Properties of Surface Compounds in Methanol Conversion on Copper-Containing Catalysts Based on CeO2 According to In Situ IR-Spectroscopic Data

摘要

Formate and carbonate complexes and bridging and linear methoxy groups were detected on the surfaces of CeO2 and 5.0% Cu/CeO2 under the reaction conditions of methanol conversion using IR spectroscopy. The reaction products were H-2, methyl formate, CO, CO2, and H2O. The bridging and linear methoxy groups were the sources of formation of bi- and monodentate formate complexes, respectively. Methyl formate was formed as a result of the interaction of the linear methoxy group and the formate complex. The study demonstrated that the recombination of hydrogen atoms on copper clusters and the decomposition of methyl formate were the main reactions of hydrogen formation. Formate and carbonate complexes were the source of CO2 formation in the gas phase, and the decomposition of methyl formate was the source of CO. It was found that the addition of water vapor to the reaction flow considerably decreased the rate of CO formation at a constant yield of hydrogen. The effects of water vapor and oxygen on the course of surface reactions and the formation of products are discussed. To explain the mechanism of methanol conversion, a scheme of surface reactions is proposed.