Turning Biodiesel Waste Glycerol into 1,3-Propanediol: Catalytic Performance of Sulphuric acid-Activated Montmorillonite Supported Platinum Catalysts in Glycerol Hydrogenolysis.

PubMed

Samudrala, Shanthi Priya; Kandasamy, Shalini; Bhattacharya, Sankar

2018-05-10

Direct C-O hydrogenolysis of bioglycerine to produce 1,3-propanediol selectively is a vital technology that can expand the scope of biodiesel industry and green chemical production from biomass. Herein we report sulphuric acid-activated montmorillonite clay supported platinum nanoparticles as highly effective solid acid catalysts for the selective production of 1,3-propanediol from glycerol. The catalytic performances of the catalysts were investigated in the hydrogenolysis of glycerol with a fixed bed reactor under ambient pressure. The results were found promising and showed that the activation of montmorillonite by sulphuric acid incorporated Brønsted acidity in the catalyst and significantly improved the selectivity to 1,3-propanediol. The catalytic performance of different platinum loaded catalysts was examined and 2 wt% Pt/S-MMT catalyst presented superior activity among others validating 62% 1,3-propanediol selectivity at 94% glycerol conversion. The catalytic activity of 2Pt/S-MMT was systematically investigated under varying reaction parameters including reaction temperature, hydrogen flow rate, glycerol concentration, weight hourly space velocity, and contact time to derive the optimum conditions for the reaction. The catalyst stability, reusability and structure-activity correlation were also elucidated. The high performance of the catalyst could be ascribed to well disperse Pt nanoparticles immobilized on acid-activated montmorillonite, wider pore-structure and appropriate acid sites of the catalyst.

Real life experimental determination of platinum group metals content in automotive catalytic converters

NASA Astrophysics Data System (ADS)

Yakoumis, I.; Moschovi, A. M.; Giannopoulou, I.; Panias, D.

2018-03-01

The real life experimental protocol for the preparation of spent automobile catalyst samples for elemental analysis is thoroughly described in the following study. Collection, sorting and dismantling, homogenization and sample preparation for X-Ray fluorescence spectroscopy and Atomic Adsorption Spectroscopy combined with Inductive coupled plasma mass spectrometry are discussed in detail for both ceramic and metallic spent catalysts. The concentrations of Platinum Group Metals (PGMs) in spent catalytic converters are presented based on typical consignments of recycled converters (more than 45,000 pieces) from the Greek Market. The conclusions clearly denoted commercial metallic catalytic foil contains higher PGMs loading than ceramic honeycombs. On the other hand, the total PGMs loading in spent ceramic catalytic converters has been found higher than the corresponding value for the metallic ones.

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

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Full scale phosphoric acid fuel cell stack technology development

NASA Technical Reports Server (NTRS)

Christner, L.; Faroque, M.

1984-01-01

The technology development for phosphoric acid fuel cells is summarized. The preparation, heat treatment, and characterization of carbon composites used as bipolar separator plates are described. Characterization included resistivity, porosity, and electrochemical corrosion. High density glassy carbon/graphite composites performed well in long-term fuel cell endurance tests. Platinum alloy cathode catalysts and low-loaded platinum electrodes were evaluated in 25 sq cm cells. Although the alloys displayed an initial improvement, some of this improvement diminished after a few thousand hours of testing. Low platinum loading (0.12 mg/sq cm anodes and 0.3 mg/sq cm cathodes) performed nearly as well as twice this loading. A selectively wetproofed anode backing paper was tested in a 5 by 15 inch three-cell stack. This material may provide for acid volume expansion, acid storage, and acid lateral distribution.

Low platinum catalyst and method of preparation

DOEpatents

Liu, Di-Jia; Chong, Lina

2017-11-21

A low platinum catalyst and method for making same. The catalyst comprises platinum-transition metal bimetallic alloy microcrystallites over a transition metal-nitrogen-carbon composite. A method of making a catalyst comprises preparation of transition metal organic frameworks, infusion of platinum, thermal treatment, and reduction to form the microcrystallites and composite.

Anion exchange membrane fuel cells: Current status and remaining challenges

NASA Astrophysics Data System (ADS)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; Bae, Chulsung; Yan, Yushan; Zelenay, Piotr; Kim, Yu Seung

2018-01-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. In this perspective article, we describe the current status of AEMFCs as having reached beginning of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. These perspectives may provide useful insights for the development of next-generation of AEMFCs.

Anion exchange membrane fuel cells: Current status and remaining challenges

DOE PAGES

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; ...

2017-09-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution

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

Komini Babu, Siddharth; Chung, Hoon T.; Zelenay, Piotr

This paper reports on the characterization of polymer electrolyte fuel cell (PEFC) cathodes featuring a platinum group metal-free (PGM-free) catalyst using nano-scale resolution X-ray computed tomography (nano-CT) and morphological analysis. PGM-free PEFC cathodes have gained significant interest in the past decade since they have the potential to dramatically reduce PEFC costs by eliminating the large platinum (Pt) raw material cost. However, several challenges remain before they are commercially viable. Since these catalysts have lower volumetric activity, the PGM-free cathodes are thicker and are subject to increased gas and proton transport resistances that reduce the performance. To better understand the efficacymore » of the catalyst and improve electrode performance, a detailed understanding the correlation between electrode fabrication, morphology, and performance is crucial. In this work, the pore/solid structure and the ionomer distribution was resolved in three dimensions (3D) using nano-CT for three PGM-free electrodes of varying Nafion® loading. The associated transport properties were evaluated from pore/particlescale simulations within the nano-CT imaged structure. These characterizations are then used to elucidate the microstructural origins of the dramatic changes in fuel cell performance with varying Nafion® ionomer loading. We show that this is primarily a result of distinct changes in ionomer’s spatial distribution. The significant impact of electrode morphology on performance highlights the importance of PGM-free electrode development in concert with efforts to improve catalyst activity and durability.« less

Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution

DOE PAGES

Komini Babu, Siddharth; Chung, Hoon T.; Zelenay, Piotr; ...

2016-11-02

This paper reports on the characterization of polymer electrolyte fuel cell (PEFC) cathodes featuring a platinum group metal-free (PGM-free) catalyst using nano-scale resolution X-ray computed tomography (nano-CT) and morphological analysis. PGM-free PEFC cathodes have gained significant interest in the past decade since they have the potential to dramatically reduce PEFC costs by eliminating the large platinum (Pt) raw material cost. However, several challenges remain before they are commercially viable. Since these catalysts have lower volumetric activity, the PGM-free cathodes are thicker and are subject to increased gas and proton transport resistances that reduce the performance. To better understand the efficacymore » of the catalyst and improve electrode performance, a detailed understanding the correlation between electrode fabrication, morphology, and performance is crucial. In this work, the pore/solid structure and the ionomer distribution was resolved in three dimensions (3D) using nano-CT for three PGM-free electrodes of varying Nafion® loading. The associated transport properties were evaluated from pore/particlescale simulations within the nano-CT imaged structure. These characterizations are then used to elucidate the microstructural origins of the dramatic changes in fuel cell performance with varying Nafion® ionomer loading. We show that this is primarily a result of distinct changes in ionomer’s spatial distribution. The significant impact of electrode morphology on performance highlights the importance of PGM-free electrode development in concert with efforts to improve catalyst activity and durability.« less

Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

PubMed

Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

2018-02-21

Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

NASA Astrophysics Data System (ADS)

Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

2014-09-01

Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells.

PubMed

Kongkanand, Anusorn; Mathias, Mark F

2016-04-07

Substantial progress has been made in reducing proton-exchange membrane fuel cell (PEMFC) cathode platinum loadings from 0.4-0.8 mgPt/cm(2) to about 0.1 mgPt/cm(2). However, at this level of cathode Pt loading, large performance loss is observed at high-current density (>1 A/cm(2)), preventing a reduction in the overall stack cost. This next developmental step is being limited by the presence of a resistance term exhibited at these lower Pt loadings and apparently due to a phenomenon at or near the catalyst surface. This issue can be addressed through the design of catalysts with high and stable Pt dispersion as well as through development and implementation of ionomers designed to interact with Pt in a way that does not constrain oxygen reduction reaction rates. Extrapolating from progress made in past decades, we are optimistic that the concerted efforts of materials and electrode designers can resolve this issue, thus enabling a large step toward fuel cell vehicles that are affordable for the mass market.

Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

DOT National Transportation Integrated Search

1997-04-01

An experimental study of sulfur tolerant zeolite platinum catalysts for aormatics hydrogenation. Platinum catalysts supported on Y-zeolite have been prepared and characterized in various ways, including the hydrogenation of toluene in a high pressure...

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Microstructural Analysis and Transport Resistances of Low-Platinum-Loaded PEFC Electrodes

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

Cetinbas, Firat C.; Wang, Xiaohua; Ahluwalia, Rajesh K.

In this study, we present microstructural characterization for polymer electrolyte fuel cell (PEFC) cathodes with low platinum loadings (low-PGM). The characterization results are used to quantify the contribution of mass transport resistances to cell voltage losses observed in polarization curve data. Three-dimensional pore morphology and ionomer distribution are resolved using nano-scale X-ray computed tomography (nano-CT). Electrode structural properties are reported along with analysis of the impact of microstructure on the effective charge and reactant transport properties. These characterizations are incorporated with a two-dimensional multi-physics model that accounts for energy, charge, and mass transport along with the effect of liquid watermore » flooding. Defining a total mass transport resistance for the whole polarization curve, contributions of transport mechanisms are identified. Analysis of the experimental polarization curves at different operating pressures and temperatures indicates that the mass transport resistance in the cathode is dominated by the transport processes in the electrode. It is shown that flooding in the electrode is a major contributor to transport losses especially at elevated operating pressures while the pressure-independent resistance at the catalyst surface due to transport through the ionomer film plays a significant role, especially at low temperatures and low catalyst loading. In addition, by performing a parametric study for varying catalyst loadings, the importance of electrode roughness (i.e, electrochemically-active surface area/geometric electrode area) in determining the mass transport losses is highlighted.« less

Microstructural Analysis and Transport Resistances of Low-Platinum-Loaded PEFC Electrodes

DOE PAGES

Cetinbas, Firat C.; Wang, Xiaohua; Ahluwalia, Rajesh K.; ...

2017-12-09

In this study, we present microstructural characterization for polymer electrolyte fuel cell (PEFC) cathodes with low platinum loadings (low-PGM). The characterization results are used to quantify the contribution of mass transport resistances to cell voltage losses observed in polarization curve data. Three-dimensional pore morphology and ionomer distribution are resolved using nano-scale X-ray computed tomography (nano-CT). Electrode structural properties are reported along with analysis of the impact of microstructure on the effective charge and reactant transport properties. These characterizations are incorporated with a two-dimensional multi-physics model that accounts for energy, charge, and mass transport along with the effect of liquid watermore » flooding. Defining a total mass transport resistance for the whole polarization curve, contributions of transport mechanisms are identified. Analysis of the experimental polarization curves at different operating pressures and temperatures indicates that the mass transport resistance in the cathode is dominated by the transport processes in the electrode. It is shown that flooding in the electrode is a major contributor to transport losses especially at elevated operating pressures while the pressure-independent resistance at the catalyst surface due to transport through the ionomer film plays a significant role, especially at low temperatures and low catalyst loading. In addition, by performing a parametric study for varying catalyst loadings, the importance of electrode roughness (i.e, electrochemically-active surface area/geometric electrode area) in determining the mass transport losses is highlighted.« less

Single-Atom Catalyst of Platinum Supported on Titanium Nitride for Selective Electrochemical Reactions.

PubMed

Yang, Sungeun; Kim, Jiwhan; Tak, Young Joo; Soon, Aloysius; Lee, Hyunjoo

2016-02-05

As a catalyst, single-atom platinum may provide an ideal structure for platinum minimization. Herein, a single-atom catalyst of platinum supported on titanium nitride nanoparticles were successfully prepared with the aid of chlorine ligands. Unlike platinum nanoparticles, the single-atom active sites predominantly produced hydrogen peroxide in the electrochemical oxygen reduction with the highest mass activity reported so far. The electrocatalytic oxidation of small organic molecules, such as formic acid and methanol, also exhibited unique selectivity on the single-atom platinum catalyst. A lack of platinum ensemble sites changed the reaction pathway for the oxygen-reduction reaction toward a two-electron pathway and formic acid oxidation toward direct dehydrogenation, and also induced no activity for the methanol oxidation. This work demonstrates that single-atom platinum can be an efficient electrocatalyst with high mass activity and unique selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

High performance platinum single atom electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

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.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

PubMed Central

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

2017-01-01

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. PMID:28737170

Fine platinum nanoparticles supported on a porous ceramic membrane as efficient catalysts for the removal of benzene.

PubMed

Liu, Hui; Li, Chengyin; Ren, Xiaoyong; Liu, Kaiqi; Yang, Jun

2017-11-29

It would be desirable to remove volatile organic compounds (VOCs) while we eliminate the dusts using silicon carbide (SiC)-based porous ceramics from the hot gases. Aiming at functionalizing SiC-based porous ceramics with catalytic capability, we herein report a facile strategy to integrate high efficient catalysts into the porous SiC substrates for the VOC removal. We demonstrate an aqueous salt method for uniformly distributing fine platinum (Pt) particles on the alumina (Al 2 O 3 ) layers, which are pre-coated on the SiC substrates as supports for VOC catalysts. We confirm that at a Pt mass loading as low as 0.176% and a weight hourly space velocity of 6000 mL g -1 h -1 , the as-prepared Pt/SiC@Al 2 O 3 catalysts can convert 90% benzene at a temperature of ca. 215 °C. The results suggest a promising way to design ceramics-based bi-functional materials for simultaneously eliminating dusts and harmful VOCs from various hot gases.

Durability of template-free Fe-N-C foams for electrochemical oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Mufundirwa, Albert; Harrington, George F.; Smid, Břetislav; Cunning, Benjamin V.; Sasaki, Kazunari; Lyth, Stephen M.

2018-01-01

Due to the high cost and limited availability of platinum, the development of non-platinum-group metals (non-PGM) catalysts is of paramount importance. A promising alternative to Pt are Fe-N-C-based materials. Here we present the synthesis, characterization and electrochemistry of a template-free nitrogen-doped carbon foam, impregnated with iron. This low-cost and gram-scale method results in materials with micron-scale pore size and large surface area (1600 m2g-1). When applied as an oxygen reduction reaction (ORR) electrocatalyst in alkaline solution, the Fe-N-C foams display extremely high initial activity, slightly out-performing commercially available non-PGM catalysts (NCP-2000, Pajarito Powder). The load-cycle durability in alkaline solution is investigated, and the performance steadily degrades over 60,000 potential cycles, whilst the commercial catalyst is remarkably stable. The post-operation catalyst microstructure is elucidated by transmission electron microscopy (TEM), to provide insight into the degradation processes. The resulting images suggest that potential cycling leads to leaching of atomically dispersed Fe-N2/4 sites in all the catalysts, whereas encapsulated iron nanoparticles are protected.

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping

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

Jones, John; Xiong, Haifeng; DelaRiva, Andrew

2016-07-08

Catalysts based on single atoms of scarce precious metals can lead to more efficient use through enhanced reactivity and selectivity. However, single atoms on catalyst supports can be mobile and aggregate into nanoparticles when heated at elevated temperatures. High temperatures are detrimental to catalyst performance unless these mobile atoms can be trapped. We used ceria powders having similar surface areas but different exposed surface facets. When mixed with a platinum/ aluminum oxide catalyst and aged in air at 800°C, the platinum transferred to the ceria and was trapped. Polyhedral ceria and nanorods were more effective than ceria cubes at anchoringmore » the platinum. Performing synthesis at high temperatures ensures that only the most stable binding sites are occupied, yielding a sinter-resistant, atomically dispersed catalyst.« less

New Pt/Alumina model catalysts for STM and in situ XPS studies

NASA Astrophysics Data System (ADS)

Nartova, Anna V.; Gharachorlou, Amir; Bukhtiyarov, Andrey V.; Kvon, Ren I.; Bukhtiyarov, Valerii I.

2017-04-01

The new Pt/alumina model catalysts for STM and in situ XPS studies based on thin alumina film formed over the conductive substrate are proposed. Procedure of platinum deposition developed for porous alumina was adapted for the model alumina support. The set of Pt/AlOx-film samples with the different mean platinum particle size was prepared. Capabilities of in situ XPS investigations of the proposed catalysts were demonstrated in study of NO decomposition on platinum nanoparticles. It is shown that proposed model catalysts behave similarly to Pt/γ-Al2O3 and provide the new opportunities for the instrumental studies of platinum catalysts due to resolving several issues (charging, heating, screening) that are typical for the investigation of the porous oxide supported catalysts.

Continuous preparation of carbon-nanotube-supported platinum catalysts in a flow reactor directly heated by electric current

PubMed Central

dos Santos, Antonio Rodolfo; Kunz, Ulrich; Turek, Thomas

2011-01-01

Summary In this contribution we present for the first time a continuous process for the production of highly active Pt catalysts supported by carbon nanotubes by use of an electrically heated tubular reactor. The synthesized catalysts show a high degree of dispersion and narrow distributions of cluster sizes. In comparison to catalysts synthesized by the conventional oil-bath method a significantly higher electrocatalytic activity was reached, which can be attributed to the higher metal loading and smaller and more uniformly distributed Pt particles on the carbon support. Our approach introduces a simple, time-saving and cost-efficient method for fuel cell catalyst preparation in a flow reactor which could be used at a large scale. PMID:22043252

Investigation of low temperature carbon monoxide oxidation catalysts. [for Spacelab atmosphere control

NASA Technical Reports Server (NTRS)

Jagow, R. B.; Katan, T.; Ray, C. D.; Lamparter, R. A.

1977-01-01

Carbon monoxide generation rates related to the use of commerical equipment in Spacelab, added to the normal metabolic and subsystem loads, will produce carbon monoxide levels in excess of the maximum allowable concentration. In connection with the sensitivity of carbon monoxide oxidation catalysts to poisoning at room temperature, catalysts for an oxidation of carbon monoxide at low temperatures have been investigated. It was found that platinum and palladium are the only effective room temperature catalysts which are effective at 333 K. Hopcalite was ineffective at ambient temperatures, but converted CO with 100 percent efficiency at 333 K. Poisoning tests showed the noble metal catalysts to be very sensitive, and Hopcalite to be very resistant to poisoning.

Synthesis of Pt/rGO catalysts with two different reducing agents and their methanol electrooxidation activity

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

Vu, Thu Ha Thi, E-mail: ptntd2004@yahoo.fr; Tran, Thanh Thuy Thi, E-mail: tranthithanhthuygl@gmail.com; Le, Hong Ngan Thi

2016-01-15

Highlights: • Pt/rGO catalysts were successfully synthesized using either NaBH{sub 4} or ethylene glycol. • Synthesis using NaBH{sub 4} could improve electrocatalytic towards methanol oxidation of Pt/rGO catalyst. • 40%Pt/rGO synthesized using NaBH{sub 4} showed the best electrocatalytic performance. - Abstract: The synthesis processes of Platinum (Pt) on reduced graphene oxide (rGO) catalysts from graphene oxide (GO) using two reducing agents including sodium borohydride and ethylene glycol is reported. Structure and morphology of Pt/rGO catalysts are characterized by X-ray powder diffraction, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrocatalytic methanol oxidation properties of these catalysts are evaluated bymore » cyclic voltammetry and chronoamperometry. The results show that catalyst synthesized using sodium borohydride has a higher metallic Pt content and an improved catalytic performance in comparison to catalyst synthesized using ethylene glycol. Moreover, effect of Pt loading amount on electrocatalytic methanol oxidation performance of catalysts synthesized using sodium borohydride is systematically investigated. The optimal Pt loading amount on graphene is determined to be 40%.« less

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

DOE PAGES

Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; ...

2015-10-09

Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation.more » γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.« less

Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

DOEpatents

Gorer, Alexander

2002-01-01

A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Chemicals and energy co-generation from direct hydrocarbons/oxygen proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Li, W. S.; Lu, D. S.; Luo, J. L.; Chuang, K. T.

A proton exchange membrane fuel cell for chemicals and energy co-generation was set up with hydrocarbons ethane, propane and butane as fuels, and the electrochemical performance of the cell was studied by using linear potential sweep, alternating current impedance and gas chromatography. The cell performance can be improved to a great extent by increasing the platinum load in the catalyst, by treating the membrane with phosphoric acid and by elevating temperature. The improvement of cell performance by the increase of platinum load is ascribed to the increase of reaction sites for hydrocarbon oxidation, that by phosphoric acid treatment to the increase of proton conductivity in Nafion membrane, and that by elevating temperature to the improvement in thermodynamic as well as kinetic aspects. Only a small fraction of the hydrocarbon is converted to carbon dioxide in this cell during its power generation. The current efficiency is 5% for the conversion of ethane to carbon dioxide in the ethane/oxygen fuel cell with 20% carbon-supported platinum as catalyst and phosphoric acid-treated membrane as proton exchange membrane at 0.2 V, 80 °C and ambient pressure. The reaction activity of hydrocarbons at the anode is in the order of propane, butane and ethane. The possible chemicals produced from the cell were hydrocarbons with more than six carbons, which are inactive at the anode under cell conditions.

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

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

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

Durability of De-Alloyed Platinum-Nickel Cathode Catalyst in Low Platinum Loading Membrane-Electrode Assemblies Subjected to Accelerated Stress Tests

DOE PAGES

Ahluwalia, R. K.; Wang, X.; Peng, J. -K.; ...

2018-04-25

Here, the durability of de-alloyed platinum-nickel catalysts supported on high-surface area carbon (d-PtNi/C) in optimized electrodes and membrane electrode assemblies (MEAs) under an accelerated stress test (AST) protocol is investigated with the objective of developing a quantitative understanding of the degradation mechanisms and their relationship to the electrode structure, pre-conditioning, and operating conditions. It is found that the cell degradation can be mitigated by controlling the voltage cycle, acid washing the MEA to remove Ni contaminants that enter the electrode and membrane during fabrication, and monitoring the operating conditions. For example, the electrochemical surface area (ECSA) loss is <25% aftermore » 30,000 triangle cycles with 0.925 V upper potential limit if the MEA is acid washed and extensive diagnostics are avoided. The parameters that exacerbate the cell degradation also accelerate the rate at which Ni leaches out from the catalyst. A mechanistic model is presented for the degradation in performance of d-PtNi/C electrodes. The model correlates a) the degradation in ORR mass and specific activities with ECSA and Ni losses, b) the decrease in limiting current density ( iL), which is inversely proportional to the O 2 mass transport resistance, with the degradation in catalyst roughness factor, and c) the increase in mass transfer overpotentials with the reduced current density, i/iL .« less

A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

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

Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong

2014-07-01

A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH 3) 4](NO 3) 2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

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

Liu, Jing; Jiao, Menggai; Lu, Lanlu

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 kWmore » –1 in the fuel cell. Good fuel cell durability is also observed. As a result, 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.« less

High performance platinum single atom electrocatalyst for oxygen reduction reaction

DOE PAGES

Liu, Jing; Jiao, Menggai; Lu, Lanlu; ...

2017-07-24

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 kWmore » –1 in the fuel cell. Good fuel cell durability is also observed. As a result, 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.« less

Rapid total volatile organic carbon quantification from microbial fermentation using a platinum catalyst and proton transfer reaction-mass spectrometry.

PubMed

Schoen, Heidi R; Peyton, Brent M; Knighton, W Berk

2016-12-01

A novel analytical system was developed to rapidly and accurately quantify total volatile organic compound (VOC) production from microbial reactor systems using a platinum catalyst and a sensitive CO 2 detector. This system allows nearly instantaneous determination of total VOC production by utilizing a platinum catalyst to completely and quantitatively oxidize headspace VOCs to CO 2 in coordination with a CO 2 detector. Measurement of respiratory CO 2 by bypassing the catalyst allowed the total VOC content to be determined from the difference in the two signals. To the best of our knowledge, this is the first instance of a platinum catalyst and CO 2 detector being used to quantify the total VOCs produced by a complex bioreactor system. Continuous recording of these CO 2 data provided a record of respiration and total VOC production throughout the experiments. Proton transfer reaction-mass spectrometry (PTR-MS) was used to identify and quantify major VOCs. The sum of the individual compounds measured by PTR-MS can be compared to the total VOCs quantified by the platinum catalyst to identify potential differences in detection, identification and calibration. PTR-MS measurements accounted on average for 94 % of the total VOC carbon detected by the platinum catalyst and CO 2 detector. In a model system, a VOC producing endophytic fungus Nodulisporium isolate TI-13 was grown in a solid state reactor utilizing the agricultural byproduct beet pulp as a substrate. Temporal changes in production of major volatile compounds (ethanol, methanol, acetaldehyde, terpenes, and terpenoids) were quantified by PTR-MS and compared to the total VOC measurements taken with the platinum catalyst and CO 2 detector. This analytical system provided fast, consistent data for evaluating VOC production in the nonhomogeneous solid state reactor system.

Catalysts for the Oxidation of Carbon Monoxide at Low Temperatures.

DTIC Science & Technology

1979-11-21

Four catalysts ( hopcalite , Whetlerite, a supported palladium, and a supported platinum) were tested for efficiency in promoting the oxidation of...carbon monoxide (CO). At room temperature and 50% RH, hopcalite has no catalytic capability and platinum has practically none. At room temperature and 15...RH, hopcalite is superior to platinum in catalyzing the oxidation of CO. Hopcalite is more efficient than either of the other three catalysts in the

Plasmon-induced artificial photosynthesis

PubMed Central

Ueno, Kosei; Oshikiri, Tomoya; Shi, Xu; Zhong, Yuqing; Misawa, Hiroaki

2015-01-01

We have successfully developed a plasmon-induced artificial photosynthesis system that uses a gold nanoparticle-loaded oxide semiconductor electrode to produce useful chemical energy as hydrogen and ammonia. The most important feature of this system is that both sides of a strontium titanate single-crystal substrate are used without an electrochemical apparatus. Plasmon-induced water splitting occurred even with a minimum chemical bias of 0.23 V owing to the plasmonic effects based on the efficient oxidation of water and the use of platinum as a co-catalyst for reduction. Photocurrent measurements were performed to determine the electron transfer between the gold nanoparticles and the oxide semiconductor. The efficiency of water oxidation was determined through spectroelectrochemical experiments aimed at elucidating the electron density in the gold nanoparticles. A set-up similar to the water-splitting system was used to synthesize ammonia via nitrogen fixation using ruthenium instead of platinum as a co-catalyst. PMID:26052419

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

PubMed

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.

Hydroisomerization of n-Hexane Using Acidified Metal-Organic Framework and Platinum Nanoparticles.

PubMed

Sabyrov, Kairat; Jiang, Juncong; Yaghi, Omar M; Somorjai, Gabor A

2017-09-13

Exceptionally high surface area and ordered nanopores of a metal-organic framework (MOF) are exploited to encapsulate and homogeneously disperse a considerable amount of phosphotungstic acid (PTA). When combined with platinum nanoparticles positioned on the external surface of the MOF, the construct shows a high catalytic activity for hydroisomerization of n-hexane, a reaction requiring hydrogenation/dehydrogenation and moderate to strong Brønsted acid sites. Characterization of the catalytic activity and acidic sites as a function of PTA loading demonstrates that both the concentration and strength of acidic sites are highest for the catalyst with the largest amount of PTA. The MOF construct containing 60% PTA by weight produces isoalkanes with 100% selectivity and 9-fold increased mass activity as compared to a more traditional aluminosilicate catalyst, further demonstrating the capacity of the MOF to contain a high concentration of active sites necessary for the isomerization reaction.

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

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

1984-01-01

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

NASA Astrophysics Data System (ADS)

Chung, Hoon T.; Cullen, David A.; Higgins, Drew; Sneed, Brian T.; Holby, Edward F.; More, Karren L.; Zelenay, Piotr

2017-08-01

Platinum group metal-free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)-based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)-air fuel cell. Herein, we demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. Current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The proposed catalytic active site, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

DOE PAGES

Chung, Hoon T.; Cullen, David A.; Higgins, Drew; ...

2017-08-04

Platinum group metal–free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)–based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H 2)–air fuel cell. We demonstrate H 2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. In current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater thanmore » ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The catalytic active site we proposed, carbon-embedded nitrogen-coordinated iron (FeN 4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.« less

Graphene-Supported Platinum Catalyst-Based Membrane Electrode Assembly for PEM Fuel Cell

NASA Astrophysics Data System (ADS)

Devrim, Yilser; Albostan, Ayhan

2016-08-01

The aim of this study is the preparation and characterization of a graphene-supported platinum (Pt) catalyst for proton exchange membrane fuel cell (PEMFC) applications. The graphene-supported Pt catalysts were prepared by chemical reduction of graphene and chloroplatinic acid (H2PtCl6) in ethylene glycol. X-ray powder diffraction, thermogravimetric analysis (TGA) and scanning electron microscopy have been used to analyze structure and surface morphology of the graphene-supported catalyst. The TGA results showed that the Pt loading of the graphene-supported catalyst was 31%. The proof of the Pt particles on the support surfaces was also verified by energy-dispersive x-ray spectroscopy analysis. The commercial carbon-supported catalyst and prepared Pt/graphene catalysts were used as both anode and cathode electrodes for PEMFC at ambient pressure and 70°C. The maximum power density was obtained for the Pt/graphene-based membrane electrode assembly (MEA) with H2/O2 reactant gases as 0.925 W cm2. The maximum current density of the Pt/graphene-based MEA can reach 1.267 and 0.43 A/cm2 at 0.6 V with H2/O2 and H2/air, respectively. The MEA prepared by the Pt/graphene catalyst shows good stability in long-term PEMFC durability tests. The PEMFC cell voltage was maintained at 0.6 V without apparent voltage drop when operated at 0.43 A/cm2 constant current density and 70°C for 400 h. As a result, PEMFC performance was found to be superlative for the graphene-supported Pt catalyst compared with the Pt/C commercial catalyst. The results indicate the graphene-supported Pt catalyst could be utilized as the electrocatalyst for PEMFC applications.

Exhaust system having a gold-platinum group metal catalyst

DOEpatents

Ragle, Christie Susan [Havana, IL; Silver, Ronald G [Peoria, IL; Zemskova, Svetlana Mikhailovna [Edelstein, IL; Eckstein, Colleen J [Metamora, IL

2011-12-06

A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

Exhaust system having a gold-platinum group metal catalyst

DOEpatents

Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

2012-08-07

A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

System catalytic neutralization control of combustion engines waste gases in mining technologies

NASA Astrophysics Data System (ADS)

Korshunov, G. I.; Solnitsev, R. I.

2017-10-01

The paper presents the problems solution of the atmospheric air pollution with the exhaust gases of the internal combustion engines, used in mining technologies. Such engines are used in excavators, bulldozers, dump trucks, diesel locomotives in loading and unloading processes and during transportation of minerals. NOx, CO, CH emissions as the waste gases occur during engine operation, the concentration of which must be reduced to the standard limits. The various methods and means are used for the problem solution, one of which is neutralization based on platinum catalysts. A mathematical model of a controlled catalytic neutralization system is proposed. The simulation results confirm the increase in efficiency at start-up and low engine load and the increase in the catalyst lifetime.

Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

DOEpatents

Gorer, Alexander

2004-01-27

A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Platinum recycling in the United States in 1998

USGS Publications Warehouse

Hilliard, Henry E.

2001-01-01

In the United States, catalytic converters are the major source of secondary platinum for recycling. Other sources of platinum scrap include reforming and chemical process catalysts. The glass industry is a small but significant source of platinum scrap. In North America, it has been estimated that in 1998 more than 20,000 kilograms per year of platinum-group metals from automobile catalysts were available for recycling. In 1998, an estimated 7,690 kilograms of platinum were recycled in the United States. U.S. recycling efficiency was calculated to have been 76 percent in 1998; the recycling rate was estimated at 16 percent.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Platinum-ruthenium-nickel fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2005-07-26

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

DOE PAGES

Chlistunoff, Jerzy; Sansinena, Jose -Maria

2016-11-17

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

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

Chlistunoff, Jerzy; Sansinena, Jose -Maria

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Platinum-ruthenium-palladium fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2006-02-07

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

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

Vukmirovic,M.B.; Sasaki, K.; Zhou, W.-P.

2008-09-15

For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supportedmore » nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution.« less

New electrocatalysts for hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Cattabriga, R. A.; Giner, J.; Parry, J.; Swette, L. L.

1970-01-01

Platinum-silver, palladium-gold, and platinum-gold alloys serve as oxygen reduction catalysts in high-current-density cells. Catalysts were tested on polytetrafluoroethylene-bonded cathodes and a hydrogen anode at an operating cell temperature of 80 degrees C.

Platinum clusters supported in zeolite LTL: Influence of catalyst morphology on performance in n-hexane reforming

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

Jentoft, R.E.; Gates, B.C.; Tsapatsis, M.

KLTL zeolite-supported platinum catalysts were synthesized from aqueous tetraammineplatinum(II) nitrate solutions and nonacidic KLTL zeolite crystallites, including some with dimensions as little as 300 x 500 {angstrom}. The zeolite crystallites had various morphologies, some being predominantly disk-shaped particles and some predominantly mosaics of rod-like domains with a range of c-dimension lengths. The activity and selectivity of each catalyst were evaluated for dehydrocyclization of n-hexane in the presence of H{sub 2} to form predominantly benzene at conversions of typically 45--90%. The data presented here provide a detailed characterization of the deactivation of such catalysts in the absence of sulfur. EXAFS datamore » show that the platinum in each catalyst was present in clusters of about 20 atoms each, on average. Electron micrographs show that the platinum clusters were nearly evenly dispersed on the surfaces of the zeolite crystallites, including the intracrystalline and extracrystalline surfaces. The catalytic performance was virtually independent of the zeolite channel length, but activity, selectivity, and resistance to deactivation were found to be correlated with the ratio of the surface area external to the crystallite domains to that within the intracrystalline pores. The catalyst performance is dependent on this ratio (which is related to the zeolite morphology) as follows: in comparison with the others, the catalysts with the relatively low fractions of platinum outside the intracrystalline pores are more active, more selective for benzene formation, and more resistant to deactivation.« less

Membrane catalyst layer for fuel cells

DOEpatents

Wilson, Mahlon S.

1993-01-01

A gas reaction fuel cell incorporates a thin catalyst layer between a solid polymer electrolyte (SPE) membrane and a porous electrode backing. The catalyst layer is preferably less than about 10 .mu.m in thickness with a carbon supported platinum catalyst loading less than about 0.35 mgPt/cm.sup.2. The film is formed as an ink that is spread and cured on a film release blank. The cured film is then transferred to the SPE membrane and hot pressed into the surface to form a catalyst layer having a controlled thickness and catalyst distribution. Alternatively, the catalyst layer is formed by applying a Na.sup.+ form of a perfluorosulfonate ionomer directly to the membrane, drying the film at a high temperature, and then converting the film back to the protonated form of the ionomer. The layer has adequate gas permeability so that cell performance is not affected and has a density and particle distribution effective to optimize proton access to the catalyst and electronic continuity for electron flow from the half-cell reaction occurring at the catalyst.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells.

PubMed

Show, Yoshiyuki; Ueno, Yutaro

2017-01-31

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2.

Formation of Platinum Catalyst on Carbon Black Using an In-Liquid Plasma Method for Fuel Cells

PubMed Central

Show, Yoshiyuki; Ueno, Yutaro

2017-01-01

Platinum (Pt) catalyst was formed on the surface of carbon black using an in-liquid plasma method. The formed Pt catalyst showed the average particle size of 4.1 nm. This Pt catalyst was applied to a polymer electrolyte membrane fuel cell (PEMFC). The PEMFC showed an open voltage of 0.85 V and a maximum output power density of 216 mW/cm2. PMID:28336864

Facile approach to prepare Pt decorated SWNT/graphene hybrid catalytic ink

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

Mayavan, Sundar, E-mail: sundarmayavan@cecri.res.in; Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, Daejeon, 305-701; Mandalam, Aditya

Highlights: • Pt NPs were in situ synthesized onto CNT–graphene support in aqueous solution. • The as-prepared material was used directly as a catalyst ink without further treatment. • Catalyst ink is active toward methanol oxidation. • This approach realizes both scalable and greener production of hybrid catalysts. - Abstract: Platinum nanoparticles were in situ synthesized onto hybrid support involving graphene and single walled carbon nanotube in aqueous solution. We investigate the reduction of graphene oxide, and platinum nanoparticle functionalization on hybrid support by X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The as-preparedmore » platinum on hybrid support was used directly as a catalyst ink without further treatment and is active toward methanol oxidation. This work realizes both scalable and greener production of highly efficient hybrid catalysts, and would be valuable for practical applications of graphene based fuel cell catalysts.« less

First Principle Calculation : Investigation on interaction of Pt/Graphene as Catalyst

NASA Astrophysics Data System (ADS)

Anugrah Putri Namari, Nuning; Suprijadi

2017-07-01

The increasing in energy needs and the lack of non-renewable energy sources becomes a challenge for the human being to be able to use renewable energy sources. One of the devices to process renewable energy is Polymer Electrolyte Membrane Fuel Cell (PEMFC) . PEMFC use hydrogen and Oxygen as an energy sources . The most important reaction in fuel cell is Oxidation and reduction process. Therefore, a catalyst is needed to help the OR process. Study of catalyst shows that the most effective fuel cell for now is Platinum. Many fuel cell have use platinum as the catalyst. However, Platinum is a rare and expensive element. Therefore, to reduce the cost of fuel cell fabrication, we need to increase the activity of platinum. In this research, we use graphene as a support material. Then, we will study about the interaction of platinum on graphene and analyze its morphological change and electronic properties.The research conduct using Density Functional Theory (DFT). The calculation result shows that Pt/graphene can break H2 into H+ and the binding between Pt cluster is stronger than binding with the substrate.

Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

DOE PAGES

DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; ...

2015-06-26

Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al 2O 3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, wemore » find that sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

Graphene-supported platinum catalyst prepared with ionomer as surfactant for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; An, L.; Zhao, G.; Yan, X. H.; Jung, C. Y.

