Support Effect and Surface Reconstruction in In2O3/ m-ZrO2Catalyzed CO2Hydrogenation

We investigate the chemical and structural dynamics at the interface of In2O3/m-ZrO2and their consequences on the CO2hydrogenation reaction (CO2HR) under reaction conditions. While acting to enrich CO2, monoclinic zirconia (m-ZrO2) was also found to serve as a chemical and structural modifier of In2O3that directly governs the outcome of the CO2HR. These modifying effects include the following: (1) Under reaction conditions (above 623 K), partially reduced In2O3, i.e., InOx(0 < x < 1.5), was found to migrate in and out of the subsurface of m-ZrO2in a semireversible manner, where m-ZrO2accommodates and stabilizes InOxby serving as a reservoir. The decreased concentration of surface InOxunder elevated temperatures coincides with significantly decreased selectivity toward methanol and a sharp increase of the reverse water-gas shift reaction. The reconstruction-induced variation of InOxconcentration appears to be one of the most important factors contributing to the altered catalytic performance of CO2HR at different reaction conditions. (2) The strong interactions and reactions between m-ZrO2and In2O3result in the activation of a pool of In-O bonds at the In2O3/m-ZrO2interface to form oxygen vacancies. On the other hand, the high dispersity of In2O3nanostructures onto m-ZrO2prevents their over-reduction under catalytically relevant conditions (up to 673 K), when bare In2O3is unavoidably reduced into the metallic phase (In0). The relationship between the extent of reduction of In2O3and catalytic performance (CO2conversion, CH3OH selectivity, or yield of CH3OH) suggests the presence of an optimum coverage of surface InOxand oxygen vacancies under reaction conditions. The conventional model that links catalytic performance solely to the coverage of oxygen vacancies appears invalid in the present case. In situ analysis also allows the observation of surface reaction intermediates and their interconversions, including the reduction of CO3∗ into formate, a precursor for