A COMBINED TEMPERATURE-PROGRAMMED REACTION SPECTROSCOPY AND FOURIER-TRANSFORM INFRARED-SPECTROSCOPY STUDY OF CO2-H2 AND CO-CO2-H2 INTERACTIONS WITH MODEL ZNO/SIO2, CU/SIO2 AND CU/ZNO/SIO2 METHANOL-SYNTHESIS CATALYSTS

The reaction of CO2 and H-2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate species on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H-2. Even after exposure of CO2-H-2 or CO-CO2-H-2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H-2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H-2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H-2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H-2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.