Characterization and oxidation states of Cu and Pd in Pd–CuO/ZnO/ZrO2 catalysts for hydrogen production by methanol partial oxidation |
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| Authors: | S. Schuyten S. Guerrero J.T. Miller T. Shibata E.E. Wolf |
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| Affiliation: | 1. Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN 46556, United States;2. Departamento de Ingenieria Química, Universidad de Chile, Casilla 2777, Santiago, Chile;3. BP Research Center, BP P.L.Complex, Naperville, IL 60563, United States;4. Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL, United States;5. BCPS Department, Illinois Institute of Technology, 3300 S. Federal Street, Chicago, IL 60616, United States;1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering & Technology, Tianjin University; Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, China;2. Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing, 210096, China;3. School of Energy Science and Engineering, Central South University, China;1. Laboratory of Industrial Chemistry, Ruhr-University Bochum, 44780 Bochum, Germany;2. Fraunhofer UMSICHT, 46047 Oberhausen, Germany;1. Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand;2. NANOTEC Center for Nanoscale Materials Design for Green Nanotechnology and Center for Advanced Studies in Nanotechnology for Chemical, Food and Agricultural Industries, Kasetsart University, Bangkok 10900, Thailand;3. Synchrotron Light Research Institute, Nakhon Ratchasima 30000, Thailand;4. Department of Materials Science and Engineering, Institute of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand;1. Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria;2. Institute of Nuclear Research, Hungarian Academy of Sciences, Debrecen, Hungary;3. CNR-Istituto per lo Studio dei materiali Nanostrutturati Via Ugo La Malfa 153, 90146 Palermo, Italy;4. Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria;5. CNR - Istituto di Scienze e Tecnologie Molecolari, via C. Golgi 19, 20133 Milano, Italy |
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| Abstract: | Copper and zinc oxide based catalysts prepared by coprecipitation were promoted with palladium and ZrO2, and their activity and selectivity for methanol oxidative reforming was measured and characterized by N2O decomposition, X-ray absorption spectroscopy, BET, X-ray photoelectron spectroscopy, X-ray diffraction, and temperature programmed reduction. Addition of ZrO2 increased copper dispersion and surface area, with little effect on activity, while palladium promotion significantly enhanced activity with little change of the catalytic structure. A catalyst promoted with both ZrO2 and palladium yielded hydrogen below 150 °C. EXAFS results under reaction conditions showed that the oxidation state of copper was influenced by palladium in the catalyst bulk. A palladium promoted catalyst contained 90% Cu0, while the copper in an unpromoted catalyst was 100% Cu1+ at the same temperature. Palladium preferentially forms an unstable alloy with copper instead of zinc during reduction, which persists during reaction regardless of copper oxidation state. A 100-h time on stream activity measurement showed growth in copper crystallites and change in copper oxidation state resulting in decreasing activity and selectivity. A kinetic model of the reaction pathway showed that palladium and ZrO2 promoters lower the activation energy of methanol combustion and steam reforming reactions. |
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