Optimization of carbon-supported platinum cathode catalysts for DMFC operation.

In this paper, we describe performance and optimization of carbon-supported cathode catalysts at low platinum loading. We find that at a loading below 0.6 mg cm-2 carbon-supported platinum outperforms platinum black as a DMFC cathode catalyst. A catalyst with a 1:1 volume ratio of the dry NafionTM to the electronically conducting phase (platinum plus carbon support) provides the best performance in oxygen reduction reaction. Thanks to improved catalyst utilization, carbon-supported catalysts with a platinum content varying from 40 wt% to 80 wt% deliver very good DMFC performance, even at relatively modest precious metal loadings investigated in this work

The Evolution of High Temperature Gas Sensors.

Gas sensor technology based on high temperature solid electrolytes is maturing rapidly. Recent advances in metal oxide catalysis and thin film materials science has enabled the design of new electrochemical sensors. We have demonstrated prototype amperometric oxygen sensors, nernstian potentiometric oxygen sensors that operate in high sulfur environments, and hydrocarbon and carbon monoxide sensing mixed potentials sensors. Many of these devices exhibit part per million sensitivities, response times on the order of seconds and excellent long-term stability

The development of a fullerene based hydrogen storage system

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The project objective was to evaluate hydrogen uptake by fullerene substrates and to probe the potential of the hydrogen/fullerene system for hydrogen fuel storage. As part of this project, the authors have completed and tested a fully automated, computer controlled system for measuring hydrogen uptake that is capable of handling both a vacuum of 1 x 10{sup -6} torr and pressures greater than 200 bars. The authors have first established conditions for significant uptake of hydrogen by fullerenes. Subsequently, hydrogenation and dehydrogenation of pure and catalyst-doped C60 was further studied to probe suitability for hydrogen storage applications. C60 {center_dot} H18.7 was prepared at 100 bar H2 and 400 C, corresponding to hydrogen uptake of 2.6 wt%. Dehydrogenation of C60 {center_dot} H18.7 was studied using thermogravimetric and powder x-ray diffraction analysis. The C60 {center_dot} H18.7 molecule was found to be stable up to 430 C in Ar, at which point the release of hydrogen took place simultaneously with the collapse of the fullerene structure. X-ray diffraction analysis performed on C60 {center_dot} H18.7 samples dehydrogenated at 454 C, 475 C, and 600 C showed an increasing volume fraction of amorphous material due to randomly oriented, single-layer graphine sheets. Evolved gas analysis using gas chromatography and mass spectroscopy confirmed the presence of both H{sub 2} and methane upon dehydrogenation, indicating decomposition of the fullerene. The remaining carbon could not be re-hydrogenated. These results provide the first complete evidence for the irreversible nature of fullerene hydrogenation and for limitations imposed on the hydrogenation/dehydrogenation cycle by the limited thermal stability of the molecular crystal of fullerene

Evidence of High Electrocatalytic Activity of Molybdenum Carbide Supported Platinum Nanorafts

The article of record as published may be found at http://dx.doi.org/10.1149/2.0991509jesThis was Paper 614 presented at the Orlando, Florida, Meeting of the Society, May 11–15, 2014.A remarkable new supported metal catalyst structure on Mo₂C substrates, ‘rafts’ of platinum consisting of less than 6 atoms, was synthesized and found to be catalytically active electrocatalyst for oxygen reduction. A novel catalytic synthesis method: Reduction- Expansion-Synthesis of Catalysts (RES-C), from rapid heating of dry mixture of solid precursors of molybdenum, platinum and urea in an inert gas environment, led to the creation of unique platinum Nanorafts on Mo₂C. The Pt Nanorafts offer a complete utilization of the Pt atoms for electrocatalysis with no “hidden” atoms. This structure is strongly affected by its interaction with the substrate as was observed by XPS. In this work, we show for the first time, evidence of electrocatalytic activity with such small clusters of non-crystalline Pt atoms as catalysts for oxygen reduction. Electrochemical half-cell characterization shows that this structure permit more efficient utilization of platinum, with mass activity conservatively measured to be 50% that of platinum particles generated using traditional approaches. Moreover, as cathode fuel cell catalysts, these novel material may dramatically enhance stability, relative to the commercial Pt/carbon catalysts.U.S. Department of Energy Fuel Cell Technologies OfficeIsrael Ministry of Defense (MAFAT