2015-02-01

In this work, we have synthesized an ionomer-coated graphene-supported platinum catalyst for anion exchange membrane fuel cells. Unlike the common surfactant stabilized colloidal method, we employ a home-made anion exchange ionomer (AEI), namely quaternary ammonia poly (2, 6-dimethyl-1, 4-phenylene oxide) (QAPPO), as the surfactant. The AEI coated on reduced graphene oxide (rGO) surfaces serves as a stabilizer to anchor the platinum precursor on rGO surfaces due to electrostatic interactions. As a result, platinum nanoparticles (Pt NPs) can be easily deposited onto rGO surfaces with a uniform distribution. The remarkable feature of the present synthesis method is that the surfactant, the coated AEI, does not need to be removed from the catalyst, but serves as hydroxide-conductive paths in the catalyst layer, leading to enhanced triple phase boundaries. It is demonstrated that the use of the catalyst obtained with the present method enables a H2/O2 AEMFC to yield a peak power density of 264.8 mW cm-2 at 60 °C, which is 30% higher than that produced from the same fuel cell but with the use of the catalyst synthesized by the conventional synthesis method.

Mesostructured platinum-free anode and carbon-free cathode catalysts for durable proton exchange membrane fuel cells.

PubMed

Cui, Xiangzhi; Shi, Jianlin; Wang, Yongxia; Chen, Yu; Zhang, Lingxia; Hua, Zile

2014-01-01

As one of the most important clean energy sources, proton exchange membrane fuel cells (PEMFCs) have been a topic of extensive research focus for decades. Unfortunately, several critical technique obstacles, such as the high cost of platinum electrode catalysts, performance degradation due to the CO poisoning of the platinum anode, and carbon corrosion by oxygen in the cathode, have greatly impeded its commercial development. A prototype of a single PEMFC catalyzed by a mesostructured platinum-free WO3/C anode and a mesostructured carbon-free Pt/WC cathode catalysts is reported herein. The prototype cell exhibited 93% power output of a standard PEMFC using commercial Pt/C catalysts at 50 and 70 °C, and more importantly, CO poisoning-free and carbon corrosion-resistant characters of the anode and cathode, respectively. Consequently, the prototype cell demonstrated considerably enhanced cell operation durability. The mesostructured electrode catalysts are therefore highly promising in the future development and application of PEMFCs. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the carbon-platinum-cerium has better catalytic activity than platinum-carbon. Due to the hybridization behavior of C and Ce could arise charge transfer, both carbon and cerium to the Platinum. Ce-C→Pt charge transfer could occur at the Ce-C/Pt interface. Thus, results in an increase in the catalytic activity of platinum-cerium-carbon when compared with carbon-platinum.

Open-source FCPEM-Performance & Durability Model Consideration of Membrane Properties on Cathode Degradation

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

Knights, Shanna; Harvey, David

The durability of PEM fuel cells is a primary requirement for large scale commercialization of these power systems in transportation and stationary market applications which target operational lifetimes of 5,000 hours and 60,000 hours by 2020, respectively. Key degradation modes contributing to fuel cell lifetime limitations have been largely associated with the platinum-based cathode catalyst layer. Furthermore, as fuel cells are driven to low cost materials and lower catalyst loadings in order to meet the cost targets for commercialization, the catalyst durability has become even more important. While over the past few years significant progress has been made in identifyingmore » the underlying causes of fuel cell degradation and key parameters that greatly influence the degradation rates, many gaps with respect to knowledge of the driving mechanisms still exist; in particular, the acceleration of the mechanisms due to different membrane compositions remains an area not well understood. The focus of this project extension was to enhance the predictive capability of the PEM Fuel Cell Performance & Durability Model called FC-APOLLO (Application Package for Open-source Long Life Operation) by including interaction effects of membrane transport properties such as water transport, changes in proton conductivity, and overall water uptake/adsorption and the state of the catalyst layer local conditions to further understand the driving forces for platinum dissolution.« less

Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

DOEpatents

Castellano, Christopher R [Ringoes, NJ; Moini, Ahmad [Princeton, NJ; Koermer, Gerald S [Basking Ridge, NJ; Furbeck, Howard [Hamilton, NJ; Schmieg, Steven J [Troy, MI; Blint, Richard J [Shelby Township, MI

2011-05-17

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver and a platinum group metal on a particulate alumina support, the atomic fraction of the platinum group metal being less than or equal to about 0.25. Methods of manufacturing catalysts are described in which silver is impregnated on alumina particles.

Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

PubMed

Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

2010-08-01

This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

Effect of Particle Size Upon Pt/SiO 2 Catalytic Cracking of n-Dodecane Under Supercritical Conditions: in situ SAXS and XANES Studies

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

Lee, Sungwon; Lee, Sungsik; Kumbhalkar, Mrunmayi

The endothermic cracking and dehydrogenation of n-dodecane is investigated over well-defined nanometer size platinum catalysts supported on SiO 2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X-ray scattering) and XAS (X-ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability ofmore » the nanoparticles in supercritical condition of n-dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.« less

Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

1987-01-01

Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

Catalyst for carbon monoxide oxidation

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Miller, Irvin M. (Inventor); Brown, David R. (Inventor); Davis, Patricia (Inventor); Schryer, David R. (Inventor); Brown, Kenneth G. (Inventor); Vannorman, John D. (Inventor)

1990-01-01

A catalyst is disclosed for the combination of CO and O2 to form CO2, which includes a platinum group metal (e.g., platinum); a reducable metal oxide having multiple valence states (e.g., SnO2); and a compound which can bind water to its structure (e.g., silica gel). This catalyst is ideally suited for application to high-powered pulsed, CO2 lasers operating in a sealed or closed-cycle condition.

Catalyst for carbon monoxide oxidation

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Miller, Irvin M. (Inventor); Brown, David R. (Inventor); Davis, Patricia P. (Inventor); Schryer, David R. (Inventor); Brown, Kenneth G. (Inventor); Vannorman, John D. (Inventor)

1991-01-01

A catalyst for the combination of CO and O2 to form CO2 which includes a platinum group metal, e.g., platinum; a reducible metal oxide having mulitple valence states, e.g., SnO2; and a compound which can bind water to its structure, e.g., silica gel. This catalyst is ideally suited for application to high powered, pulsed, CO2 lasers operating in a sealed or closed cycle condition.

Platinum nanocatalysts prepared with different surfactants for C1-C3 alcohol oxidations and their surface morphologies by AFM

NASA Astrophysics Data System (ADS)

Ertan, Salih; Şen, Fatih; Şen, Selda; Gökağaç, Gülsün

2012-06-01

In this study, platinum nanoparticle catalysts have been prepared using PtCl4 as a starting material and 1-octanethiol, 1-decanethiol, 1-dodecanethiol, and 1-hexadecanethiol as surfactants for methanol, ethanol, and 2-propanol oxidation reactions. The structure, particle sizes, and surface morphologies of the catalysts were characterized by X-ray diffraction (XRD), atomic force microscopy and transmission electron microscopy (TEM). XRD and TEM results indicate that all prepared catalysts have a face-centered cubic structure and are homogeneously dispersed on the carbon support with a narrow size distribution (2.0-1.3 nm). X-ray photoelectron spectra of the catalysts were examined and it is found that platinum has two different oxidation states, Pt (0) and Pt(IV), oxygen and sulfur compounds are H2Oads and OHads, bound and unbound thiols. The electrochemical and electrocatalytic properties of these catalysts were investigated with respect to C1-C3 alcohol oxidations by cyclic voltammetry and chronoamperometry. The highest electrocatalytic activity was obtained from catalyst I which was prepared with 1-octanethiol. This may be attributed to a decrease in the ratio of bound to unbound thiol species increase in Pt (0)/Pt(IV), H2Oads/OHads ratios, electrochemical surface area, CO tolerance and percent platinum utility.

Nanoceria Supported Single-Atom Platinum Catalysts for Direct Methane Conversion

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

Xie, Pengfei; Pu, Tiancheng; Nie, Anmin

Nanoceria-supported atomic Pt catalysts (denoted as Pt 1@CeO 2) have been synthesized and demonstrated with advanced catalytic performance for the non-oxidative, direct conversion of methane. These catalysts were synthesized by calcination of Pt-impregnated porous ceria nanoparticles at high temperature (ca. 1,000 °C), with the atomic dispersion of Pt characterized by combining aberra-tion-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spec-troscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses. The Pt 1@CeO 2 catalysts exhibited much superior catalytic performance to its nanoparticulated counterpart, achieving 14.4% of methane conversion at 975 °C andmore » 74.6% selectivity toward C 2 products (ethane, ethylene and acetylene). Comparative studies of the Pt1@CeO 2 catalysts with different loadings as well as the nanoparticulated counterpart reveal the single-atom Pt to be the active sites for selective conversion of methane into C 2 hydrocarbons.« less

Nanoceria Supported Single-Atom Platinum Catalysts for Direct Methane Conversion

DOE PAGES

Xie, Pengfei; Pu, Tiancheng; Nie, Anmin; ...

2018-04-03

Nanoceria-supported atomic Pt catalysts (denoted as Pt 1@CeO 2) have been synthesized and demonstrated with advanced catalytic performance for the non-oxidative, direct conversion of methane. These catalysts were synthesized by calcination of Pt-impregnated porous ceria nanoparticles at high temperature (ca. 1,000 °C), with the atomic dispersion of Pt characterized by combining aberra-tion-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption spec-troscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses. The Pt 1@CeO 2 catalysts exhibited much superior catalytic performance to its nanoparticulated counterpart, achieving 14.4% of methane conversion at 975 °C andmore » 74.6% selectivity toward C 2 products (ethane, ethylene and acetylene). Comparative studies of the Pt1@CeO 2 catalysts with different loadings as well as the nanoparticulated counterpart reveal the single-atom Pt to be the active sites for selective conversion of methane into C 2 hydrocarbons.« less

Realization of Both High-Performance and Enhanced Durability of Fuel Cells: Pt-Exoskeleton Structure Electrocatalysts.

PubMed

Kim, Ok-Hee; Cho, Yoon-Hwan; Jeon, Tae-Yeol; Kim, Jung Won; Cho, Yong-Hun; Sung, Yung-Eun

2015-07-01

Core-shell structure nanoparticles have been the subject of many studies over the past few years and continue to be studied as electrocatalysts for fuel cells. Therefore, many excellent core-shell catalysts have been fabricated, but few studies have reported the real application of these catalysts in a practical device actual application. In this paper, we demonstrate the use of platinum (Pt)-exoskeleton structure nanoparticles as cathode catalysts with high stability and remarkable Pt mass activity and report the outstanding performance of these materials when used in membrane-electrode assemblies (MEAs) within a polymer electrolyte membrane fuel cell. The stability and degradation characteristics of these materials were also investigated in single cells in an accelerated degradation test using load cycling, which is similar to the drive cycle of a polymer electrolyte membrane fuel cell used in vehicles. The MEAs with Pt-exoskeleton structure catalysts showed enhanced performance throughout the single cell test and exhibited improved degradation ability that differed from that of a commercial Pt/C catalyst.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1981-01-01

The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst supported on a carbon substrate. During operation, the small platinum crystallites sinter, causing loss in cell performance. A support was developed that stabilizes platinum in the high surface area condition by retarding or preventing the sintering process. The approach is to form etch pits in the carbon by oxidizing the carbon in the presence of a metal oxide catalyst, remove the metal oxide by an acid wash, and then deposit platinum in these pits. Results confirm the formation of etch pits in each of the three supports chosen for investigation: Vulcan XC-72R, Vulcan XC-72 that was graphized at 2500 C, and Shawinigan Acetylene Black.

Enhanced Dissolution of Platinum Group Metals Using Electroless Iron Deposition Pretreatment

NASA Astrophysics Data System (ADS)

Taninouchi, Yu-ki; Okabe, Toru H.

2017-12-01

In order to develop a new method for efficiently recovering platinum group metals (PGMs) from catalyst scraps, the authors investigated an efficient dissolution process where the material was pretreated by electroless Fe deposition. When Rh-loaded alumina powder was kept in aqua regia at 313 K (40 °C) for 30 to 60 minutes, the Rh hardly dissolved. Meanwhile, after electroless Fe plating using a bath containing sodium borohydride and potassium sodium tartrate as the reducing and complexing agents, respectively, approximately 60 pct of Rh was extracted by aqua regia at 313 K (40 °C) after 30 minutes. Furthermore, when heat treatment was performed at 1200 K (927 °C) for 60 minutes in vacuum after electroless plating, the extraction of Rh approached 100 pct for the same leaching conditions. The authors also confirmed that the Fe deposition pretreatment enhanced the dissolution of Pt and Pd. These results indicate that an effective and environmentally friendly process for the separation and extraction of PGMs from catalyst scraps can be developed utilizing this Fe deposition pretreatment.

Ganoderma-Like MoS2 /NiS2 with Single Platinum Atoms Doping as an Efficient and Stable Hydrogen Evolution Reaction Catalyst.

PubMed

Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu

2018-05-27

Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel Cell Measurements with Cathode Catalysts of Sputtered Pt3 Y Thin Films.

PubMed

Lindahl, Niklas; Eriksson, Björn; Grönbeck, Henrik; Lindström, Rakel Wreland; Lindbergh, Göran; Lagergren, Carina; Wickman, Björn

2018-05-09

Fuel cells are foreseen to have an important role in sustainable energy systems, provided that catalysts with higher activity and stability are developed. In this study, highly active sputtered thin films of platinum alloyed with yttrium (Pt 3 Y) are deposited on commercial gas diffusion layers and their performance in a proton exchange membrane fuel cell is measured. After acid pretreatment, the alloy is found to have up to 2.5 times higher specific activity than pure platinum. The performance of Pt 3 Y is much higher than that of pure Pt, even if all of the alloying element was leached out from parts of the thin metal film on the porous support. This indicates that an even higher performance is expected if the structure of the Pt 3 Y catalyst or the support could be further improved. The results show that platinum alloyed with rare earth metals can be used as highly active cathode catalyst materials, and significantly reduce the amount of platinum needed, in real fuel cells. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

PubMed

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

Microcalorimetric, {sup 13}C NMR spectroscopic, and reaction kinetic studies of silica- and L-zeolite-supported platinum catalysts for n-hexane conversion

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

Sharma, S.B.; Ouraipryvan, P.; Nair, H.A.

Reaction kinetics measurement of n-hexane conversion over 4% Pt/SiO{sub 2} and 1% Pt/SiO{sub 2} and 1% Pt/K(Ba)-L catalysts were made at a pressure of 3 atm and temperatures from 698 to 750 K. The rates of benzene and methylcyclopentane formation decrease with time during reaction over Pt/SiO{sub 2}, while 1% Pt/K(Ba)-L does not deactivate significantly. Microcalorimetric measurements at 353 K show that the heat of carbon monoxide adsorption is the same on freshly reduced Pt/SiO{sub 2} and Pt/K(Ba)-L catalysts; however, carbonaceous species that accumulate on Pt/SiO{sub 2} during n-hexane conversion decrease the total number of adsorption sites and the numbermore » of sites that adsorb carbon monoxide strongly. The 1% Pt/K(Ba)-L catalyst retains the adsorptive properties of the freshly reduced catalyst. Nuclear magnetic resonance studies of {sup 13}CO adsorption show that cluster-sized platinum particles are more resistant to deactivation by self-poisoning reactions than larger platinum particles. The greater catalyst stability and higher steady-state activity of L-zeolite-supported platinum catalysts may be attributed to the ability of L-zeolite to stabilize cluster-sized particles under reaction conditions. Differences in dehydrocyclization activity between catalysts may be related to differences in the number of strong adsorption sites that are present under reaction conditions. 31 refs., 7 figs., 4 tabs.« less

Catalytic method for synthesizing hydrocarbons

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

Catalytic method for synthesizing hydrocarbons

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1984-01-01

A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

Effect of Graphitic Content on Carbon Supported Catalyst Performance

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

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen

2011-07-01

The effect of graphitic content on carbon supported platinum catalysts was investigated in order to investigate its influence on catalyst performance. Four catalysts of varying surface areas and graphitic content were analyzed using XPS, HREELS, and tested using RDE experiments. The catalysts were also heat treated at 150oC and 100%RH as means to uniformly age them. The heat treated samples were analyzed using the same methods to determine what changes had occurred due to this aging process. When compared to the BOL catalysts, heat treated catalysts displayed increased graphitic carbon and platinum metalic content, however they also showed depressed catalyticmore » activity. The primary cause is still under investigation, though it is believed to be related to loss of amorphous carbon content.« less

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

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

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

DOE PAGES

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

2018-05-14

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

2018-05-01

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

DOE PAGES

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke; ...

2018-03-09

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke

Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layersmore » at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.« less

Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays.

PubMed

Barrera-Vargas, M; Valencia-Rios, J; Vicente, M A; Korili, S A; Gil, A

2005-12-15

The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases.

Catalytic oxidative dehydrogenation process

DOEpatents

Schmidt, Lanny D.; Huff, Marylin

2002-01-01

A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

Pretreatment of Platinum/Tin Oxide-Catalyst

NASA Technical Reports Server (NTRS)

Hess, Robert V.; Paulin, Patricia A.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M.; Upchurch, Billy T.; Brown, Kenneth G.

1987-01-01

Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

Low platinum loading for high temperature proton exchange membrane fuel cell developed by ultrasonic spray coating technique

NASA Astrophysics Data System (ADS)

Su, Huaneng; Jao, Ting-Chu; Barron, Olivia; Pollet, Bruno G.; Pasupathi, Sivakumar

2014-12-01

This paper reports use of an ultrasonic-spray for producing low Pt loadings membrane electrode assemblies (MEAs) with the catalyst coated substrate (CCS) fabrication technique. The main MEA sub-components (catalyst, membrane and gas diffusion layer (GDL)) are supplied from commercial manufacturers. In this study, high temperature (HT) MEAs with phosphoric acid (PA)-doped poly(2,5-benzimidazole) (AB-PBI) membrane are fabricated and tested under 160 °C, hydrogen and air feed 100 and 250 cc min-1 and ambient pressure conditions. Four different Pt loadings (from 0.138 to 1.208 mg cm-2) are investigated in this study. The experiment data are determined by in-situ electrochemical methods such as polarization curve, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The high Pt loading MEA exhibits higher performance at high voltage operating conditions but lower performances at peak power due to the poor mass transfer. The Pt loading 0.350 mg cm-2 GDE performs the peak power density and peak cathode mass power to 0.339 W cm-2 and 0.967 W mgPt-1, respectively. This work presents impressive cathode mass power and high fuel cell performance for high temperature proton exchange membrane fuel cells (HT-PEMFCs) with low Pt loadings.

A molecule-like PtAu24(SC6H13)18 nanocluster as an electrocatalyst for hydrogen production

PubMed Central

Kwak, Kyuju; Choi, Woojun; Tang, Qing; Kim, Minseok; Lee, Yongjin; Jiang, De-en; Lee, Dongil

2017-01-01

The theoretically predicted volcano plot for hydrogen production shows the best catalyst as the one that ensures that the hydrogen binding step is thermodynamically neutral. However, the experimental realization of this concept has suffered from the inherent surface heterogeneity of solid catalysts. It is even more challenging for molecular catalysts because of their complex chemical environment. Here, we report that the thermoneutral catalyst can be prepared by simple doping of a platinum atom into a molecule-like gold nanocluster. The catalytic activity of the resulting bimetallic nanocluster, PtAu24(SC6H13)18, for the hydrogen production is found to be significantly higher than reported catalysts. It is even better than the benchmarking platinum catalyst. The molecule-like bimetallic nanocluster represents a class of catalysts that bridge homogeneous and heterogeneous catalysis and may provide a platform for the discovery of finely optimized catalysts. PMID:28281526

Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst

NASA Astrophysics Data System (ADS)

Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

2016-06-01

The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst.

PubMed

Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

2016-06-30

The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

Dispersion enhanced metal/zeolite catalysts

DOEpatents

Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

1987-03-31

Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

Dispersion enhanced metal/zeolite catalysts

DOEpatents

Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

1987-01-01

Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

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

Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian

2012-05-04

A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of Pt ML/Pd ML/Ir 2Re 1,more » Pt ML/Pd 2layers/Ir 2Re 1, and Pt ML/Pd 2layers/Ir 7Re 3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O 2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the Pt ML/Pd ML/Ir 2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.« less

Modeling Electrochemical Performance of the Hierarchical Morphology of Precious Group Metal-free Cathode for Polymer Electrolyte Fuel Cell

DOE PAGES

Komini Babu, Siddharth; Chung, Hoon Taek; Zelenay, Piotr; ...

2017-08-04

Here, this paper presents a two-dimensional (2D) computational model of a polymer electrolyte fuel cell (PEFC) with a platinum group metal-free (PGM-free) catalyst cathode that can significantly reduce PEFC costs by eliminating the need for expensive platinum catalysts. Due to their comparatively low volumetric activity, PGM-free cathodes are an order of magnitude thicker than their Pt-based counterpart. The resulting need for greater electrode thickness to achieve sufficient power density requires careful attention to the transport losses across the thicker cathodes. The presented model is used to correlate the composition and morphology of the cathode to PEFC performance. The model ismore » a complete cell, continuum model that includes an advanced agglomerate model for a microstructurally consistent representation of the cathode. A unique feature of the approach is the integration of morphology and transport parameter statistics extracted from nano-scale resolution X-ray computed tomography (nano-CT) imaging of PGM-free cathodes. The model was validated with experimental results of PGM-free cathodes with varying Nafion loading. Lastly, our key findings are a need for increased cathode hydrophobicity and increased ionomer conductivity through either reduced tortuosity or increased bulk conductivity. We further use the model to evaluate targets for the volumetric activity and active site density for future catalysts.« less

Modeling Electrochemical Performance of the Hierarchical Morphology of Precious Group Metal-free Cathode for Polymer Electrolyte Fuel Cell

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

Komini Babu, Siddharth; Chung, Hoon Taek; Zelenay, Piotr

Here, this paper presents a two-dimensional (2D) computational model of a polymer electrolyte fuel cell (PEFC) with a platinum group metal-free (PGM-free) catalyst cathode that can significantly reduce PEFC costs by eliminating the need for expensive platinum catalysts. Due to their comparatively low volumetric activity, PGM-free cathodes are an order of magnitude thicker than their Pt-based counterpart. The resulting need for greater electrode thickness to achieve sufficient power density requires careful attention to the transport losses across the thicker cathodes. The presented model is used to correlate the composition and morphology of the cathode to PEFC performance. The model ismore » a complete cell, continuum model that includes an advanced agglomerate model for a microstructurally consistent representation of the cathode. A unique feature of the approach is the integration of morphology and transport parameter statistics extracted from nano-scale resolution X-ray computed tomography (nano-CT) imaging of PGM-free cathodes. The model was validated with experimental results of PGM-free cathodes with varying Nafion loading. Lastly, our key findings are a need for increased cathode hydrophobicity and increased ionomer conductivity through either reduced tortuosity or increased bulk conductivity. We further use the model to evaluate targets for the volumetric activity and active site density for future catalysts.« less

Interactions of platinum metals and their complexes in biological systems.

PubMed Central

LeRoy, A F

1975-01-01

Platinum-metal oxidation catalysts are to be introduced in exhaust systems of many 1975 model-year automobiles in the U.S. to meet Clean Air Act standards. Small quantities of finely divided catalyst have been found issuing from prototype systems; platinum and palladium compounds may be found also. Although platinum exhibits a remarkable resistance to oxidation and chemical attack, it reacts chemically under some conditions producing coordination complex compounds. Palladium reacts more readily than platinum. Some platinum-metal complexes interact with biological systems as bacteriostatic, bacteriocidal, viricidal, and immunosuppressive agents. Workers chronically exposed to platinum complexes often develop asthma-like respiratory distress and skin reactions called platinosis. Platinum complexes used alone and in combination therapy with other drugs have recently emerged as effective agents in cancer chemotherapy. Understanding toxic and favorable interactions of metal species with living organisms requires basic information on quantities and chemical characteristics of complexes at trace concentrations in biological materials. Some basic chemical kinetic and thermodynamic data are presented to characterize the chemical behavior of the complex cis-[Pt(NH3)2Cl2] used therapeutically. A brief discussion of platinum at manogram levels in biological tissue is discussed. PMID:50943

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

DOE PAGES

Tian, Xinlong; Tang, Haibo; Luo, Junming; ...

2017-04-25

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

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

Tian, Xinlong; Tang, Haibo; Luo, Junming

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less

The effects of platinum on nickel electrodes in the nickel hydrogen cell

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1991-01-01

Interactions of platinum and platinum compounds with the nickel electrode that are possible in the nickel hydrogen cell, where both the nickel electrode and a platinum catalyst hydrogen electrode are in intimate contact with the alkaline electrolyte, are examined. Additionally, a mechanism of nickel cobalt oxyhydroxide formation in NiH2 cells is presented.

XPS and Raman studies of Pt catalysts supported on activated carbon

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Varma, Salil; Bharadwaj, S. R.

2018-04-01

Activated carbon is a widely used support for dispersing noble metals in addition to its many applications. We have prepared platinum catalyst supported on activated carbon for HI decomposition reaction of I-S thermochemical process of hydrogen generation. These catalysts were characterized by XPS and Raman before and after using for the reaction. It was observed that platinum is present in zero oxidation state, while carbon is present is both sp2 and sp3 hybridized forms along with some amount of it bonded to oxygen.

Effect of Particle Size and Operating Conditions on Pt 3Co PEMFC Cathode Catalyst Durability

DOE PAGES

Gummalla, Mallika; Ball, Sarah; Condit, David; ...

2015-05-29

The initial performance and decay trends of polymer electrolyte membrane fuel cells (PEMFC) cathodes with Pt 3Co catalysts of three mean particle sizes (4.9 nm, 8.1 nm, and 14.8 nm) with identical Pt loadings are compared. Even though the cathode based on 4.9 nm catalyst exhibited the highest initial electrochemical surface area (ECA) and mass activity, the cathode based on 8.1 nm catalyst showed better initial performance at high currents. Owing to the low mass activity of the large particles, the initial performance of the 14.8 nm Pt3Co-based electrode was the lowest. The performance decay rate of the electrodes withmore » the smallest Pt 3Co particle size was the highest and that of the largest Pt 3Co particle size was lowest. Interestingly, with increasing number of decay cycles (0.6 to 1.0 V, 50 mV/s), the relative improvement in performance of the cathode based on 8.1 nm Pt 3Co over the 4.9 nm Pt 3Co increased, owing to better stability of the 8.1 nm catalyst. The electron microprobe analysis (EMPA) of the decayed membrane-electrode assembly (MEA) showed that the amount of Co in the membrane was lower for the larger particles, and the platinum loss into the membrane also decreased with increasing particle size. This suggests that the higher initial performance at high currents with 8.1 nm Pt 3Co could be due to lower contamination of the ionomer in the electrode. Furthermore, lower loss of Co from the catalyst with increased particle size could be one of the factors contributing to the stability of ECA and mass activity of electrodes with larger cathode catalyst particles. To delineate the impact of particle size and alloy effects, these results are compared with prior work from our research group on size effects of pure platinum catalysts. The impact of PEMFC operating conditions, including upper potential, relative humidity, and temperature on the alloy catalyst decay trends, along with the EMPA analysis of the decayed MEAs, are reported.« less

Nitrogen-doped three-dimensional graphene-supported platinum catalysts for polymer electrolyte membrane fuel cells application

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Li, Xingxing; Yuan, Wensen; Zhu, Huanhuan; Qin, Yong; Zhang, Shuai; Yuan, Ningyi; Lin, Bencai; Ding, Jianning

Catalysts are a key component of polymer electrolyte membrane fuel cells (PEMFCs). In this work, nitrogen-doped three-dimensional graphene-supported platinum (Pt-3DNG) catalysts are successfully prepared and characterized. SEM and TEM images show the Pt nanoparticles are uniformly dispersed in the sheets of nitrogen-doped 3DNG. Compared with that of the commercial Pt/C catalysts, Pt-3DNG show much better oxygen reduction reaction (ORR) activity and cycling stability, and the reduction in limit current density after 1000 cycles is only about 1.6% for the Pt-3DNG catalysts, whereas 7.2% for the commercial Pt/C catalysts. The single cell using Pt-3DNG catalysts in both the anode and the cathode show a higher peak power density (21.47mW cm-2) than that using commercial Pt/C catalysts (20.17mW cm-2) under the same conditions. These properties make this type of catalyst suitable for the application in PEMFCs.

Gold–promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction

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

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here, we report on a structurally ordered Au₁₀Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that via addition of gold atoms PdCo nanoparticles undergo at elevated temperatures an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets. The superior stability of this catalyst compared to platinum after 10,000 potential cycles in alkaline media is attributedmore » to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matters.« less

Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

DOE PAGES

Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; ...

2016-06-29

Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor inmore » enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. Furthermore, this work may represent a key step towards scalable production of high performance platinum-based nanowires for applications in catalysis and energy conversion.« less

Platinum- and membrane-free swiss-roll mixed-reactant alkaline fuel cell.

PubMed

Aziznia, Amin; Oloman, Colin W; Gyenge, Előd L

2013-05-01

Eliminating the expensive and failure-prone proton exchange membrane (PEM) together with the platinum-based anode and cathode catalysts would significantly reduce the high capital and operating costs of low-temperature (<373 K) fuel cells. We recently introduced the Swiss-roll mixed-reactant fuel cell (SR-MRFC) concept for borohydride-oxygen alkaline fuel cells. We now present advances in anode electrocatalysis for borohydride electrooxidation through the development of osmium nanoparticulate catalysts supported on porous monolithic carbon fiber materials (referred to as an osmium 3D anode). The borohydride-oxygen SR-MRFC operates at 323 K and near atmospheric pressure, generating a peak power density of 1880 W m(-2) in a single-cell configuration by using an osmium-based anode (with an osmium loading of 0.32 mg cm(-2)) and a manganese dioxide gas-diffusion cathode. To the best of our knowledge, 1880 W m(-2) is the highest power density ever reported for a mixed-reactant fuel cell operating under similar conditions. Furthermore, the performance matches the highest reported power densities for conventional dual chamber PEM direct borohydride fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prediction of electrocatalytic activity of boron nanostructures

NASA Astrophysics Data System (ADS)

Owens, Frank J.

2018-01-01

The dissociation of O2 and HO2 are important reactions that occur at the cathode of fuel cells producing H2O and use platinum as a catalyst. There is a need to replace platinum with less expensive catalysts. Here the possibility of boron nanostructures as catalysts for the reactions is considered using density functional theory. The calculations show that the bond dissociation energies to remove O and OH from O2 and O2H bonded to boron nanostructures are less than those necessary to dissociate free O2 and O2H indicating that some of the boron nanostructures could be catalysts for the dissociation of O2 and HO2.

Efficient photocatalytic hydrogen production by platinum-loaded carbon-doped cadmium indate nanoparticles.

PubMed

Thornton, Jason M; Raftery, Daniel

2012-05-01

Undoped and carbon doped cadmium indate (CdIn(2)O(4)) powders were synthesized using a sol-gel pyrolysis method and evaluated for hydrogen generation activity under UV-visible irradiation without the use of a sacrificial reagent. Each catalyst powder was loaded with a platinum cocatalyst in order to increase electron-hole pair separation and promote surface reactions. Carbon-doped indium oxide and cadmium oxide were also prepared and analyzed for comparison. UV-vis diffuse reflectance spectra indicate the band gap for C-CdIn(2)O(4) to be 2.3 eV. C-doped In(2)O(4) showed a hydrogen generation rate approximately double that of the undoped material. When compared to platinized TiO(2) in methanol, which was used as a control material, C-CdIn(2)O(4) showed a 4-fold increase in hydrogen production. The quantum efficiency of the material was calculated at different wavelength intervals and found to be 8.7% at 420-440 nm. The material was capable of hydrogen generation using visible light only and with good efficiency even at 510 nm.

Dynamic wet-ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere.

PubMed

Yoshida, Kenta; Bright, Alexander N; Ward, Michael R; Lari, Leonardo; Zhang, Xudong; Hiroyama, Tomoki; Boyes, Edward D; Gai, Pratibha L

2014-10-24

The gas injection line of the latest spherical aberration-corrected environmental transmission electron microscope has been modified for achieving real-time/atomic-scale observations in moisturised gas atmospheres for the first time. The newly developed Wet-TEM system is applied to platinum carbon electrode catalysts to investigate the effect of water molecules on the platinum/carbon interface during deactivation processes such as sintering and corrosion. Dynamic in situ movies obtained in dry and 24% moisturised nitrogen environments visualize the rapid rotation, migration and agglomeration of platinum nanoparticles due to the physical adsorption of water and the hydroxylation of the carbon surface. The origin of the long-interconnected aggregation of platinum nanoparticles was discovered to be a major deactivation process in addition to conventional carbon corrosion.

Methods of producing porous platinum-based catalysts for oxygen reduction

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

Erlebacher, Jonah D.; Snyder, Joshua D.

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m 2/g and less than 75 m 2/g. A method ofmore » producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt xNi 1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.« less

Porous platinum-based catalysts for oxygen reduction

DOEpatents

Erlebacher, Jonah D; Snyder, Joshua D

2014-11-25

A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

Membrane-electrode structures for molecular catalysts for use in fuel cells and other electrochemical devices

DOEpatents

Kerr, John B.; Zhu, Xiaobing; Hwang, Gi Suk; Martin, Zulima; He, Qinggang; Driscoll, Peter; Weber, Adam; Clark, Kyle

2016-09-27

Water soluble catalysts, (M)meso-tetra(N-Methyl-4-Pyridyl)Porphinepentachloride (M=Fe, Co, Mn & Cu), have been incorporated into the polymer binder of oxygen reduction cathodes in membrane electrode assemblies used in PEM fuel cells and found to support encouragingly high current densities. The voltages achieved are low compared to commercial platinum catalysts but entirely consistent with the behavior observed in electroanalytical measurements of the homogeneous catalysts. A model of the dynamics of the electrode action has been developed and validated and this allows the MEA electrodes to be optimized for any chemistry that has been demonstrated in solution. It has been shown that improvements to the performance will come from modifications to the structure of the catalyst combined with optimization of the electrode structure and a well-founded pathway to practical non-platinum group metal catalysts exists.

n-hydrocarbons conversions over metal-modified solid acid catalysts

NASA Astrophysics Data System (ADS)

Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

2013-12-01

The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

NASA Astrophysics Data System (ADS)

Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

2015-02-01

Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

Determination of human body burden baseline date of platinum through autopsy tissue analysis.

PubMed Central

Vandiver, F; Duffield, F V; Yoakum, A; Bumgarner, J; Moran, J

1976-01-01

Results of analysis for platinum in 97 autopsy sets are presented. Analysis was performed by a specially developed emission spectrochemical method. Almost half of the individuals studied were found to have detectable platinum in one or more tissue samples. Platinum was found to be deposited in 13 of 21 tissue types investigated. Surprisingly high values were observed in subcutaneous fat, previously not considered to be a target site for platinum deposition. These data will serve as a human tissue platinum burden baseline in EPA's Catalyst Research Program. PMID:1001291

Highly Dispersed Alloy Catalyst for Durability

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

Vivek S. Murthi; Izzo, Elise; Bi, Wu

2013-01-08

Achieving DOE's stated 5000-hr durability goal for light-duty vehicles by 2015 will require MEAs with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of PEMFC stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them withmore » existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.« less

Highly active non-PGM catalysts prepared from metal organic frameworks

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; ...

2015-06-11

Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/N x/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/N x/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity mustmore » be demonstrated in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.« less

Hydrogenation of cottonseed oil with nickel, palladium and platinum catalysts

USDA-ARS?s Scientific Manuscript database

A number of commercial catalysts have been used to study hydrogenation of cottonseed oil, with the goal of minimizing trans fatty acid (TFA) content. Despite the different temperatures used, catalyst levels, and reaction times, the data from each catalyst type fall on the same curve when the TFA le...

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

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Platinum/zeolite catalyst for reforming n-hexane: Kinetic and mechanistic considerations

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

Lane, G.S.; Modica, F.S.; Miller, J.T.

A platinum/L-zeolite-reforming catalyst exhibits activity and selectivity for converting n-hexane into benzene than other Pt catalyst. The reaction pathways indicate that for all catalysts, e.g., Pt/K L or Pt/K Y, benzene is formed as a primary product by one-six-ring closure and methylcyclopentane is formed as a primary product via one-five-ring closure. The ratio for one-six to one-five-ring closure, however, is about two times greater for the Pt/K L than for the Pt/K Y, or other platinum catalysts. The preference for the one-six-ring closure in L zeolite appears to be related to the optimum pore size of the L zeolite. Inmore » addition to an increased selectivity for one-six-ring closure, the Pt/K L-zeolite catalyst also displays increased reactivity. For example, the turnover frequency of the Pt/K L-zeolite catalyst is 10 times higher for formation of benzene and 3.3 times higher for formation of methylcyclopentane compared with the Pt/K Y-zeolite catalyst. Although the Pt/K L is more reactive than Pt/K Y, the apparent activation energies, 54 kcal/mol for one-six-ring closure and 39 kcal/mol for one-five-ring closure, are the same for both catalysts. Differences in reactivity are associated with an increase in the preexponential term for the Pt/K L catalyst. The increased aromatics selectivity for Pt/K L is consistent with the confinement model which proposes that n-hexane is adsorbed as a six-ring pseudo-cycle resembling the transition state for one-six-ring closure.« less

Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst

PubMed Central

Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

2016-01-01

The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst. PMID:27357731

Manganese dioxide as a new cathode catalyst in microbial fuel cells

NASA Astrophysics Data System (ADS)

Li, Xiang; Hu, Boxun; Suib, Steven; Lei, Yu; Li, Baikun

This study focused on manganese oxides with a cryptomelane-type octahedral molecular sieve (OMS-2) structure to replace platinum as a cathode catalyst in microbial fuel cells (MFCs). Undoped (ud-OSM-2) and three catalysts doped with cobalt (Co-OMS-2), copper (Cu-OMS-2), and cerium (Ce-OMS-2) to enhance their catalytic performances were investigated. The novel OMS-2 cathodes were examined in granular activated carbon MFC (GACMFC) with sodium acetate as the anode reagent and oxygen in air as the cathode reagent. The results showed that after 400 h of operation, the Co-OMS-2 and Cu-OMS-2 exhibited good catalytic performance in an oxygen reduction reaction (ORR). The voltage of the Co-OMS-2 GACMFC was 217 mV, and the power density was 180 mW m -2. The voltage of the Cu-OMS-2 GACMFC was 214 mV and the power density was 165 mW m -2. The internal resistance (R in) of the OMS-2 GACMFCs (18 ± 1 Ω) was similar to that of the platinum GACMFCs (17 Ω). Furthermore, the degradation rates of organic substrates in the OMS-2 GACMFCs were twice those in the platinum GACMFCs, which enhance their wastewater treatment efficiencies. This study indicated that using OMS-2 manganese oxides to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs.

