lime Citrus aurantiifolia from Aceh Indonesia.

Science.gov (United States)

Mubarak, Zaki; Soraya, Cut

2018-01-01

Background:  The objective of the present study was to evaluate the acid tolerance response and pH adaptation when Enterococcus faecalis interacted with extract of lime ( Citrus aurant iifolia ). Methods : We used E. faecalis ATCC 29212 and lime extract from Aceh, Indonesia. The microbe was analyzed for its pH adaptation, acid tolerance response, and adhesion assay using a light microscope with a magnification of x1000. Further, statistical tests were performed to analyze both correlation and significance of the acid tolerance and pH adaptation as well as the interaction activity. Results : E. faecalis was able to adapt to a very acidic environment (pH 2.9), which was characterized by an increase in its pH (reaching 4.2) at all concentrations of the lime extract (p lime extract based on spectrophotometric data (595 nm) (p lime extract was relatively stable within 6 up to 12 hours (p 0.05) based on the mass profiles of its interaction activity. Conclusions : E. faecalis can adapt to acidic environments (pH 2.9-4.2); it is also able to tolerate acid generated by Citrus auranti ifolia extract, revealing a stable interaction in the first 6-12 hours.

Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

Science.gov (United States)

McCrory, Charles C L; Jung, Suho; Peters, Jonas C; Jaramillo, Thomas F

2013-11-13

Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.

Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell.

Science.gov (United States)

Lei, M; Wang, J; Li, J R; Wang, Y G; Tang, H L; Wang, W J

2014-08-11

Replacing precious and nondurable Pt catalysts with cheap materials is a key issue for commercialization of fuel cells. In the case of oxygen reduction reaction (ORR) catalysts for direct methanol fuel cell (DMFC), the methanol tolerance is also an important concern. Here, we develop AlN nanowires with diameters of about 100-150 nm and the length up to 1 mm through crystal growth method. We find it is electrochemically stable in methanol-contained alkaline electrolyte. This novel material exhibits pronounced electrocatalytic activity with exchange current density of about 6.52 × 10(-8) A/cm(2). The single cell assembled with AlN nanowire cathodic electrode achieves a power density of 18.9 mW cm(-2). After being maintained at 100 mA cm(-2) for 48 h, the AlN nanowire-based single cell keeps 92.1% of the initial performance, which is in comparison with 54.5% for that assembled with Pt/C cathode. This discovery reveals a new type of metal nitride ORR catalyst that can be cheaply produced from crystal growth method.

Synthesis and spectroscopic stereospecificity assay of the deuterated quinolizidine alkaloids (2S)-( sup 2 H)- and (2R)-( sup 2 H)-sparteine

Energy Technology Data Exchange (ETDEWEB)

Ebner, T.; Meese, C.O. (Fischer-Bosch Inst. fuer Klinische Pharmakologie, Stuttgart (Germany, F.R.)); Rebell, J. (Stuttgart Univ. (Germany, F.R.). Inst. fuer Organische Chemie); Fischer, P. (Stuttgart Univ. (Germany, F.R.). Inst. fuer Organische Chemie Fischer-Bosch Inst. fuer Klinische Pharmakologie, Stuttgart (Germany, F.R.))

1989-04-01

Borohydride reduction of the (+)-1,2-dehydrosparteinium salts proceeds almost exclusively from the Si side, yielding, respectively, the stereoselectively (2S)({beta})-deuterated (-)-sparteine and the (2R)({alpha})-deuterated (-)-sparteine. Stereo-chemistry and isotopic purity of the deuterium label ({>=}98%) are established unequivocally by {sup 1}H, {sup 2}H and {sup 13}C NMR spectroscopy. (author).

A Method for the Simultaneous Cleansing of H2S and SO2

Directory of Open Access Journals (Sweden)

Dzhamal R. Uzun

2016-01-01

Full Text Available A method for the simultaneous electrochemical purification of hydrogen sulfide and sulfur dioxide from sea water or industrial wastes is proposed. Fundamentally the method is based on the electrochemical affinity of the pair H2S and SO2. The reactions (oxidation of H2S and reduction of SO2 proceed on а proper catalyst in a flow reactor, without an external power by electrochemical means. The partial curves of oxidation of H2S and reduction of SO2 have been studied electrochemically on different catalysts. Following the additive principle the rate of the process has been found by intersection of the curves. The overall process rate has been studied in a flow type reactor. Similar values of the process rate have been found and these prove the electrochemical mechanism of the reactions. As a result the electrochemical method at adequate conditions is developed. The process is able to completely convert the initial reagents (concentrations CH2S, SO2=0, which is difficult given the chemical kinetics.

Rudimentary simple, single step fabrication of nano-flakes like AgCd alloy electro-catalyst for oxygen reduction reaction in alkaline fuel cell

International Nuclear Information System (INIS)

Bhandary, Nimai; Basu, Suddhasatwa; Ingole, Pravin P.

2016-01-01

In this work, for the first time, we report rudimentary simple, single step fabrication of an electro-catalyst based on AgCd alloy nanoparticles with flakes like geometry which shows highly efficient activity towards oxygen reduction reaction (ORR). A simple potentiostatic deposition method has been employed for co-depositing AgCd alloy nanostructures with flakes like shapes along with dendrites on the surface of carbon fibre paper. The chemico-physical properties of the catalyst are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS). Electro-catalytic activity of AgCd alloy based electro-catalyst towards ORR is studied in alkaline medium by cyclic voltammetry and rotating ring disk electrode (RRDE) technique. Electrochemical in-situ FTIR measurements are also performed to identify the species generated during ORR process. Based on the results from electro-catalysis experiment, it is concluded that nano-alloyed AgCd electrodeposited on carbon paper shows excellent activity for ORR, following four electron pathways with H_2O_2 yield less than 15%. The combination of low cost of Ag and Cd, fast and facile method of its fabrication and higher activity towards ORR makes the AgCd electro-catalyst an attractive catalyst of choice for alkaline fuel cell.