Electrocatalysis of Oxygen Reduction with in-Situ formed Pt Nano-Rafts on Molybdenum Carbide Support

Proton exchange membrane fuel cell (PEMFC), is a technology that has the potential to economically replace combustion engines for transport with high efficiency, and clean (only water emission) energy. The US department of energy (DOE) identifies two remaining major hurdles to the deployment of this alternative: cost and durability of the cathode. Reducing the amount of platinum, still the only material with the needed catalytic activity for oxygen reduction reaction on the cathode, and the most expensive component, will help overcome the first problem and the creation of a new, ‘non-carbon’, more oxidation-resistant catalyst support material could overcome the second.US Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technology and Fuel Cell Technology Program

Role of heterogeneous catalysis in the gas-sensing selectivity of high-temperature mixed potential sensors

The sensitivity of a mixed potential electrochemical sensor is determined by the concentration of the analyte gas at the gas/electrode/electrolyte interface. These concentrations, along with the kinetic properties of the three-phase interface and oxygen partial pressure, establish the mixed potential generated by the device. The selectivity of mixed potential sensors is therefore strongly influenced by the heterogeneous catalytic properties of the surfaces that closely surround the sensor including: the metal oxide electrode, solid electrolyte, other components of the sensor body, and the sensor enclosure. Analysis of the change in CO, C3H6, and C3H8 concentration using gas chromatography shows that the observed preferential sensitivity of a LaCrO3//YSZ//Pt bulk mixed potential sensor towards C3H8 is largely due to heterogeneous catalysis of the C3H6 on the sensor body, which in this work, is YSZ. By blocking YSZ heterogeneous catalysis by using a coating of thick Au, the sensor exhibits nearly identical sensitivity to both C3H6 and C3H8. Although a similar amount of heterogeneous catalytic oxidation of CO takes place, the LaCrO3//YSZ//Pt sensor exhibits only a small response to CO and this therefore may be associated with the electrode kinetics and electrocatalytic properties of the sensor interface towards the electro-oxidation of the CO. Data for HC and CO selectivity will be presented at 1% O2 / 12% CO2 / N2 and at temperatures between 550 and 600 C

Application of x-ray tomography to optimization of new NOx/NH3 mixed potential sensors for vehicle on-board emissions control

Mixed potential sensors for the detection of hydrocarbons, NO{sub x}, and NH{sub 3} have been previously developed at Los Alamos National Laboratory (LANL). The LANL sensors have a unique design incorporating dense ceramic-pelletlmetal-wire electrodes and porous electrolytes. The performance of current-biased sensors using an yttria-stabilized zirconia (YSZ) electrolyte and platinum and La{sub 0.8}Sr{sub 0.2}CrO{sub 3} electrodes is reported. X-ray tomography has been applied to non-destructively examine internal structures of these sensors. NO{sub x} and hydrocarbon response of the sensors under various bias conditions is reported, and very little NO{sub x} response hysteresis was observed. The application of a 0.6 {mu}A bias to these sensors shifts the response from a hydrocarbon response to a NO{sub x} response equal for both NO and NO{sub 2} species at approximately 500 {sup o}C in air

Understanding the response behavior of potentiometric gas sensors for non-equilibrium gas mixtures

Many applications of gas sensors require concentration measurements of reactive gases in mixtures that are out of thermodynamic equilibrium. These applications include: hydrogen and hydrocarbon fuel gas sensors operating in ambient air for explosion hazard detection, carbon monoxide detection in ambient air for health protection, combustion efficiency sensors for stoichiometry control, and nitric oxide sensors for air pollution monitoring. Many potentiometric and amperometric electrochemical sensor technologies have been developed for these applications. A class of the potentiometric sensors developed for gas mixtures are the non-Nerstian sensors. This presentation defines a categorization and theoretical analysis of three distinct electrochemical processes that can produce a non-Nernstian sensor response