Selective oxidation of carbon monoxide in fuel processor gas

NASA Astrophysics Data System (ADS)

Manasilp, Akkarat

The trace amount of CO present in the hydrogen-rich stream coming from fuel reformers poisons the platinum anode electrode of proton exchange membrane (PEM) fuel cells and reduces the power output. Removal of low levels of CO present in the reformed gas must take place before the gas enters the fuel cell. The tolerable level of CO is around 10 ppm. We investigated the performance of single step sol-gel prepared Pt/alumina catalyst and Pt supported on sol gel made alumina. The effect of water vapor, carbon dioxide, CO and oxygen concentrations, temperature, and Pt loading on the activity and selectivity are presented. Our results showed that a 2%Pt/alumina sol-gel catalyst can selectively oxide CO down to a few ppm with constant selectivity and high space velocity. Water vapor in the feed increases the activity of catalysts dramatically and in the absence of water vapor, CO2 in the feed stream decreases the activity of the catalysts significantly. We also found that the presence of potassium as an electron donor did not improve the performance of Pt/alumina catalyst to the selective CO oxidation. For Pt supported on sol gel made alumina, we found that the combination of CO2 and H2O in the gas feed has a strong effect on selective CO oxidation over Pt/Al2O3. It could be a positive or negative effect depending upon Pt loading in the catalyst. With high Pt loading, the CO2 effect tends to dominate the H2O effect resulting in the decrease in CO conversion. Moreover, the presence of CeO2 as an oxygen storage compound promotes the performance of Pt supported on alumina at low temperature ˜90°C when Pt loading was 5%. Amongst the examined catalysts, the 5%Pt/15%CeO2/Al 2O3 catalyst showed the highest selectivity, with high CO conversion at a low temperature ˜90°C. The beneficial effect of the addition of CeO2 is most likely due to spillover of O2 from CeO2 to Pt at the Pt sites at the interface of Pt and CeO 2.

Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts.

PubMed

Jennings, Paul C; Pollet, Bruno G; Johnston, Roy L

2012-03-07

A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.

Fuel cell with Pt/Pd electrocatalyst electrode

DOEpatents

Stonehart, Paul

1983-01-01

An electrode for use in a phosphoric acid fuel cell comprising a graphitized or partially graphitized carbon support having a platinum/palladium electrocatalyst thereon. Preferably, the platinum/palladium catalyst comprises 20 to 65 weight percent palladium.

Platinum Monolayer Shell on Non-Noble Metal Core Electrocatalysts for the Hydrogen Oxidation Reaction

NASA Astrophysics Data System (ADS)

Teeluck, Krishani Malini

According to the United States Environmental Protection Agency, as of 2015, transportation accounted for 32% of the carbon dioxide emissions in the United States (and all carbon dioxide emissions in the U.S. accounted for 82.2% of all greenhouse gases from human activity). A hydrogen fuel cell is a device that efficiently produces electrical energy directly from a chemical reaction, with zero carbon emissions, and therefore holds great promise in alleviating our dependence on harmful use of energy sources. Due to their clean emissions and high efficiencies, there has been focus on the hydrogen fuel cell for vehicle applications using proton exchange membrane and alkaline fuel cells. Although the proton exchange membrane fuel cell is currently being used in vehicles, their high cost limits their feasibility in the market. This has inspired the development of the alkaline fuel cell whose efficiency and simplicity suggest the possibility of manufacturing high power fuel cell vehicles at a low cost, since the electrocatalysts in the alkaline fuel cell can be made from non-noble metals. Although the hydrogen oxidation reaction is one of the fastest electrochemical reactions in acidic media, it is two orders of magnitude slower in alkaline media, which hinders the overall efficiency of the alkaline fuel cell. Pure platinum is currently the best catalyst for the hydrogen oxidation reaction, but platinum’s high cost and rarity yields economic issues, rendering the technology futile if it cannot be commercialized. Furthermore, platinum’s hydrogen binding energy is slightly stronger than the optimal hydrogen binding energy. As the hydrogen oxidation reaction happens only on the surface of the catalyst, there is no need for platinum content beyond the exterior. Since tungsten and nickel are cheap, as well as abundant, they are ideal elements to replace the core of the catalyst with, while leaving a platinum shell surrounding this core. The activity of the hydrogen oxidation reaction when using a platinum monolayer shell on a nickel tungsten core electrocatalyst is explored, and it was found that the novel catalyst created here exhibits kinetics that rival pure platinum, but at less than half the platinum content, suggesting that nickel and tungsten modify the electronic properties of platinum in a way that enhances its activity for the hydrogen oxidation reaction. Furthermore, the hydrogen binding energy of this novel electrocatalyst was found to be weaker than the optimal binding energy (rather than stronger, as seen in pure platinum), indicating the possibility of modifying the electronic properties of platinum for a more optimal hydrogen binding energy.

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Hydrothermal Synthesis of Platinum-Group-Metal-Free Catalysts: Structural Elucidation and Oxygen Reduction Catalysis

DOE PAGES

Gokhale, Rohan; Tsui, Lok-Kun; Roach, Kristin; ...

2017-12-07

In this paper, a hydrothermal approach to generate a platinum-group-metal-free (PGM-free) Fe-N-C catalyst for the oxygen reduction reaction (ORR) is introduced. The process involves partial carbonization by hydrothermal means followed by thermal treatment to obtain the final catalysts. Detailed X-ray scattering analysis of the glucose-imidazole catalysts (termed as GLU-IMID-C catalysts), obtained for the first time with the use of CarbonXS GUI program, reveals the presence of face-centered cubic (FCC) iron nanoparticles embedded in partially graphitic carbon in all catalyst variations. We also report the physical characterization of these catalysts by using X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area analysis, and transmissionmore » electron microscopy. The electrocatalytic behavior of the catalysts towards oxygen reduction is studied separately in acidic and alkaline electrolytes by rotating ring disk electrode measurements. The catalysts exhibit high ORR activity in acidic (0.5 M H 2SO 4) and alkaline (0.1 M KOH) electrolytes. Lastly, a precursor structure-performance relationship of these catalysts and their performance trends in both electrolytes has been discussed in this work.« less

Hydrothermal Synthesis of Platinum-Group-Metal-Free Catalysts: Structural Elucidation and Oxygen Reduction Catalysis

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

Gokhale, Rohan; Tsui, Lok-Kun; Roach, Kristin

In this paper, a hydrothermal approach to generate a platinum-group-metal-free (PGM-free) Fe-N-C catalyst for the oxygen reduction reaction (ORR) is introduced. The process involves partial carbonization by hydrothermal means followed by thermal treatment to obtain the final catalysts. Detailed X-ray scattering analysis of the glucose-imidazole catalysts (termed as GLU-IMID-C catalysts), obtained for the first time with the use of CarbonXS GUI program, reveals the presence of face-centered cubic (FCC) iron nanoparticles embedded in partially graphitic carbon in all catalyst variations. We also report the physical characterization of these catalysts by using X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area analysis, and transmissionmore » electron microscopy. The electrocatalytic behavior of the catalysts towards oxygen reduction is studied separately in acidic and alkaline electrolytes by rotating ring disk electrode measurements. The catalysts exhibit high ORR activity in acidic (0.5 M H 2SO 4) and alkaline (0.1 M KOH) electrolytes. Lastly, a precursor structure-performance relationship of these catalysts and their performance trends in both electrolytes has been discussed in this work.« less

Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

NASA Astrophysics Data System (ADS)

Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

2016-12-01

This work focused on the catalytic transformation of methane (CH4) and carbon dioxide (CO2) into syngas (mixture of CO and H2). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400-700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

Preparation, structural characterization, and catalytic performance of Pd(II) and Pt(II) complexes derived from cellulose Schiff base

NASA Astrophysics Data System (ADS)

Baran, Talat; Yılmaz Baran, Nuray; Menteş, Ayfer

2018-05-01

In this study, we reported production, characterization, and catalytic behavior of two novel heterogeneous palladium(II) and platinum(II) catalysts derived from cellulose biopolymer. In order to eliminate the use of toxic organic or inorganic solvents and to reduce the use of excess energy in the coupling reactions, we have developed a very simple, rapid, and eco-friendly microwave irradiation protocol. The developed microwave-assisted method of Suzuki cross coupling reactions produced excellent reaction yields in the presence of cellulose supported palladium and platinum (II) catalysts. Moreover, the catalysts easily regenerated after simple filtration, and they gave good reusability. This study revealed that the designed catalysts and method provide clean, simple, rapid, and impressive catalytic performance for Suzuki coupling reactions.

A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

NASA Astrophysics Data System (ADS)

Workman, Michael J., Jr.

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of focused ion beam tomography is modified and optimized for platinum-group metal free catalyst layers, facilitating direct observation of catalyst integration into catalyst layers. I present evidence supporting the hypothesis that atomically dispersed iron coordinated with nitrogen are the dominant active sites in these catalysts. Further, that the concentration of surface oxides in the carbon structure, which can be directly influenced by synthesis parameters, correlates with both the concentration of active sites in the material and with fuel cell performance. Catalyst performance is hindered by the addition of carbon nanotubes and by the presence of metallic iron. Evidence consistent with the catalytic active sites residing in the graphitic plane is also presented.

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

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

1980-01-01

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

Dissolution of Platinum in the Operational Range of Fuel Cells

PubMed Central

Keeley, Gareth P.; Geiger, Simon; Zeradjanin, Aleksandar R.; Hodnik, Nejc; Kulyk, Nadiia

2015-01-01

Abstract One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 VRHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 VRHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 VRHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered. PMID:27525206

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

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

2015-03-16

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

Airborne concentrations of metals and total dust during solid catalyst loading and unloading operations at a petroleum refinery.

PubMed

Lewis, Ryan C; Gaffney, Shannon H; Le, Matthew H; Unice, Ken M; Paustenbach, Dennis J

2012-09-01

Workers handle catalysts extensively at petroleum refineries throughout the world each year; however, little information is available regarding the airborne concentrations and plausible exposures during this type of work. In this paper, we evaluated the airborne concentrations of 15 metals and total dust generated during solid catalyst loading and unloading operations at one of the largest petroleum refineries in the world using historical industrial hygiene samples collected between 1989 and 2006. The total dust and metals, which included aluminum, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, platinum, silicon, silver, vanadium, and zinc, were evaluated in relation to the handling of four different types of solid catalysts associated with three major types of catalytic processes. Consideration was given to the known components of the solid catalysts and any metals that were likely deposited onto them during use. A total of 180 analytical results were included in this analysis, representing 13 personal and 54 area samples. Of the long-term personal samples, airborne concentrations of metals ranged from <0.001 to 2.9mg/m(3), and, in all but one case, resulted in concentrations below the current U.S. Occupational Safety and Health Administration's Permissible Exposure Limits and the American Conference of Governmental Industrial Hygienists' Threshold Limit Values. The arithmetic mean total dust concentration resulting from long-term personal samples was 0.31mg/m(3). The data presented here are the most complete set of its kind in the open literature, and are useful for understanding the potential exposures during solid catalyst handling activities at this petroleum refinery and perhaps other modern refineries during the timeframe examined. Copyright © 2011 Elsevier GmbH. All rights reserved.

Organometallic catalysts for primary phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Walsh, Fraser

1987-01-01

A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

Local Platinum Environments in a Solid Analogue of the Molecular Periana Catalyst

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

Soorholtz, Mario; Jones, Louis C.; Samuelis, Dominik

2016-02-16

Combining advantages of homogeneous and heterogeneous catalysis by incorporating active species on a solid support is often an effective strategy for improving overall catalyst performance, although the influences of the support are generally challenging to establish, especially at a molecular level. In this paper, we report the local compositions, and structures of platinum species incorporated into covalent triazine framework (Pt-CTF) materials, a solid analogue of the molecular Periana catalyst, Pt(bpym)Cl 2, both of which are active for the selective oxidation of methane in the presence of concentrated sulfuric acid. By using a combination of solid-state 195Pt nuclear magnetic resonance (NMR)more » spectroscopy, aberration-corrected scanning transmission electron microscopy (AC-STEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), important similarities and differences are observed between the Pt-CTF and Periana catalysts, which are likely related to their respective macroscopic reaction properties. In particular, wide-line solid-state 195Pt NMR spectra enable direct measurement, identification, and quantification of distinct platinum species in as-synthesized and used Pt-CTF catalysts. The results indicate that locally ordered and disordered Pt sites are present in as-synthesized Pt-CTF, with the former being similar to one of the two crystallographically distinct Pt sites in crystalline Pt(bpym)Cl 2. A distribution of relatively disordered Pt moieties is also present in the used catalyst, among which are the principal active sites. Similarly XAS shows good agreement between the measured data of Pt-CTF and a theoretical model based on Pt(bpym)Cl 2. Analyses of the absorption spectra of Pt-CTF used for methane oxidation suggests ligand exchange, as predicted for the molecular catalyst. XPS analyses of Pt(bpym)Cl 2, Pt-CTF, as well as the unmodified ligands, further corroborate platinum coordination by pyridinic N atoms. Aberration-corrected high-angle annular dark-field STEM proves that Pt atoms are distributed within Pt-CTF before and after catalysis. Finally, the overall results establish the close similarities of Pt-CTF and the molecular Periana catalyst Pt(bpym)Cl 2, along with differences that account for their respective properties.« less

Sorption and recovery of platinum from simulated spent catalyst solution and refinery wastewater using chemically modified biomass as a novel sorbent.

PubMed

Garole, Dipak J; Choudhary, Bharat C; Paul, Debajyoti; Borse, Amulrao U

2018-04-01

In this study, Lagerstroemia speciosa biomass modified by polyethylenimine (PEI-LS) was developed as a potential biosorbent for sorption and recovery of platinum(II) from platinum bearing waste solutions. Batch experiments were conducted to study the effect of various parameters on the sorption and recovery of platinum(II) using PEI-LS. The equilibrium time for platinum(II) sorption process was found to be 6 h. Both the sorption kinetics and sorption isotherm data fits pseudo second-order kinetic model and Langmuir isotherm, respectively. The maximum sorption capacity of platinum(II) onto PEI-LS at pH 2 for the studied temperature range (25-45 °C) is in the range of 122-154 mg/g. Evaluation of thermodynamic parameters suggests that the platinum(II) sorption is spontaneous and endothermic in nature. The regeneration of PEI-LS can be achieved using acidic thiourea as an eluent for recovery of platinum from the biosorbent. Fourier transform infrared (FT-IR) analysis suggests many functional groups were involved in platinum(II) sorption onto PEI-LS. Both the scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) and X-ray photoelectron spectroscopy (XPS) analysis suggest a successful modification of raw biomass with PEI. The XPS analysis further concludes that platinum(II) sorption is governed by ion-exchange and co-ordination reaction. Finally, the PEI-LS was shown to recover ≥ 90% of platinum from two simulated solutions: the acid-leached spent catalyst solution and refinery wastewater. The biosorbent developed in this study is a low-cost and eco-friendly media that can be effectively used for platinum recovery from industrial wastewater.

n-Hexane conversion over supported Pt catalysts: Reply to Zoltan Paal

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

Sharma, S.B.; Dumesic, J.A.

In the accompanying letter to the Journal of Catalysis, Paal has questioned the findings and conclusions of the author`s recently published paper. It is important to stress that many of these conclusions are based on the combined interpretation of the data from the author`s recently published paper with results form spectroscopic and microcalorimetric studies of various supported platinum catalysts. In short, the authors have shown that highly dispersed, cluster-sized platinum particles supported in L-zeolite have the same heats of H{sub 2} and CO adsorption as larger platinum particles supported on silica; however, Pt/L-zeolite catalysts are more resistant to self-poisoning reactions,more » exhibit higher turnover frequencies, and show enhanced formation of benzene and methylcyclopentane (MCP) compared to larger particles of Pt supported on silica during n-hexane conversion at total pressures of 3 atm and hydrogen pressures near 276 kPa. 13 refs., 1 tab.« less

1. Catalytic asymmetric hydroformylation. 2. Hydroformylation with polymer-supported platinum complexes. 3. The reaction between dicobalt octacarbonyl and alcohols

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

Bortinger, A.

1977-01-01

Chiral polymer-supported metal complexes were catalytically active in the hydroformylation of prochiral olefins, but they induced only small optical activity. All the optical rotations in 2-phenylpropanal, obtained by the hydroformylation of styrene, were positive. In studies of asymmetric hydroformylation with homogeneous catalysts, no correlation was found between the optical inductions and ligand structure. Polymer-supported platinum catalysts having similar structure to their homogeneous counterparts showed the same high selectivity toward the formation of straight-chain aldehyde (89-95%) as the homogeneous catalysts in the hydroformylation of 1-hexene. Aldehyde yields were low (up to 45%); no reduction to alcohol occurred.

Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

NASA Astrophysics Data System (ADS)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

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

Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

NASA Astrophysics Data System (ADS)

Merati, Zohreh; Basiri Parsa, Jalal

2018-03-01

Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

Progress in catalytic ignition fabrication and modeling : fabrication part 2.

DOT National Transportation Integrated Search

2012-06-01

The ignition temperature and heat generation from oxidation of methane on a platinum catalyst were : determined experimentally. A 127 micron diameter platinum coiled wire was placed crosswise in a : quartz tube of a plug flow reactor. A source meter ...

Catalysts for low temperature oxidation

DOEpatents

Toops, Todd J.; Parks, III, James E.; Bauer, John C.

2016-03-01

The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Mahmood, Javeed; Li, Feng; Jung, Sun-Min; Okyay, Mahmut Sait; Ahmad, Ishfaq; Kim, Seok-Jin; Park, Noejung; Jeong, Hu Young; Baek, Jong-Beom

2017-05-01

The hydrogen evolution reaction (HER) is a crucial step in electrochemical water splitting and demands an efficient, durable and cheap catalyst if it is to succeed in real applications. For an energy-efficient HER, a catalyst must be able to trigger proton reduction with minimal overpotential and have fast kinetics. The most efficient catalysts in acidic media are platinum-based, as the strength of the Pt-H bond is associated with the fastest reaction rate for the HER. The use of platinum, however, raises issues linked to cost and stability in non-acidic media. Recently, non-precious-metal-based catalysts have been reported, but these are susceptible to acid corrosion and are typically much inferior to Pt-based catalysts, exhibiting higher overpotentials and lower stability. As a cheaper alternative to platinum, ruthenium possesses a similar bond strength with hydrogen (˜65 kcal mol-1), but has never been studied as a viable alternative for a HER catalyst. Here, we report a Ru-based catalyst for the HER that can operate both in acidic and alkaline media. Our catalyst is made of Ru nanoparticles dispersed within a nitrogenated holey two-dimensional carbon structure (Ru@C2N). The Ru@C2N electrocatalyst exhibits high turnover frequencies at 25 mV (0.67 H2 s-1 in 0.5 M H2SO4 solution; 0.75 H2 s-1 in 1.0 M KOH solution) and small overpotentials at 10 mA cm-2 (13.5 mV in 0.5 M H2SO4 solution; 17.0 mV in 1.0 M KOH solution) as well as superior stability in both acidic and alkaline media. These performances are comparable to, or even better than, the Pt/C catalyst for the HER.

Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

PubMed

Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

2014-12-01

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimetallic Nanocatalysts in Mesoporous Silica for Hydrogen Production from Coal-Derived Fuels

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

Kuila, Debasish; Ilias, Shamsuddin

2013-02-13

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

Platinum/Tin Oxide/Silica Gel Catalyst Oxidizes CO

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Davis, Patricia P.; Schryer, David R.; Miller, Irvin M.; Brown, David; Van Norman, John D.; Brown, Kenneth G.

1991-01-01

Heterogeneous catalyst of platinum, tin oxide, and silica gel combines small concentrations of laser dissociation products, CO and O2, to form CO22 during long times at ambient temperature. Developed as means to prevent accumulation of these products in sealed CO2 lasers. Effective at ambient operating temperatures and installs directly in laser envelope. Formulated to have very high surface area and to chemisorb controlled quantities of moisture: chemisorbed water contained within and upon its structure, makes it highly active and very longlived so only small quantity needed for long times.

Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

DOE PAGES

Barkholtz, Heather M.; Liu, Di -Jia

2016-11-14

Over the past several years, metal-organic framework (MOF)-derived platinum group metal free (PGM-free) electrocatalysts have gained considerable attention due to their high efficiency and low cost as potential replacement for platinum in catalyzing oxygen reduction reaction (ORR). In this review, we summarize the recent advancements in design, synthesis and characterization of MOF-derived ORR catalysts and their performances in acidic and alkaline media. As a result, we also discuss the key challenges such as durability and activity enhancement critical in moving forward this emerging electrocatalyst science.

Patched bimetallic surfaces are active catalysts for ammonia decomposition.

PubMed

Guo, Wei; Vlachos, Dionisios G

2015-10-07

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Patched bimetallic surfaces are active catalysts for ammonia decomposition

NASA Astrophysics Data System (ADS)

Guo, Wei; Vlachos, Dionisios G.

2015-10-01

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

I.C. Engine emission reduction by copper oxide catalytic converter

NASA Astrophysics Data System (ADS)

Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

2017-05-01

The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

Analyzing the influence of high electrode potentials on intrinsic properties of catalyst coated membranes using impedance spectroscopy

NASA Astrophysics Data System (ADS)

Alink, Robert; Schüßler, Martina; Pospischil, Maximilian; Erath, Denis; Gerteisen, Dietmar

2016-09-01

Catalyst layers (CLs) with varying ionomer contents are produced using a stencil coating and screen printing technique. The optimum ionomer content of 31-34 wt% confirms the findings of other groups and performance is found to be independent of production technique. A new CL impedance transition line model is developed and fitted to in-situ data. The results indicate that the protonic contact resistance between CL and membrane is an important factor for the used transfer-decal process, especially for CLs with low ionomer loading. When subjected to potentials higher than 1.2 V, an increased performance is observed for low ionomer loading CLs. It is found that by applying the high potential to the electrode a significantly increased proton conductivity is counteracting and superimposing the loss of electrochemical surface area (ECSA) due to carbon corrosion. After aging, the performance of the 15 wt% CL is at the same level as the 31-34 wt% ionomer content CLs at the beginning of life, even though the ECSA is reduced due to carbon corrosion or platinum dissolution. The findings indicate that for the optimization of the ionomer loading, either the changing wetting properties or the redistribution of ionomer during lifetime have to be taken into account.

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

DOE PAGES

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

2016-01-14

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

PubMed Central

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

2016-01-01

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES: CLEAN DIESEL TECHNOLOGIES FUEL-BORNE CATALYST WITH MITSUI/PUREARTH CATALYZED WIRE MESH FILTER

EPA Science Inventory

The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with Mitsui/PUREarth Catalyzed Wire Mesh Filter manufactured by Clean Diesel Technologies, Inc. The technology is a platinum/cerium fuel-borne catalyst in commerci...

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

Ionita, G.; Stefanescu, I.

The nature and performance of our patented catalysts, with platinum on carbon and polytetrafluorethylene [Pt/C/PTFE] and platinum on styrenedivynilbenzene and polystyrene [Pt/STB/PS], used in a water-hydrogen isotope exchange process are presented. The behaviour of the two catalysts in tritiated water was tested by determining their physical and structural characteristics as well as the catalytic activity before and after immersion in tritiated water. The test results emphasized that the two catalysts are highly active in the hydrogen - water vapor (H{sub 2(g)}-H{sub 2}O{sub (v)}) isotopic exchange and highly stable to tritium radiation. It was discovered that Pt/SDB/PS catalyst proved to bemore » quite unstable in the hydrogen- water vapor - water (H{sub 2(g)}-H{sub 2}O{sub (v)}-H{sub 2}O{sub (1)}) isotopic exchange, while the Pt/C/PTFE catalyst was highly stable. Thus, the Pt/C/PTFE catalyst was chosen for hydrogen isotope separation by liquid hydrogen cryogenic distillation combined with water - hydrogen isotopic exchange in a demonstration scale plant. 5 refs., 8 figs., 2 tabs.« less

Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions

NASA Astrophysics Data System (ADS)

Hejral, Uta; Müller, Patrick; Balmes, Olivier; Pontoni, Diego; Stierle, Andreas

2016-03-01

Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

Sources of anthropogenic platinum-group elements (PGE): Automotive catalysts versus PGE-processing industries.

PubMed

Zereini, F; Dirksen, F; Skerstupp, B; Urban, H

1998-01-01

Soil samples from the area of Hanau (Hessen, Germany) were analyzed for anthropogenic platinum-group elements (PGE). The results confirm the existence of two different sources for anthropogenic PGE: 1. automotive catalysts, and 2. PGE-processing plants. Both sources emit qualitatively and quantitatively different PGE spectra and PGE interelemental ratios (especially the Pt/Rh ratio). Elevated PGE values which are due to automotive catalysts are restricted to a narrow-range along roadside soil, whereas those due to PGE-processing plants display a large-area dispersion. The emitted PGE-containing particles in the case of automotive catalysts are subject to transport by wind and water, whereas those from PGE-processing plants are preferably transported by wind. This points to a different aerodynamic particle size. Pt, Pd, and Rh concentrations along motorways are dependent on the amount of traffic and the driving characteristics.

Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

NASA Astrophysics Data System (ADS)

Ahmed, Muthanna J.

2012-02-01

The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

Mineral resource of the month: platinum group metals

USGS Publications Warehouse

Loferski, Patricia J.

2010-01-01

The article focuses on platinum group metals (PGMs) and their properties. According to the author, PGMs, which include iridium, osmium, palladium, platinum, rhodium, and ruthenium, are among the rarest mineral commodities in the Earth's crust. PGMs are primarily used as catalytic converters that clean harmful exhaust from vehicle engines. They are also used in the chemical industry as catalysts in the production of nitric acid and in the petroleum refining industry.

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

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

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

DOE PAGES

Sabyrov, Kairat; Musselwhite, Nathan; Melaet, Gérôme; ...

2017-01-01

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-syntheticmore » aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.« less

2D Nanoporous Fe-N/C Nanosheets as Highly Efficient Non-Platinum Electrocatalysts for Oxygen Reduction Reaction in Zn-Air Battery.

PubMed

Yang, Zheng Kun; Lin, Ling; Xu, An-Wu

2016-11-01

It is an ongoing challenge to fabricate nonprecious oxygen reduction reaction (ORR) catalysts that can be comparable to or exceed the efficiency of platinum. A highly active non-platinum self-supporting Fe-N/C catalyst has been developed through the pyrolysis of a new type of precursor of iron coordination complex, in which 1,4-bis(1H-1,3,7,8-tetraazacyclopenta(1)phenanthren-2-yl)benzene (btcpb) functions as a ligand complexing Fe(II) ions. The optimal catalyst pyrolyzed at 700 °C (Fe-N/C-700) shows the best ORR activity with a half-wave potential (E 1/2 ) of 840 mV versus reversible hydrogen electrode (RHE) in 0.1 m KOH, which is more positive than that of commercial Pt/C (E 1/2 : 835 mV vs RHE). Additionally, the Fe-N/C-700 catalyst also exhibits high ORR activity in 0.1 m HClO 4 with the onset potential and E 1/2 comparable to those of the Pt/C catalyst. Notably, the Fe-N/C-700 catalyst displays superior durability (9.8 mV loss in 0.1 m KOH and 23.6 mV loss in 0.1 m HClO 4 for E 1/2 after 8000 cycles) and better tolerance to methanol than Pt/C. Furthermore, the Fe-N/C-700 catalyst can be used for fabricating the air electrode in Zn-air battery with a specific capacity of 727 mA hg -1 at 5 mA cm -2 and a negligible voltage loss after continuous operation for 110 h. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The nature of platinum in silicones for biomedical and healthcare use.

PubMed

Lambert, James M

2006-07-01

Silicone is an important biomaterial in many different biomedical and healthcare applications. Network formation in one type of silicone relies upon a chemical crosslinking reaction that typically employs a platinum catalyst. As a consequence, low concentrations of platinum may remain in certain medical devices designed for human use. The characteristics of platinum in silicone before, during, and after the crosslinking reaction have been well described in the literature. This review summarizes the relevant literature on the organometallic and analytical chemistry of platinum in silicone and thus provides a foundation for understanding the effects this platinum may have, if any, in the various biomedical and healthcare applications where it may be present.

Synthesis and Characterization of CO-and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

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

Shamsuddin Ilias

2005-12-22

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we synthesized four Pt-based electrocatalysts catalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) on Vulcan XG72 Carbon support by both conventional and ultra-sonication method. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. Sonication method appears to provide better dispersion of catalysts on carbon support.« less

Advanced technology lightweight fuel cell program

NASA Technical Reports Server (NTRS)

Martin, R. E.

1981-01-01

The potential of the alkaline electrolyte fuel cell as the power source in a multi hundred kilowatt orbital energy storage system was studied. The total system weight of an electrolysis cell energy storage system was determined. The tests demonstrated: (1) the performance stability of a platinum on carbon anode catalyst configuration after 5000 hours of testing has no loss in performance; (2) capability of the alkaline fuel cell to operate to a cyclical load profile; (3) suitability of a lightweight graphite electrolyte reservoir plate for use in the alkaline fuel cell; (4) long life potential of a hybrid polysulfone cell edge frame construction; and (5) long term stability of a fiber reinforced potassium titanate matrix structure. The power section tested operates with passive water removal eliminating the requirement for a dynamic hydrogen pump water separator thereby allowing a powerplant design with reduced weight, lower parasite power, and a potential for high reliability and extended endurance. It is concluded that two perovskites are unsuitable for use as a catalyst or as a catalyst support at the cathode of an alkaline fuel cell.

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

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

Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my; Ali, Sardar, E-mail: alikhan-635@yahoo.com; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

2014-10-24

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances comparedmore » to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.« less

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

NASA Astrophysics Data System (ADS)

Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

2014-10-01

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H2-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions

NASA Astrophysics Data System (ADS)

Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

2014-09-01

Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. Electronic supplementary information (ESI) available: Detailed RDE and RRDE experiments, additional tables and figures. See DOI: 10.1039/c4nr03185g

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

PubMed Central

Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

2015-01-01

The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells.

PubMed

Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

2015-02-01

The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells.

Life cycle assessment of gas atomised sponge nickel for use in alkaline hydrogen fuel cell applications

NASA Astrophysics Data System (ADS)

Wilson, Benjamin P.; Lavery, Nicholas P.; Jarvis, David J.; Anttila, Tomi; Rantanen, Jyri; Brown, Stephen G. R.; Adkins, Nicholas J.

2013-12-01

This paper presents a cradle-to-grave comparative Life Cycle Assessment (LCA) of new gas atomised (GA) sponge nickel catalysts and evaluates their performance against the both cast and crush (CC) sponge nickel and platinum standards currently used in commercial alkaline fuel cells (AFC). The LCA takes into account the energy used and emissions throughout the entire life cycle of sponge nickel catalysts - ranging from the upstream production of materials (mainly aluminium and nickel), to the manufacturing, to the operation and finally to the recycling and disposal. Through this assessment it was found that the energy and emissions during the operational phase associated with a given catalyst considerably outweigh the primary production, manufacturing and recycling. Primary production of the nickel (and to a lesser extent dopant materials) also has a significant environmental impact but this is offset by operational energy savings over the electrode's estimated lifetime and end of life recyclability. From the results it can be concluded that higher activity spongy nickel catalysts produced by gas atomisation could have a significantly lower environmental impact than either CC nickel or platinum. Doped GA sponge nickel in particular showed comparable performance to that of the standard platinum electrode used in AFCs.

The effect of Sn on the reactions of n-hexane and cyclohexane over polycrystalline Pt foils

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

Fujikawa, T.; Ribeiro, F.H.; Somorjai, G.A.

The modification of the catalytic properties of a polycrystalline platinum foil by the addition of tin was studied by the reactions of n-hexane and cyclohexane in excess H{sub 2}. The reactions were studied at 13.3 kPa of n-hexane, 450 kPa of H{sub 2} and 740 K, and 6.7 kPa of cyclohexane, 450 kPa of H{sub 2} and 573 K. The Pt-Sn catalyst was characterized by Auger electron spectroscopy and by temperature-programmed desorption of CO before and after the reactions. The sites that bind CO most strongly on the Pt foil also have the highest initial turnover rate and are themore » first ones to be poisoned by carbon deposits from hydrocarbon reactions or by sulfur when a sulfur-containing compound (thiophene) is present in the feed. The addition of tin can block these sites preferentially, thus decreasing the undesirable high initial hydrogenolysis rate of platinum catalysts in reforming reactions and eliminating the need for presulfiding the catalyst. Also, tin suppressed the hydrogenolysis reaction preferentially to the isomerization and cyclization reactions thus increasing the selectivities to isomerization and cyclization. The amount of carbon deposited was smaller on tin containing platinum catalysts during the dehydrogenation of cyclohexane and n-hexane.« less

Development of advanced fuel cell system, phase 3

NASA Technical Reports Server (NTRS)

Handley, L. M.; Meyer, A. P.; Bell, W. F.

1975-01-01

A multiple task research and development program was performed to improve the weight, life, and performance characteristics of hydrogen-oxygen alkaline fuel cells for advanced power systems. Gradual wetting of the anode structure and subsequent long-term performance loss was determined to be caused by deposition of a silicon-containing material on the anode. This deposit was attributed to degradation of the asbestos matrix, and attention was therefore placed on development of a substitute matrix of potassium titanate. An 80 percent gold 20 percent platinum catalyst cathode was developed which has the same performance and stability as the standard 90 percent gold - 10 percent platinum cathode but at half the loading. A hybrid polysulfone/epoxy-glass fiber frame was developed which combines the resistance to the cell environment of pure polysulfone with the fabricating ease of epoxy-glass fiber laminate. These cell components were evaluated in various configurations of full-size cells. The ways in which the baseline engineering model system would be modified to accommodate the requirements of the space tug application are identified.

Preparation and characteristics of carbon-supported platinum catalyst and its application in the removal of phenolic pollutants in aqueous solution by microwave-assisted catalytic oxidation.

PubMed

Bo, Longli; Quan, Xie; Wang, Xiaochang; Chen, Shuo

2008-08-30

Granular activated carbon-supported platinum (Pt/GAC) catalysts were prepared by microwave irradiation and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). Pt particles dispersing onto the surface of GAC could be penetrated by microwave and acted as "reaction centre" in the degradations of p-nitrophenol (PNP) and pentachlorophenol (PCP) in aqueous solution by microwave-assisted catalytic oxidation. The reaction was carried out through a packed bed reactor under ambient pressure and continuous flow mode. Under the conditions of microwave power 400 W, influent flow 6.4 mL min(-1) and air flow 120 mL min(-1), phenolic solutions with high concentration (initial concentrations of PNP and PCP solutions were 1469 and 1,454 mg L(-1), respectively) were treated effectively by Pt/GAC, 86% PNP and 90% PCP were degraded and total organic carbon (TOC) removal reached 85% and 71%, respectively. Compared with GAC, loaded Pt apparently accelerated oxidative reaction so that Pt/GAC had a better degrading and mineralizing efficiencies for PNP. Hydraulic retention time was only 16 min in experiment, which was shortened greatly compared with catalytic wet air oxidation. Pyrolysis and oxidation of phenolic pollutants occurred simultaneously on the surface of Pt/GAC by microwave irradiation.

Electrocatalyst compositions

DOEpatents

Mallouk, Thomas E.; Chan, Benny C.; Reddington, Erik; Sapienza, Anthony; Chen, Guoying; Smotkin, Eugene; Gurau, Bogdan; Viswanathan, Rameshkrishnan; Liu, Renxuan

2001-09-04

Compositions for use as catalysts in electrochemical reactions are described. The compositions are alloys prepared from two or more elemental metals selected from platinum, molybdenum, osmium, ruthenium, rhodium, and iridium. Also described are electrode compositions including such alloys and electrochemical reaction devices including such catalysts.

SEM method for direct visual tracking of nanoscale morphological changes of platinum based electrocatalysts on fixed locations upon electrochemical or thermal treatments.

PubMed

Zorko, Milena; Jozinović, Barbara; Bele, Marjan; Hodnik, Nejc; Gaberšček, Miran

2014-05-01

A general method for tracking morphological surface changes on a nanometer scale with scanning electron microscopy (SEM) is introduced. We exemplify the usefulness of the method by showing consecutive SEM images of an identical location before and after the electrochemical and thermal treatments of platinum-based nanoparticles deposited on a high surface area carbon. Observations reveal an insight into platinum based catalyst degradation occurring during potential cycling treatment. The presence of chloride clearly increases the rate of degradation. At these conditions the dominant degradation mechanism seems to be the platinum dissolution with some subsequent redeposition on the top of the catalyst film. By contrast, at the temperature of 60°C, under potentiostatic conditions some carbon corrosion and particle aggregation was observed. Temperature treatment simulating the annealing step of the synthesis reveals sintering of small platinum based composite aggregates into uniform spherical particles. The method provides a direct proof of induced surface phenomena occurring on a chosen location without the usual statistical uncertainty in usual, random SEM observations across relatively large surface areas. Copyright © 2014 Elsevier B.V. All rights reserved.

Deposition of platinum nanoparticles on carbon nanotubes by supercritical fluid method.

PubMed

Yen, Clive H; Cui, Xiaoli; Pan, Horng-Bin; Wang, Shaofen; Lin, Yuehe; Wai, Chien M

2005-11-01

Carbon nanotube-supported platinum nanoparticles with a 5-15 nm diameter size range can be synthesized by hydrogen reduction of platinum(ll) acetylacetonate in methanol modified supercritical carbon dioxide. X-ray photoelectron spectroscopy and X-ray diffraction spectra indicate that the carbon nanotubes contain zero-valent platinum metal and high-resolution transmission electron microscopy images show that the visible lattice fringes of platinum nanoparticles are crystallites. Carbon nanotubes synthesized with 25% by weight of platinum nanoparticles exhibit a higher activity for hydrogenation of benzene compared with a commercial carbon black platinum catalyst. The carbon nanotube-supported platinum nanocatalyst can be reused at least six times for the hydrogenation reaction without losing activity. The carbon nanotube-supported platinum nanoparticles are also highly active for electrochemical oxidation of methanol and for reduction of oxygen suggesting their potential use as a new electrocatalyst for proton exchange membrane fuel cell applications.

