An in situ DRIFTS mechanistic study of CeO2-catalyzed acetylene semihydrogenation reaction

摘要

CeO2-Catalyzed C2H2 semihydrogenation reaction is a newly emerging catalytic reaction, but the reaction mechanism is not established. We herein report a comprehensive mechanistic study by in situ diffuse reflectance infrared Fourier transformed spectroscopy. Various types of surface species were observed to form upon C2H2 and C2H4 adsorption on CeO2 at different temperatures, including molecularly-adsorbed pi-bonded and di-s-bonded species, dissociatively-adsorbed species of C2H and C2H3, carbonates and formate species, and oligomers species, respectively. During the C2H2 semihydrogenation reaction, the CeO2 surface is partially reduced and strongly hydroxylated. Both O and Ce sites on CeO2 are capable of catalyzing C2H2 semihydrogenation reaction to C2H4, and the O site is more active than the Ce site. The reaction mechanism was elucidated with observed molecularlyadsorbed C2H2 species, a C2H3 intermediate and adsorbed C2H4 species on CeO2. The p-bonded C2H2 species at the O site was identified as the dominant active surface species for CeO2-catalyzed C2H2 semihydrogenation reaction. These results greatly advance the fundamental understanding of CeO2-catalyzed C2H2 semihydrogenation reaction.