Gorte, Raymond J
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PublicationAn Examination of SOFC Anode Functional Layers Based on Ceria in YSZ(2007-08-21) Vohs, John M; Gorte, Raymond J; Vohs, John M; Gorte, Raymond JThe properties of solid oxide fuel cell (SOFC) anode functional layers prepared by impregnation of ceria and catalytic metals into porous yttria-stabilized zirconia (YSZ) have been examined for operation at 973 K. By varying the thickness of the functional layer, the conductivity of the ceria-YSZ composite was determined to be only 0.015–0.02 S/cm. The initial performance of anodes made with ceria loadings of 40 or 60 wt % were similar but the anodes with lower loadings lost conductivity above 1073 K due to sintering of the ceria. The addition of dopant levels of catalytic metals was found to be critical. The addition of 1 wt % Pd or Ni decreased the anode impedances in humidified H2 dramatically, while the improvement with 5 wt % Cu was significant but more modest. Pd doping also decreased the anode impedance in dry CH4 much more than did Cu doping; however, addition of either Pd or Cu led to similar improvements for operation in n-butane. Based on these results, suggestions are made for ways to improve SOFC anode functional layers. PublicationEngineering Composite Oxide SOFC Anodes for Efficient Oxidation of Methane(2008-02-14) Kim, Guntae; Vohs, John M; Gorte, Raymond J; Vohs, John M; Gorte, Raymond JCeramic anodes for solid oxide fuel cells SOFCs were prepared by aqueous impregnation of nitrate salts to produce composites with 45 wt % La0.8Sr0.2Cr0.5Mn0.5O3 (LCSM)in a 65% porous yttria-stabilized zirconia (YSZ) scaffold. Scanning electron micrographs indicate that the LSCM coats the YSZ pores following calcination at 1473 K. Composites produced in this manner exhibit conductivities at 1073 K of approximately 1 S/cm in air and 0.1 S/cm in humidified H2. A SOFC with a composite anode composed of 45 wt % LSCM, 0.5 wt % Pd, and 5 wt % ceria exhibited maximum power densities at 1073 K of 1.1 and 0.71 W cm−2 in humidified (3% H2O) H2 and methane, respectively. PublicationAnalysis of the Performance of the Electrodes in a Natural Gas Assisted Steam Electrolysis Cell(2008-02-01) Gorte, Raymond J; Vohs, John M; Gorte, Raymond J; Vohs, John MThe performance of solid oxide electrolysis (SOE) cells while operating in the natural gas assisted steam electrolysis (NGASE) mode was evaluated. The SOE cells used yttria-stabilized-zirconia (YSZ) as the oxygen ion conducting electrolyte, Co–CeO2–YSZ as the H2–H2O electrode, and Pd-doped CeO2 YSZ source as the CH4-oxidation electrode. The cell electrochemical performance was evaluated as a function of the H2O/H2 ratio and the extent of conversion of CH4. The results of this study provide insight into the factors that control electrode performance and further demonstrate the viability of an NGASE cell for the production of H2. PublicationPreparation of SOFC Anodes by Electrodeposition(2007-10-11) Vohs, John M; Gorte, Raymond J; Vohs, John M; Gorte, Raymond JAnodes for solid oxide fuel cells (SOFCs) have been prepared by electrodeposition of either Co or Ni into a layer of porous yttria-stabilized zirconia (YSZ), 60 µm thick. The YSZ, having 65% porosity, was prepared by tape casting with graphite pore formers and was attached to the dense YSZ electrolyte. After adding 10 vol % CeO2 by impregnation of aqueous solutions of CeNO3)3, followed by calcination at 723 K, the porous YSZ was made conductive by exposing it to n-butane at 1123 K to form a coating of carbon. As much as 40 vol % metal could be added to the porous layers, while the carbon could then be removed by exposing the anode to humidified H2 at SOFC operating temperatures. The ohmic losses in cells containing 40 vol % Co or 30 vol % Ni were unaffected by heating to 1173 K. Finally, a cell with 15 vol % Cu and 15 vol % Co was prepared by electrodeposition of Cu onto electrodeposited Co. No carbon formation was observed on the Cu–Co anode following exposure to dry methane at 1073 K. PublicationSOFC Anodes Based on Infiltration of La0.3Sr0.7TiO3(2008-09-22) Lee, Shiwoo; Vohs, John M; Lee, Shiwoo; Gorte, Raymond J; Kim, Guntae; Vohs, John M; Gorte, Raymond JComposites formed by infiltration of 45 wt % La0.3Sr0.7TiO3 (LST) into 65% porous yttria-stabilized zirconia (YSZ) were examined for application as solid oxide fuel cell (SOFC) anodes. Although LST does not react with YSZ, the structure of the LST deposits was strongly affected by the calcination temperature. At 1373 K, the LST formed loosely packed, 0.1 µm particles that filled the YSZ pores. The conductivity of this composite depended strongly on the pretreatment conditions but was greater than 0.4 S/cm after heating to 1173 K in humidified (3% H,2O) H2. Following calcination at 1573 K, the LST had sintered significantly, decreasing the conductivity of the composite by a factor of approximately 5. The addition of a catalyst was critical for achieving reasonable electrochemical performance, with the addition of 0.5 wt % Pd and 5 wt % ceria increasing the power density of otherwise identical cells from less than 20 to 780 mW/cm2 for operation in humidified (3% H2O) H2 at 1073 K. Electrodes prepared from LST deposits calcined at 1373 K were found to exhibit a much better performance than those prepared from LST deposits calcined at 1573 K, demonstrating that the structure of the composite is critical for achieving high performance. PublicationA Comparison of LSM, LSF, and LSCo for Solid Oxide Electrolyzer Anodes(2006-09-11) Wang, Wensheng; Vohs, John M; Gorte, Raymond J; Vohs, John M; Gorte, Raymond JComposite electrodes of yttria-stabilized zirconia (YSZ) with La0.8Sr0.2MnO3 (LSM), La0.8Sr0.2FeO3 (LSF), and La0.8Sr0.2CoO3 (LSCo) were prepared and tested as solid oxide electrolyzer (SOE) anodes and solid oxide fuel cell (SOFC) cathodes at 973 K, using cells with a YSZ electrolyte and a Co-ceria-YSZ counter electrode. The LSM-YSZ electrode was activated by cathodic polarization but the enhanced performance was found to be unstable during electrolysis, with the electrode impedance increasing to near its unenhanced state after 24 h. LSF-YSZ and LSCo-YSZ electrodes exhibited a nearly constant impedance, independent of current density, during both SOE and SOFC operation. The performance of an LSF-YSZ composite for electrolysis current densities above 200 mA/cm2 was unaffected by changing the O2 partial pressure from ~10–2 to 1 atm, while the lower O2 pressure harmed the performance of the LSCo-YSZ composite. The implications of these results for the characterization and optimization of SOE anodes is discussed. PublicationA Comparison of Ceria and Sm-Doped Ceria for Hydrocarbon Oxidation Reactions(2004-12-08) Gorte, Raymond J; Gorte, Raymond JThe oxidation of methane, ethane, propane, and n-butane has been studied over CeO2 and Ce0.8Sm0.2Ox (SDC) catalysts. The rates for methane and ethane were found to be indistinguishable over the two catalysts, while the rates for propane and n-butane were much higher on ceria compared to SDC. The difference between n-butane oxidation over ceria and SDC is shown to result from a low-temperature rate process on ceria that is not present on SDC. Measurements using CD4 and C4D10 show that both low- and high-temperature rates exhibit a similar kinetic-isotope effect; however, the low-temperature process is half-order in O2, while the high-temperature process is zeroth-order. Pulse studies demonstrate that oxygen from the bulk becomes accessible for reaction at approximately the same temperature as that at which the high-temperature rate process becomes important. The implications of these results for understanding the effect of doping on reactions over ceria, and for characterization of oxides using standard test reactions, are discussed. PublicationNano-Socketed Nickel Particles with Enhanced Coking Resistance Grown in situ by Redox Exsolution(2015-01-01) Neagu, Dragos; Oh, Tae-Sik; Miller, David N; Ménard, Hervé; Bukhari, Syed M; Gorte, Raymond J; Gamble, Stephen R; Vohs, John M; Gorte, Raymond J; Vohs, John M; Irvine, John T. SMetal particles supported on oxide surfaces are used as catalysts for a wide variety of processes in the chemical and energy conversion industries. For catalytic spplications, metal particles are generally formed on an oxide support by physical or chemical deposition, or less commonly by exsolution from it. Although fundamentally different, both methods might be assumed to produce morphologically and functionally similar particles. Here we show that unlike nickel particles deposited on perovskite oxides, exsolved analogues are socketed into the parent perovskite, leading to enhanced stability and a significant decrease in the propensity for hydrocarbon coking, indicative of a stronger metal-oxide interface. In addition, we reveal key surface effects and defect interactions critical for future design of exsolution-based perovskite materials for catalytic and other functionalities. This study provides a new dimenstion for tailoring particle-substrate interactions in the context of increasing interest for emergent interfactial phenomena. PublicationAn Examination of SOFC Anode Functional Layers Based on Ceria in YSZ(2007-05-22) Vohs, John M; Gorte, Raymond J; Vohs, John M; Gorte, Raymond JThe properties of solid oxide fuel cell (SOFC) anode functional layers prepared by impregnation of ceria and catalytic metals into porous yttria-stabilized zirconia (YSZ) have been examined for operation at 973 K. By varying the thickness of the functional layer, the conductivity of the ceria-YSZ composite was determined to be only 0.015–0.02 S/cm. The initial performance of anodes made with ceria loadings of 40 or 60 wt % were similar but the anodes with lower loadings lost conductivity above 1073 K due to sintering of the ceria. The addition of dopant levels of catalytic metals was found to be critical. The addition of 1 wt % Pd or Ni decreased the anode impedances in humidified H2 dramatically, while the improvement with 5 wt % Cu was significant but more modest. Pd doping also decreased the anode impedance in dry CH4 much more than did Cu doping; however, addition of either Pd or Cu led to similar improvements for operation in n-butane. Based on these results, suggestions are made for ways to improve SOFC anode functional layers. PublicationOxidation Enthalpies for Reduction of Ceria Surfaces(2007-06-15) Zhou, Gong; Shah, Parag R; Montini, Tiziano; Gorte, Raymond J; Gorte, Raymond JThe thermodynamic properties of surface ceria were investigated through equilibrium isotherms determined by flow-titration and coulometric-titration measurements on high-surface-area ceria and ceria supported on La-modified alumina (LA). While the surface area of pure ceria was found to be unstable under redox conditions, the extent of reduction at 873 K and a P(O2) of 1.6x10-26 atm increased with surface area. Because ceria/LA samples were stable, equilibrium isotherms were determined between 873 and 973 K on a 30-wt% ceria sample. Oxidation enthalpies on ceria/LA were found to vary with the extent of reduction, ranging from -500 kJ/mol O2 at low extents of reduction to near the bulk value of -760 kJ/mol O2 at higher extents. To determine whether +3 dopants could affect the oxidation enthalpies for ceria, isotherms were measured for Sm+3-doped ceria (SDC) and Y+3-doped ceria. These dopants were found to remove the phase transition observed in pure ceria below 973 K but appeared to have minimal effect on the oxidation enthalpies. Implications of these results for catalytic applications of ceria are discussed.