The Investigation and Development of Low Cost Hardware Components for Proton-Exchange Membrane Fuel Cells - Final Report

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

George A. Marchetti

1999-12-15

Proton exchange membrane (PEM) fuel cell components, which would have a low-cost structure in mass production, were fabricated and tested. A fuel cell electrode structure, comprising a thin layer of graphite (50 microns) and a front-loaded platinum catalyst layer (600 angstroms), was shown to produce significant power densities. In addition, a PEM bipolar plate, comprising flexible graphite, carbon cloth flow-fields and an integrated polymer gasket, was fabricated. Power densities of a two-cell unit using this inexpensive bipolar plate architecture were shown to be comparable to state-of-the-art bipolar plates.

Carbon aerogel electrodes for direct energy conversion

DOEpatents

Mayer, Steven T.; Kaschmitter, James L.; Pekala, Richard W.

1997-01-01

A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome.

Stereocontrolled Additions to a Rigid Bicyclo [3.3.0] Octane Ring System

DTIC Science & Technology

2008-05-05

bridgehead carbon. The metals studied were palladium, platinum, and the Raney nickel catalyst . The catalysts themselves are usually absorbed on an...Catalytic Hydrogenation Reaction The Raney nickel catalyst yielded extremely pure product in a single isomeric form when the reaction was run with...ethyl acetate was 68.7%, a noted increase over that obtained with the Raney nickel catalyst . 31 Disappearance of the double bond peak again

Bi-metallic nanoparticles as cathode electrocatalysts

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

Lu, Jun; Amine, Khalil; Wang, Xiaoping

A lithium-air battery cathode catalyst includes core-shell nanoparticles on a carbon support, wherein: a core of the core-shell nanoparticles is platinum metal; and a shell of the core-shell nanoparticles is copper metal; wherein: the core-shell nanoparticles have a weight ratio of the copper metal to the platinum metal from about 4% to about 6% copper to from about 2% to about 12% platinum, with a remaining percentage being the carbon support.

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

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

Cha, Jennifer N.; Wang, Joseph

2014-08-31

The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds,more » (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.« less

Pt/Ceria-based Catalysts for Small Alcohol Electrooxidation

NASA Astrophysics Data System (ADS)

Menendez-Mora, Christian L.

High emissions of fossil-based energy sources have led to scientists around the world to develop new alternatives for the future. In this sense, fuel cells are a remarkable and promising energy option with less environmental impact. The most used fuels for this technology are hydrogen and small chain alcohols, which can be oxidized to transform their chemical energy into electrical power. To do this, fuel cells need catalysts that will act as an active surface where the oxidation can take place. The problem with platinum catalysts is its possible CO poisoning with intermediates that are produced before the complete oxidation of alcohol to CO2. Different approaches have been taken to try to resolve this issue. In this case, cerium oxide (ceria) was selected as a co-catalyst to mitigate the effect of CO poisoning of platinum. Ceria is a compound that has the ability to work as an "oxygen tank" and can donate oxygen to carbon monoxide that is strongly adsorbed at platinum surface to produce CO2 (carbon dioxide), regenerating the Pt surface for further alcohol oxidation. Therefore, enhancing the current density as well as the power output of a fuel cell. First, an occlusion deposition technique was used to prepare platinum/ceria composite electrodes and tested them towards small chain alcohol oxidation such as methanol oxidation reaction in acidic and alkaline media. The preliminary results demonstrated that the Pt/ceria electrodes were more efficient towards methanol electrooxidation when compared to Pt electrodes. This enhancement was attributed to the presence of ceria. A second preparation method was selected for the synthesis of ceria/Pt catalysts. In this case, a hydrothermal method was used and the catalysis were studied for the effect of MeOH, EtOH and n-BuOH oxidation. The observed effect was that electrodes made of Pt/Pt:CeO2-x showed better catalytic effect than Pt/ceria and platinum electrodes. Moreover, a comparison between ceria nanorods versus nanoparticles as substrates was done. The general result was that ceria nanoparticles showed better electrocatalytic behavior towards the oxidation of methanol in alkaline medium. Finally, as an outreach activity, an educational module to reinforce the electrochemical concepts in the General Chemistry Laboratory course at UPR-RP was developed. The module was based on Volta's Experiment and an improvement on students learning was detected when comparing this activity with the normal Daniel's cell experience that is used in most Universities at the undergraduate level. In summary, the findings of this thesis conclude that ceria is a compound that may enhance platinum catalytic activity by CO oxidation, promoting the oxidation of alcohols in acidic and alkaline medium. Moreover, catalysis depends on the morphology of the ceria that is used as the catalysts support.

A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

DOE PAGES

Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; ...

2015-10-13

The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure. [1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt. [5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application. [10-12] A potential strategy tomore » address this tremendous challenge is alloying Pt NPs with the transition metals (TM). [13-16]« less

Analysis of alkaline exchange membrane fuel cells performance at different operating conditions using DC and AC methods

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana; Odgaard, Madeleine; Schlueter, Debbie; Serov, Alexey

2018-01-01

Membrane electrode assemblies (MEAs) for anion exchange membrane fuel cells (AEMFCs) were manufactured from commercial materials: Pt/C catalyst, A201 AEM and AS4 ionomer by using an industrial mass-production digital printing method. The MEA designs selected are close to those recommended by US Department of Energy, including low loading of platinum on the cathode side (0.2 mg cm-2). Polarization curves and electrochemical impedance spectroscopy (EIS) were applied for MEA evaluation in fuel cell conditions with variation of gas humidification and oxygen partial pressure (air vs oxygen). The typical impedance curves recorded at H2/O2 gas configuration consist of high- and medium-frequency arcs responsible for hydrogen oxidation and oxygen reduction, respectively. Operation with air as a cathode feed gas resulted in a decrease in AEMFC performance due to possible CO2 poisoning and mass transfer losses. At the same time, EIS demonstrated formation of a low frequency loop due to diffusion limitations. Despite the low loading of platinum on the cathode (0.2 mg cm-2), a peak power density of ∼330 mW cm-2 was achieved (at 50/50% of RH on anode and cathode), which is substantially higher performance than for AEMFC MEAs tested at similar conditions.

METHOD OF PURIFYING CATALYSTS

DOEpatents

Joris, G.G.

1958-09-01

It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

Particle size and support effects in electrocatalysis.

PubMed

Hayden, Brian E

2013-08-20

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.

Oxygen-reducing catalyst layer

DOEpatents

O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

2011-03-22

An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1982-01-01

Platinum sintering on phosphoric acid fuel cell cathodes is discussed. The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst dispersed on a conductive carbon support to minimize both cathode polarization and fabrication costs. During operation, however, the active surface area of these electrodes decreases, which in turn leads to decreased cell performance. This loss of active surface area is a major factor in the degradation of fuel cell performance over time.

Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

PubMed

Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

2011-11-01

This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. Copyright © 2011 Elsevier Ltd. All rights reserved.

Correlation between the Knight shift of chemisorbed CO and the Fermi level local density of states at clean platinum catalyst surfaces

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

Tong, Y.Y.; Rice, C.; Godbout, N.

1999-04-07

Due to its fundamental importance in heterogeneous catalysis, as well as in electrocatalysis, the chemisorption and reaction of CO on transition metal surfaces has been an important focus of modern surface science. Here, the NMR spectroscopy of {sup 13}CO adsorbed onto transition metal surfaces has been shown to be a very powerful probe of molecular structure and dynamics of CO itself, as well as a probe of the electronic properties of the transition metal surfaces onto which it is adsorbed. The authors have investigated the {sup 195}Pt and {sup 13}C nuclear magnetic resonance (NMR) spectroscopy of clean-surface platinum catalysts andmore » of CO chemisorbed onto Pt catalysts surfaces. They use Knight shift, relaxation, and J-coupling data to deduce information about the Fermi level local density of states (E{sub f}-LDOS) at catalyst surfaces. There is a linear correlation between the Knight shifts of chemisorbed CO and the clean surface E{sub f}-LDOS of platinum onto which the CO is bound, as determined by {sup 13}C and {sup 195}Pt NMR. The correlation amounts to {approximately} 12 ppm/Ry{sup {minus}1} {center_dot} atom{sup {minus}1}, the same as that which can be deduced for CO on palladium, as well as from the electrode potential dependence of {sup 13}C Knight shifts and infrared vibrational frequencies, {nu}{sub CO}, and the relationship between {nu}{sub CO} and the E{sub f}-LDOS at clean platinum surfaces. The ability to now directly relate meal and adsorbate electronic properties opens up new avenues for investigating metal-ligand interactions in heterogeneous catalysis and electrocatalysis.« less

Foamed-metal-based catalytic afterburners in automotive exhaust systems

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

Pestryakov, A.N.; Ametov, V.A.

1994-08-10

Properties of exhaust afterburning catalysts based on porous cellular materials (foamed metals) have been investigated. Catalysts containing oxides of base metals provide a two-to-threefold reduction of CO emission. Platinum-containing foamed catalysts lower the toxicity of exhaust by 85-90%. A favorable effect is demonstrated by the combined use of afterburners and a motor oil additive based on ultradispersed copper.

Fuel cell performance of palladium-platinum core-shell electrocatalysts synthesized in gram-scale batches

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

Khateeb, Siddique; Su, Dong; Guerreo, Sandra

This article presents the performance of palladium-platinum core-shell catalysts (Pt/Pd/C) for oxygen reduction synthesized in gram-scale batches in both liquid cells and polymer-electrolyte membrane fuel cells. Core-shell catalyst synthesis and characterization, ink fabrication, and cell assembly details are discussed. The Pt mass activity of the Pt/Pd core-shell catalyst was 0.95 A mg –1 at 0.9 V measured in liquid cells (0.1 M HClO4), which was 4.8 times higher than a commercial Pt/C catalyst. The performances of Pt/Pd/C and Pt/C in large single cells (315 cm 2) were assessed under various operating conditions. The core-shell catalyst showed consistently higher performance thanmore » commercial Pt/C in fuel cell testing. A 20–60 mV improvement across the whole current density range was observed on air. Sensitivities to temperature, humidity, and gas composition were also investigated and the core-shell catalyst showed a consistent benefit over Pt under all conditions. However, the 4.8 times activity enhancement predicated by liquid cell measurements was not fully realized in fuel cells.« less

Fuel cell performance of palladium-platinum core-shell electrocatalysts synthesized in gram-scale batches

DOE PAGES

Khateeb, Siddique; Su, Dong; Guerreo, Sandra; ...

2016-05-03

This article presents the performance of palladium-platinum core-shell catalysts (Pt/Pd/C) for oxygen reduction synthesized in gram-scale batches in both liquid cells and polymer-electrolyte membrane fuel cells. Core-shell catalyst synthesis and characterization, ink fabrication, and cell assembly details are discussed. The Pt mass activity of the Pt/Pd core-shell catalyst was 0.95 A mg –1 at 0.9 V measured in liquid cells (0.1 M HClO4), which was 4.8 times higher than a commercial Pt/C catalyst. The performances of Pt/Pd/C and Pt/C in large single cells (315 cm 2) were assessed under various operating conditions. The core-shell catalyst showed consistently higher performance thanmore » commercial Pt/C in fuel cell testing. A 20–60 mV improvement across the whole current density range was observed on air. Sensitivities to temperature, humidity, and gas composition were also investigated and the core-shell catalyst showed a consistent benefit over Pt under all conditions. However, the 4.8 times activity enhancement predicated by liquid cell measurements was not fully realized in fuel cells.« less

Comparative assessment of synthetic strategies toward active platinum-rhodium-tin electrocatalysts for efficient ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Erini, Nina; Krause, Paul; Gliech, Manuel; Yang, Ruizhi; Huang, Yunhui; Strasser, Peter

2015-10-01

The present work explores the effect of autoclave-based autogenous-pressure vs. ambient pressure conditions on the synthesis and properties of carbon-supported Pt-Rh-Sn nanoparticle electrocatalysts. The Pt-Rh-Sn nanoparticles were characterized by X-ray spectroscopy, electron microscopy and mass spectroscopy and deployed as catalysts for the electrocatalytic ethanol oxidation reaction. Pt-Rh-Sn catalysts precipitated with carbon already present showed narrow particle size distribution around 7 nm, while catalysts supported on carbon after particle formation showed broader size distribution ranging from 8 to 16 nm, similar metal loadings between 40 and 48 wt.% and similar atomic ratios of Pt:Rh:Sn of 30:10:60. The highest ethanol oxidation activity at low overpotentials associated with exceptionally early ethanol oxidation onset potential was observed for ambient-pressure catalysts with the active ternary alloy phase formed in presence of the carbon supports. In contrast, catalysts prepared under ambient pressure in a two-step approach, involving alloy particle formation followed by particle separation and subsequent deposition on the carbon support, yielded the highest overall mass activities. Based on the observed synthesis-activity correlations, a comparative assessment is provided of the synthetic techniques at high vs. low pressures, and in presence and absence of carbon support. Plausible hypotheses in terms of particle dispersion and interparticle distance accounting for these observed differences are discussed.

Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-10-10

We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, inducedmore » by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Phosphoric acid fuel cell platinum use study

NASA Technical Reports Server (NTRS)

Lundblad, H. L.

1983-01-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Phosphoric acid fuel cell platinum use study

NASA Astrophysics Data System (ADS)

Lundblad, H. L.

1983-05-01

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Multi-walled carbon nanotubes decorated by platinum catalyst nanoparticles--examination and microanalysis using scanning and transmission electron microscopies.

PubMed

Guinel, M J-F; Brodusch, N; Verde-Gómez, Y; Escobar-Morales, B; Gauvin, R

2013-10-01

Carbon nanotubes (CNTs) decorated with platinum (Pt) nanoparticles (NPs) have been characterized using a cold field-emission scanning electron microscope (SEM) and a high resolution field-emission transmission electron microscope (TEM). With this particular composite material, the complementary nature of the two instruments was demonstrated. Although the long CNTs were found to be mostly bent and defective in some parts, the nucleation of Pt occurred randomly and uniformly covered the CNTs. The NPs displayed a large variation in size, were sometimes defective with twins and stacking faults, and were found to be faceted with the presence of surface steps. The shape and size of the NPs and the presence of defects may have significant consequences on the activity of the Pt catalyst material. Also, thin layers of platinum oxide were identified on the surface of some NPs. © 2013 The Authors Journal of Microscopy © 2013 Royal Microscopical Society.

Biosynthetic porphyrins and the origin of photosynthesis

NASA Technical Reports Server (NTRS)

Mauzerall, D.; Ley, A.; Mercer-Smith, J. A.

1986-01-01

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

DOE PAGES

Ogawa, S.; Komini Babu, S.; Chung, H. T.; ...

2016-08-22

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Direct Simulations of Coupled Transport and Reaction on Nano-Scale X-Ray Computed Tomography Images of Platinum Group Metal-Free Catalyst Cathodes

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

Ogawa, S.; Komini Babu, S.; Chung, H. T.

The nano/micro-scale geometry of polymer electrolyte fuel cell (PEFC) catalyst layers critically affects cell performance. The small length scales and complex structure of these composite layers make it challenging to analyze cell performance and physics at the particle scale by experiment. We present a computational method to simulate transport and chemical reaction phenomena at the pore/particle-scale and apply it to a PEFC cathode with platinum group metal free (PGM-free) catalyst. Here, we numerically solve the governing equations for the physics with heterogeneous oxygen diffusion coefficient and proton conductivity evaluated using the actual electrode structure and ionomer distribution obtained using nano-scalemore » resolution X-ray computed tomography (nano-CT). Using this approach, the oxygen concentration and electrolyte potential distributions imposed by the oxygen reduction reaction are solved and the impact of the catalyst layer structure on performance is evaluated.« less

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

DOE PAGES

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; ...

2016-09-16

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. In this paper, we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transitionmore » metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.« less

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

NASA Astrophysics Data System (ADS)

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

2016-09-01

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

Controlling the Growth and Catalytic Activity of Platinum Nanoparticles Using Peptide and Polymer Ligands

NASA Astrophysics Data System (ADS)

Forbes, Lauren Marie

Heterogeneous catalysts have widespread industrial applications. Platinum nanomaterials in particular, due to their particularly high electrocatalytic activity and durability, are used to catalyze a wide variety of reactions, including oxygen reduction, which is frequently used as the cathode reaction in fuel cells. As platinum is a very expensive material, a high priority in fuel cell research is the exploration of less expensive, more efficient catalysts for the oxygen reduction reaction (ORR). We demonstrate here the use of phage display to identify peptides that bind to Pt (100) which were then used to synthesize platinum cubes in solution. However, while the peptides were able to control particle growth, the bio-synthesized Pt particles showed extremely poor activity when tested for ORR. This could be attributed to peptide coverage on the surface or strong interactions between particular amino acids and the metal that are detrimental for catalysis. To investigate this further, we decided to investigate the role of individual amino acids on Pt nanocrystal synthesis and catalysis. For this, we conjugated the R-groups of single amino acids to polyethylene glycol (PEG) chains. Through this work we have determined that the identity of the amino acid R-group is important in both the synthesis and the catalytic activity of the particles. For Pt nanoparticle synthesis, we found that the hydrophobicity of the functional groups affected their ability to interact well with the particles during nucleation and growth, and thus only the hydrophilic functional groups were capable of mediating the synthesis to produce well-defined faceted particles. With respect to ORR, we found distinct trends that showed that the inclusion of certain amino acids could significantly enhance catalysis---even at high polymer loadings. This work presents evidence that counters the common conception that organic capping ligands decrease catalytic activity; in fact activity may actually be improved over bare metal through judicious choice and design of ligands that inhibit Pt oxidation and control chain packing at the Pt surface. Therefore, it may be possible to have ligands on a nanoparticle surface that allow the particles to be well-dispersed on an electrode surface, while simultaneously enhancing catalysis.

Photoelectrochemical characteristics of dye-sensitized solar cells incorporating innovative and inexpensive materials

NASA Astrophysics Data System (ADS)

Harlow, Lisa Jean

The use of energy is going to continue to increase rapidly due to population and economic advances occurring throughout the world. The most widely used energies produce carbon dioxide during their combustion and have finite limits on how much of these resources are available. A strong push to utilizing renewable energy is necessary to keep up with the demand. The only renewable energy that has unlimited supply is solar. Our goal is to find cost-effective alternatives to historically the most extensively used materials in dye-sensitized solar cells. In order to rely on efficiency changes coinciding with the introduction of a new component, a standard baseline of performance is necessary to establish. A reproducible fabrication procedure composed of standard materials was instituted; the efficiency parameters exhibited a less than 10% standard deviation for any set of solar cells. Any modifications to the cell components would be apparent in the change in efficiency. Our cell modifications focused on economical alternatives to the electrolyte, the counter electrode and the chromophore. Solution-based electrolytes were replaced with a non-volatile ionic liquid, 1-methyl-3-propylimidazolium iodide, and then a poly(imidazole-functionalized) silica nanoparticle. Solid-state electrolytes reduce or prevent leakage and could ease manufacturing in large-scale devices. Platinum has been the counter electrode catalyst primarily used with the iodide/triiodide redox couple, but is a rare metal making it rather costly. We reduce platinum loading by introducing a novel counter electrode that employs platinum nanoparticles embedded on a graphene nanoplatelet paper. The highly conductive carbon base also negates the use of the expensive conductive substrate necessary for the platinum catalyst, further reducing cost. We also study the differences in transitioning from ruthenium polypyridyls to iron-based chromophores in dye-sensitized solar cells. Iron introduces low-lying ligand field states which the charge-transfer transitions necessary for electron injection deactivate to. We study a series of molecules that converts from a historically well-known ruthenium dye stepwise to an iron-based chromophore that has exhibited photocurrent previously. Converting to iron proves to be complicated and we aim to continue our investigation in order to gain a better understanding of the complexity.

Cobalt porphyrin-based material as methanol tolerant cathode in single chamber microbial fuel cells (SCMFCs)

NASA Astrophysics Data System (ADS)

Liu, Bingchuan; Brückner, Cristian; Lei, Yu; Cheng, Yue; Santoro, Carlo; Li, Baikun

2014-07-01

This study focused on the development of novel cathode material based on the pyrolysis of [meso-tetrakis(2-thienyl)porphyrinato]Co(II) (CoTTP) for use in single chamber microbial fuel cells (SCMFCs) to treat wastewater containing methanol. The cathodes produced at two loadings (0.5 and 1.0 mg cm-2) were examined in batch mode SCMFCs treating methanol of different concentrations (ranging from 0.005 to 0.04 M) over a 900 h operational period. Methanol was completely removed in SCMFCs, and the cycle duration was prolonged at high methanol concentrations, indicating methanol was used as fuel in SCMFCs. Methanol had more poisoning effects to the traditional platinum (Pt) cathodes than to the CoTTP cathodes. Specifically, power generations from SCMFCs with Pt cathodes gradually decreased over time, while the ones with CoTTP cathodes remained stable, even at the highest methanol concentration (0.04 M). Cathode linear sweep voltammetry (LSVs) indicated that the electrocatalytic activity of the Pt cathode was suppressed by methanol. Higher CoTTP loadings had similar open circuit potential (OCP) but higher electrocatalytic activity than lower loadings. This study demonstrated that methanol can be co-digested with wastewater and converted to power in MFCs, and a novel cathode CoTTP catalyst exhibits higher tolerance towards methanol compared with traditional Pt catalyst.

Low platinum loading cathode modified with Cs3H2PMo10V2O40 for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Renzi, M.; D'Angelo, G.; Marassi, R.; Nobili, F.

2016-09-01

The catalytic activity of commercial Pt nanoparticles mixed with mesoporous polyoxometalate Cs3H2PMo10V2O40 towards oxygen reduction reaction is evaluated. The polyoxometalate co-catalyst is prepared by titration of an aqueous solution of phosphovanadomolibdic acid. SEM micrography shows reduction particle size to less than 300 nm, while XRD confirms that the resulting salt maintains the Kegging structure. The composite catalyst is prepared by mixing the POM salt with Pt/C by sonication. RRDE studies show better kinetics for ORR with low Pt loading at the electrode surface. A MEA is assembled by using a Pt/POM-based cathode, in order to assess performance in a working fuel cell. Current vs. potential curves reveals comparable or better performances at 100%, 62% and 17% relative humidity for the POM-modified MEA with respect to a commercial MEA with higher Pt loading at the cathode. Electrochemical impedance spectroscopy (EIS) confirms better kinetics at low relative humidity. Finally, an accelerated stress test (AST) with square wave (SW) between 0.4 V and 0.8 V is performed to evaluate MEA stability for at least 100 h and make predictions about lifetime, showing that after initial losses the catalytic system can retain stable performance and good morphological stability.

Electrifying model catalysts for understanding electrocatalytic reactions in liquid electrolytes.

PubMed

Faisal, Firas; Stumm, Corinna; Bertram, Manon; Waidhas, Fabian; Lykhach, Yaroslava; Cherevko, Serhiy; Xiang, Feifei; Ammon, Maximilian; Vorokhta, Mykhailo; Šmíd, Břetislav; Skála, Tomáš; Tsud, Nataliya; Neitzel, Armin; Beranová, Klára; Prince, Kevin C; Geiger, Simon; Kasian, Olga; Wähler, Tobias; Schuster, Ralf; Schneider, M Alexander; Matolín, Vladimír; Mayrhofer, Karl J J; Brummel, Olaf; Libuda, Jörg

2018-07-01

Electrocatalysis is at the heart of our future transition to a renewable energy system. Most energy storage and conversion technologies for renewables rely on electrocatalytic processes and, with increasing availability of cheap electrical energy from renewables, chemical production will witness electrification in the near future 1-3 . However, our fundamental understanding of electrocatalysis lags behind the field of classical heterogeneous catalysis that has been the dominating chemical technology for a long time. Here, we describe a new strategy to advance fundamental studies on electrocatalytic materials. We propose to 'electrify' complex oxide-based model catalysts made by surface science methods to explore electrocatalytic reactions in liquid electrolytes. We demonstrate the feasibility of this concept by transferring an atomically defined platinum/cobalt oxide model catalyst into the electrochemical environment while preserving its atomic surface structure. Using this approach, we explore particle size effects and identify hitherto unknown metal-support interactions that stabilize oxidized platinum at the nanoparticle interface. The metal-support interactions open a new synergistic reaction pathway that involves both metallic and oxidized platinum. Our results illustrate the potential of the concept, which makes available a systematic approach to build atomically defined model electrodes for fundamental electrocatalytic studies.

Silicon drift detectors as a tool for time-resolved fluorescence XAFS on low-concentrated samples in catalysis.

PubMed

Kappen, Peter; Tröger, Larc; Materlik, Gerhard; Reckleben, Christian; Hansen, Karsten; Grunwaldt, Jan-Dierk; Clausen, Bjerne S

2002-07-01

A silicon drift detector (SDD) was used for ex situ and time-resolved in situ fluorescence X-ray absorption fine structure (XAFS) on low-concentrated catalyst samples. For a single-element and a seven-element SDD the energy resolution and the peak-to-background ratio were verified at high count rates, sufficient for fluorescence XAFS. An experimental set-up including the seven-element SDD without any cooling and an in situ cell with gas supply and on-line gas analysis was developed. With this set-up the reduction and oxidation of a zeolite supported catalyst containing 0.3 wt% platinum was followed by fluorescence near-edge scans with a time resolution of 10 min each. From ex situ experiments on low-concentrated platinum- and gold-based catalysts fluorescence XAFS scans could be obtained with sufficient statistical quality for a quantitative analysis. Structural information on the gold and platinum particles could be extracted by both the Fourier transforms and the near-edge region of the XAFS spectra. Moreover, it was found that with the seven-element SDD concentrations of the element of interest as low as 100 ppm can be examined by fluorescence XAFS.

Design and fabrication of miniaturized PEM fuel cell combined microreactor with self-regulated hydrogen mechanism

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Synthesis and Characterization of CO- and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

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

Shamsuddin Ilias

2006-05-18

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we used four Pt-based electrocatalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) in MEAs and these were evaluated for CO-tolerance with 20 and 100 ppm CO concentration in H{sub 2}-fuel. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. From preliminary cost analysis it appears that could of the catalyst metal loading can reduced by 40% to 60% depending on the selection of metal combinations without compromising the fuel cell performance.« less

Electrochemical behavior of platinum nanoparticles on a carbon xerogel support modified with a [(trifluoromethyl)-benzenesulfonyl]imide electrolyte.

PubMed

Liu, Bing; Mei, Hua; DesMarteau, Darryl; Creager, Stephen E

2014-12-11

A monoprotic [(trifluoromethyl)benzenesulfonyl]imide (SI) superacid electrolyte was used to covalently modify a mesoporous carbon xerogel (CX) support via reaction of the corresponding trifluoromethyl aryl sulfonimide diazonium zwitterion with the carbon surface. Electrolyte attachment was demonstrated by elemental analysis, acid-base titration, and thermogravimetric analysis. The ion-exchange capacity of the fluoroalkyl-aryl-sulfonimide-grafted carbon xerogel (SI-CX) was ∼0.18 mequiv g(-1), as indicated by acid-base titration. Platinum nanoparticles were deposited onto the SI-grafted carbon xerogel samples by the impregnation and reduction method, and these materials were employed to fabricate polyelectrolyte membrane fuel-cell (PEMFC) electrodes by the decal transfer method. The SI-grafted carbon-xerogel-supported platinum (Pt/SI-CX) was characterized by X-ray diffraction and transmission electron microscopy to determine platinum nanoparticle size and distribution, and the findings are compared with CX-supported platinum catalyst without the grafted SI electrolyte (Pt/CX). Platinum nanoparticle sizes are consistently larger on Pt/SI-CX than on Pt/CX. The electrochemically active surface area (ESA) of platinum catalyst on the Pt/SI-CX and Pt/CX samples was measured with ex situ cyclic voltammetry (CV) using both hydrogen adsorption/desorption and carbon monoxide stripping methods and by in situ CV within membrane electrode assemblies (MEAs). The ESA values for Pt/SI-CX are consistently lower than those for Pt/CX. Some possible reasons for the behavior of samples with and without grafted SI layers and implications for the possible use of SI-grafted carbon layers in PEMFC devices are discussed.

An Exploration of Geometric and Electronic Effects in Metal Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Childers, David

The goal of this thesis is to investigate the influence geometric and electronic effects on metal nanoparticle catalysis. There are three main methods which alter a catalyst's properties: changing support material, changing nanoparticle size and alloying a second metal. This work will focus on the latter two methods using Pt-group metals and alloys. Platinum and palladium were chosen as the active metals due to a large amount of industry significance and prior literature to draw upon. Neopentane conversion and propane dehydrogenation were the two probe reactions used to evaluate these catalysts mainly due to their relative simplicity and ease of operation on a laboratory scale. The effect of particle size was studied with Pt and Pd monometallic catalysts using neopentane hydrogenolysis/isomerization as the probe reaction. Particle size studies have been done previously using this reaction so there is literature data to compare this study's results. This data will also be used as comparison for the bimetallic studies conducted later so that particle size effects can be accounted for when attempting to determine the effect of alloying a second metal. Bimetallic catalysts have several different possible structures depending on a number of factors from the identity of the two metals to the synthesis procedure. Homogeneous, core-shell and intermetallic alloys are the three structures evaluated in this work. Determining the surface composition of a homogeneous alloy can be difficult especially if both metals adsorb CO. PtPd homogeneous alloys were used to evaluate the ability of EXAFS to give information about surface composition using CO adsorption. These catalysts were also tested using neopentane conversion to evaluate changes in catalytic performance. Core-shell catalysts can also exhibit unique properties although it is not clear whether the identity of the core metal is relevant or if surface changes are most important to changing catalytic behavior. PdAu catalysts were synthesized with varying Pd loadings to determine if the Au-rich core would continue to influence neopentane conversion performance with increasing Pd layers on the surface of the nanoparticle. Finally, intermetallic alloys have produced some very interesting literature results and can drastically alter catalyst surface structure. PdZn showed the potential to improve neopentane isomerization selectivity past that of Pt based on calculated electronic properties. Two PdZn catalysts with different loadings were synthesized to evaluate the electronic and geometric effects using both neopentane conversion and propane dehydrogenation.

Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution

PubMed Central

Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.

2016-01-01

The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable. PMID:27767178

Carbon aerogel electrodes for direct energy conversion

DOEpatents

Mayer, S.T.; Kaschmitter, J.L.; Pekala, R.W.

1997-02-11

A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes is described, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome. 1 fig.

High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

PubMed

Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

2018-02-26

The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

Patched bimetallic surfaces are active catalysts for ammonia decomposition

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

Guo, Wei; Vlachos, Dionisios G.

In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

Patched bimetallic surfaces are active catalysts for ammonia decomposition

DOE PAGES

Guo, Wei; Vlachos, Dionisios G.

2015-10-07

In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

Growing Platinum-Ruthenium-Tin ternary alloy nanoparticles on reduced graphene oxide for strong ligand effect toward enhanced ethanol oxidation reaction.

PubMed

Xia, Qing Qing; Zhang, Lian Ying; Zhao, Zhi Liang; Li, Chang Ming

2017-11-15

Uniform Pt 1 Ru 0.5 Sn 0.5 ternary alloy nanoparticles are in situ deposited on reduced graphene oxide (Pt 1 Ru 0.5 Sn 0.5 -RGO) through its functional groups and defects as nucleation sites to greatly electrocatalyze ethanol oxidation reaction for much higher mass current densities, larger apparent specific current densities and better stability than commercial Pt-C catalyst (Pt-C(commer)). Mechanistic studies indicate that the excellent electrocatalytic activity and anti-poisoning are resulted from a strong ligand effect of the ternary alloy components, in which the charge transfer is boosted while decreasing the density of states close to the Fermi level of Pt to reduce bond energy between Pt and CO-like adsorbates for greatly improved anti-poisoning ability. This work holds a great promise to fabricate a high performance anode catalyst with a low Pt loading for direct ethanol fuel cells. Copyright © 2017. Published by Elsevier Inc.

Catalyst and electrode research for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Antoine, A. C.; King, R. B.

1987-01-01

An account is given of the development status of phosphoric acid fuel cells' high performance catalyst and electrode materials. Binary alloys have been identified which outperform the baseline platinum catalyst; it has also become apparent that pressurized operation is required to reach the desired efficiencies, calling in turn for the use of graphitized carbon blacks in the role of catalyst supports. Efforts to improve cell performance and reduce catalyst costs have led to the investigation of a class of organometallic cathode catalysts represented by the tetraazaannulenes, and a mixed catalyst which is a mixture of carbons catalyzed with an organometallic and a noble metal.

Controllable deposition of platinum nanoparticles on single-wall carbon nanohorns as catalyst for direct methanol fuel cells.

PubMed

Niu, Ben; Xu, Wei; Guo, Zhengduo; Zhou, Nengzhi; Liu, Yang; Shi, Zujin; Lian, Yongfu

2012-09-01

Uniform and well dispersed platinum nanoparticles were successfully deposited on single-walled carbon nanohorns with the assistance of 4,4-dipydine and ion liquids, respectively. In particular, the size of platinum nanoparticles could be controlled in a very narrow range (2.2 to 2.5 nm) when ion liquids were applied. The crystalline nature of these platinum nanoparticles was confirmed by high resolution transmission electron microscopy observation and X-ray power diffraction analysis, and two species of platinum Pt(0) and Pt(II) were detected by X-ray photoelectron spectroscopy. Electrochemical studies revealed that thus obtained nanocomposites had much better electrocatalytic activity for the methanol oxidation than those prepared with carbon nanotubes as supporter.

Hydrodeoxygenation of phenols as lignin models under acid-free conditions with carbon-supported platinum catalysts.

PubMed

Ohta, Hidetoshi; Kobayashi, Hirokazu; Hara, Kenji; Fukuoka, Atsushi

2011-11-28

Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols.

Oxygen reduction reaction: A framework for success

DOE PAGES

Allendorf, Mark D.

2016-05-06

Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

PubMed Central

Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

2014-01-01

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

Raney Ni-Sn catalyst for H2 production from biomass-derived hydrocarbons.

PubMed

Huber, G W; Shabaker, J W; Dumesic, J A

2003-06-27

Hydrogen (H2) was produced by aqueous-phase reforming of biomass-derived oxygenated hydrocarbons at temperatures near 500 kelvin over a tin-promoted Raney-nickel catalyst. The performance of this non-precious metal catalyst compares favorably with that of platinum-based catalysts for production of hydrogen from ethylene glycol, glycerol, and sorbitol. The addition of tin to nickel decreases the rate of methane formation from C-O bond cleavage while maintaining the high rates of C-C bond cleavage required for hydrogen formation.

Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Su, Jianwei; Yang, Yang; Xia, Guoliang; Chen, Jitang; Jiang, Peng; Chen, Qianwang

2017-04-01

The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm-2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon-hydrogen bond, thereby lowing ΔGH* of HER.

Platinum Nickel Nanowires as Methanol Oxidation Electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Neyerlin, Kenneth C.; ...

2015-08-27

We investigated platinum(Pt) nickel (Ni) nanowires (PtNiNWs) as methanol oxidation reaction (MOR) catalysts in rotating disk electrode (RDE) half-cells under acidic conditions. Pt-ruthenium (Ru) nanoparticles have long been the state of the art MOR catalyst for direct methanol fuel cells (DMFCs) where Ru provides oxophilic sites, lowering the potential for carbon monoxide oxidation and the MOR onset. Ru, however, is a precious metal that has long term durability concerns. Ni/Ni oxide species offer a potential to replace Ru in MOR electrocatalysis. PtNiNWs were investigated for MOR and oxygen annealing was investigated as a route to improve catalyst performance (mass activitymore » 65% greater) and stability to potential cycling. Our results presented show that PtNiNWs offer significant promise in the area, but also result in Ni ion leaching that is a concern requiring further evaluation in fuel cells.« less

Fuel cell electric power production

DOEpatents

Hwang, Herng-Shinn; Heck, Ronald M.; Yarrington, Robert M.

1985-01-01

A process for generating electricity from a fuel cell includes generating a hydrogen-rich gas as the fuel for the fuel cell by treating a hydrocarbon feed, which may be a normally liquid feed, in an autothermal reformer utilizing a first monolithic catalyst zone having palladium and platinum catalytic components therein and a second, platinum group metal steam reforming catalyst. Air is used as the oxidant in the hydrocarbon reforming zone and a low oxygen to carbon ratio is maintained to control the amount of dilution of the hydrogen-rich gas with nitrogen of the air without sustaining an insupportable amount of carbon deposition on the catalyst. Anode vent gas may be utilized as the fuel to preheat the inlet stream to the reformer. The fuel cell and the reformer are preferably operated at elevated pressures, up to about a pressure of 150 psia for the fuel cell.

Synthesis and properties of a novel catalyst for the combustion of methane. Final report, January 1986-December 1989

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

Hicks, R.F.

1990-10-17

The objective of the research, which was funded by the Physical Sciences Department of the Gas Research Institute, was to understand how to design precious metal catalysts for methane combustion. These catalyst must be stable in the combustion environment and exhibit high rates of oxidation. The authors have found that palladium on alumina does not lose active surface area in air below 900C. Whereas, platinum vaporizes above 600C. The rate of methane oxidation per exposed metal atom depends on the metal used, platinum or palladium, and whether the metal is completely oxidized or covered with adsorbed oxygen during reaction. Themore » percentage of metal oxidized depends on the size, morphology and crystallinity of the metal particles. The relative rates of methane oxidation are: dispersed PtO2: dispersed PdO: crystalline Pt: crystalline Pd = 1:6:16:100.« less

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

Gunnarsson, Fredrik; Pihl, Josh A.; Toops, Todd J.

