Abstract
Cu/ZnO/$Al_2O_3$ is widely used methanol synthesis catalyst at elevated pressures P (50 to 100 bar) and temperatures T (473 to 573 K) using $CO_2$, CO, $H_2$ syngas mixture. Although Cu step and planar defects have been regarded as active sites in this catalyst, detailed $CO_2$ hydrogenation procedure has been still unknown and debated as well as initial intermediate. In this study, we investigated the mechanism of $CO_2$ hydrogenation on Cu(111) model surface at P (1 bar) and T (298 to 450 K) using reflection absorption infrared spectroscopy (RAIRS). Two distinct formates by hydrogenation of $CO_2$, on step and on terrace, show different behavior with elevating temperature. The peak intensity of on step formate was continuously decreased above 360 K up to 450K in contrast to the increase of on terrace formate. These phenomena are strong possibilities that the formate is initial intermediate and is desorbed by hydrogenation reaction because thermal desorption temperature of formate (~470 K) is much higher than desorption of on step formate. And the formate production peak of on step site was weakly correlated with CO formation.