Distinctly different active sites of ZnO-ZrO2 catalysts in CO2 and CO hydrogenation to methanol reactions

Abstract The active site of a solid catalyst varies sensitively with the catalyzed reaction. Herein, using experimentally measured elementary surface reaction kinetics of CO 2 or CO hydrogenation reactions over a ZnO-ZrO 2 catalyst under working conditions in combinations with comprehensive structural characterizations and theoretical simulations, we unveil the distinctly different active sites in catalyzing the CO 2 or CO hydrogenation to methanol reaction. Zn 2+ cations with different local environments are present on the ZnO-ZrO 2 surface, including Zn 1 single atoms exclusively with a Zn-O-Zr local structure and Zn n clusters with both Zn-O-Zr and Zn-O-Zn local structures. The -Zr-O-Zr- structure bonded to the Zn n clusters is more easily to be reduced than that bonded to the Zn 1 single atoms. The Zn 1 -single atom (-Zr-O-Zn-O-Zr-) is the active site for catalyzing the CO 2 hydrogenation to methanol reaction, whereas the Zn n cluster bonded to an in situ formed -Zr-V o -Zr- structure (-Zn-O-Zn(-O-Zr-V o -Zr-)-O-Zr-) is the active site for catalyzing the CO hydrogenation to methanol reaction. These results provide a reliable and effective methodology of elementary surface reaction kinetics for identifications of active sites of working catalysts in complex reactions and unveil how sensitively the active site structure varies with the catalyzed reaction.