This paper focuses on the activity for lean NO x reduction over sol-gel synthesized silver alumina (Ag/Al 2O 3) catalysts, with and without platinum doping, using ethanol (EtOH), EtOH/C 3H 6 and EtOH/gasoline blends as reducing agents. The effect of ethanol concentration, both by varying the hydrocarbon-to-NO x ratio and by alternating the gasoline concentration in the EtOH/gasoline mixture, is investigated. High activity for NO x reduction is demonstrated for powder catalysts for EtOH and EtOH/C 3H 6 as well as for monolith coated catalysts (EtOH and EtOH/gasoline). The results show that pure Ag/Al 2O 3 catalysts display higher NOmore » x reduction and lower light-off temperature as compared to the platinum doped samples. The 4 wt.% Ag/Al 2O 3 catalyst displays 100% reduction in the range 340–425 °C, with up to 37% selectivity towards NH 3. These results are also supported by DRIFTS (Diffuse reflection infrared Fourier transform spectroscopy) experiments. Finally, the high ammonia formation could, in combination with an NH 3-SCR catalyst, be utilized to construct a NO x reduction system with lower fuel penalty cf. stand alone HC-SCR. In addition, it would result in an overall decrease in CO 2 emissions.« less

Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

NASA Astrophysics Data System (ADS)

Taninouchi, Yu-ki; Okabe, Toru H.

2018-05-01

The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

Pyrometallurgical Recovery of Platinum Group Metals from Spent Catalysts

NASA Astrophysics Data System (ADS)

Peng, Zhiwei; Li, Zhizhong; Lin, Xiaolong; Tang, Huimin; Ye, Lei; Ma, Yutian; Rao, Mingjun; Zhang, Yuanbo; Li, Guanghui; Jiang, Tao

2017-09-01

As an important secondary resource with abundant platinum group metals (PGMs), spent catalysts demand recycling for both economic and environmental benefits. This article reviews the main pyrometallurgical processes for PGM recovery from spent catalysts. Existing processes, including smelting, vaporization, and sintering processes, are discussed based in part on a review of the physiochemical characteristics of PGMs in spent catalysts. The smelting technology, which produces a PGM-containing alloy, is significantly influenced by the addition of various collectors, such as lead, copper, iron, matte, or printed circuit board (PCB), considering their chemical affinities for PGMs. The vaporization process can recover PGMs in vapor form at low temperatures (250-700°C), but it suffers high corrosion and potential environmental and health risks as a result of involvement of the hazardous gases, mainly Cl2 and CO. The sintering process serves as a reforming means for recycling of the spent catalysts by in situ reduction of their oxidized PGMs components. Among these processes, the smelting process seems more promising although its overall performance can be further improved by seeking a suitable target-oriented collector and flux, together with proper pretreatment and process intensification using an external field.

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction

NASA Astrophysics Data System (ADS)

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, Jiexu

2017-03-01

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg-1Pt. This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys.

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction.

PubMed

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, JieXu

2017-03-30

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg -1 Pt . This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys.

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

NASA Astrophysics Data System (ADS)

Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

2015-10-01

We propose a new strategy for alleviating the reverse current phenomenon using a unique ;atmospheric resistive switching mechanism; (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

Lean NO x reduction over Ag/alumina catalysts via ethanol-SCR using ethanol/gasoline blends

DOE PAGES

Gunnarsson, Fredrik; Pihl, Josh A.; Toops, Todd J.; ...

2016-09-04

This paper focuses on the activity for lean NO x reduction over sol-gel synthesized silver alumina (Ag/Al 2O 3) catalysts, with and without platinum doping, using ethanol (EtOH), EtOH/C 3H 6 and EtOH/gasoline blends as reducing agents. The effect of ethanol concentration, both by varying the hydrocarbon-to-NO x ratio and by alternating the gasoline concentration in the EtOH/gasoline mixture, is investigated. High activity for NO x reduction is demonstrated for powder catalysts for EtOH and EtOH/C 3H 6 as well as for monolith coated catalysts (EtOH and EtOH/gasoline). The results show that pure Ag/Al 2O 3 catalysts display higher NOmore » x reduction and lower light-off temperature as compared to the platinum doped samples. The 4 wt.% Ag/Al 2O 3 catalyst displays 100% reduction in the range 340–425 °C, with up to 37% selectivity towards NH 3. These results are also supported by DRIFTS (Diffuse reflection infrared Fourier transform spectroscopy) experiments. Finally, the high ammonia formation could, in combination with an NH 3-SCR catalyst, be utilized to construct a NO x reduction system with lower fuel penalty cf. stand alone HC-SCR. In addition, it would result in an overall decrease in CO 2 emissions.« less

Near-ambient solid polymer fuel cell

NASA Technical Reports Server (NTRS)

Holleck, G. L.

1993-01-01

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Domestic Production Issues in Chromium and Platinum-Group Metals

DTIC Science & Technology

1988-09-01

iridium, and minor amounts of osmium. 12 Uses. Platinum-group metals (PGM) are critical as catalysts in fossil fuel processing and electronic...metals (PGM) were then described as critical in fossil fuel production, and in electronic and electrical components. The international market is...this research process . ii Table of Contents Page Preface.. .............. ii List of Figures ................ vi List of Tables ................ vi

Features of the hydrosilylation of polyfunctional methylvinyl- and methylhydrosiloxanes

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

Kopylov, V.M.; Kovyazine, T.G.; Buslaeva, T.M.

1987-11-10

A study of the reactivity of polyfunctional methylvinyl- and methylhydrosiloxanes in the presence of platinum catalysts has shown that the reactivity of the Si-CH=CH/sub 2/ groups is unchanged, but that of the Si-H groups decreases as the extent of reaction of the functional groups increases. Examination of the influence of the type of catalysts, comprising H/sub 2/PtCl/sub 6/ x 6H/sub 2/O and tetraorganoammonium platinum salts, on the reactions of polyfunctional methylvinyl- and methylhydrosiloxanes has shown that the catalytic activity of the salts is lower than that of H/sub 2/PtCl/sub 6/ x 6H/sub 2/O, and varies over a wide range withmore » changes in the organic radical in the tetraorganoammonium cation, the oxidation state of the platinum, and the nature of the acido ligand. In the presence of these tetraorganoammonium platinum salts, addition of silicon hydrides to methylvinylcycloxiloxanes takes place predominantly in the ..beta..-position. The PMR spectra of the addition products were obtained on Bruker WM-90 and WM-250 instruments, operating frequencies 90 and 250 MHz, in CCl/sub 4/ and CDCl/sub 3/, cyclohexane being used as internal standard.« less

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Improved Anode for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Process for Making a Noble Metal on Tin Oxide Catalyst

NASA Technical Reports Server (NTRS)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir Branko

2010-04-06

The present invention relates to particle and nanoparticle composites useful as oxygen-reduction electrocatalysts. The particle composites are composed of a palladium or palladium-alloy particle or nanoparticle substrate coated with an atomic submonolayer, monolayer, bilayer, or trilayer of zerovalent platinum atoms. The invention also relates to a catalyst and a fuel cell containing the particle or nanoparticle composites of the invention. The invention additionally includes methods for oxygen reduction and production of electrical energy by using the particle and nanoparticle composites of the invention.

Enhanced photo-degradation of paracetamol on n-platinum-loaded TiO2: The effect of ultrasound and OH/hole scavengers.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2016-11-01

Elimination/mineralization of paracetamol (PCT) was investigated by catalytic oxidation under ultrasound, UV and both. The catalyst was synthesized by immobilization of nPt on TiO2 to benefit from the ability of Pt to facilitate charge transfer processes and to separate e(-)/h(+) pairs. It was found that increasing the Pt-loading enhanced the rate of sonochemical reactions, but retarded that of photolytic reactions, due to reduced UV absorption on the surface. Simultaneous application of sonolysis and photolysis was synergistic due to disaggregation of the particles and homogenization of the active species over the catalyst surface. The decay of PCT was highly dependent on the availability of OH, as the reactions were nearly terminated in the presence of a strong OH scavenger-2-propanol. However, a remarkable rate enhancement was observed in the presence of a suitable dose of I(-), which scavenges both OH and hvb(+). The result was explained by the production of excess radicals upon sonolysis of iodide solutions, and the reactivity of PCT with them. Finally, carbon mineralization was significantly hindered in the presence of both scavengers due to increased competition for OH and inefficient formation of hydroquinone arising from reduced availability of hvb(+). Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrocatalytic properties of graphite nanofibers-supported platinum catalysts for direct methanol fuel cells.

PubMed

Park, Soo-Jin; Park, Jeong-Min; Seo, Min-Kang

2009-09-01

Graphite nanofibers (GNFs) treated at various temperatures were used as carbon supports to improve the efficiency of PtRu catalysts. The electrochemical properties of the PtRu/GNFs catalysts were then investigated to evaluate their potential for application in DMFCs. The results indicated that the particle size and dispersibility of PtRu in the catalysts were changed by heat treatment, and the electrochemical activity of the catalysts was improved. Consequently, it was found that heat treatments could have an influence on the surface and structural properties of GNFs, resulting in enhancing an electrocatalytic activity of the catalysts for DMFCs.

Compression Ratio and Catalyst Aging Effects on Aqueous Ethanol Ignition (Year 2) : Part 2 Catalyst Aging and Effects of Water on Ignition

DOT National Transportation Integrated Search

2009-09-01

A tubular plug-flow reactor under low Reynolds Numbers Re flow regimes, along with a 127 um diameter coiled platinum (Pt) wire, were used to study catalytic surface reactions of nonflammable, fuel-lean mixtures of propane, oxygen, and water vapor dil...

High-temperature catalytically assisted combustion. Final report, 1 August 1981-31 July 1983

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

Bracco, F.V.; Royce, B.S.H.; Santavicca, D.A.

1983-07-31

Results of research on a two-dimensional, transient catalytic combustion model and on a high temperature perovskite catalyst are presented. A recently developed two-dimensional, transient model was used to study the ignition of carbon monoxide/air mixtures in a platinum-coated catalytic honeycomb. Comparisons between calculated and measured steady-state substrate temperature profiles and exhaust-gas compositions show good agreement. A platinum-doped perovskite catalyst proposed will exhibit low-temperature light off and high-temperature stability. Preliminary tests using a perovskite powder with 1 wt.% platinium are encouraging, showing very little change in surface activity when used with propane fuel. Variations in catalytic activity from sample to samplemore » were also found, and after extensive testing the cause of these variations could not be identified. However, preliminary tests using Fourier-transform infrared photoacoustic spectroscopy do indicate differences in the various catalyst samples that may be related to the difference in catalytic activity. The use of bench-top-oven and differential-scanning-calorimetry techniques for screening catalysts in terms of relative activity and aging characteristics were also demonstrated.« less

Atomic layer deposited highly dispersed platinum nanoparticles supported on non-functionalized multiwalled carbon nanotubes for the hydrogenation of xylose to xylitol

NASA Astrophysics Data System (ADS)

Liang, Xinhua; Jiang, Chengjun

2013-09-01

Highly dispersed platinum nanoparticles were deposited on gram quantities of non-functionalized multiwalled carbon nanotubes (MWCNTs) by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. (Methylcyclopentadienyl) trimethylplatinum and oxygen were used as precursors. The results of TEM analysis showed that 1.3 nm Pt nanoparticles were highly dispersed on non-functionalized MWCNTs. The porous structures of MWCNTs did not change with the deposition of Pt nanoparticles. For comparison, the commercial 3 wt% Pt/C catalyst was also characterized. The ALD-prepared Pt/MWCNT was used for the hydrogenation of xylose to xylitol. The ALD-prepared Pt/MWCNT showed the best catalytic performance with 100 % conversion of xylose and 99.3 % selectivity to xylitol, compared to commercially available Pt/C, Ru/C, and Raney Ni catalysts. The stability of ALD produced Pt/MWCNT catalyst was higher than that of the commercial Pt/C, due to the presence of surface defects on the MWCNTs and the strong metal-support interaction for the ALD-prepared Pt/MWCNT catalyst.

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

NASA Astrophysics Data System (ADS)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

pH-dependent release of trace elements including platinum group elements (PGEs) from gasoline and diesel catalysts

NASA Astrophysics Data System (ADS)

Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav

2014-05-01

The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (< 0.5 mg.kg-1, < 0.1 mg.kg-1, respectively). To evaluate leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

PubMed Central

Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

2013-01-01

Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Comparative study of different carbon-supported Fe2O3-Pt catalysts for oxygen reduction reaction.

PubMed

Tellez-Cruz, M M; Padilla-Islas, M A; Pérez-González, M; Solorza-Feria, O

2017-11-01

One of the challenges in electrocatalysis is the adequate dispersion of the catalyst on an appropriate porous support matrix, being up to now the most commonly used the carbon-based supports. To overcome this challenge, carbon supports must first be functionalized to guide the catalyst's nucleation, thereby, improving the dispersion and allowing the use of smaller amount of the catalyst material to achieve a higher electrochemically active surface area. This study present the effect of functionalized Vulcan carbon XC72 (FVC) and functionalized Black Pearl carbon (FBPC) as supports on the catalytic activity of decorated Fe 2 O 3 with Pt. Both carbons were functionalized with HNO 3 and subsequently treated with ethanolamine. Fe 2 O 3 nanoparticles were synthesized by chemical reduction and decorated with platinum by epitaxial growth. Pt and Fe 2 O 3 structural phases were identified by XRD and XPS; the Pt content was measured by XPS, and results showed to a high Pt content in Fe 2 O 3 -Pt/FBPC. TEM micrographs reveal nanoparticles with an average size of 2 nm in both supported catalysts. The Fe 2 O 3 -Pt/FVC catalyst presents the highest specific activity and mass activity, 0.21 mA cm -2 Pt and 140 mA mg Pt -1 , respectively, associated to the appropriate distribution of platinum on the Fe 2 O 3 nanoparticles.

General and selective C-3 alkylation of indoles with primary alcohols by a reusable Pt nanocluster catalyst.

PubMed

Siddiki, S M A Hakim; Kon, Kenichi; Shimizu, Ken-Ichi

2013-10-18

The platinum rule: Heterogeneous, additive-free C-3 selective alkylation of indoles by aliphatic and aromatic alcohols proceeded under transfer hydrogenation conditions with the reusable Pt/θ-Al2 O3 catalyst (see scheme; TON=turnover number). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

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

Holby, Edward F.; Zelenay, Piotr

Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

DOE PAGES

Holby, Edward F.; Zelenay, Piotr

2016-05-17

Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by thesemore » materials.« less

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction

PubMed Central

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, JieXu

2017-01-01

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg−1Pt. This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys. PMID:28358143

The pH-dependent release of platinum group elements (PGEs) from gasoline and diesel fuel catalysts: Implication for weathering in soils.

PubMed

Suchá, Veronika; Mihaljevič, Martin; Ettler, Vojtěch; Strnad, Ladislav

2016-04-15

Powdered samples of new and old gasoline catalysts (Pt, Pd, Rh) and new and old diesel (Pt) catalysts were subjected to a pH-static leaching procedure (pH 2-9) coupled with thermodynamic modeling using PHREEQC-3 to verify the release and mobility of PGEs (platinum group elements). PGEs were released under acidic conditions, mostly exhibiting L-shaped leaching patterns: diesel old: 5.47, 0.005, 0.02; diesel new: 68.5, 0.23, 0.11; gasoline old: 0.1, 11.8, 4.79; gasoline new 2.6, 25.2, 35.9 in mg kg(-1) for Pt, Pd and Rh, respectively. Only the new diesel catalyst had a strikingly different leaching pattern with elevated concentrations at pH 4, probably influenced by the dissolution of the catalyst carrier and washcoat. The pH-static experiment coupled with thermodynamic modeling was found to be an effective instrument for understanding the leaching behavior of PGEs under various environmental conditions, and indicated that charged Pt and Rh species may be adsorbed on the negatively charged surface of kaolinite or Mn oxides in the soil system, whereas uncharged Pd and Rh species may remain mobile in soil solutions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

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

Jiang, Liming; Fu, Honggang, E-mail: fuhg@vip.sina.com; Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superiormore » to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.« less

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Cathode catalyst for primary phosphoric fuel cells

NASA Technical Reports Server (NTRS)

Walsh, F.

1980-01-01

Alkylation of Vulcan XC-72 provided the most stable bond type for linking CoTAA to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA has catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available PTFE was shown to be stable for four months in 200 C 85% phosphoric acid based on lack of change in surface wetting properties, IR and physical characteristics. When stressed electrochemically in 150 C 85% phosphoric acid, PTFE also showed no changes after one month.

Insights into PEMFC Performance Degradation from HCl in Air

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

O Baturina; A Epshteyn; P Northrup

2011-12-31

The performance degradation of a proton exchange membrane fuel cell (PEMFC) is studied in the presence of HCl in the air stream. The cathode employing carbon-supported platinum nanoparticles (Pt/C) was exposed to 4 ppm HCl in air while the cell voltage was held at 0.6 V. The HCl poisoning results in generation of chloride and chloroplatinate ions on the surface of Pt/C catalyst as determined by a combination of electrochemical tests and ex-situ chlorine K-edge X-Ray absorption near-edge structure (XANES) spectroscopy. The chloride ions inhibit the oxygen reduction reaction (ORR) and likely affect the wetting properties of diffusion media/catalyst layer,more » while the chloroplatinate ions are responsible for enhanced platinum particle growth most likely due to platinum dissolution-redeposition. The chloride ions can cause corrosion of the Pt nanoparticles in the presence of aqueous HCl in air even if no potential is applied. Although the majority of chloride ions are desorbed from the Pt surface by hydrogen treatment of the cathode, they partially remain in the system and re-adsorb on platinum at cell voltages of 0.5-0.9 V. Chloride ions are removed from the system and fuel cell performance at 0.5-0.7 V is restored by multiple exposures to low potentials.« less

TePtFe Nanotubes as High-Performing Bifunctional Electrocatalysts for the Oxygen Reduction Reaction and Hydrogen Evolution Reaction.

PubMed

Li, Wenqiang; Amiinu, Ibrahim Saana; Ye, Bei; Wang, Zhe; Zhu, Jiawei; Kou, Zongkui; Mu, Shichun

2018-04-25

Currently, a multicomponent platinum-based alloy has been applied as a promising electrocatalyst to improve catalysis and lower the usage of the noble metal platinum. Herein, a tellurium nanowire (NW)-derived ternary TePtFe nanotube (NT) electrocatalyst has been prepared by the Kirkendall effect. The TePtFe NT formed consists of small single-crystal nanoparticles and voids with an open-end and hollow structure. The TePtFe NT electrocatalyst presents an impressive catalytic activity and stability for both the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Its ORR specific activity and mass activity are 8.5 and 2.4 times, respectively, improved relative to those of commercial platinum catalysts. It is also impressive that, for the HER, a very low overpotential of 28.1 mV at 10 mA cm -2 can be achieved; this is lower than that of platinum (51.8 mV) catalysts in 0.1 m HClO 4 , and the activity is improved, even after 5000 cycles. This work reveals that TePtFe NTs can be employed as nanocatalysts with an impressive catalytic activity and stability for application in fuel cells and hydrogen production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of Carbon-Platinum Interdigitated Array Electrodes and Their Application for Investigating Homogeneous Hydrogen Evolution Catalysis

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

Liu, F.; Divan, R.; Parkinson, B. A.

2015-01-01

Interdigitated array electrodes (IDAEs) with one carbon electrode and the other platinum electrode were constructed by electrodepositing platinum on one set of the carbon electrodes. Platinum deposition was confirmed by scanning electron microscope (SEM) and cyclic voltammetry. The width of the carbon and platinum digits is less than 2 μm and the gap between two adjacent digits is around 3 μm. The carbon-platinum IDAEs benefit from the characteristics of both carbon and platinum in that carbon can provide a wide nonreactive potential window while platinum is a good catalyst for hydrogen reactions making it useful to characterize the catalytic hydrogenmore » production cycle of the molecular electrocatalyst [Ni(PPh2NPh2)2(CH3CN)](BF4)2 (where PPh2NPh2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane). With properly set potentials, the molecular electrocatalyst was reduced at the carbon digits to initiate a homogeneous H2 production reaction while the platinum digits detect the H2 by oxidation, providing direct evidence of its production rate from the catalytic cycles.« less

The Role of Non-Conventional Supports for Single-Atom Platinum-Based Catalysts in Fuel-Cell Technology: A Theoretical Surface Science Approach

DTIC Science & Technology

2013-02-05

could be a promising catalyst for PEM fuel cells. Introduction: Proton exchange membrane fuel cells ( PEMFCs ) have found wide potential...Unfortunately, due to their high cost and low lifespan, wide-scale commercialization of PEMFCs has been greatly impeded and much effort has been made to...lower its cost as well as to improve its durability over time. In an attempt to alleviate the high-cost associated with conventional PEMFC catalysts

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Template Effect and Ligand Substitution Methods for the Synthesis of Iron Catalysts: A Two-Part Experiment for Inorganic Chemistry

ERIC Educational Resources Information Center

Sues, Peter E.; Cai, Kuihua; McIntosh, Douglas F.; Morris, Robert H.

2015-01-01

Asymmetric transfer hydrogenation is an important transformation for the production of fine chemicals. Traditionally, platinum group metals are used to catalyze this reaction, but recent pressure for greener practices has driven the development of base-metal catalysts. Due to the growing interest in this area of research, the underlying concepts…

In situ fabricated platinum—poly(vinyl alcohol) nanocomposite thin film: a highly reusable ‘dip catalyst’ for hydrogenation

NASA Astrophysics Data System (ADS)

Divya Madhuri, U.; Kesava Rao, V.; Hariprasad, E.; Radhakrishnan, T. P.

2016-04-01

A simple protocol for the in situ generation of platinum nanoparticles in a poly(vinyl alcohol) (PVA) thin film is developed. Chloroplatinic acid as well as potassium platinum(II) chloride are used as precursors and the film is fabricated by spin coating followed by mild thermal annealing. The chemical process occurring inside the film, wherein the polymer itself acts as the reducing agent, is explored through different spectroscopy and microscopy techniques. The Pt-PVA film, <100 nm thick and containing ˜1 nm size Pt nanoparticles, is shown to be a highly efficient catalyst for the reduction of methylene blue using sodium borohydride. The ease of retrieval and reuse of the thin film is highlighted by the term ‘dip catalyst’. The reaction yield, kinetics and rate are reproducible through several reuses of the same catalyst film. Turnover number (TON = number of mols of product/number of mols of catalyst) and turnover frequency (TOF = TON/reaction time) are significantly higher than those reported earlier for this reaction using metal nanocatalysts. Utility of Pt-PVA film as an efficient catalyst for other hydrogenation reactions is demonstrated.

Enhanced performance of polybenzimidazole-based high temperature proton exchange membrane fuel cell with gas diffusion electrodes prepared by automatic catalyst spraying under irradiation technique

NASA Astrophysics Data System (ADS)

Su, Huaneng; Pasupathi, Sivakumar; Bladergroen, Bernard Jan; Linkov, Vladimir; Pollet, Bruno G.

2013-11-01

Gas diffusion electrodes (GDEs) prepared by a novel automatic catalyst spraying under irradiation (ACSUI) technique are investigated for improving the performance of phosphoric acid (PA)-doped polybenzimidazole (PBI) high temperature proton exchange membrane fuel cell (PEMFC). The physical properties of the GDEs are characterized by pore size distribution and scanning electron microscopy (SEM). The electrochemical properties of the membrane electrode assembly (MEA) with the GDEs are evaluated and analyzed by polarization curve, cyclic voltammetry (CV) and electrochemistry impedance spectroscopy (EIS). Effects of PTFE binder content, PA impregnation and heat treatment on the GDEs are investigated to determine the optimum performance of the single cell. At ambient pressure and 160 °C, the maximum power density can reach 0.61 W cm-2, and the current density at 0.6 V is up to 0.38 A cm-2, with H2/air and a platinum loading of 0.5 mg cm-2 on both electrodes. The MEA with the GDEs shows good stability for fuel cell operating in a short term durability test.

Irradiation of DNA loaded with platinum containing molecules by fast atomic ions C(6+) and Fe(26+).

PubMed

Usami, N; Kobayashi, K; Furusawa, Y; Frohlich, H; Lacombe, S; Sech, C Le

2007-09-01

In order to study the role of the Linear Energy Transfer (LET) of fast atomic ions in platinum-DNA complexes inducing breaks, DNA Plasmids were irradiated by C(6+) and Fe(26+) ions. DNA Plasmids (pBR322) loaded with different amounts of platinum contained in a terpyridine-platinum molecule (PtTC) were irradiated by C(6+) ions and Fe(26+) ions. The LET values ranged between 13.4 keV/microm and 550 keV/microm. In some experiments, dimethyl sulfoxide (DMSO) was added. In all experiments, a significant increase in DNA strand breaks was observed when platinum was present. The yield of breaks induced per Gray decreased when the LET increased. The yield of single and double strand breaks per plasmid per track increased with the LET, indicating that the number of DNA breaks per Gray was related to the number of tracks through the medium. These findings show that more DNA breaks are induced by atomic ions when platinum is present. This effect increases for low LET heavy atoms. As DSB induction may induce cell death, these results could open new perspectives with the association of hadrontherapy and chemotherapy. Thus the therapeutic index might be improved by loading the tumour with platinum salts.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Green Synthesis, Characterization and Uses of Palladium/Platinum Nanoparticles

NASA Astrophysics Data System (ADS)

Siddiqi, Khwaja Salahuddin; Husen, Azamal

2016-11-01

Biogenic synthesis of palladium (Pd) and platinum (Pt) nanoparticles from plants and microbes has captured the attention of many researchers because it is economical, sustainable and eco-friendly. Plant and their parts are known to have various kinds of primary and secondary metabolites which reduce the metal salts to metal nanoparticles. Shape, size and stability of Pd and Pt nanoparticles are influenced by pH, temperature, incubation time and concentrations of plant extract and that of the metal salt. Pd and Pt nanoparticles are broadly used as catalyst, as drug, drug carrier and in cancer treatment. They have shown size- and shape-dependent specific and selective therapeutic properties. In this review, we have discussed the biogenic fabrication of Pd/Pt nanoparticles, their potential application as catalyst, medicine, biosensor, medical diagnostic and pharmaceuticals.

Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

PubMed

Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

2011-10-01

Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hong; King, Glen C.; Watt, Gerald D.

2007-01-01

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Electrochemical Interfaces and Electrode Processes: Electrochemical Oxidation of Small Organisms

DTIC Science & Technology

1994-09-01

temperatures up to I 50°C. The electrode kinetics have been compared with methane and other small hydrocarbons in acid media. The formation of strongly...methanol, ethanol ). Bridge bonded CO(ads) is also observed in some instances with FTIR. The adsorbed CO is very strongly adsorbed on the platinum...research has demonstrated, however, that this problem is substantially lessened at higher temperatures (>I 50’C). The use of platinum alloy catalysts

On-line ion-exchange preconcentration and determination of traces of platinum by electrothermal atomic absorption spectrometry.

PubMed

González García, M M; Sánchez Rojas, F; Bosch Ojeda, C; García de Torres, A; Cano Pavón, J M

2003-04-01

A method to determine trace amounts of platinum in different samples based on electrothermal atomic absorption spectrometry is described. The preconcentration step is performed on a chelating resin microcolumn [1,5-bis(2-pyridyl)-3-sulfophenyl methylene thiocarbonohydrazide (PSTH) immobilized on an anion-exchange resin (Dowex 1x8-200)] placed in the autosampler arm. The combination of a peristaltic pump for sample loading and the atomic absorption spectrometer pumps for elution through a selection valve simplifies the hardware. The peristaltic pump and the selection valve are easily controlled electronically with two switches placed in the autosampler, which are activated when the autosampler arm is down. Thus, the process is fully automated without any modification of the software of the atomic absorption spectrometer. Under the optimum conditions with a 60-s preconcentration time, a sample flow rate of 2.4 mL min(-1), and an injection volume of eluent of 40 microL, a linear calibration graph was obtained in the range 0-100 ng mL(-1). The enrichment factor was 14. The detection limit under these conditions is 1 ng mL(-1), and the relative standard deviation (RSD) is 1.6% for 10 ng mL(-1) of Pt. The method has been applied to the determination of platinum in catalyst, vegetation, soil, and natural water samples. The results showed good agreement with the certified value and the recoveries of Pt added to samples were 98-105%.

Platinum Nanoparticle Decorated SiO2 Microfibers as Catalysts for Micro Unmanned Underwater Vehicle Propulsion.

PubMed

Chen, Bolin; Garland, Nathaniel T; Geder, Jason; Pruessner, Marius; Mootz, Eric; Cargill, Allison; Leners, Anne; Vokshi, Granit; Davis, Jacob; Burns, Wyatt; Daniele, Michael A; Kogot, Josh; Medintz, Igor L; Claussen, Jonathan C

2016-11-16

Micro unmanned underwater vehicles (UUVs) need to house propulsion mechanisms that are small in size but sufficiently powerful to deliver on-demand acceleration for tight radius turns, burst-driven docking maneuvers, and low-speed course corrections. Recently, small-scale hydrogen peroxide (H 2 O 2 ) propulsion mechanisms have shown great promise in delivering pulsatile thrust for such acceleration needs. However, the need for robust, high surface area nanocatalysts that can be manufactured on a large scale for integration into micro UUV reaction chambers is still needed. In this report, a thermal/electrical insulator, silicon oxide (SiO 2 ) microfibers, is used as a support for platinum nanoparticle (PtNP) catalysts. The mercapto-silanization of the SiO 2 microfibers enables strong covalent attachment with PtNPs, and the resultant PtNP-SiO 2 fibers act as a robust, high surface area catalyst for H 2 O 2 decomposition. The PtNP-SiO 2 catalysts are fitted inside a micro UUV reaction chamber for vehicular propulsion; the catalysts can propel a micro UUV for 5.9 m at a velocity of 1.18 m/s with 50 mL of 50% (w/w) H 2 O 2 . The concomitance of facile fabrication, economic and scalable processing, and high performance-including a reduction in H 2 O 2 decomposition activation energy of 40-50% over conventional material catalysts-paves the way for using these nanostructured microfibers in modern, small-scale underwater vehicle propulsion systems.

Autothermal reforming catalyst having perovskite structure

DOEpatents

Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

2009-03-24

The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

DOE PAGES

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih; ...

2017-05-18

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less

Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability

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

Goodman, Emmett D.; Dai, Sheng; Yang, An-Chih

Bimetallic catalytic materials are in widespread use for numerous reactions, as the properties of a monometallic catalyst are often improved upon addition of a second metal. In studies with bimetallic catalysts, it remains challenging to establish clear structure–property relationships using traditional impregnation techniques, due to the presence of multiple coexisting active phases of different sizes, shapes, and compositions. Here, a convenient approach to prepare small and uniform Pt/Pd bimetallic nanocrystals with tailorable composition is demonstrated, despite the metals being immiscible in the bulk. By depositing this set of controlled nanocrystals onto a high-surface-area alumina support, we systematically investigate the effectmore » of adding platinum to palladium catalysts for methane combustion. At low temperatures and in the absence of steam, all bimetallic catalysts show activity nearly identical with that of Pt/Al 2O 3, with much lower rates in comparison to that of the Pd/Al 2O 3 sample. BUt, unlike Pd/Al 2O 3, which experiences severe low-temperature steam poisoning, all Pt/Pd bimetallic catalysts maintain combustion activity on exposure to excess steam. These features are due to the influence of Pt on the Pd oxidation state, which prevents the formation of a bulk-type PdO phase. Despite lower initial combustion rates, hydrothermal aging of the Pd-rich bimetallic catalyst induces segregation of a PdO phase in close contact to a Pd/Pt alloy phase, forming more active and highly stable sites for methane combustion. Altogether, this work unambiguously clarifies the activity and stability attributes of Pt/Pd phases which often coexist in traditionally synthesized bimetallic catalysts and demonstrates how well-controlled bimetallic catalysts elucidate structure–property relationships.« less

Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Ticianelli, E. A.; Derouin, C. R.; Redondo, A.

1987-01-01

The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

DOEpatents

Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

2010-04-27

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

Catalysts for oxidation of mercury in flue gas

DOEpatents

Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

2010-08-17

Two new classes of catalysts for the removal of heavy metal contaminants, especially mercury (Hg) from effluent gases. Both of these classes of catalysts are excellent absorbers of HCl and Cl.sub.2 present in effluent gases. This adsorption of oxidizing agents aids in the oxidation of heavy metal contaminants. The catalysts remove mercury by oxidizing the Hg into mercury (II) moieties. For one class of catalysts, the active component is selected from the group consisting of iridium (Ir) and iridum-platinum (Ir/Pt) alloys. The Ir and Ir/Pt alloy catalysts are especially corrosion resistant. For the other class of catalyst, the active component is partially combusted coal or "Thief" carbon impregnated with Cl.sub.2. Untreated Thief carbon catalyst can be self-activating in the presence of effluent gas streams. The Thief carbon catalyst is disposable by means of capture from the effluent gas stream in a particulate collection device (PCD).

Nano-structured Platinum-based Catalysts for the Complete Oxidation of Ethylene Glycol and Glycerol

NASA Astrophysics Data System (ADS)

Falase, Akinbayowa

Direct alcohol fuel cells are a viable alternative to the traditional hydrogen PEM fuel cell. Fuel versatility, integration with existing distribution networks, and increased safety when handling these fuels increases their appeal for portable power applications. In order to maximize their utility, the liquid fuel must be fully oxidized to CO2 so as to harvest the full amount of energy. Methanol and ethanol are widely researched as potential fuels to power these devices, but methanol is a toxic substance, and ethanol has a much lower energy density than other liquids such as gasoline or glucose. Oxidation of complex fuels is difficult to realize, due to difficulty in breaking carbon-carbon bonding and poisoning of the catalysts by oxidative byproducts. In order to achieve the highest efficiency, an anode needs to be engineered in such a way as to maximize activity while minimizing poisoning effects of reaction byproducts. We have engineered an anode that uses platinum-based catalysts that is capable of completely oxidizing ethylene glycol and glycerol in neutral and alkaline media with little evidence of CO poisoning. We have constructed a hybrid anode consisting of a nano-structured PtRu electrocatayst with an NAD-dependent alcohol dehydrogenase for improved oxidation of complex molecules. A nano-structured PtRu catalyst was used to oxidize ethylene glycol and glycerol in neutral media. In situ infrared spectroscopy was used to verify complete oxidation via CO2 generation. There was no evidence of poisoning by CO species. A pH study was performed to determine the effect of pH on oxidative current. The peak currents did not trend at 60 mV/pH unit as would be expected from the Nernst equation, suggesting that adsorption of fuel to the surface of the electrode is not an electron-transfer step. We synthesized nano-structured PtRu, PtSn, and PtRuSn catalysts for oxidation of ethylene glycol and glycerol in alkaline media. The PtRu electrocatalyst the highest oxidative currents and highest stability compared to a nano-structured platinum, PtSn, and PtRuSn catalyst. In situ infrared spectroscopy showed complete oxidation of each fuel occurred by the presence of CO 2, with very little poisoning CO species present. In order to increase oxidative performance in neutral media, a hybrid anode based on nano-structured PtRu and a NAD-dependent alcohol dehydrogenase for the oxidation of ethanol and ethylene glycol was developed. Steady state polarization showed that the hybrid anode had higher current densities than the enzyme or the PtRu electrocatalyst alone. The hybrid anode had higher current densities at concentrations up to 3 M while oxidizing ethanol and ethylene glycol. The catalyst synthesis, characterization, and experimental results demonstrate the feasibility of fuel cells that can oxidize higher order fuels that platinum based catalysts or enzymes cannot oxidize alone. The cooperative mechanism from co-catalysis using inorganic and organic catalysts will allow for deep oxidation and improved power generation.

Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mahoney, Elizabeth G.; Sheng, Wenchao; Cheng, Mei; Lee, Kevin X.; Yan, Yushan; Chen, Jingguang G.

2016-02-01

Platinum modified gold (Pt/Au) catalysts are evaluated for the electrooxidation of ethylene glycol (EG) and glucose (Glc). The Pt/Au catalysts are synthesized on an Au disk and supported Au/C particles through the galvanic displacement of a copper monolayer with Pt. The Pt/Au catalysts are compared to monometallic Pt and Au catalysts for the oxidation of EG and Glc in alkaline electrolyte. The Pt/Au disk has an onset potential for these reactions that is similar to Pt and is lower than Au. The supported catalysts are less active toward the electrooxidation of EG and Glc than the corresponding disk electrodes, but the Pt/Au/C also has an onset potential similar to Pt/C. In-situ FTIR is used to analyze the C-C bond scission in both reactions on the surfaces of Pt, Au, and Pt/Au disks. While the Pt/Au disk is found to have a low onset potential for the oxidation of EG, it does not produce as much CO2 as bulk Pt. On the other hand, the FTIR results show that CO2 is produced for the oxidation of Glc on the Pt/Au disk. These results show promise for the possibility of decreasing the amount of Pt needed for the electrooxidation of polyol molecules.

Solvothermal synthesis of platinum alloy nanoparticles for oxygen reduction electrocatalysis.

PubMed

Carpenter, Michael K; Moylan, Thomas E; Kukreja, Ratandeep Singh; Atwan, Mohammed H; Tessema, Misle M

2012-05-23

Platinum alloy nanoparticles show great promise as electrocatalysts for the oxygen reduction reaction (ORR) in fuel cell cathodes. We report here on the use of N,N-dimethylformamide (DMF) as both solvent and reductant in the solvothermal synthesis of Pt alloy nanoparticles (NPs), with a particular focus on Pt-Ni alloys. Well-faceted alloy nanocrystals were generated with this method, including predominantly cubic and cuboctahedral nanocrystals of Pt(3)Ni, and octahedral and truncated octahedral nanocrystals of PtNi. X-ray diffraction (XRD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), coupled with energy dispersive spectroscopy (EDS), were used to characterize crystallite morphology and composition. ORR activities of the alloy nanoparticles were measured with a rotating disk electrode (RDE) technique. While some Pt(3)Ni alloy nanoparticle catalysts showed specific activities greater than 1000 μA/cm(2)(Pt), alloy catalysts prepared with a nominal composition of PtNi displayed activities close to 3000 μA/cm(2)(Pt), or almost 15 times that of a state-of-the-art Pt/carbon catalyst. XRD and EDS confirmed the presence of two NP compositions in this catalyst. HAADF-STEM examination of the PtNi nanoparticle catalyst after RDE testing revealed the development of hollows in a number of the nanoparticles due to nickel dissolution. Continued voltage cycling caused further nickel dissolution and void formation, but significant activity remained even after 20,000 cycles.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Development of Ultra-Low Platinum Alloy Cathode Catalysts for PEM Fuel Cells

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

Popov, Branko N.; Weidner, John

2016-01-07

The goal of this project is to synthesize a low cost PEM fuel cell cathode catalyst and support with optimized average mass activity, stability of mass activity, initial high current density performance under H 2/air (power density), and catalyst and support stability able to meet 2017 DOE targets for electrocatalysts for transportation applications. Pt*/ACCS-2 catalyst was synthesized according to a novel methodology developed at USC through: (i) surface modification, (ii) metal catalyzed pyrolysis and (iii) chemical leaching to remove excess meal used to dope the support. Pt* stands for suppressed platinum catalyst synthesized with Co doped platinum. The procedure resultsmore » in increasing carbon graphitization, inclusion of cobalt in the bulk and formation of non-metallic active sites on the carbon surface. Catalytic activity of the support shows an onset potential of 0.86 V for the oxygen reduction reaction (ORR) with well-defined kinetic and mass transfer regions and 2.5% H 2O 2 production. Pt*/ACCS-2 catalyst durability under 0.6-1.0 V potential cycling and support stability under 1.0-1.5 V potential cycling was evaluated. The results indicated excellent catalyst and support performance under simulated start-up/shut down operating conditions (1.0 – 1.5 V, 5000 cycles) which satisfy DOE 2017 catalyst and support durability and activity. The 30% Pt*/ACCS-2 catalyst showed high initial mass activity of 0.34 A/mg PGM at 0.9 ViR-free and loss of mass activity of 45% after 30,000 cycles (0.6-1.0 V). The catalyst performance under H 2-air fuel cell operating conditions showed only 24 mV (iR-free) loss at 0.8 A/cm 2 with an ECSA loss of 42% after 30,000 cycles (0.6-1.0 V). The support stability under 1.0-1.5 V potential cycling showed mass activity loss of 50% and potential loss of 8 mV (iR-free) at 1.5 A/cm 2. The ECSA loss was 22% after 5,000 cycles. Furthermore, the Pt*/ACCS-2 catalyst showed an initial power density (rated) of 0.174 g PGM/kW. Excellent activity and stability of the catalyst are due to synergistic effect of the catalytic activity and stability of ACCS-2, its enhanced hydrophobicity as well as activity of compressive Pt* lattice catalysts. For the first time, we report a carbon based support which is stable under simulated start-up/shut down operating conditions. Five 25cm 2 MEA’s were fabricated at USC using Pt*/ACCS-2 cathode catalyst for independent evaluation at National Renewable Energy. In the Final NREL report they summarize their results as follow: (1) Initial ORR activity and performance of the USC MEA’s Pt*/ACCS-2 under oxygen air, evaluated at NREL were comparable to that measured and reported by USC in their report: (2) Cyclic durability studies indicate that Pt*/ACCS-2 catalysts has minimal losses in activity and performant under 1-1.5 V potential cycling indicating a robust corrosion resistant support.« less

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

1989-01-01

Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

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

Aubart, M.A.; Dor Koch, J.F.; Pignolet, L.H.

The authors developed a homogeneous catalytic system for exchange of deuterium onto water. Platinum-gold phosphine cations catylze this exchange in pyridine. The authors probed these reactions kinetically and studied the catalysts by NMR allowing them to propose a reaction mechanism.

Nickel-silver composition shows promise as catalyst for hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Magerl, J. A.; Murray, J. N.

1970-01-01

Carburized 3-1 nickel-silver preparation exhibits considerable catalytic activity, although not as high as platinum black. Cost and availability factors warrant further evaluation of nickel-silver materials.

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts.

PubMed

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J; De Los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-20

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al₂O₃ 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al₂O₃ support helped to stabilize the furfural molecule on the surface.

Desorption of Furfural from Bimetallic Pt-Fe Oxides/Alumina Catalysts

PubMed Central

Dimas-Rivera, Gloria Lourdes; de la Rosa, Javier Rivera; Lucio-Ortiz, Carlos J.; De los Reyes Heredia, José Antonio; González, Virgilio González; Hernández, Tomás

2014-01-01

In this work, the desorption of furfural, which is a competitive intermediate during the production of biofuel and valuable aromatic compounds, was studied using pure alumina, as well as alumina impregnated with iron and platinum oxides both individually and in combination, using thermogravimetric analysis (TGA). The bimetallic sample exhibited the lowest desorption percentage for furfural. High-resolution transmission electron microscopy (HRTEM) imaging revealed the intimate connection between the iron and platinum oxide species on the alumina support. The mechanism of furfural desorption from the Pt-Fe/Al2O3 0.5%-0.5% sample was determined using physisorbed furfural instead of chemisorbed furfural; this mechanism involved the oxidation of the C=O group on furfural by the catalyst. The oxide nanoparticles on γ-Al2O3 support helped to stabilize the furfural molecule on the surface. PMID:28788472

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.

PubMed

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-04-06

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production-which far exceeds that of previously reported low-temperature APRM catalysts-to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Revealing the semiconductor–catalyst interface in buried platinum black silicon photocathodes

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

Aguiar, Jeffery A.; Anderson, Nicholas C.; Neale, Nathan R.

2016-01-01

Nanoporous 'black' silicon semiconductors interfaced with buried platinum nanoparticle catalysts have exhibited stable activity for photoelectrochemical hydrogen evolution even after months of exposure to ambient conditions. The mechanism behind this stability has not been explained in detail, but is thought to involve a Pt/Si interface free from SiOx layer that would adversely affect interfacial charge transfer kinetics. In this paper, we resolve the chemical composition and structure of buried Pt/Si interfaces in black silicon photocathodes from a micron to sub-nanometer level using aberration corrected analytical scanning transmission electron microscopy. Through a controlled electrodeposition of copper on samples aged for onemore » month in ambient conditions, we demonstrate that the main active catalytic sites are the buried Pt nanoparticles located below the 400-800 nm thick nanoporous SiOx layer. Though hydrogen production performance degrades over 100 h under photoelectrochemical operating conditions, this burying strategy preserves an atomically clean catalyst/Si interface free of oxide or other phases under air exposure and provides an example of a potential method for stabilizing silicon photoelectrodes from oxidative degradation in photoelectrochemical applications.« less

A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

PubMed

Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

2016-05-10

One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance.

PubMed

Alia, Shaun M; Pivovar, Bryan S

2018-04-27

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

Advanced PEFC development for fuel cell powered vehicles

NASA Astrophysics Data System (ADS)

Kawatsu, Shigeyuki

Vehicles equipped with fuel cells have been developed with much progress. Outcomes of such development efforts include a Toyota fuel cell electric vehicle (FCEV) using hydrogen as the fuel which was developed and introduced in 1996, followed by another Toyota FCEV using methanol as the fuel, developed and introduced in 1997. In those Toyota FCEVs, a fuel cell system is installed under the floor of each RAV4L, to sports utility vehicle. It has been found that the CO concentration in the reformed gas of methanol reformer can be reduced to 100 ppm in wide ranges of catalyst temperature and gas flow rate, by using the ruthenium (Ru) catalyst as the CO selective oxidizer, instead of the platinum (Pt) catalyst known from some time ago. It has been also found that a fuel cell performance equivalent to that with pure hydrogen can be ensured even in the reformed gas with the carbon monoxide (CO) concentration of 100 ppm, by using the Pt-Ru (platinum ruthenium alloy) electrocatalyst as the anode electrocatalyst of a polymer electrolyte fuel cell (PEFC), instead of the Pt electrocatalyst known from some time ago.

Method for making oxygen-reducing catalyst layers

DOEpatents

O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; O'Neill, David G.

2010-06-22

Methods are provided for making oxygen-reducing catalyst layers, which include simultaneous or sequential stops of physical vapor depositing an oxygen-reducing catalytic material onto a substrate, the catalytic material comprising a transition metal that is substantially free of platinum; and thermally treating the catalytic material. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Composite catalysts supported on modified carbon substrates and methods of making the same

DOEpatents

Popov, Branko N [Columbia, SC; Subramanian, Nalini [Kennesaw, GA; Colon-Mercado, Hector R [Columbia, SC

2009-11-17

A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

PubMed

Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

2016-12-06

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW -1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

2016-12-01

Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

Investigation of platinum and palladium as potential anodic catalysts for direct borohydride and ammonia borane fuel cells

NASA Astrophysics Data System (ADS)

Olu, Pierre-Yves; Deschamps, Fabien; Caldarella, Giuseppe; Chatenet, Marian; Job, Nathalie

2015-11-01

Platinum and palladium are investigated as anodic catalysts for direct borohydride and direct ammonia borane fuel cells (DBFC and DABFC). Half-cell characterizations performed at 25 °C using NH3BH3 or NaBH4 alkaline electrolytes demonstrate the lowest open-circuit potential and highest electrocatalytic activity for the NH3BH3 alkaline electrolyte for Pd and Pt rotating disk electrodes, respectively. Voltammograms performed in fuel cell configuration at 25 °C confirm this trend: the highest open circuit voltage (1.05 V) and peak power density (181 mW·cm-2) are monitored for DABFC using Pd/C and Pt/C anodes, respectively. Increasing the temperature heightens the peak power density (that reaches 420 mW·cm-2 at 60 °C for DBFC using Pt/C anodes), but strongly generates gas from the fuel hydrolysis, hindering the overall fuel cells performances. The anode texture strongly influences the fuel cell performances, highlighting: (i) that an open anode texture is required to efficiently circulate the anolyte and (ii) the difficulty to compare potential anodic catalysts characterized using different fuel cell setups within the literature. Furthermore, TEM imaging of Pt/C and Pd/C catalysts prior/post DBFC and DABFC operation shows fast degradation of the carbon-supported nanoparticles.

Etching nano-holes in silicon carbide using catalytic platinum nano-particles

NASA Astrophysics Data System (ADS)

Moyen, E.; Wulfhekel, W.; Lee, W.; Leycuras, A.; Nielsch, K.; Gösele, U.; Hanbücken, M.

2006-09-01

The catalytic reaction of platinum during a hydrogen etching process has been used to perform controlled vertical nanopatterning of silicon carbide substrates. A first set of experiments was performed with platinum powder randomly distributed on the SiC surface. Subsequent hydrogen etching in a hot wall reactor caused local atomic hydrogen production at the catalyst resulting in local SiC etching and hole formation. Secondly, a highly regular and monosized distribution of Pt was obtained by sputter deposition of Pt through an Au membrane serving as a contact mask. After the lift-off of the mask, the hydrogen etching revealed the onset of well-controlled vertical patterned holes on the SiC surface.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

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

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Presidential Green Chemistry Challenge: 2016 Academic Award

EPA Pesticide Factsheets

Presidential Green Chemistry Challenge 2016 award winner, Professor Chirik, discovered a class of catalysts used to produce silicones for consumer goods without using hard-to-mine platinum (less mining, reduces costs, greenhouse gas emissions, and waste).

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

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

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Long-life high performance fuel cell program

NASA Technical Reports Server (NTRS)

Martin, R. E.

1985-01-01

A multihundred kilowatt Regenerative Fuel Cell for use in a space station is envisioned. Three 0.508 sq ft (471.9 cm) active area multicell stacks were assembled and endurance tested. The long term performance stability of the platinum on carbon catalyst configuration suitability of the lightweight graphite electrolyte reservoir plate, the stability of the free standing butyl bonded potassium titanate matrix structure, and the long life potential of a hybrid polysulfone cell edge frame construction were demonstrated. A 18,000 hour demonstration test of multicell stack to a continuous cyclical load profile was conducted. A total of 12,000 cycles was completed, confirming the ability of the alkaline fuel cell to operate to a load profile simulating Regenerative Fuel Cell operation. An orbiter production hydrogen recirculation pump employed in support of the cyclical load profile test completed 13,000 hours of maintenance free operation. Laboratory endurance tests demonstrated the suitability of the butyl bonded potassium matrix, perforated nickel foil electrode substrates, and carbon ribbed substrate anode for use in the alkaline fuel cell. Corrosion testing of materials at 250 F (121.1 C) in 42% wgt. potassium identified ceria, zirconia, strontium titanate, strontium zirconate and lithium cobaltate as candidate matrix materials.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

From bio-mineralisation to fuel cells: biomanufacture of Pt and Pd nanocrystals for fuel cell electrode catalyst.

PubMed

Yong, P; Paterson-Beedle, M; Mikheenko, I P; Macaskie, L E

2007-04-01

Biosynthesis of nano-scale platinum and palladium was achieved via enzymatically-mediated deposition of metal ions from solution. The bio-accumulated Pt(0) and Pd(0) crystals were dried, applied onto carbon paper and tested as anodes in a polymer electrolyte membrane (PEM) fuel cell for power production. Up to 100% and 81% of the maximum power generation was achieved by the bio-Pt and bio-Pd catalysts, respectively, compared to commercial fuel cell grade Pt catalyst. Hence, biomineralisation could pave the way for economical production of fuel cell catalysts since previous studies have shown that precious metals can be biorecovered from wastes into catalytically active bionanomaterials.

Atomic cobalt on nitrogen-doped graphene for hydrogen generation

PubMed Central

Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L.G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

2015-01-01

Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

Catalytic Combustion of Ethanol and Butanol

DTIC Science & Technology

2009-09-01

demonstrated 75% conversion of ethanol. I then selected a more active rhodium -coated alumina foam with a larger surface area and attained 100...catalysts composed of thermally stabilized, ion-exchanged zeolite, palladium on stabilized alumina, and catalysts doped with cerium (Ce) and nickel...platinum mesh weighed about 0.50 g and was roughly 0.5 mm thick. The rhodium (Rh)/aluminum oxide (Al2O3) foam contained 0.061 g of Rh and was prepared

Catalytic partial oxidation of hydrocarbons

DOEpatents

Schmidt, Lanny D.; Krummenacher, Jakob J.; West, Kevin N.

2007-08-28

A process for the production of a reaction product including a carbon containing compound. The process includes providing a film of a fuel source including at least one organic compound on a wall of a reactor, contacting the fuel source with a source of oxygen, forming a vaporized mixture of fuel and oxygen, and contacting the vaporized mixture of fuel and oxygen with a catalyst under conditions effective to produce a reaction product including a carbon containing compound. Preferred products include .alpha.-olefins and synthesis gas. A preferred catalyst is a supported metal catalyst, preferably including rhodium, platinum, and mixtures thereof.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

DOE PAGES

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

2018-03-13

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1990-05-15

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Single-Atom Pt as Co-Catalyst for Enhanced Photocatalytic H2 Evolution.

PubMed

Li, Xiaogang; Bi, Wentuan; Zhang, Lei; Tao, Shi; Chu, Wangsheng; Zhang, Qun; Luo, Yi; Wu, Changzheng; Xie, Yi

2016-03-23

Isolated single-atom platinum (Pt) embedded in the sub-nanoporosity of 2D g-C3 N4 as a new form of co-catalyst is reported. The highly stable single-atom co-catalyst maximizes the atom efficiency and alters the surface trap states of g-C3 N4 , leading to significantly enhanced photocatalytic H2 evolution activity, 8.6 times higher than that of Pt nanoparticles and up to 50 times that for bare g-C3 N4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

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

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Catalytic partial oxidation of hydrocarbons

DOEpatents

Schmidt, Lanny D [Minneapolis, MN; Krummenacher, Jakob J [Minneapolis, MN; West, Kevin N [Minneapolis, MN

2009-05-19

A process for the production of a reaction product including a carbon containing compound. The process includes providing a film of a fuel source including at least one organic compound on a wall of a reactor, contacting the fuel source with a source of oxygen, forming a vaporized mixture of fuel and oxygen, and contacting the vaporized mixture of fuel and oxygen with a catalyst under conditions effective to produce a reaction product including a carbon containing compound. Preferred products include .alpha.-olefins and synthesis gas. A preferred catalyst is a supported metal catalyst, preferably including rhodium, platinum, and mixtures thereof.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

In Situ Biosynthesis of Fluorescent Platinum Nanoclusters: Toward Self-Bioimaging-Guided Cancer Theranostics.

PubMed

Chen, Donghua; Zhao, Chunqiu; Ye, Jing; Li, Qiwei; Liu, Xiaoli; Su, Meina; Jiang, Hui; Amatore, Christian; Selke, Matthias; Wang, Xuemei

2015-08-19

Among the noble-metal clusters, very few reports about platinum clusters were used as bioimaging probes of tumors except as a reducing catalyst. It is first established herein that the biocompatible platinum nanoclusters are spontaneously biosynthesized by cancerous cells (i.e., HepG2 (human hepatocarcinoma), A549 (lung cancer), and others) rather than noncancerous cells (i.e., L02 (human embryo liver cells)) when incubated with micromolar chloroplatinic acid solutions. These in situ biosynthesized platinum nanoclusters could be readily realized in a biological environment and emit a bright fluorescence at 460 nm, which could be further utilized to facilitate an excellent cancer-cell-killing efficiency when combined with porphyrin derivatives for photothermal treatment. This raises the possibility of providing a promising and precise bioimaging strategy for specific fluorescent self-biomarking of tumor locations and realizing fluorescence imaging-guided photothermal therapy of tumors.

Synthesis and Characterization of Mixed-Conducting Corrosion Resistant Oxide Supports

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

Ramani, Vijay K.

An extensive search and evaluation of electrochemically stable catalyst supports (including metal oxides like RuO2-SiO2, RuO2-TiO2, and ITO was perfomed during the 4 years of the project. The suports were also catalyzed by deposition of Pt and tested for its performance and electrochemical stability in RDE and fuel cell experiments. For testing the electrochemical stability and fuel cell performance of the catalysts and supports, we have employed the protocols in use at the Department of Energy and Nissan Technological Center North America (NTCNA). The use of such procedures allows a precise and reproducible estimation of the performance and stability ofmore » the materials and permits comparisons among laboratories and DOE funded projects. RuO2-SiO2 catalyst supports showed no loss in surface area during start-stop stability tests that were performed by cycling the electrode potential between 0 V to 1.8 V for 1000 cycles. Catalyzed support (40% Pt/RuO2-SiO2; 1:1 mole ratio) were tested in a PEFC, resulting in a current density of 750 mA/cm2 at 0.6 Volts, and a maximum power density of 570 mW/cm2. Measurements were conducted at 80 ºC with 75% relative humidity of the inlet gases (H2/O2); Pt loadings were 0.4 mg/cm2 at the cathode and 0.2 mg/cm2 at the anode. Start-stop stability tests for support and catalyzed support performed in RDE and PEFC set-ups have confirmed RuO2-TiO2 support stability. The beginning of life performance was exactly equal to end of life performance (in an MEA that has been subjected to severe start-stop cycling for 10,000 start/stop cycles between 1 V to 1.5 V). This result was in sharp contrast to baseline Pt/C catalyst that showed significant performance deterioration after accelerated stability tests. The Pt/TRO showed minimal loss in performance upon exposure to start-stop cycles. The loss in cell voltage at 1 A/cm2 at 100% RH was almost 700 mV for Pt/C whereas it was only ca. 15 mV for Pt/TRO. 40% RH data (of inlet gases) revealed a similar trend in terms of stability – exceptional stability for Pt/TRO as opposed to very poor stability for Pt/HSAC. These observations were attributed to the much higher stability of the TRO support compared to Carbon. The carbon dioxide concentration in the cathode exit stream during the accelerated degradation test with Pt/TRO (start-stop protocol) was extremely low (between 3 to 10 ppm of CO2). In contrast, the CO2 emission levels from a conventional Pt/C catalyst were found to be approx. 200 ppm. This observation was a clear indicator that the main source of carbon being oxidized to carbon dioxide in an MEA was the carbon catalyst support, and not the gas diffusion layer or the graphite flow fields. Indium tin oxide (ITO) was also evaluated as a catalyst support for PEFCs. Pt/ITO was very stable under start-up/shutdown accelerated degradation protocol (RDE tests in perchloric acid). The ECSA change was less than 4% over 10,000 cycles. The load cycling accelerated protocol (from 0.6 to 0.95 V vs. RHE) resulted in a loss of approximately 34% of the initial ECSA after 10,000 cycles. However, fuel cell testing resulted in a very low performing catalyst. XPS spectroscopy was employed to investigate the changes in the catalysts occuring during fuel cell operation. It was observed a shift of In 3d5/2 and In 3d3/2 peaks towards higher binding energies. This can be explained by the formation of hydroxides or oxy-hydroxides in the surface of the catalyst. O1s spectrum for Pt/ITO catalyst after being operated in the fuel cell, also confirmed the formation of significant amounts of surface hydroxides (12 to 16%). The presence of surface hydroxides in the catalyst increased the electrode resistivity affecting fuel cell performance. NTCNA performed a detailed analysis of transport phenomena (reactants and products to/from the Pt active sites) in both commercial catalyst and Pt/RTO (in order to have a better understanding at the basic level). The proton resistance (Rionomer) in Pt/C and Pt/RTO cathode catalyst layers were 150 and 12 mΩ-cm2, respectively. Pt/RTO catalyst layer has about an order or magnitude lower proton transfer resistance than Pt/C catalyst layer. Since the ionomer/support ratio that was used in formulating the ink for both catalysts was the same (0.9), it is expected that the volumetric coverage of ionomer of both catalysts will be significantly different due to the disparity in the surface areas (Pt/C had ~ 800 m2/g, while Pt/RTO had ~ 50 m2/g). The differences in the ionomer volumetric coverage and the ionomer film thickness may explain the significantly higher proton conductivity in the Pt/RTO catalyst layer when compared to Pt/HSAC. It is therefore very important to optimize the ionomer loadings when synthesizing new catalyst supports (and never rely on values for carbon-based commercial catalysts). Finally, NTCNA has elaborated a cost model for non-carbon support materials considering their durability benefits. Material costs for production of Pt/ RuO2-TiO2 electrodes were compared to Pt/C. RuO2-TiO2 support was more expensive than carbon but the total material cost was still dominated by platinum cost. Though ruthenium is considered a precious metal, its cost is far less than platinum. It should also be noted that ruthenium only makes up 38% of the mass of the support, while the rest is inexpensive TiO2. After considering the durability advantages of Pt/RTO, cost model showed that even with almost double the Pt loading (0.35 vs 0.18 mgPt/cm2), Pt/RTO ($22.7/kWnet) is only slightly more expensive than Pt/C ($21.9/kWnet).« less

Polymer Nanocarriers to Enhance the Efficiency of Platinum-Based Chemotherapeutics

NASA Astrophysics Data System (ADS)

Callari, Manuela

The aim of this Thesis was to design and prepare polymer nanocarriers capable of encapsulating, carrying and delivering platinum-based chemotherapeutics. Polymer nanocarrier have been widely studied and employed as platinum drug delivery systems with the primary scope to overcome limitations presented by platinum-based chemotherapeutics. The conjugation of platinum onto polymers, however, presents some challenges, and, although there has been great progress in the field of drug delivery in the past years, to date only three polymer nanocarriers for platinum drugs have found their way to the clinic. In this Thesis, hydrophilic block copolymers were synthesised via reversible addition fragmentation chain transfer (RAFT) polymerisation or N-carboxyanhydride ring-opening polymerization (NCA-ROP). Upon attachment of a hydrophobic platinum drug the block copolymer becomes amphiphilic and can self-assemble in aqueous media into nanoparticles of different morphology depending on the block copolymer features. Spherical micelles consisting of a poly(methacrylic acid) core which conjugates and encapsulates the platinum chemotherapeutic and a hydrophilic shell made of sugar blocks were prepared and their biological activities compared in vitro. Among the sugars considered here, fructose based micelles showed promising results in terms of their targeting ability towards breast cancer cells. Consequently, fructose-shelled micelles were selected to explore the effect of different loading quantities of platinum drug. It was discovered that the amount of platinum in the core of the micelle highly influences the internal morphology of the micelle which, in turn, affects the micelle-cell interactions. Micelles with low dual drug loading had better cellular uptake and higher toxicity than the micelles with high drug loading, despite having the same fructose-based outer shell. Interestingly, this aspect had been neglected by literature so far, and is important to explore. Micelles made of a fructose shell were then compared to micelles with a non-targeting hydrophilic shell made of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA). The aim was to compare the process of cellular uptake and the mechanism of platinum release inside the cell. For this scope, a fluorescent platinum drug was synthesised as a probing tool. Finally, a polymer vesicle based on PEG and poly(glutamic acid) was designed to co-deliver a platinum drug and the cancer inhibitor, paclitaxel, simultaneously. The two drugs have a synergistic effect when used in combination or co-delivered by the vesicles. Moreover, a viability study using multicellular tumour spheroids (MCTS) showed a significant decrease in cell proliferation when the MCTS were treated with single drug, a combination of free drugs and dual-drug loaded vesicles compared with untreated MCTS. An improvement is observed in the case of the dual-drug vesicles.

Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation

DOEpatents

Adzic, Radoslav; Brankovic, Stanko; Wang, Jia

2003-12-30

An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbon monoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

Modified WO3 nanorod with Pt nanoparticle as retrievable materials in catalytic and photocatalytic aerobic oxidation of alcohols

NASA Astrophysics Data System (ADS)

Hosseini, Farnaz; Safaei, Elham; Mohebbi, Sajjad

2017-07-01

This study has focused on catalytic and photocatalytic oxidation of aromatic alcohols using WO3 nanorod and a series of Pt/WO3 nanocomposite Pt nanoparticles was loaded on WO3 nanorod with several mass ratios 0.1, 0.2, and 0.3 via a photoreduction process (PRP) and characterized by TEM, FE-SEM imaging, EDAX, XRD, DRS, ICP, and XPS. WO3 nanorods were obtained monodispersed with average 40-nm diameter and square cross section without significant size change by the loading of platinum nanoparticles on it. Progress of oxidation reaction was monitored by GC and the yield of aerobic photocatalytic oxidation of alcohols reached up to 98% for Pt/WO3 and 69% for WO3 while, no oxidation was detected in the absence of light. The highest photocatalytic performance was obtained for mass ratio 0.2 with the selectivity >99%. So, this nanocomposite has potentials to be used as high-performance heterogeneous catalyst and photocatalyst under visible light irradiation with advantages of high activity, high selectivity, and reusability.

Enhanced Oxidation Catalysts for Water Reclamation

NASA Technical Reports Server (NTRS)

Jolly, Clifford D.

1999-01-01

This effort seeks to develop and test high-performance, long operating life, physically stable catalysts for use in spacecraft water reclamation systems. The primary goals are to a) reduce the quantity of expendable water filters used to purify water aboard spacecraft, b) to extend the life of the oxidation catalysts used for eliminating organic contaminants in the water reclamation systems, and c) reduce the weight/volume of the catalytic oxidation systems (e.g. VRA) used. This effort is targeted toward later space station utilization and will consist of developing flight-qualifiable catalysts and long-term ground tests of the catalyst prior to their utilization in flight. Fixed -bed catalytic reactors containing 5% platinum on granular activated carbon have been subjected to long-term dynamic column tests to measure catalyst stability vs throughput. The data generated so far indicate that an order of magnitude improvement can be obtained with the treated catalysts vs the control catalyst, at only a minor loss (approx 10%) in the initial catalytic activity.

Failure mechanism characterization of platinum alloy

NASA Technical Reports Server (NTRS)

Rosen, J. M.; Mcfarlen, W. T.

1986-01-01

This article describes procedures and results of testing performed on a platinum/10-percent rhodium, thin-wall tubular product. The purpose of the testing was to develop exemplar SEM fractographs to be used to characterize failures under various environmental conditions. Conditions evaluated for the platinum alloys included high temperature, hydrogen environment, braze metal contamination, and cyclic loading.

Robust Platinum-Based Electrocatalysts for Fuel Cell Applications

NASA Astrophysics Data System (ADS)

Coleman, Eric James

Polymer electrolyte fuel cells (PEMFCs) are energy conversion devices that exploit the energetics of the reaction between hydrogen fuel and O 2 to generate electricity with water as the only byproduct. PEMFCs have attracted substantial attention due to their high conversion efficiency, high energy density, and low carbon footprint. However, PEMFC performance is hindered by the high activation barrier and slow reaction rates at the cathode where O2 undergoes an overall 4-electron reduction to water. The most efficient oxygen reduction reaction (ORR) catalyst materials to date are Pt group metals due to their high catalytic activity and stability in a wide range of operating conditions. Before fuel cells can become economically viable, efforts must be taken to decrease Pt content while maintaining a high level of ORR activity. This work describes the design and synthesis of a Pt-Cu electrocatalyst with ORR activity exceeding that of polycrystalline Pt. Production of this novel catalyst is quite simple and begins with synthesis of a porous Cu substrate, formed by etching Al from a Cu-Al alloy. The porous Cu substrate is then coated with a Pt layer via a spontaneous electrochemical process known as galvanic replacement. The Pt layer enhances the ORR activity (as measured by a rotating ring-disk electrode (RRDE)) and acts as a barrier towards corrosion of the Cu understructure. Growth of the Pt layer can be manipulated by time, temperature, concentration of Pt precursor, and convection rate during galvanic replacement. Data from analytical and electrochemical techniques confirm multiple Pt loadings have been achieved via the galvanic replacement process. The boost in ORR activity for the PtCu catalyst was determined to be a result of its lower affinity towards (site-blocking) OH adsorption. A unique catalyst degradation study explains the mechanism of initial catalyst ORR deactivation for both monometallic and bimetallic Pt-based catalysts. Finally, a rigorous and pioneering examination of how Pt surface passivation affects ORR dynamics is presented.

Crack-tips enriched platinum-copper superlattice nanoflakes as highly efficient anode electrocatalysts for direct methanol fuel cells.

PubMed

Zheng, Lijun; Yang, Dachi; Chang, Rong; Wang, Chengwen; Zhang, Gaixia; Sun, Shuhui

2017-07-06

We have developed "crack-tips" and "superlattice" enriched Pt-Cu nanoflakes (NFs), benefiting from the synergetic effects of "crack-tips" and "superlattice crystals"; the Pt-Cu NFs exhibit 4 times higher mass activity, 6 times higher specific activity and 6 times higher stability than those of the commercial Pt/C catalyst, respectively. Meanwhile, the Pt-Cu NFs show more enhanced CO tolerance than the commercial Pt/C catalyst.

Characterization of Catalyst Materials for Production of Aerospace Fuels

NASA Technical Reports Server (NTRS)

Best, Lauren M.; De La Ree, Ana B.; Hepp, Aloysius F.

2012-01-01

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

Characterization of Catalyst Materials for Production of Aerospace Fuels

NASA Technical Reports Server (NTRS)

DeLaRee, Ana B.; Hepp, Aloysius F.

2011-01-01

Due to environmental, economic, and security issues, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. Additionally, efforts are concentrated on reducing costs coupled with fuel production from non-conventional sources. One solution to this issue is Fischer-Tropsch gas-to-liquid technology. Fischer-Tropsch processing of synthesis gas (CO/H2) produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fisher-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur or aromatic compounds. This process is most commonly catalyzed by heterogeneous (in this case, silver and platinum) catalysts composed of cobalt supported on alumina or unsupported alloyed iron powders. Physisorption, chemisorptions, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) are described to better understand the potential performance of Fischer-Tropsch cobalt on alumina catalysts promoted with silver and platinum. The overall goal is to preferentially produce C8 to C18 paraffin compounds for use as aerospace fuels. Progress towards this goal will eventually be updated and achieved by a more thorough understanding of the characterization of catalyst materials. This work was supported by NASA s Subsonic Fixed Wing and In-situ Resource Utilization projects.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

DOE PAGES

Alia, Shaun M.; Pivovar, Bryan S.

2018-01-01

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

Platinum Assisted Vapor–Liquid–Solid Growth of Er–Si Nanowires and Their Optical Properties

PubMed Central

2010-01-01

We report the optical activation of erbium coated silicon nanowires (Er–SiNWs) grown with the assist of platinum (Pt) and gold (Au), respectively. The NWs were grown on Si substrates by using a chemical vapor transport process using SiCl4 and ErCl4 as precursors. Pt as well as Au worked successfully as vapor–liquid–solid (VLS) catalysts for growing SiNWs with diameters of ~100 nm and length of several micrometers, respectively. The SiNWs have core–shell structures where the Er-crystalline layer is sandwiched between silica layers. Photoluminescence spectra analyses showed the optical activity of SiNWs from both Pt and Au. A stronger Er3+ luminescence of 1,534 nm was observed from the SiNWs with Pt at room- and low-temperature (25 K) using the 488- and/or 477-nm line of an Ar laser that may be due to the uniform incorporation of more Er ions into NWs with the exclusion of the formation of catalyst-induced deep levels in the band-gap. Pt would be used as a VLS catalyst for high performance optically active Er–SiNWs. PMID:20672113

Platinum assisted vapor-liquid-solid growth of er-si nanowires and their optical properties.

PubMed

Kim, Myoung-Ha; Kim, Il-Soo; Park, Yong-Hee; Park, Tae-Eon; Shin, Jung H; Choi, Heon-Jin

2009-11-14

We report the optical activation of erbium coated silicon nanowires (Er-SiNWs) grown with the assist of platinum (Pt) and gold (Au), respectively. The NWs were grown on Si substrates by using a chemical vapor transport process using SiCl4 and ErCl4 as precursors. Pt as well as Au worked successfully as vapor-liquid-solid (VLS) catalysts for growing SiNWs with diameters of ~100 nm and length of several micrometers, respectively. The SiNWs have core-shell structures where the Er-crystalline layer is sandwiched between silica layers. Photoluminescence spectra analyses showed the optical activity of SiNWs from both Pt and Au. A stronger Er3+ luminescence of 1,534 nm was observed from the SiNWs with Pt at room- and low-temperature (25 K) using the 488- and/or 477-nm line of an Ar laser that may be due to the uniform incorporation of more Er ions into NWs with the exclusion of the formation of catalyst-induced deep levels in the band-gap. Pt would be used as a VLS catalyst for high performance optically active Er-SiNWs.

Platinum Assisted Vapor-Liquid-Solid Growth of Er-Si Nanowires and Their Optical Properties

NASA Astrophysics Data System (ADS)

Kim, Myoung-Ha; Kim, Il-Soo; Park, Yong-Hee; Park, Tae-Eon; Shin, Jung H.; Choi, Heon-Jin

2010-02-01

We report the optical activation of erbium coated silicon nanowires (Er-SiNWs) grown with the assist of platinum (Pt) and gold (Au), respectively. The NWs were grown on Si substrates by using a chemical vapor transport process using SiCl4 and ErCl4 as precursors. Pt as well as Au worked successfully as vapor-liquid-solid (VLS) catalysts for growing SiNWs with diameters of ~100 nm and length of several micrometers, respectively. The SiNWs have core-shell structures where the Er-crystalline layer is sandwiched between silica layers. Photoluminescence spectra analyses showed the optical activity of SiNWs from both Pt and Au. A stronger Er3+ luminescence of 1,534 nm was observed from the SiNWs with Pt at room- and low-temperature (25 K) using the 488- and/or 477-nm line of an Ar laser that may be due to the uniform incorporation of more Er ions into NWs with the exclusion of the formation of catalyst-induced deep levels in the band-gap. Pt would be used as a VLS catalyst for high performance optically active Er-SiNWs.

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

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

Alia, Shaun M.; Pivovar, Bryan S.

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

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-05-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

PubMed Central

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-01-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

The effect of H2O and pretreatment on the activity of a Pt/SnO2 catalyst

NASA Technical Reports Server (NTRS)

Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.

1990-01-01

CO oxidation catalysts with high activity at 25 C to 100 C are important for long-life, closed-cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 has been shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment or no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady-state yield is attained. This dip has been found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

The effects of pretreatment conditions on a Pt/SnO2 catalyst for the oxidation of CO in CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Vannorman, John D.; Brown, Kenneth G.; Schryer, Jacqueline

1989-01-01

CO oxidation catalysts with high activity at 25 to 100 C are important for long life, closed cycle operation of pulsed CO2 lasers. A reductive pretreatment with either CO or H2 was shown to significantly enhance the activity of a commercially available platinum on tin (IV) oxide (Pt/SnO2) catalyst relative to an oxidative or inert pretreatment of no pretreatment. Pretreatment at temperatures of 175 C and above causes an initial dip in the observed CO2 yield before the steady state yield is attained. This dip was found to be caused by dehydration of the catalyst during pretreatment and is readily eliminated by humidifying the catalyst or the reaction gas mixture. It is hypothesized that the effect of humidification is to increase the concentration of OH groups on the catalyst surface which play a role in the reaction mechanism.

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

Binder, Andrew J.; Toops, Todd J.; Unocic, Raymond R.

Platinum group metal (PGM) catalysts are the current standard for control of pollutants in automotive exhaust streams. Aside from their high cost, PGM catalysts struggle with CO oxidation at low temperatures (<200 °C) due to inhibition by hydrocarbons in exhaust streams. Here we present a ternary mixed oxide catalyst composed of copper oxide, cobalt oxide, and ceria (dubbed CCC) that outperforms synthesized and commercial PGM catalysts for CO oxidation in simulated exhaust streams while showing no signs of inhibition by propene. Diffuse reflectance IR (DRIFTS) and light-off data both indicate low interaction between propene and the CO oxidation active sitemore » on this catalyst, and a separation of adsorption sites is proposed as the cause of this inhibition resistance. In conclusion, this catalyst shows great potential as a low-cost component for low temperature exhaust streams that are expected to be a characteristic of future automotive systems.« less

Conversion of deuterium gas to heavy water by catalytic isotopic exchange using wetproof catalyst

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

Quaiattini, R.J.; McGauley, M.P.; Burns, D.L.

The invention at Chalk River Nuclear Laboratories of a simple method of wetproofing platinum catalysts allows them to retain their activity in liquid water. High performance catalysts for the hydrogen-water isotope exchange reaction that remain active for years can now be routinely produced. The first commercial application using the ordered-bed-type wetproofed isotope exchange catalyst developed and patented by Atomic Energy of Canada Ltd. has been successfully completed. Approximately 9100 m/sup 3/ of deuterium gas stored at Brookhaven National Laboratory was converted to high grade heavy water. Conversion efficiency exceeded 99.8%. The product D/sub 2/O concentration was 6.7 percentage points highermore » than the feed D/sub 2/ gas.« less

Nanostructured TiOx as a catalyst support material for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Phillips, Richard S.

Recent interest in the development of new catalyst support materials for proton exchange membrane fuel cells (PEMFCs) has stimulated research into the viability of TiO2-based support structures. Specifically, substoichiometric TiO2 (TiOx) has been reported to exhibit a combination of high conductivity, stability, and corrosion resistance. These properties make TiOx-based support materials a promising prospect when considering the inferior corrosion resistance of traditional carbon-based supports. This document presents an investigation into the formation of conductive and stable TiOx thin films employing atomic layer deposition (ALD) and a post deposition oxygen reducing anneal (PDORA). Techniques for manufacturing TiOx-based catalyst support nanostructures by means of ALD in conjunction with carbon black (CB), anodic aluminum oxide (AAO) and silicon nanowires (SiNWs) will also be presented. The composition and thickness of resulting TiOx thin films was determined with the aid of Auger electron spectroscopy (AES), Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM). Film crystal structure was determined with X-ray diffraction (XRD) analysis. Film conductivity was calculated using four-point probe (4-PP) and film thickness measurement data. Resulting thin films show a significant decrease of oxygen in ALD TiOx films corresponding with a great increase in conductivity following the PDORA. The effectiveness of the PDORA was also found to be highly dependent on ALD process parameters. TiOx-based nanostructures were coated with platinum using one of three Pt deposition techniques. First, liquid phase deposition (LPD), which was performed at room temperature, provided equal access to catalyst support material surfaces which were suspended in solution. Second, plasma enhanced atomic layer deposition (PEALD), which was performed at 450°C, provided good Pt particle dispersion and particle size controllability. Third, physical vapor deposition (PVD), which was also performed at room temperature, was used as a low temperature vapor-phase deposition technique for comparison with PEALD Pt coated materials. The temperature of the Pt deposition technique is an important parameter to consider due to the potential adverse effects of the strong metal support interaction (SMSI) which may take place at temperatures above 200°C. Platinum coated nanostructures were analyzed electrochemically using cyclic voltammetry (CV), rotating disk electrode (RDE) and accelerated stress tests (ASTs). CV and RDE results generally show that platinum activity values are initially not as high as those typically observed for platinum on carbon; however, AST results indicate that TiO x-based materials are much more stable long-term and hence their level of activity is likely to overtake traditional platinum on carbon materials in a PEMFC system.

METHOD OF REDUCING PLUTONIUM COMPOUNDS

DOEpatents

Johns, I.B.

1958-06-01

A method is described for reducing plutonium compounds in aqueous solution from a higher to a lower valence state. This reduction of valence is achieved by treating the aqueous solution of higher valence plutonium compounds with hydrogen in contact with an activated platinum catalyst.

Carbon Nanotubes as Support in the Platinum-Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane.

PubMed

Chen, Wenyao; Duan, Xuezhi; Qian, Gang; Chen, De; Zhou, Xinggui

2015-09-07

We report remarkable support effects for carbon nanotubes (CNTs) in the Pt/CNT-catalyzed hydrolytic dehydrogenation of ammonia borane. The origin of the support-dependent activity and durability is elucidated by combining the catalytic and durability testing with characterization by a range of spectroscopy and high-angle annular dark-field scanning transmission electron microscopy techniques and ICP analysis. The effects mainly arise from different electronic properties and different abilities for the adsorption of boron-containing species on platinum surfaces and changes in size and shape of the platinum particles during the reaction. Defect-rich CNTs in particular are a promising support material, as it not only enhances the platinum binding energy, leading to the highest hydrogen generation rate, but also inhibits the adsorption of boron-containing species and stabilizes the platinum nanoparticles to resist the agglomeration during the reaction, leading to the highest durability. The insights revealed herein may pave the way for the rational design of highly active and durable metal/carbon catalysts for the hydrolytic dehydrogenation of ammonia borane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

PubMed

Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

2012-04-14

Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

NASA Astrophysics Data System (ADS)

Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

2016-02-01

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

Method for forming gold-containing catalyst with porous structure

DOEpatents

Biener, Juergen; Hamza, Alex V; Baeumer, Marcus; Schulz, Christian; Jurgens, Birte; Biener, Monika M.

2014-07-22

A method for forming a gold-containing catalyst with porous structure according to one embodiment of the present invention includes producing a starting alloy by melting together of gold and at least one less noble metal that is selected from the group consisting of silver, copper, rhodium, palladium, and platinum; and a dealloying step comprising at least partial removal of the less noble metal by dissolving the at least one less noble metal out of the starting alloy. Additional methods and products thereof are also presented.

Investigation of the In-Situ Oxidation of Methanol in Fuel Cells.

DTIC Science & Technology

1981-09-01

ability of the catalyst to tolerate carbon monoxide. Finally, a performance curve was obtained for the anodic oxidation of methanol : CH3OH ... CH3OH + H20 •» C02 + 3H2 In present methanol -air fuel cell power plants , the steam reforming process is usually carried out in a unit which is...KCY YIO"(CS (Continue on reverse ride it neeessnry and identity ay block number) Fuel Cell Platinum Catalysts Methanol Direct Oxidation Internal

Enhancement of Pt/SnO2 Catalysts by Addition of H2O

NASA Technical Reports Server (NTRS)

Schryer, David R.; Sidney, Barry D.; Van Norman, John D.; Brown, Kenneth G.; Schryer, Jacqueline; Upchurch, Billy T.

1990-01-01

Water vapor in pretreatment gas restores essential hydroxyl groups. Platinum on tin oxide (Pt/SnO2) is good catalyst for oxidation of carbon monoxide (CO) at temperatures from about 25 degrees C to 100 degress C. Activity of Pt/SnO2 for CO oxidation significantly enhanced by pretreating it at approximately 225 degrees C with reducing gas such as CO. Technique useful in manufacture of high-power CO2 lasers for industrial and scientific uses.

Highly Active and Stable Pt–Pd Alloy Catalysts Synthesized by Room‐Temperature Electron Reduction for Oxygen Reduction Reaction

PubMed Central

Wang, Wei; Wang, Zongyuan; Wang, Jiajun; Zhong, Chuan‐Jian

2017-01-01

Carbon‐supported platinum (Pt) and palladium (Pd) alloy catalyst has become a promising alternative electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. In this work, the synthesis of highly active and stable carbon‐supported Pt–Pd alloy catalysts is reported with a room‐temperature electron reduction method. The alloy nanoparticles thus prepared show a particle size around 2.6 nm and a core–shell structure with Pt as the shell. With this structure, the breaking of O–O bands and desorption of OH are both promoted in electrocatalysis of ORR. In comparison with the commercial Pt/C catalyst prepared by conventional method, the mass activity of the Pt–Pd/C catalyst for ORR is shown to increase by a factor of ≈4. After 10 000‐cycle durability test, the Pt–Pd/C catalyst is shown to retain 96.5% of the mass activity, which is much more stable than that of the commercial Pt/C catalyst. PMID:28435780

Low-temperature CO oxidation over a ternary oxide catalyst with high resistance to hydrocarbon inhibition

DOE PAGES

Binder, Andrew J.; Toops, Todd J.; Unocic, Raymond R.; ...

2015-09-11

Platinum group metal (PGM) catalysts are the current standard for control of pollutants in automotive exhaust streams. Aside from their high cost, PGM catalysts struggle with CO oxidation at low temperatures (<200 °C) due to inhibition by hydrocarbons in exhaust streams. Here we present a ternary mixed oxide catalyst composed of copper oxide, cobalt oxide, and ceria (dubbed CCC) that outperforms synthesized and commercial PGM catalysts for CO oxidation in simulated exhaust streams while showing no signs of inhibition by propene. Diffuse reflectance IR (DRIFTS) and light-off data both indicate low interaction between propene and the CO oxidation active sitemore » on this catalyst, and a separation of adsorption sites is proposed as the cause of this inhibition resistance. In conclusion, this catalyst shows great potential as a low-cost component for low temperature exhaust streams that are expected to be a characteristic of future automotive systems.« less

Platinum Nanoparticle Loading of Boron Nitride Aerogel and Its Use as a Novel Material for Low-Power Catalytic Gas Sensing

DOE PAGES

Harley-Trochimczyk, Anna; Pham, Thang; Chang, Jiyoung; ...

2015-12-09

We report that a high-surface-area, highly crystalline boron nitride aerogel synthesized with nonhazardous reactants has been loaded with crystalline platinum nanoparticles to form a novel nanomaterial that exhibits many advantages for use in a catalytic gas sensing application. The platinum nanoparticle-loaded boron nitride aerogel integrated onto a microheater platform allows for calorimetric propane detection. The boron nitride aerogel exhibits thermal stability up to 900 °C and supports disperse platinum nanoparticles, with no sintering observed after 24 h of high-temperature testing. The high thermal conductivity and low density of the boron nitride aerogel result in an order of magnitude faster responsemore » and recovery times (<2 s) than reported on alumina support and allow for 10% duty cycling of the microheater with no loss in sensitivity. Lastly, the resulting 1.5 mW sensor power consumption is two orders of magnitude less than commercially available catalytic gas sensors and unlocks the potential for wireless, battery-powered catalytic gas sensing.« less

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

NASA Technical Reports Server (NTRS)

Udom, I.; Goswami, D. Y.; Ram, M. K.; Stefanakos, E. K.; Heep, A. F.; Kulis, M. J.; McNatt, J. S.; Jaworske, D. A.; Jones, C. A.

2013-01-01

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

Synthesis of carbon nanotubes over 3D cubical Co-KIT-6 and nickel decorated graphene by Hummer's method, its application as counter electrode in dye sensitive solar cell

NASA Astrophysics Data System (ADS)

Subramanian, Sunu; Pandurangan, Arumugam

2016-04-01

The challenges on carbon nanotubes and graphene are still the subject of many research works due to its unique properties. There are three main methods to synthesis carbon nanotubes in which chemical vapor deposition (CVD) method can use for large scale production. The principle of CVD is the decomposition of various hydrocarbons over transition metal supported catalyst. KIT-6 molecular sieve was used as a support to prepare cobalt catalyst for CVD method using metal impregnation method to produce cobalt loadings of 2, 4 and 6 wt%. The catalysts were characterized by XRD, FTIR &TEM. Carbon nanotubes (CNTs) synthesized on Co-KIT-6 was also characterized by XRD, TGA, SEM & Raman spectra. Graphene was synthesized by Hummers method, which is the most common method for preparing graphene oxide. Graphene oxide was prepared by oxidation of graphite using some oxidizing agents like sulphuric acid, sodium nitrate and potassium permanganate. This graphene oxide is further treated with hydrazine solution to convert it into chemically converted graphene and also decorated with nickel metal and characterized. Hummer's method is important for large scale production of graphene. Both Graphene and carbon nanotubes are used in different fields due to its unique properties. Both Graphene and carbon nanotubes are fabricated in counter electrode of Dye sensitized solar cells (DSSC). By cyclic voltammetry study, it confirms that both materials are good and efficient to replace platinum in the DSSC.

Progress in catalytic ignition fabrication, modeling and infrastructure : (part 1) catalytic ignition studies.

DOT National Transportation Integrated Search

2014-02-01

Platinum has been recognized as a viable combustion catalyst for use in transportation : engines operating at fuel-lean conditions. Its change in electrical resistance with temperature : has been used to measure light-off temperatures and rates of he...

Diffusion and Surface Reaction in Heterogeneous Catalysis

ERIC Educational Resources Information Center

Baiker, A.; Richarz, W.

1978-01-01

Ethylene hydrogenation on a platinum catalyst, electrolytically applied to a tube wall, is a good system for the study of the interactions between diffusion and surface reaction in heterogeneous catalysis. Theoretical background, apparatus, procedure, and student performance of this experiment are discussed. (BB)

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

NASA Astrophysics Data System (ADS)

Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

2014-11-01

High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Narayan, Sri R. (Inventor); Hays, Charles C. (Inventor)

2015-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Nanostructured Platinum Alloys for Use as Catalyst Materials

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor); Narayan, Sri R. (Inventor)

2013-01-01

A series of binary and ternary Pt-alloys, that promote the important reactions for catalysis at an alloy surface; oxygen reduction, hydrogen oxidation, and hydrogen and oxygen evolution. The first two of these reactions are essential when applying the alloy for use in a PEMFC.

Fuel Cell Performance Implications of Membrane Electrode Assembly Fabrication with Platinum-Nickel Nanowire Catalysts

DOE PAGES

Mauger, Scott A.; Neyerlin, K. C.; Alia, Shaun M.; ...

2018-03-13

Platinum-nickel nanowire (PtNiNW) catalysts have shown exceptionally high oxygen reduction mass activity in rotating disk electrode measurements. However, the ability to successfully incorporate PtNiNWs into high performance membrane electrode assemblies (MEAs) has been challenging due to their size, shape, density, dispersion characteristics, and corrosion-susceptible nickel core. We have investigated the impact of specific processing steps and electrode composition on observed fuel cell performance and electrochemical properties in order to optimize performance. We have found that nickel ion contamination is a major concern for PtNiNWs that can be addressed through ion exchange in fabricated/tested MEAs or by acid leaching of catalystmore » materials prior to MEA incorporation, with the latter being the more successful method. Additionally, decreased ionomer incorporation has led to the highest performance demonstrating 238 mA/mg Pt (0.9 V IR-free) for PtNiNWs (pre-leached to 80 wt% Pt) with 9 wt% ionomer incorporation.« less

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

PubMed

Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

2018-01-22

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

NASA Astrophysics Data System (ADS)

Maksoed, Wh-

2016-11-01

Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (<<1 %/KwH). "The oceans contain enough deuterium to satisfy the Earth's energy needs for many millions of year" to keep "maria"/Latin name of seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy

PubMed Central

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-01-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER. PMID:27034988

l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

PubMed

Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

2017-10-15

In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Fuel Cell Performance Implications of Membrane Electrode Assembly Fabrication with Platinum-Nickel Nanowire Catalysts

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

Mauger, Scott A.; Neyerlin, K. C.; Alia, Shaun M.

Platinum-nickel nanowire (PtNiNW) catalysts have shown exceptionally high oxygen reduction mass activity in rotating disk electrode measurements. However, the ability to successfully incorporate PtNiNWs into high performance membrane electrode assemblies (MEAs) has been challenging due to their size, shape, density, dispersion characteristics, and corrosion-susceptible nickel core. We have investigated the impact of specific processing steps and electrode composition on observed fuel cell performance and electrochemical properties in order to optimize performance. We have found that nickel ion contamination is a major concern for PtNiNWs that can be addressed through ion exchange in fabricated/tested MEAs or by acid leaching of catalystmore » materials prior to MEA incorporation, with the latter being the more successful method. Additionally, decreased ionomer incorporation has led to the highest performance demonstrating 238 mA/mg Pt (0.9 V IR-free) for PtNiNWs (pre-leached to 80 wt% Pt) with 9 wt% ionomer incorporation.« less

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

PubMed

Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

2016-03-01

Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

DOE PAGES

Chen, Chen; Kang, Yijin; Huo, Ziyang; ...

2014-02-27

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi 3 polyhedra, transforms in solution by interior erosion into Pt 3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi 3 polyhedra are maintained in the final Pt 3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skinmore » structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt 3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.« less

Platinum and rhenium extraction from a spent refinery catalyst using Bacillus megaterium as a cyanogenic bacterium: statistical modeling and process optimization.

PubMed

Motaghed, M; Mousavi, S M; Rastegar, S O; Shojaosadati, S A

2014-11-01

The present study evaluated the potential of Bacillus megaterium as a cyanogenic bacterium to produce cyanide for solubilization of platinum and rhenium from a spent refinery catalyst. Response surface methodology was applied to study the effects and interaction between two main effective parameters including initial glycine concentration and pulp density. Maximum Pt and Re recovery was obtained 15.7% and 98%, respectively, under optimum conditions of 12.8 g/l initial glycine concentration and 4% (w/v) pulp density after 7 days. Increasing the free cyanide concentration to 3.6 mg/l, varying the pH from 6.7 to 9, and increasing the dissolved oxygen from 2 to 5mg/l demonstrated the growth characteristics of B. megaterium during bioleaching process. The modified shrinking core model was used to determine the rate limiting step of the process. It was found that diffusion through the product layer is the rate controlling step. Copyright © 2014 Elsevier Ltd. All rights reserved.

Probing Interaction Between Platinum Group Metal (PGM) and Non-PGM Support Through Surface Characterization and Device Performance

NASA Astrophysics Data System (ADS)

Saha, Shibely

High cost and limited abundance of Platinum (Pt) have hindered effective commercialization of Proton Exchange Membrane Fuel Cell and Electrolyzer. Efforts have been undertaken to reduce precious group metal (PGM) requirement for these devices without compromising the activity of the catalyst by using transition metal carbides (TMC) as non-PGM support thanks to their similar electronic and geometric structures as Pt. In this work Mo2C was selected as non-PGM support and Pt was used as the PGM of interest. We hypothesize that the hollow nanotube morphology of Mo2C support combined with Pt nano particles deposited on it via atomic layer deposition (ALD) technique would allow increased interaction between them which may increase the activity of Pt and Mo2C as well as maximize the Pt active surface area. Specifically, a rotary ALD equipment was used to grow Pt particles from atomic level to 2--3 nanometers by simply adjusting number of ALD cycles in order to probe the interaction between the deposited Pt nanoparticles and Mo2C nanotube support. Interaction between the Pt and Mo2 C was analyzed via surface characterization and electrochemical characterization. Interaction between Pt and Mo2C arises due to the lattice mismatch between Pt and Mo2C as well as electron migration between them. Lattice spacing analysis using high resolution transmission electron microscopy (HRTEM) images, combined with Pt binding energy shift in XPS results, clearly showed strong bonding between Pt nanoparticles and the Mo2C nanotube support in all the resultant Pt/Mo2C samples. We postulate that this strong interaction is responsible for the significantly enhanced durability observed in our constant potential electrolysis (CPE) and accelerated degradation testing (ADT). Of the three samples from different ALD cycles (15, 50 and 100), Mo2C nanotubes modified by 50 (1.07 wt% Pt loading) and 100 cycles (4.4 wt% Pt) of Pt deposition, showed higher HER and HOR activity per Pt mass than commercial 20% Pt supported on carbon black. Finally, we report the systematic investigation of the feasibility of this nanoscale Pt/Mo 2C catalyst in a practical device setting. The ORR activity of 100 Pt/Mo 2C was determined using the catalyst in the cathode of the MEA. Performance of this catalyst led the Pt utilization to be 10.35kWgPt-1 outperforming the target set by DOE for 2017--2020 by 30%.

Alloy formation and metal oxide segregation on Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

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

Wagstaff, N.; Prins, R.

1979-10-15

Catalysts resembling reforming catalysts were prepared to contain finely dispersed 0.75% Pt, 0.7% Re, or 0.35% Pt plus 0.1-2% Re on chlorided ..gamma..-alumina. The catalysts were dried in an oxidizing atmosphere and studied by temperature-programed reduction. Up to a Re/Pt ratio of 0.6:1 the metals were completely reduced in hydrogen below 255/sup 0/C, i.e., the platinum catalyzed rhenium reduction. A small amount of added water (< 50 ppm) also promoted rhenium reduction. Segregation of the metals occurred in oxygen above 200/sup 0/C, but at 100/sup 0/C, the rate of segregation was slow. These results suggested that under reforming conditions, Pt-Remore » catalysts are completely reduced bimetallic clusters. The mechanisms of reduction, cluster formation, and oxidative segregation are discussed.« less

Dehydration of glycerol over niobia-supported silicotungstic acid catalysts.

PubMed

Lee, Young Yi; Ok, Hye Jeong; Moon, Dong Ju; Kim, Jong Ho; Park, Nam Cook; Kim, Young Chul

2013-01-01

Liquid-phase dehydration of glycerol to acrolein over nanosized niobia-supported silicotungstic acid catalysts was performed to investigate the effect of the silicotungstic acid loading on the catalytic performance of the catalysts. The catalysts were prepared by following an impregnation method with different HSiW loadings in the range of 10-50 wt%. The prepared catalysts were characterized by N2 physisorption, XRD, FT-IR, TPD of ammonia, and TGA. Dehydration of glycerol was conducted in an autoclave reactor under the conditions of controlled reaction temperatures under corresponding pressure. Increasing HSiW loading rapidly increased the acidity of HSiW/Nb205 catalyst and rate of glycerol conversion, but acrolein selectivity decreased due to enhanced deactivation of the catalyst by carbon deposit. Consequently, it was confirmed that catalytic activity for the dehydration of glycerol to acrolein was dependant on the acidity of catalyst and can be controlled by HSiW loading.

Enhanced electrocatalytic activity and stability of monodisperse Pt nanocomposites for direct methanol fuel cells.

PubMed

Eris, Sinan; Daşdelen, Zeynep; Sen, Fatih

2018-03-01

Direct methanol fuel cells (DMFCs) are one of the most important fuel cells operating at low temperature using methanol as fuel and they need very efficient catalysts to activate the methanol. Generally, the most efficient fuel cell catalysts are platinum-based nanoparticles that can be used by different supporting materials such as different as prepared and functionalized carbon derivatives. For this purpose, herein, the carbon black has been mainly functionalized with an acidification process in order to increase the electrical conductivity and heterogeneous electron transfer rate of supporting materials. After functionalization of carbon black (f-CB), platinum salt (PtCl 4 ) was stabilized with propylamine (PA) in the presence of ethylene glycol (EG) and f-CB by microwave synthesis method. XPS, XRD, TEM and Raman Spectroscopy techniques were used to determine the morphology of the prepared catalyst. The results showed that the prepared nanocatalyst has face-centered cubic (fcc) structure and uniformly distribution on supporting material. Besides, chronoamperometry (CA) and cyclic voltammetry (CV) techniques were used to determine the electrochemical activity of functionalized carbon black supported Pt NPs (Pt/f-CB) towards methanol. From the results obtained from the CV and CA, it was found that the activity of the Pt/f-CB NPs (50 mA/cm 2 ) was almost 4-5 times higher than that of the Pt/CB NPs and commercial available Pt/C catalyst (ETEK). Copyright © 2017 Elsevier Inc. All rights reserved.

Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

PubMed

Yuan, Heyang; He, Zhen

2017-07-01

Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioinspired Electrocatalysis of Oxygen Reduction Reaction in Fuel Cells Using Molecular Catalysts.

PubMed

Zion, Noam; Friedman, Ariel; Levy, Naomi; Elbaz, Lior

2018-04-23

One of the most important chemical reactions for renewable energy technologies such as fuel cells and metal-air batteries today is oxygen reduction. Due to the relatively sluggish reaction kinetics, catalysts are necessary to generate high power output. The most common catalyst for this reaction is platinum, but its scarcity and derived high price have raised the search for abundant nonprecious metal catalysts. Inspired from enzymatic processes which are known to catalyze oxygen reduction reaction efficiently, employing transition metal complexes as their catalytic centers, many are working on the development of bioinspired and biomimetic catalysts of this class. This research news article gives a glimpse of the recent progress on the development of bioinspired molecular catalyst for oxygen reduction, highlighting the importance of the molecular structure of the catalysts, from advancements in porphyrins and phthalocyanines to the most recent work on corroles, and 3D networks such as metal-organic frameworks and polymeric networks, all with nonpyrolyzed, well-defined molecular catalysts for oxygen reduction reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of liposomal technologies for delivery of platinum analogs in oncology

PubMed Central

Liu, Demin; He, Chunbai; Wang, Andrew Z; Lin, Wenbin

2013-01-01

Platinum-based chemotherapy, such as cisplatin, oxaliplatin, and carboplatin, is one of the most widely utilized classes of cancer therapeutics. While highly effective, the clinical applications of platinum-based drugs are limited by their toxicity profiles as well as suboptimal pharmacokinetic properties. Therefore, one of the key research areas in oncology has been to develop novel platinum analog drugs and engineer new platinum drug formulations to improve the therapeutic ratio further. Such efforts have led to the development of platinum analogs including nedaplatin, heptaplatin, and lobaplatin. Moreover, reformulating platinum drugs using liposomes has resulted in the development of L-NDPP (Aroplatin™), SPI-77, Lipoplatin™, Lipoxal™, and LiPlaCis®. Liposomes possess several attractive biological activities, including biocompatibility, high drug loading, and improved pharmacokinetics, that are well suited for platinum drug delivery. In this review, we discuss the various platinum drugs and their delivery using liposome-based drug delivery vehicles. We compare and contrast the different liposome platforms as well as speculate on the future of platinum drug delivery research. PMID:24023517

Synthesis of SWNT/Pt nanocomposites for their effective role in hydrogen storage applications

NASA Astrophysics Data System (ADS)

Sharma, Anshu; Andreas, Rossos; Nehra, S. P.

2018-05-01

Single Wall Carbon Nanotubes (SWNTs) decorated with platinum were synthesized for hydrogen storage applications. Platinum was deposited on the nanotubes using hexachloroplatinic acid (H2PtCl6.6H2O) as a precursor. Commercial SWNTs were also used to compare the results. The obtained SWNTs/Pt nanocomposite was characterized by various techniques such as powder X-ray diffractrometry (XRD), Raman Spectroscopy and Scanning Electron Microscopy (SEM). Furthermore, in the case of SWNTs/Pt, Pt nanoparticles are found to be uniformly dispersed and bound to the SWNTs acting like a single atom catalyst.

Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.

PubMed

Andersen, Shuang Ma; Skou, Eivind

2014-10-08

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

The effect of platinum precursor concentrations on chlorine sensing characteristics of platinum nanoparticles-loaded single walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Choi, Sun-Woo; Byun, Young Tae

2018-03-01

The correlation between platinum (Pt) functionalization and chlorine (Cl2) sensing capability in single-walled carbon nanotubes (SWCNTs) was investigated. Utilizing a photoreduction technique via ultraviolet (UV) irradiation, the Pt nanoparticles (NPs) with various diameters of 7-80 nm, which were controlled by Pt precursor concentrations, were successfully functionalized on the sidewalls of SWCNTs. The discrete Pt NP-loaded SWCNTs exhibited significantly enhanced response value (-(ΔR/R0) × 100 = 33.8%) for 1 ppm Cl2 at room temperature (25 °C) compared with that (no response) of pure SWCNTs. On the other hand, in case of continuous Pt NP-loaded SWCNTs, Cl2 sensing capabilities were significantly degraded. The Cl2 sensing capabilities of fabricated sensors tended to correlate with geometric configurations of the catalytic Pt NPs on the sidewalls of SWCNTs, due to differences in the electron pathway.

Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

NASA Astrophysics Data System (ADS)

Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

2018-01-01

Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

Direct alcohol fuel cells: Increasing platinum performance by modification with sp-group metals

NASA Astrophysics Data System (ADS)

Figueiredo, Marta C.; Sorsa, Olli; Doan, Nguyet; Pohjalainen, Elina; Hildebrand, Helga; Schmuki, Patrik; Wilson, Benjamin P.; Kallio, Tanja

2015-02-01

By using sp group metals as modifiers, the catalytic properties of Pt can be improved toward alcohols oxidation. In this work we report the performance increase of direct alcohol fuel cells (DAFC) fuelled with ethanol or 2-propanol with platinum based anode electrodes modified with Bi and Sb adatoms. For example, by simply adding Sb to the Pt/C based anode ink during membrane electrode assembly fabrication of a direct ethanol fuel cell (DEFC) its performance is improved three-fold, with more than 100 mV increase in the open circuit potential. For the fuel cell fuelled with 2-propanol high power densities are obtained at very high potentials with these catalyst materials suggesting a great improvement for practical applications. Particularly in the case of Pt/C-Bi, the improvement is such that within 0.6 V (from 0.7 to 0.1 V) the power densities are between 7 and 9 mW/cm2. The results obtained with these catalysts are in the same range as those obtained with other bimetallic catalysts comprising of PtRu and PtSn, which are currently considered to be the best for these type of fuel cells and that are obtained by more complicated (and consequently more expensive) methods.

Cathode catalysts for primary phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

1981-01-01

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Highly sensitive silicon microreactor for catalyst testing

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

Henriksen, Toke R.; Hansen, Ole; Department of Physics, Danish National Research Foundation's Center for Individual Nanoparticle Functionality

2009-12-15

A novel microfabricated chemical reactor for highly sensitive measurements of catalytic activity and surface kinetics is presented. The reactor is fabricated in a silicon chip and is intended for gas-phase reactions at pressures ranging from 0.1 to 5.0 bar. A high sensitivity is obtained by directing the entire gas flow through the catalyst bed to a mass spectrometer, thus ensuring that nearly all reaction products are present in the analyzed gas flow. Although the device can be employed for testing a wide range of catalysts, the primary aim of the design is to allow characterization of model catalysts which canmore » only be obtained in small quantities. Such measurements are of significant fundamental interest but are challenging because of the low surface areas involved. The relationship between the reaction zone gas flow and the pressure in the reaction zone is investigated experimentally. A corresponding theoretical model is presented, and the gas flow through an on-chip flow-limiting capillary is predicted to be in the intermediate regime. The experimental data for the gas flow are found to be in good agreement with the theoretical model. At typical experimental conditions, the total gas flow through the reaction zone is around 3x10{sup 14} molecules s{sup -1}, corresponding to a gas residence time in the reaction zone of about 11 s. To demonstrate the operation of the microreactor, CO oxidation on low-area platinum thin film circles is employed as a test reaction. Using temperature ramping, it is found that platinum catalysts with areas as small as 15 {mu}m{sup 2} are conveniently characterized with the device.« less

Aromatization of n-hexane by platinum-containing molecular sieves. 2. n-Hexane reactivity

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

Mielczarski, E.; Suk Bong Hong; Davis, M.E.

Pt/KL, Pt/BaKL, Pt/KBaKL, Pt/NaY, Pt/CsNaY, Pt/NaFAU(C), Pt/hex, Pt/SSZ-24, Pt/silica, and Pt/carbon were tested as catalysts for the aromatization of n-hexane at 460-510 C and atmospheric total pressure in order to study the influence of Pt cluster size and support acidity/basicity, microstructure, and chemical composition on activity and selectivity. Analysis of the catalytic and NH{sub 3} temperature-programmed desorption results from Pt/KL, Pt/BaKL, and Pt/KBaKL reveals that the presence of any acidity increases hydrogenolysis at the expense of benzene production. In addition, no increase in aromatization selectivity is observed by the addition of base sites to a Pt/zeolite catalyst, confirming that aromatizationmore » of n-hexane over Pt clusters on nonacidic carriers is monofunctional. High selectivity to benzene over most of the zeolite samples demonstrates that support microstructure does not contribute directly to the aromatization selectivity over Pt catalysts. High selectivity to benzene is observed for a Pt/carbon catalyst suggesting that a zeolitic support is not necessary for good performance. In fact, similar reactivity is obtained from microporous (Pt/SSZ-24) and nonmicroporous (Pt/silica) silica supported platinum catalysts with similar H/Pt values. A clear trend of increasing benzene selectivity with decreasing Pt cluster size is found. These observations suggest that the exceptional reactivity of Pt/KL for the aromatization of n-hexane results from the lack of any acidity in the support and the ability of zeolite L to stabilize the formation of extremely small Pt clusters.« less

Stable, Ultra-Low Residence Time Partial Oxidation

DOEpatents

Schmidt, Lanny D.; Hickman, Daniel A.

1997-07-15

A process for the catalytic partial oxidation of methane in gas phase at very short residence time (800,000 to 12,000,000 hr.sup.-1) by contacting a gas stream containing methane and oxygen with a metal supported catalyst, such as platinum deposited on a ceramic monolith.

Effect of Nitrogen Post-Doping on a Commercial Platinum-Ruthenium/Carbon Anode Catalyst

DTIC Science & Technology

2014-02-15

polymer electrolyte membrane fuel cells ( PEMFCs ) closer to commercial viability. However, further improvements in fuel cell durability, particularly...have recently led to significant improvements [3e5]. The genesis of interest in modified carbon support materials for PEMFCs and DMFCs originated in

Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

2015-08-01

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s-1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

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

Michling, R.; Braun, A.; Cristescu, I.

2015-03-15

Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during themore » H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)« less

Advantages of electrodes with dendrimer-protected platinum nanoparticles and carbon nanotubes for electrochemical methanol oxidation.

PubMed

Siriviriyanun, Ampornphan; Imae, Toyoko

2013-04-14

Electrochemical sensors consisting of electrodes loaded with carbon nanotubes and Pt nanoparticles (PtNPs) protected by dendrimers have been developed using a facile method to fabricate them on two types of disposable electrochemical printed chips with a screen-printed circular gold or a screen-printed circular glassy carbon working electrode. The electrochemical performance of these sensors in the oxidation of methanol was investigated by cyclic voltammetry. It was revealed that such sensors possess stable durability and high electrocatalytic activity: the potential and the current density of an anodic peak in the oxidation of methanol increased with increasing content of PtNPs on the electrodes, indicating the promotion of electrocatalytic activity in relation to the amount of catalyst. The low anodic potential suggests the easy electrochemical reaction, and the high catalyst tolerance supports the almost complete oxidation of methanol to carbon dioxide. The significant performance of these sensors in the detection of methanol oxidation comes from the high electrocatalytic ability of PtNPs, excellent energy transfer of carbon nanotubes and the remarkable ability of dendrimers to act as binders. Thus these systems are effective for a wide range of applications as chemical, biomedical, energy and environmental sensors and as units of direct methanol fuel cells.

Hydrogenotitanates nanotubes supported platinum anode for direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Abida, Bochra; Chirchi, Lotfi; Baranton, Stève; Napporn, Teko Wilhelmin; Morais, Cláudia; Léger, Jean-Michel; Ghorbel, Abdelhamid

2013-11-01

Hydrogenotitanates nanotubes (HTNs) are prepared from TiO2 powder via hydrothermal processing in 11.25 M NaOH aq. The reaction temperature is 130 °C for 20 h. Afterward a heat treatment is done during 2 h at 500 °C in air, to obtain calcined HTNs (HTNs-cal). The structural change on the molecular TiO2 during the hydrothermal treatment is investigated in detail by various analytic techniques such as XRD and TEM, which reveal that the crystal structure of the HTNs materials is similar to that of H2Ti2O5·H2O nanotubes with 160 nm in length and 10 nm in diameter. Nitrogen adsorption-desorption isotherms indicate that synthesized solids are mesoporous materials with a multiwalled nanotubular structure and high specific surface area. Platinum nanoparticles are deposited on the HTNs by the impregnation method for a total noble metal loading of 10 wt%. The electrocatalytic activity of these electrocatalysts is evaluated by cyclic voltammetry in acid medium. Typical CO stripping voltammetry in acidic solutions is investigated. The results demonstrate that the HTNs can greatly enhance the catalytic activity of Pt for methanol oxidation. The CO stripping test shows that the Pt/HTNs can shift the CO oxidation potential to lower direction than Pt/C (XC72) and Pt/HTNs-cal catalysts.

Elucidating the alkaline oxygen evolution reaction mechanism on platinum

DOE PAGES

Favaro, M.; Valero-Vidal, C.; Eichhorn, J.; ...

2017-03-07

Understanding the interplay between surface chemistry, electronic structure, and reaction mechanism of the catalyst at the electrified solid/liquid interface will enable the design of more efficient materials systems for sustainable energy production. The substantial progress in operando characterization, particularly using synchrotron based X-ray spectroscopies, provides the unprecedented opportunity to uncover surface chemical and structural transformations under various (electro)chemical reaction environments. In this work, we study a polycrystalline platinum surface under oxygen evolution conditions in an alkaline electrolyte by means of ambient pressure X-ray photoelectron spectroscopy performed at the electrified solid/liquid interface. We elucidate previously inaccessible aspects of the surface chemistrymore » and structure as a function of the applied potential, allowing us to propose a reaction mechanism for oxygen evolution on a platinum electrode in alkaline solutions.« less

Supported polyethylene glycol stabilized platinum nanoparticles for chemoselective hydrogenation of halonitrobenzenes in scCO2.

PubMed

Cheng, Haiyang; Meng, Xiangchun; He, Limin; Lin, Weiwei; Zhao, Fengyu

2014-02-01

Polyethylene glycol stabilized platinum nanoparticles were immobilized on solid supports such as γ-Al2O3, SBA-15, TiO2 and active carbon, forming supported polyethylene glycol stabilized platinum nanoparticles (SPPNs). In the hydrogenation of p-chloronitrobenzene (p-CNB) in supercritical carbon dioxide (scCO2), the SPPN showed high selectivity to p-chloroaniline (>99.3%) in the whole range of conversion. Such high selectivity to corresponding haloanilines (HANs) (>99.1%) was also obtained in the hydrogenation of o-CNB, m-CNB, 2-chloro-6-nitrotoluene, p-bromonitrobenzene and m-iodonitrobenzene. The dehalogenation and the accumulation of intermediates were fully inhibited simultaneously in scCO2. The SPPN catalysts could be reused several times without loss of high selectivity in present reaction system. Copyright © 2013 Elsevier Inc. All rights reserved.

Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

NASA Astrophysics Data System (ADS)

Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

2018-03-01

The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

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

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Microbial fuel cells with highly active aerobic biocathodes

NASA Astrophysics Data System (ADS)

Milner, Edward M.; Popescu, Dorin; Curtis, Tom; Head, Ian M.; Scott, Keith; Yu, Eileen H.

2016-08-01

Microbial fuel cells (MFCs), which convert organic waste to electricity, could be used to make the wastewater infrastructure more energy efficient and sustainable. However, platinum and other non-platinum chemical catalysts used for the oxygen reduction reaction (ORR) at the cathode of MFCs are unsustainable due to their high cost and long-term degradation. Aerobic biocathodes, which use microorganisms as the biocatalysts for cathode ORR, are a good alternative to chemical catalysts. In the current work, high-performing aerobic biocathodes with an onset potential for the ORR of +0.4 V vs. Ag/AgCl were enriched from activated sludge in electrochemical half-cells poised at -0.1 and + 0.2 V vs. Ag/AgCl. Gammaproteobacteria, distantly related to any known cultivated gammaproteobacterial lineage, were identified as dominant in these working electrode biofilms (23.3-44.3% of reads in 16S rRNA gene Ion Torrent libraries), and were in very low abundance in non-polarised control working electrode biofilms (0.5-0.7%). These Gammaproteobacteria were therefore most likely responsible for the high activity of biologically catalysed ORR. In MFC tests, a high-performing aerobic biocathode increased peak power 9-fold from 7 to 62 μW cm-2 in comparison to an unmodified carbon cathode, which was similar to peak power with a platinum-doped cathode at 70 μW cm-2.

New iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1988-03-31

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a cabon monoxide containing gas to a product which could substitute for high density polyethylene.