2S protein Ara h 7.0201 has unique epitopes compared to other Ara h 7 isoforms and is comparable to 2S proteins Ara h 2 and 6 in basophil degranulation capacity.

Science.gov (United States)

Hayen, S M; Ehlers, A M; den Hartog Jager, C F; Garssen, J; Knol, E F; Knulst, A C; Suer, W; Willemsen, L E M; Otten, H G

2018-07-01

Screening for specific IgE against 2S albumin proteins Ara h 2 and 6 has good positive predictive value in diagnosing peanut allergy. From the third 2S member Ara h 7, 3 isoforms have been identified. Their allergenicity has not been elucidated. This study investigated the allergenicity of Ara h 7 isoforms compared to Ara h 2 and 6. Sensitization of 15 DBPCFC-confirmed peanut-allergic patients to recombinant Ara h 2.0201, Ara h 6.01 and isoforms of recombinant Ara h 7 was determined by IgE immunoblotting strips. A basophil activation test (BAT) was performed in 9 patients to determine IgE-cross-linking capacities of the allergens. Sensitivity to the allergens was tested in 5 patients who were sensitized to at least 1 Ara h 7 isoform, by a concentration range in the BAT. 3D prediction models and sequence alignments were used to visualize differences between isoforms and to predict allergenic epitope regions. Sensitization to Ara h 7.0201 was most frequent (80%) and showed to be equally potent as Ara h 2.0201 and 6.01 in inducing basophil degranulation. Sensitization to Ara h 7.0201 together with Ara h 2.0201 and/or 6.01 was observed, indicating the presence of unique epitopes compared to the other 2 isoforms. Differences between the 3 Ara h 7 isoforms were observed in C-terminal cysteine residues, pepsin and trypsin cleavage sites and 3 single amino acid substitutions. The majority of peanut-allergic patients are sensitized to isoform Ara h 7.0201, which is functionally as active as Ara h 2.0201 and 6.01. Unique epitopes are most likely located in the C-terminus or an allergenic loop region which is a known allergenic epitope region for Ara h 2.0201 and 6.01. Due to its unique epitopes and allergenicity, it is an interesting candidate to improve the diagnostic accuracy for peanut allergy. © 2018 The Authors. Clinical & Experimental Allergy Published by John Wiley & Sons Ltd.

Formation of H(2s) atoms by excitation in 10-100 keV H+-H collisions

International Nuclear Information System (INIS)

Higgins, D.P.; Geddes, J.; Gilbody, H.B.

1996-01-01

Cross sections for 2s excitation of H atoms in 10-100 keV H + -H collisions have been determined using a modulated crossed-beam technique. The measurements have been based on observations of the Lyman alpha radiation emitted during electric-field-induced decay of the metastable H(2s) collision products. The results extend the range of the 5-26 keV cross sections measured by Morgan and co-workers to intermediate energies where theoretical predictions based on close-coupling methods are known to be strongly dependent on the choice of the expansion basis. The present cross sections pass through a broad maximum at about 40 keV. Over the range 5-100 keV the available experimental data exhibit an undulatory structure similar to that predicted by some close-coupling calculations but good quantitative agreement is very limited. Close-coupling calculations which employ large basis sets and include a large number of projectile states at the expense of target states are shown to agree less satisfactorily with experiment than those which include only the dominant 1s capture projectile channel. (Author)

The crystal structure of Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Winkler, Verena; Schlosser, Marc; Pfitzner, Arno [Regensburg Univ. (Germany). Inst. fuer Anorganische Chemie

2016-08-01

A reinvestigation of the alkali metal thiosulfates has led to the new phase Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. At first cesium thiosulfate monohydrate was obtained as a byproduct of the synthesis of Cs{sub 4}In{sub 2}S{sub 5}. Further investigations were carried out using the traditional synthesis reported by J. Meyer and H. Eggeling. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O crystallizes in transparent, colorless needles. The crystal structure of the title compound was determined by single crystal X-ray diffraction at room temperature: space group C2/m (No. 12), unit cell dimensions: a = 11.229(4), b = 5.851(2), c = 11.260(5) Aa, β = 95.89(2) , with Z = 4 and a cell volume of V = 735.9(5) Aa{sup 3}. The positions of all atoms including the hydrogen atoms were located in the structure refinement. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O is isotypic with Rb{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. Isolated tetrahedra [S{sub 2}O{sub 3}]{sup 2-} are coordinated by the alkali metal cations, and in addition they serve as acceptors for hydrogen bonding. For both Cs atoms the shortest distances are observed to oxygen atoms of the S{sub 2}O{sub 3}{sup 2-} anions whereas the terminating sulfur atom has its shortest contacts to the water hydrogen atoms. Thus, an extended hydrogen bonding network is formed. The title compound has also been characterized by IR spectroscopy. IR spectroscopy reveals the vibrational bands of the water molecules at 3385 cm{sup -1}. They show a red shift in the OH stretching and bending modes as compared to free water. This is due both to the S..H hydrogen bonding and to the coordination of H{sub 2}O molecules to the cesium atoms.

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

Science.gov (United States)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen