Effect of carburization protocols on molybdenum carbide synthesis and study on its performance in CO hydrogenation

•We examine structure diversity of MoCx at various preparation conditions.•Carbon deposition phenomenon was studied by Raman spectroscopy.•The carburization degree of Mo2C increased with carburization temperature.•We explore structure–property relationship on Mo2C in CO hydrogenation.

Molybdenum carbides were prepared under different carburization conditions. The role of carburization protocol was studied while their CO hydrogenating performances were evaluated in a fixed-bed reactor at 280 °C, 3.1 MPa, and H2/CO = 2.0. The structure of the carbides mainly depended on the type and concentration of carbon source while the crystallite size depended on carbon source and temperature. The surface area, morphology and surface carbon deposition phenomenon of the carbides were sensitive to heating rate and holding time other than the above factors. Though the bulk structure was the same at a carburization temperature range from 630 to 760 °C, the carburization degree of the carbides was changing continuously. This diversity led the bond strength of molecular adsorbed CO weaken at a higher carburization temperature while the adsorptive strength of H2 was hardly changed. Both the adsorptive quantities of CO and H2 followed the same trend, with the highest amount on the carbide prepared at 630 °C. The activities of the catalysts correlated well with their adsorptive quantities of CO and H2, and the product selectivity was related to their hydrogenation capacity.

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