The water-gas shift (WGS) reaction over a series of cobalt-molybdenum carbide catalysts was Studied at 453 K. The cobalt-molybdenum\ (CoxMo1-x) oxides were prepared using a mixture of aqueous solutions of cobalt nitrate and ammonium heptainolybdate and carburized by a temperature-programmed reaction with a 20% CH4/H-2 mixture. The catalysts were characterized using X-ray diffraction, CO adsorption, carburization (TPC) with a 20% CH4/H-2) mixture, X-ray photoelectron spectroscopy, and transmission electronic microscopy. The 873 K-carburized Co0.5Mo0.5 was found to be the most active among the Co-Mo carbide catalysts; it was more active than a commercial CuZn at 5 min but less active than CuZn at 300 min. The TPC experiment determined the reduction and/or carburization of the Mo and CoMo oxides into the carbides through the oxycarbides. The TPC of the Co0.5Mo0.5 oxide showed that the first peak of H2O at 747 K was due to the reduction and/or carburization of MoO3 to MoO2 and Mo oxycarbide and of CoMoO4 to the Co-Mo oxycarbide, and the second peak at 893 K was due to the carburization of the Co-Mo oxycarbide to beta-Mo2C with Co metal and amorphous Co-Mo carbide. In addition, the Co0.5Mo0.5 carbide catalyst contained beta-Mo2C, Co metal, and the amorphous Co-Mo oxycarbide (the composition of CoMoC6.2O1.4), which grew into crystallites of Co3Mo3C after being heated in H-2. The amorphous Co-Mo oxycarbide is responsible for the WGS reaction. (c) 2006 Elsevier Inc. All rights reserved.