Support Effect and Surface Reconstruction in In₂O₃/<i>m-</i>ZrO₂ Catalyzed CO₂ Hydrogenation

We investigate the chemical and structural dynamics at interface of In2O3/m-ZrO2 their consequences on CO2 hydrogenation reaction (CO2HR) under conditions. While acting to enrich CO2, monoclinic zirconia (m-ZrO2) was also found serve as a modifier In2O3 that directly governs outcome CO2HR. These modifying effects include following: (1) Under conditions (above 623 K), partially reduced In2O3, i.e., InOx (0 < x 1.5), migrate in out subsurface m-ZrO2 semireversible manner, where accommodates stabilizes by serving reservoir. The decreased concentration surface elevated temperatures coincides with significantly selectivity toward methanol sharp increase reverse water–gas shift reaction. reconstruction-induced variation appears be one most important factors contributing altered catalytic performance CO2HR different (2) strong interactions reactions between result activation pool In–O bonds form oxygen vacancies. On other hand, high dispersity nanostructures onto prevents over-reduction catalytically relevant (up 673 when bare is unavoidably into metallic phase (In0). relationship extent reduction (CO2 conversion, CH3OH selectivity, or yield CH3OH) suggests presence an optimum coverage vacancies conventional model links solely invalid present case. In situ analysis allows observation intermediates interconversions, including CO3* formate, precursor for formation CO. combinative ex study sheds light mechanism In2O3/m-ZrO2-based catalysts. Our findings large-scale reconstructions, support effect, may apply related metal oxide catalyzed reactions.