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

PubMed

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-07

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.

DETERMINATION OF GOLD, PLATINUM AND PALLADIUM IN BELGIAN CONGO ORES

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

Crowther, A.B. et al.

1955-01-31

A survey of analytical methods for determination of gold, platinum, and palladium in urauium ore is presented. A fire assay method to obtain a silver load in which the other elements are determined appears feasible. (J.R.D.)

A novel binary Pt 3Te x/C nanocatalyst for ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Huang, Meihua; Wang, Fei; Li, Lirong; Guo, Yonglang

The Pt 3Te x/C nanocatalyst was prepared and its catalytic performance for ethanol oxidation was investigated for the first time. The Pt 3Te/C nanoparticles were characterized by an X-ray diffractometer (XRD), transmission electron microscope (TEM) and energy dispersive X-ray spectroscopy equipped with TEM (TEM-EDX). The Pt 3Te/C catalyst has a typical fcc structure of platinum alloys with the presence of Te. Its particle size is about 2.8 nm. Among the synthesized catalysts with different atomic ratios, the Pt 3Te/C catalyst has the highest anodic peak current density. The cyclic voltammograms (CV) show that the anodic peak current density for the Pt 3Te/C, commercial PtRu/C and Pt/C catalysts reaches 1002, 832 and 533 A g -1, respectively. On the current-time curve, the anodic current on the Pt 3Te/C catalyst was higher than those for the catalysts reported. So, these findings show that the Pt 3Te/C catalyst has uniform nanoparticles and the best activity among the synthesized catalysts, and it is better than commercial PtRu/C and Pt/C catalysts for ethanol oxidation at room temperature.

Catalysts as sensors--a promising novel approach in automotive exhaust gas aftertreatment.

PubMed

Moos, Ralf

2010-01-01

Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NO(x) traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NO(x)-loading of lean NO(x) traps, and the soot loading of Diesel particulate filters.

Catalysts as Sensors—A Promising Novel Approach in Automotive Exhaust Gas Aftertreatment

PubMed Central

Moos, Ralf

2010-01-01

Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NOx traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NOx-loading of lean NOx traps, and the soot loading of Diesel particulate filters. PMID:22163575

Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

DOEpatents

Long, Jeffrey R.; Chang, Christopher J.; Karunadasa, Hemamala I.; Majda, Marcin

2016-11-22

New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS.sub.2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W.sub.2)MoS.sub.2].sup.x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H.sub.2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H.sub.2 per mole of catalyst.

A surfactant free preparation of ultradispersed surface-clean Pt catalyst with highly stable electrocatalytic performance

NASA Astrophysics Data System (ADS)

Tao, Lu; Zhao, Yueping; Zhao, Yufeng; Huang, Shifei; Yang, Yunxia; Tong, Qi; Gao, Faming

2018-02-01

High efficiency platinum-based catalyst demands the ultrafine size and well dispersion of Pt nanoparticles (NPs), with clean surface and strong interactions between the supports. In this work, we demonstrate a simple strategy for the preparation of ultra-dispersed surface-clean Pt catalyst with high stability, in which the Pt nanoparticles (NPs) with 1.8 ± 0.6 nm in size are anchored tightly on a 3D hierarchical porous graphitized carbon (3D-HPG) through galvanic replacement reaction. The as-obtained catalyst can undergo 2000 voltage cycles with negligible activity decay and no apparent structure and size changes for MOR during the durability test, and its mass activity for ORR only reduce 18.3% after 5000 cycles. The excellent performance is attributed to strong anchoring effect between carbon support and Pt nanoparticles.

Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

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

Long, Jeffrey R.; Chang, Christopher J.; Karunadasa, Hemamala I.

New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS.sub.2, a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W.sub.2)MoS.sub.2].sup.x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H.sub.2 per mole catalyst per second, with a turnover number (overmore » a 20 hour period) of at least 19,000,000 moles H.sub.2 per mole of catalyst.« less

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Laser Ablation Increases PEM/Catalyst Interfacial Area

NASA Technical Reports Server (NTRS)

Whitacre, Jay; Yalisove, Steve

2009-01-01

An investigational method of improving the performance of a fuel cell that contains a polymer-electrolyte membrane (PEM) is based on the concept of roughening the surface of the PEM, prior to deposition of a thin layer of catalyst, in order to increase the PEM/catalyst interfacial area and thereby increase the degree of utilization of the catalyst. The roughening is done by means of laser ablation under carefully controlled conditions. Next, the roughened membrane surface is coated with the thin layer of catalyst (which is typically platinum), then sandwiched between two electrode/catalyst structures to form a membrane/ele c t - rode assembly. The feasibility of the roughening technique was demonstrated in experiments in which proton-conducting membranes made of a perfluorosulfonic acid-based hydrophilic, protonconducting polymer were ablated by use of femtosecond laser pulses. It was found that when proper combinations of the pulse intensity, pulse-repetition rate, and number of repetitions was chosen, the initially flat, smooth membrane surfaces became roughened to such an extent as to be converted to networks of nodules interconnected by filaments (see Figure 1). In further experiments, electrochemical impedance spectroscopy (EIS) was performed on a pristine (smooth) membrane and on two laser-roughened membranes after the membranes were coated with platinum on both sides. Some preliminary EIS data were interpreted as showing that notwithstanding the potential for laser-induced damage, the bulk conductivities of the membranes were not diminished in the roughening process. Other preliminary EIS data (see Figure 2) were interpreted as signifying that the surface areas of the laser-roughened membranes were significantly greater than those of the smooth membrane. Moreover, elemental analyses showed that the sulfur-containing molecular groups necessary for proton conduction remained intact, even near the laser-roughened surfaces. These preliminary results can be taken as indications that laser-roughened PEMs should function well in fuel cells and, in particular, should exhibit current and power densities greater than those attainable by use of smooth membranes.

TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

NASA Astrophysics Data System (ADS)

Naeem, Rabia; Ahmed, Riaz; Shahid Ansari, Muhammad

2014-06-01

Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO2, Pt/TiO2-C, Pt/Al2O3 and Pt/Al2O3-C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO2-C and Pt/Al2O3-C nanocomposite catalysts was much higher than the Pt/TiO2 and Pt/Al2O3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO2-C was much higher than mass activity of Pt/Al2O3-C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably.

Redox competition mode of scanning electrochemical microscopy (RC-SECM) for visualisation of local catalytic activity.

PubMed

Eckhard, Kathrin; Chen, Xingxing; Turcu, Florin; Schuhmann, Wolfgang

2006-12-07

In order to locally analyse catalytic activity on modified surfaces a transient redox competition mode of scanning electrochemical microscopy (SECM) has been developed. In a bi-potentiostatic experiment the SECM tip competes with the sample for the very same analyte. This leads to a current decrease at the SECM tip, if it is positioned in close proximity to an active catalyst site on the surface. Specifically, local catalytic activity of a Pt-catalyst modified sample with respect to the catalytic reduction of molecular oxygen was investigated. At higher local catalytic activity the local 02 partial pressure within the gap between accurately positioned SECM tip and sample is depleted, leading to a noticeable tip current decrease over active sites. A flexible software module has been implemented into the SECM to adapt the competition conditions by proper definition of tip and sample potentials. A potential pulse profile enables the localised electrochemically induced generation of molecular oxygen prior to the competition detection. The current decay curves are recorded over the entire duration of the applied reduction pulse. Hence, a time resolved processing of the acquired current values provides movies of the local oxygen concentration against x,y-position. The SECM redox competition mode was verified with a macroscopic Pt-disk electrode as a test sample to demonstrate the feasibility of the approach. Moreover, highly dispersed electro-deposited spots of gold and platinum on glassy carbon were visualised using the redox competition mode of SECM. Catalyst spots of different nature as well as activity inhomogeneities within one spot caused by local variations in Pt-loading were visualised successfully.

Microwave decoration of Pt nanoparticles on entangled 3D carbon nanotube architectures as PEM fuel cell cathode.

PubMed

Sherrell, Peter C; Zhang, Weimin; Zhao, Jie; Wallace, Gordon G; Chen, Jun; Minett, Andrew I

2012-07-01

Proton-exchange membrane fuel cells (PEMFCs) are expected to provide a complementary power supply to fossil fuels in the near future. The current reliance of fuel cells on platinum catalysts is undesirable. However, even the best-performing non-noble metal catalysts are not as efficient. To drive commercial viability of fuel cells forward in the short term, increased utilization of Pt catalysts is paramount. We have demonstrated improved power and energy densities in a single PEMFC using a designed cathode with a Pt loading of 0.1 mg cm(-2) on a mesoporous conductive entangled carbon nanotube (CNT)-based architecture. This electrode allows for rapid transfer of both fuel and waste to and from the electrode, respectively. Pt particles are bound tightly, directly to CNT sidewalls by a microwave-reduction technique, which provided increased charge transport at this interface. The Pt entangled CNT cathode, in combination with an E-TEK 0.2 mg cm(-2) anode, has a maximum power and energy density of 940 mW cm(-2) and 2700 mA cm(-2), respectively, and a power and energy density of 4.01 W mg(Pt)(-1) and 6.35 A mg(Pt)(-1) at 0.65 V. These power densities correspond to a specific mass activity of 0.81 g Pt per kW for the combined mass of both anode and cathode electrodes, approaching the current US Department of Energy efficiency target. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tin-Platinum catalysts interactions on titania and silica

NASA Astrophysics Data System (ADS)

Nava, N.; Del Angel, P.; Salmones, J.; Baggio-Saitovitch, E.; Santiago, P.

2007-09-01

Pt-Sn was supported on titania and silica, and the resulting interactions between the components in prepared samples and the resulting interactions between the components before and after treatment with hydrogen were characterized by Mössbauer spectroscopy, X-ray diffraction, Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and catalytic tests data. Results show the presence of Pt and SnO 2 after calcinations, and Pt 3Sn, PtSn and PtSn 3 after reduction. Rietveld analysis shows that some Ti 4+ are replaced by Sn 4+ atoms in the titania structure. Finally, HRTEM and the practically absence of activity observed confirms that metallic platinum is encapsulated.

[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

PubMed

Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

2013-06-01

Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

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

Tesfaye, Meron; MacDonald, Andrew N.; Dudenas, Peter J.

Local gas transport limitation attributed to the ionomer thin-film in the catalyst layer is a major deterrent to widespread commercialization of polymer-electrolyte fuel cells. So far functionality and limitations of these thin-films have been assumed identical in the anode and cathode. In this study, Nafion ionomer thin-films on platinum(Pt) support were exposed to H 2 and air as model schemes, mimicking anode and cathode catalyst layers. Findings indicate decreased swelling, increased densification of ionomer matrix, and increased humidity-induced aging rates in reducing environment, compared to oxidizing and inert environments. Observed phenomenon could be related to underlying Pt-gas interaction dictating Pt-ionomermore » behavior. Presented results could have significant implications about the disparate behavior of ionomer thin-film in anode and cathode catalyst layers.« less

Chemical and petrochemical industry

NASA Astrophysics Data System (ADS)

Staszak, Katarzyna

2018-03-01

The potential sources of various metals in chemical and petrochemical processes are discussed. Special emphasis is put on the catalysts used in the industry. Their main applications, compositions, especially metal contents are presented both for fresh and spent ones. The focus is on the main types of metals used in catalysts: the platinum-group metals, the rare-earth elements, and the variety of transition metals. The analysis suggested that chemical and petrochemical sectors can be considered as the secondary source of metals. Because the utilization of spent refinery catalysts for metal recovery is potentially viable, different methods were applied. The conventional approaches used in metal reclamation as hydrometallurgy and pyrometallurgy, as well as new methods include bioleaching, were described. Some industrial solutions for metal recovery from spent solution were also presented.

Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

NASA Technical Reports Server (NTRS)

Srinivasan, Vakula S.; Singer, Joseph

1986-01-01

This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

NASA Astrophysics Data System (ADS)

Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

2018-01-01

A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

Microstructural observation of fuel cell catalyst inks by Cryo-SEM and Cryo-TEM.

PubMed

Shimanuki, Junichi; Takahashi, Shinichi; Tohma, Hajime; Ohma, Atsushi; Ishihara, Ayumi; Ito, Yoshiko; Nishino, Yuri; Miyazawa, Atsuo

2017-06-01

In order to improve the electricity generation performance of fuel cell electric vehicles, it is necessary to optimize the microstructure of the catalyst layer of a polymer electrolyte fuel cell. The catalyst layer is formed by a wet coating process using catalyst inks. Therefore, it is very important to observe the microstructure of the catalyst ink. In this study, the morphology of carbon-supported platinum (Pt/C) particles in catalyst inks with a different solvent composition was investigated by cryogenic scanning electron microscopy (cryo-SEM). In addition, the morphology of the ionomer, which presumably influences the formation of agglomerated Pt/C particles in a catalyst ink, was investigated by cryogenic transmission electron microscopy (cryo-TEM). The results of a cryo-SEM observation revealed that the agglomerated Pt/C particles tended to become coarser with a higher 1-propanol (NPA) weight fraction. The results of a cryo-TEM observation indicated that the actual ionomer dispersion in a catalyst ink formed a network structure different from that of the ionomer in the solvent. © The Author 2017. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Hierarchical Nanoporous Gold-Platinum with Heterogeneous Interfaces for Methanol Electrooxidation

PubMed Central

Xiao, Shuang; Xiao, Fei; Hu, Yuan; Yuan, Songliu; Wang, Shuai; Qian, Lihua; Liu, Yunqi

2014-01-01

The electrocatalysts utilized as the prospective electrodes in fuel cells and high efficient energy conversion devices require both the interconnected channels for efficient electrolyte transportation and the superior catalytic activity with long service life. In this work, nanoporous gold with the rigid skeletons in three dimensions is partially decorated by porous platinum shell containing nanoscale interstitials, aiming to create the heterogeneous gold-platinum interfaces and facilitate the electrolyte transportation as well. In comparison with no catalytic activity of bare nanoporous gold, the catalytic activity of hierarchical nanoporous gold-platinum towards electrochemical oxidation of methanol increases with the loading level of platinum shells, resulting in the highest electrochemical area of 70.4 m2·g−1 after the normalization by the mass of platinum. Heterogeneous gold-platinum interfaces affect the tolerance of the absorbed intermediate species because of the oxidization by the oxygenated species absorbed on the gold surface and the enhanced ion transportation within the porous platinum shell. PMID:24621809

Favorable effect of in-situ generated platinum in the membrane on fuel cell membrane durability

NASA Astrophysics Data System (ADS)

Macauley, Natalia; Wong, Ka Hung; Watson, Mark; Kjeang, Erik

2015-12-01

The overall lifetime of polymer electrolyte fuel cells is often determined by the membrane durability. Platinum, which may dissolve from the catalyst layers during fuel cell operation and deposit in the membrane, has been shown to have both positive and negative effects on membrane stability. In the present work, we analyze what specific conditions are required in order to reach a favorable, membrane stabilizing effect with the controlled use of platinum in the membrane. Using accelerated membrane durability testing, field operated membrane samples, and electron microscopy, we demonstrate that a high platinum concentration with specific particle shapes and sizes is essential for enhanced membrane stability. Specifically, star shaped and dendritic particles with high particle density and high surface area are shown to be preferable. These particles contain high levels of Pt(111) and are expected to have high catalytic activity toward peroxide quenching and crossover gas consumption, thereby mitigating chemical membrane degradation. On the other hand, small, dispersed cubic particles are found to have no effect or the opposite, negative effect on membrane stability.

Epitaxial crystals of Bi₂Pt₂O₇ pyrochlore through the transformation of δ–Bi₂O₃ fluorite

DOE PAGES

Gutiérrez–Llorente, Araceli; Joress, Howie; Woll, Arthur; ...

2015-03-01

Bi₂Pt₂O₇ pyrochlore is thought to be one of the most promising oxide catalysts for application in fuel cell technology. Unfortunately, direct film growth of Bi₂Pt₂O₇ has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt⁴⁺. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial δ–Bi₂O₃ and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the nonuniform annealed films contain the first epitaxial crystals of Bi₂Pt₂O₇. We also visualized the pyrochlore structure by scanning transmission electron microscopy,more » and observed ordered cation vacancies in the epitaxial crystals formed in a bismuth-rich film but not in those formed in a platinum-rich film. The similarity between the δ–Bi₂O₃ and Bi₂Pt₂O₇ structures appears to facilitate the pyrochlore formation. These results provide the only route to date for the formation of epitaxial Bi₂Pt₂O₇.« less

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

Winter, Lea R.; Gomez, Elaine; Yan, Binhang

CO 2 hydrogenation over Fe-modified Ni/CeO 2 catalysts was investigated in a batch reactor using time-resolved in situ FTIR spectroscopy. Low loading of Ni/CeO 2 was associated with high selectivity to CO over CH 4, while higher Ni loading improved CO 2 hydrogenation activity with a reduced CO selectivity. X-ray absorption near-edge structure (XANES) analysis revealed Ni to be metallic for all catalysts including the CO-selective low loading 0.5% Ni catalyst, suggesting that the selectivity trend is due to structural rather than oxidation state effects. The loading amount of 1.5% Ni was selected for co-impregnation with Fe, based on themore » significant shift in product selectivity towards CH 4 for that loading amount, in order to shift the selectivity towards CO while maintaining high activity. Temperature programmed reduction (TPR) results indicated bimetallic interactions between Ni and Fe, and XANES analysis showed that about 70% of Fe in the bimetallic catalysts was oxidized. The Ni-Fe catalysts demonstrated improved selectivity towards CO without significantly compromising activity, coupling the high activity of Ni catalysts and the high CO selectivity of Fe. The general trends in Ni loading and bimetallic modification should guide efforts to develop non-precious metal catalysts for the selective production of CO by CO 2 hydrogenation.« less

Pt-free carbon-based fuel cell catalyst prepared from spherical polyimide for enhanced oxygen diffusion

PubMed Central

Nabae, Yuta; Nagata, Shinsuke; Hayakawa, Teruaki; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Isoda, Ayano; Matsunaga, Atsushi; Tanaka, Kazuhisa; Aoki, Tsutomu

2016-01-01

The development of a non-precious metal (NPM) fuel cell catalyst is extremely important to achieve globalization of polymer electrolyte fuel cells due to the cost and scarcity of platinum. Here, we report on a NPM cathode catalyst prepared by the pyrolysis of spherical polyimide nanoparticles that contain small amounts of Fe additive. 60 nm diameter Fe-containing polyimide nanoparticles were successfully synthesized by the precipitation polymerization of pyromellitic acid dianhydride and 1,3,5-tris(4-aminophenyl)benzene with Fe(acac)3 (acac = acetylacetonate) as an additive. The particles were subsequently carbonized by multistep pyrolysis to obtain the NPM catalyst while retaining the small particle size. The catalyst has good performance and promising durability for fuel cell applications. The fuel cell performance under a 0.2 MPa air atmosphere at 80 °C of 1.0 A cm−2 at 0.46 V is especially remarkable and better than that previously reported. PMID:26987682

Alloy formation and metal oxide segregation in Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

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

Wagstaff, N.; Prins, R.

1979-10-15

Temperature-programmed reduction has been used to characterize the finely dispersed metal compounds in a series of Pt-Re/..gamma..-Al/sub 2/O/sub 3/ catalysts. Strong evidence has been obtained that zerovalent Pt and Re atoms are in intimate contact with each other after catalyst reduction. The formation of bimetallic clusters supports the alloy explanation for the improved performance of this type of bimetallic reforming catalyst. Treatment of the reduced catalysts with oxygen above about 200/sup 0/C causes segregation of platinum and rhenium oxides. Adsorption of oxygen at temperatures up to 100/sup 0/C leaves the bimetallic clusters largely intact, but subsequent high-temperature treatment in themore » absence of extra oxygen leads to segregation of Pt and Re species. This suggests that in the presence of adsorbed oxygen the Pt-Re clusters are thermodynamically unstable, but that under mild conditions the rate of segregation is slow. 10 figures, 4 tables.« less

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

PubMed Central

Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

2013-01-01

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

DOE PAGES

Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

2016-12-28

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

Polyfunctional fluorosilicone composition, method for making, and use

NASA Technical Reports Server (NTRS)

Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor)

2002-01-01

A fluorosilicone crosslinker and method for making is provided. Reaction is effected between a silanol terminated polyfluoroalkyl silicone fluid and a polyalkoxysilane in the presence of a Platinum Group Metal catalyst. The fluorosilicone crosslinker can be used in combination with a silanol terminated fluoroalkyl substituted polydiorganosiloxane to formulate a neutral, condensation curable, solvent resistant sealant.

Stable catalyst layers for hydrogen permeable composite membranes

DOEpatents

Way, J. Douglas; Wolden, Colin A

2014-01-07

The present invention provides a hydrogen separation membrane based on nanoporous, composite metal carbide or metal sulfide coated membranes capable of high flux and permselectivity for hydrogen without platinum group metals. The present invention is capable of being operated over a broad temperature range, including at elevated temperatures, while maintaining hydrogen selectivity.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

1980-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Impregnated metal-polymeric functional beads

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Volksen, Willi (Inventor)

1978-01-01

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Platinum-paper micromotors: an urchin-like nanohybrid catalyst for green monopropellant bubble-thrusters.

PubMed

Claussen, Jonathan C; Daniele, Michael A; Geder, Jason; Pruessner, Marius; Mäkinen, Antti J; Melde, Brian J; Twigg, Mark; Verbarg, Jasenka M; Medintz, Igor L

2014-10-22

Platinum nanourchins supported on microfibrilated cellulose films (MFC) were fabricated and evaluated as hydrogen peroxide catalysts for small-scale, autonomous underwater vehicle (AUV) propulsion systems. The catalytic substrate was synthesized through the reduction of chloroplatinic acid to create a thick film of Pt coral-like microstructures coated with Pt urchin-like nanowires that are arrayed in three dimensions on a two-dimensional MFC film. This organic/inorganic nanohybrid displays high catalytic ability (reduced activation energy of 50-63% over conventional materials and 13-19% for similar Pt nanoparticle-based structures) during hydrogen peroxide (H2O2) decomposition as well as sufficient propulsive thrust (>0.5 N) from reagent grade H2O2 (30% w/w) fuel within a small underwater reaction vessel. The results demonstrate that these layered nanohybrid sheets are robust and catalytically effective for green, H2O2-based micro-AUV propulsion where the storage and handling of highly explosive, toxic fuels are prohibitive due to size-requirements, cost limitations, and close person-to-machine contact.

Bioinspired Molecular Co-Catalysts Bonded to a Silicon Photocathode for Solar Hydrogen Evolution

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

Hou, Yidong

2011-11-08

The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution earth-abundant alternatives are needed for large-scale use. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum. The incomplete cubane-like clusters (Mo{sub 3}S{sub 4}) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor that harvests red photons in the solar spectrum. The current densities atmore » the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10% (ref. 16). The experimental observations are supported by density functional theory calculations of the Mo{sub 3}S{sub 4} clusters adsorbed on the hydrogen-terminated Si(100) surface, providing insights into the nature of the active site.« less

Platinum phosphinothiolato hydride complexes: synthesis, structure and evaluation as tin-free hydroformylation catalysts.

PubMed

Real, Julio; Prat-Gil, Esther; Pagès-Barenys, Montserrat; Polo, Alfonso; Piniella, Joan F; Álvarez-Larena, Ángel

2016-03-07

Ligand 2-diphenylphosphinothiophenol (Hsarp) reacted with Pt(PPh3)4 to yield trans-[PtH(sarp)(PPh3)], which undergoes fast exchange with free PPh3 on the NMR time scale and very slowly and reversibly formed some cis-[PtH(sarp)(PPh3)] over time in solution (11%, 24 h). Reaction of trans-[PtH(sarp)(PPh3)] with Hsarp in boiling toluene gave cis- and trans-[Pt(sarp)2]; the cis isomer being more stable. These complexes were characterized by (1)H and (31)P NMR and also analyzed by XRD in the case of trans-[PtH(sarp)(PPh3)], trans-[Pt(sarp)2], and cis-[Pt(sarp)2]. trans-[PtH(sarp)(PPh3)] was evaluated as a preformed, tin-free hydroformylation catalyst on styrene and found active at 100 °C, at pressures over 75 bar, yielding phenylpropanal (regioselectivities up to 83% in 2-phenylpropanal), with total conversions to aldehydes up to 100% at styrene/platinum ratios from 400/1 to 1000/1 and minimal hydrogenation products.

Homogeneous coating of ionomer on electrocatalyst assisted by polybenzimidazole as an adhesive layer and its effect on fuel cell performance

NASA Astrophysics Data System (ADS)

Yang, Zehui; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-12-01

The fabrication of homogeneous ionomer distribution in fuel cell catalyst layers is necessary and important to improve the platinum utilization as well as the power density. Here, we focus on the effect of poly[2,2‧-(2,6-pyridine)-5,5‧-bibenzimidazole] (PyPBI) wrapped on multi-walled carbon nanotubes (MWNTs) for anchoring Nafion ionomer to the electrocatalyst, in which PyPBI functions as the binding sites for platinum nanoparticles (Pt-NPs) used as a catalyst. Based on the result using a control composite without having PyPBI, a strong interaction of the Nafion onto the PyPBI layer is recognized. Importantly, we find that the membrane-electrode assembly (MEA) shows a much higher maximum power density than that of the MEA without PyPBI. A homogeneous coating of Nafion on the electrocatalyst using the PyPBI forms a long-range network of the ionomer, leading to an improved Pt-NP utilization efficiency as well as an enhanced power density of the MEA.

Tuning of platinum nano-particles by Au usage in their binary alloy for direct ethanol fuel cell: Controlled synthesis, electrode kinetics and mechanistic interpretation

NASA Astrophysics Data System (ADS)

Dutta, Abhijit; Mondal, Achintya; Datta, Jayati

2015-06-01

Understanding of the electrode-kinetics and mechanism of ethanol oxidation reaction (EOR) is of considerable interest for optimizing electro-catalysis in direct ethanol fuel cell (DEFC). This work attempts to design Pt based electro-catalyst on carbon support, tuned with gold nano-particles (NPs), for their use in DEFC operating in alkaline medium. The platinum-gold alloyed NPs are synthesized at desired compositions and size (2-10 nm) by controlled borohydride reduction method and successfully characterized by XRD, TEM, EDS and XPS techniques. The kinetic parameters along with the activation energies for the EOR are evaluated over the temperature range 20-80 °C and the oxidation reaction products estimated through ion chromatographic analysis. Compared to single Pt/C catalyst, the over potential of EOR is reduced by ca. 500 mV, at the onset during the reaction, for PtAu/C alloy with only 23% Pt content demonstrating the ability of Au and/or its surface oxides providing oxygen species at much lower potentials compared to Pt. Furthermore, a considerable increase in the peak power density (>191%) is observed in an in-house fabricated direct ethanol anion exchange membrane fuel cell, DE(AEM)FC using the best performing Au covered Pt electrode (23% Pt) compared to the monometallic Pt catalyst.

Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

DOEpatents

Tong, YuYe; Du, Bingchen

2015-08-11

A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

Rapid synthesis of dendritic Pt/Pb nanoparticles and their electrocatalytic performance toward ethanol oxidation

NASA Astrophysics Data System (ADS)

Zhang, Ke; Xu, Hui; Yan, Bo; Wang, Jin; Gu, Zhulan; Du, Yukou

2017-12-01

This article reports a rapid synthetic method for the preparation of dendritic platinum-lead bimetallic catalysts by using an oil bath for 5 min in the presence of hexadecyltrimethylammonium chloride (CTAC) and ascorbic acid (AA). CTAC acts as a shape-direction agent, and AA acts as a reducing agent during the reaction process. A series of physical techniques are used to characterize the morphology, structure and electronic properties of the dendritic Pt/Pb nanoparticles, indicating the Pt/Pb dendrites are porous, highly alloying, and self-supported nanostructures. Various electrochemical techniques were also investigated the catalytic performance of the Pt/Pb catalysts toward the ethanol electrooxidation reaction. Cyclic voltammetry and chronoamperometry indicated that the synthesized dendritic Pt/Pb nanoparticles possessed much higher electrocatalytic performance than bulk Pt catalyst. This study may inspire the engineering of dendritic bimetallic catalysts, which are expected to have great potential applications in fuel cells.

Rapid Catalyst Capture Enables Metal-Free para-Hydrogen-Based Hyperpolarized Contrast Agents.

PubMed

Barskiy, Danila A; Ke, Lucia A; Li, Xingyang; Stevenson, Vincent; Widarman, Nevin; Zhang, Hao; Truxal, Ashley; Pines, Alexander

2018-05-10

Hyperpolarization techniques based on the use of para-hydrogen provide orders of magnitude signal enhancement for magnetic resonance spectroscopy and imaging. The main drawback limiting widespread applicability of para-hydrogen-based techniques in biomedicine is the presence of organometallic compounds (the polarization transfer catalysts) in solution with hyperpolarized contrast agents. These catalysts are typically complexes of platinum-group metals, and their administration in vivo should be avoided. Herein, we show how extraction of a hyperpolarized compound from an organic phase to an aqueous phase combined with a rapid (less than 10 s) Ir-based catalyst capture by metal scavenging agents can produce pure para-hydrogen-based hyperpolarized contrast agents, as demonstrated by high-resolution nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The presented methodology enables fast and efficient means of producing pure hyperpolarized aqueous solutions for biomedical and other uses.

Effect of Pt and Fe catalysts in the transformation of carbon black into carbon nanotubes

NASA Astrophysics Data System (ADS)

Asokan, Vijayshankar; Myrseth, Velaug; Kosinski, Pawel

2015-06-01

In this research carbon nanotubes and carbon nano onion-like structures were synthesized from carbon black using metal catalysts at 400 °C and 700 °C. Platinum and iron-group metals were used as catalysts for the transformation of CB into graphitized nanocarbon and the effect of both metals was compared. The synthesized products were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The characterization shows that this process is very efficient in the synthesis of high quality graphitized products from amorphous carbon black, even though the process temperature was relatively low in comparison with previous studies. Distinguished graphitic walls of the newly formed carbon nanostructures were clearly visible in the HRTEM images. Possible growth difference related to the type of catalyst used is briefly explained with the basis of electron vacancies in d-orbitals of metals.

Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst

NASA Astrophysics Data System (ADS)

Dudnik, Alexander S.; Weidner, Victoria L.; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J.

2014-12-01

Developing earth-abundant, non-platinum metal catalysts for high-value chemical transformations is a critical challenge to contemporary chemical synthesis. Dearomatization of pyridine derivatives is an important transformation to access a wide range of valuable nitrogenous natural products, pharmaceuticals and materials. Here, we report an efficient 1,2-regioselective organolanthanide-catalysed pyridine dearomatization process using pinacolborane, which is compatible with a broad range of pyridines and functional groups and employs equimolar reagent stoichiometry. Regarding the mechanism, derivation of the rate law from NMR spectroscopic and kinetic measurements suggests first order in catalyst concentration, fractional order in pyridine concentration and inverse first order in pinacolborane concentration, with C=N insertion into the La-H bond as turnover-determining. An energetic span analysis affords a more detailed understanding of experimental activity trends and the unusual kinetic behaviour, and proposes the catalyst ‘resting’ state and potential deactivation pathways.

Bioinspired hierarchical nanotubular titania immobilized with platinum nanoparticles for photocatalytic hydrogen production.

PubMed

Liu, Xiaoyan; Li, Jiao; Zhang, Yiming; Huang, Jianguo

2015-05-11

A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three- dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h(-1)  g(-1) , and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water-splitting processes results in its sufficient photocatalytic stability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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.

Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution

PubMed Central

Liang, Hai-Wei; Brüller, Sebastian; Dong, Renhao; Zhang, Jian; Feng, Xinliang; Müllen, Klaus

2015-01-01

Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt–nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt–N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5 s−1 at an overpotential of 100 and 200 mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols. PMID:26250525

Research on catalysts for long-life closed-cycle CO2 laser oaperation

NASA Technical Reports Server (NTRS)

Sidney, Barry D.; Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Spectrometric determination of platinum with methoxypromazine maleate

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

Thimmegowda, A.; Sankegowda, H.; Gowda, N.M.M.

1984-03-01

A simple, rapid, and sensitive spectrophotometric method has been developed for the determination of platinum in solution. The chromogenic reagent, methoxypromazine maleate, reacts with platinum(IV) almost instantaneously in phosphoric acid medium containing copper(II) catalyst to form a bluish pink 1:1 complex with an absorption maximum at 562 nm. The complexation is complete within 1 min. A 30-fold molar excess of the reagent over metal ion is necessary for completion of the reaction. Beer's law is obeyed over the concentration range of 0.4-9.8 ppm of platinum(IV) with an optimal range of 1.5-8.6 ppm. The molar absorptivity is 1.71 x 10/sub 4/more » L mol/sup -1/ cm/sup -1/ and the Sandell sensitivity is 11.4 ng cm/sup -2/. The apparent stability constant of the complex is log K = 5.58 +/- 0.1 at 27/sup 0/C. The effects of acid concentration, time, temperature, concentration of the reagent and copper, order of addition of reagents, and the interferences from various ions are investigated. The method has been used for the determination of platinum in synthetic solutions that approximate the composition of some alloys and minerals. 25 references, 1 figure, 2 tables.« less

Platinum-free catalysts for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Lastovina, Tatiana; Pimonova, Julia; Budnyk, Andriy

2017-04-01

In this work, we have successfully prepared Zn/Co-N/C and Zn/Co-Fe/N/C composites, both derived from single zeolitic imidazolate framework (ZIF) precursor Zn/Co-ZIF containing equivalent quantities of Zn and Co metal sites. The composites were formed by pyrolysis of the precursor at 700 °C in inert gas atmosphere as such and after mixing it with Fe(II) salt and 1,10-phenontraline in ethanol. Catalytic tests for oxygen reduction reaction (ORR) in electrochemical cell demonstrated promising results allowing us to consider these composites as potential Pt-free catalysts for low temperature fuel cells.

A micro alkaline direct ethanol fuel cell with platinum-free catalysts

NASA Astrophysics Data System (ADS)

Verjulio, R. W.; Alcaide, F.; Álvarez, G.; Sabaté, N.; Torres-Herrero, N.; Esquivel, J. P.; Santander, J.

2013-11-01

This paper presents the fabrication and characterization of a micro alkaline direct ethanol fuel cell. The device has been conceived as a feasibility demonstrator, using microtechnologies for the fabrication of the current collectors and traditional techniques for the membrane electrode assembly production. The fuel cell works in passive mode, as expected for the simplicity required for micro power systems. Non-noble catalysts have been used in order to implement the main advantage of alkaline systems, showing the feasibility of such a device as a potential very-low-cost power device at mini- and micro scales.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Cell membrane penetration and mitochondrial targeting by platinum-decorated ceria nanoparticles

NASA Astrophysics Data System (ADS)

Torrano, Adriano A.; Herrmann, Rudolf; Strobel, Claudia; Rennhak, Markus; Engelke, Hanna; Reller, Armin; Hilger, Ingrid; Wixforth, Achim; Bräuchle, Christoph

2016-07-01

In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and focus on their fast uptake and association with mitochondria, the cell's powerhouse. Using live-cell imaging and electron microscopy we clearly show that 46 nm platinum-decorated ceria nanoparticles can rapidly penetrate cell membranes and reach the cytosol. Moreover, if suitably targeted, these particles are able to selectively attach to mitochondria. These results are complemented by cytotoxicity assays, thus providing insights into the biological effects of these particles on cells. Interestingly, no permanent membrane disruption or any other significant adverse effects on cells were observed. The unusual uptake behavior observed for 46 nm nanoparticles was not observed for equivalent but larger 143 nm and 285 nm platinum-decorated particles. Our results demonstrate a remarkable particle size effect in which particles smaller than ~50-100 nm escape the usual endocytic pathway and translocate directly into the cytosol, while particles larger than ~150 nm are internalized by conventional endocytosis. Since the small particles are able to bypass endocytosis they could be explored as drug and gene delivery vehicles. Platinum-decorated nanoparticles are therefore highly interesting in the fields of nanotoxicology and nanomedicine.In this work we investigate the interaction between endothelial cells and nanoparticles emitted by catalytic converters. Although catalyst-derived particles are recognized as growing burden added to environmental pollution, very little is known about their health impact. We use platinum-decorated ceria nanoparticles as model compounds for the actual emitted particles and focus on their fast uptake and association with mitochondria, the cell's powerhouse. Using live-cell imaging and electron microscopy we clearly show that 46 nm platinum-decorated ceria nanoparticles can rapidly penetrate cell membranes and reach the cytosol. Moreover, if suitably targeted, these particles are able to selectively attach to mitochondria. These results are complemented by cytotoxicity assays, thus providing insights into the biological effects of these particles on cells. Interestingly, no permanent membrane disruption or any other significant adverse effects on cells were observed. The unusual uptake behavior observed for 46 nm nanoparticles was not observed for equivalent but larger 143 nm and 285 nm platinum-decorated particles. Our results demonstrate a remarkable particle size effect in which particles smaller than ~50-100 nm escape the usual endocytic pathway and translocate directly into the cytosol, while particles larger than ~150 nm are internalized by conventional endocytosis. Since the small particles are able to bypass endocytosis they could be explored as drug and gene delivery vehicles. Platinum-decorated nanoparticles are therefore highly interesting in the fields of nanotoxicology and nanomedicine. Electronic supplementary information (ESI) available: Further information on the characterization of nanoparticles and additional live-cell imaging studies. See DOI: 10.1039/c5nr08419a

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

DOE PAGES

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; ...

2016-05-26

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts

NASA Astrophysics Data System (ADS)

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-03-01

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production—which far exceeds that of previously reported low-temperature APRM catalysts—to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Biogenic platinum and palladium nanoparticles as new catalysts for the removal of pharmaceutical compounds.

PubMed

Martins, Mónica; Mourato, Cláudia; Sanches, Sandra; Noronha, João Paulo; Crespo, M T Barreto; Pereira, Inês A C

2017-01-01

Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment. Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nanoparticles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin, sulfamethoxazole, ibuprofen and 17β-estradiol. The catalytic activity of the biological nanoparticles was compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17β-estradiol, sulfamethoxazole and ciprofloxacin, respectively. In addition, the estrogenic activity of 17β-estradiol was strongly reduced after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics and endocrine disrupting compounds, the most problematic PhP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

PubMed

Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

2014-12-01

Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.