Hydrogen production by oxidative methanol reforming on Pd/ZnO

Abstract Pd/ZnO catalysts with Pd loadings of between 1 and 45% were prepared by impregnation and coprecipitation methods; their catalytic performances during oxidative methanol reforming for the production of hydrogen were investigated under various reaction conditions. The prepared catalysts showed high activity and selectivity towards hydrogen formation. At higher Pd loading (exceeding 5%), the coprecipitation method was superior to the impregnation method for the preparation of the catalyst. Highly active Pd/ZnO that is comparable to commercial Cu–Zn catalyst can be obtained with high Pd loadings. On the other hand, CO formation was greatly reduced by increasing the Pd loading. Excess amounts of Pd on the ZnO decreased the conversion of methanol and increased CO formation. XRD characterization of freshly prepared and spent catalysts confirmed the formation of the Pd–Zn alloy. The sizes of both the ZnO and the Pd–Zn crystallites affect the catalytic performance. A strong interaction between the Pd–Zn alloy and the ZnO support is believed to be essential for the selective formation of hydrogen. The reaction mechanism and the CO formation route are also discussed, based on the results that we obtained.

[1]  J. Funk Thermochemical hydrogen production: past and present , 2001 .

[2]  N. Iwasa,et al.  Steam Reforming of Methanol Over Pd-Zn Catalysts , 2000 .

[3]  David L. Trimm,et al.  ONBOARD FUEL CONVERSION FOR HYDROGEN-FUEL-CELL-DRIVEN VEHICLES , 2001 .

[4]  J. Fierro,et al.  Oxidative Methanol Reforming Reactions on CuZnAl Catalysts Derived from Hydrotalcite-like Precursors , 2001 .

[5]  L. Ilharco,et al.  The Decomposition Pathways of Methanol on Clean Ru(0001), Studied by Reflection−Absorption Infrared Spectroscopy (RAIRS) , 2001 .

[6]  Mark S. Wainwright,et al.  KINETIC MECHANISM FOR THE REACTION BETWEEN METHANOL AND WATER OVER A CU-ZNO-AL2O3 CATALYST , 1993 .

[7]  D. Trimm,et al.  Dehydrogenation of methanol to methyl formate over copper catalysts , 1984 .

[8]  O. Yamamoto,et al.  Dehydrogenation of methanol to methyl formate over palladium/zinc oxide catalysts , 1991 .

[9]  Tangshun Huang,et al.  Kinetics of partial oxidation of methanol over a copper—zinc catalyst , 1988 .

[10]  Brant A. Peppley,et al.  Methanol–steam reforming on Cu/ZnO/Al2O3 catalysts. Part 2. A comprehensive kinetic model , 1999 .

[11]  L. F. Brown A comparative study of fuels for on-board hydrogen production for fuel-cell-powered automobiles , 2001 .

[12]  N. Takezawa,et al.  The mechanism of steam reforming of methanol over a copper-silica catalyst , 1982 .

[13]  J. Rodríguez Interactions in bimetallic bonding. Electronic and chemical properties of PdZn surfaces , 1994 .

[14]  M. Kumagai,et al.  Methanol decomposition to synthesis gas over supported Pd catalysts prepared from synthetic anionic clays , 1999 .

[15]  J. Kubota,et al.  Formation of Formate in the Deep Oxidation of Methanol on Pt(111) under UHV Condition Studied by IRAS , 2000 .

[16]  Alice Dohnalkova,et al.  Steam Reforming of Methanol Over Highly Active Pd/ZnO Catalyst. , 2002 .

[17]  A. Bell,et al.  A mechanistic study of methanol decomposition over Cu/SiO2, ZrO2/SiO2, and Cu/ZrO2/SiO2 , 1999 .

[18]  J. Kubota,et al.  In Situ IRAS Observation of Catalytic Deep Oxidation of Methanol on Pt(111) under Ambient Pressure Conditions , 2001 .

[19]  Kenzi Suzuki,et al.  Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts , 2001 .

[20]  Sun Wang,et al.  Hydrogen production via partial oxidation of methanol over copper-zinc catalysts , 1986 .

[21]  J. Fierro,et al.  Selective Production of Hydrogen by Partial Oxidation of Methanol over ZnO-Supported Palladium Catalysts , 1998 .

[22]  P. L. Lee,et al.  Time-Resolved XANES Investigation of CuO/ZnO in the Oxidative Methanol Reforming Reaction , 2001 .

[23]  Kenzi Suzuki,et al.  Oxidative Steam Reforming of Methanol over CuZnAl(Zr)-Oxide Catalysts for the Selective Production of Hydrogen for Fuel Cells: Catalyst Characterization and Performance Evaluation , 2000 .

[24]  P. Wehner,et al.  XPS study of the reduction and reoxidation of ZnO-supported palladium , 1984 .

[25]  P. Wehner,et al.  Catalytic hydrogenation of esters over Pd/ZnO , 1992 .

[26]  N. Iwasa,et al.  Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals , 1997 .

[27]  Shetian Liu,et al.  Hydrogen production by oxidative methanol reforming on Pd/ZnO catalyst: effects of Pd loading , 2003 .

[28]  D. Trimm,et al.  Kinetic study of steam reforming of methanol over copper-based catalysts , 1993 .

[29]  N. Iwasa,et al.  Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction , 1995 .

[30]  D. Trimm,et al.  Methanol synthesis and water-gas shift reactions on Raney copper catalysts , 1995 .

[31]  M. Krumpelt,et al.  Hydrogen from hydrocarbon fuels for fuel cells , 2001 .

[32]  Brant A. Peppley,et al.  Methanol–steam reforming on Cu/ZnO/Al2O3. Part 1: the reaction network , 1999 .