Insitucarburizationofmetallicmolybdenumduringcatalytic.PDFVIP

Catalysis Letters 20 (1993)97-106 97 In situ carburization of metallic molybdenum during catalytic reactions of carbon-containing gases Jae Sung Lee 1 Department of ChemicalEngineering, PohangInstitute of Science and Technology (POSTECH), PO Box 125,Pohang,Korea and Michel Boudart Department of ChemicalEngineering, Stanford University,Stanford, CA 94305, USA Supported molybdenum clusters were prepared by sublimation of Mo(CO)6 onto dehy- droxylated alumina followed by decomposition in flowing dihydrogen at 970 K. These alu- mina-supported molybdenum clusters were found by XAFS to transform into Mo2C if heated in a 20% methane/H2 mixture at 950 K. For the hydrogenolysis of n-butane at 510 K and CO-H2 reactions at 570 K, both at atmospheric pressure, molybdenum and carburized molyb- denum showed similar, but different for each reaction, turnover rates. The product distribu- tion was the same for each reaction on Mo and Mo2C. In both reactions, in situ XAFS data for fresh and used catalysts indicated that Mo dusters progressively transformed into Mo2C under the reaction conditions Keywords: Molybdenum carbide catalysts; alumina-supported; n-butane hydrogenolysis; CO hydrogenation; in situ carburization; XAFS 1. I n t r o d u c t i o n In the past decade, carbides of M o and W have been tried as substitute catalytic materials for noble metals. New methods for the preparation of supported and unsupported metal carbides with high specific surface areas have been revi