Thermo-driven photocatalytic CO reduction and H2 oxidation over ZnO via regulation of reactant gas adsorption electron transfer behavior

Abstract

Photothermal catalysis is a widely researched field in which the reaction mechanism is usually investigated based on the photochemical behavior of the catalytic material. Considering that the adsorption of reactants is essential for catalytic reactions to occur, in this study, the synergistic effect of photothermal catalysis is innovatively elucidated in terms of the electron transfer behavior of reactant adsorption. For the H2 + O2 or CO + H2 reaction systems over a ZnO catalyst, UV irradiation at 25 °C or heat without UV irradiation did not cause H2 oxidation or CO reduction; only photothermal conditions (100 or 150 °C + UV light) initiated the two reactions. This result is related to the electron transfer behavior associated with the adsorption of CO or H2 on ZnO, in which H2 or CO that lost an electron could be oxidized by O2 or hydroxyls. However, the electron-accepting CO could be reduced by the electron-donating H2 into CH4 under photothermal conditions. Based on the in-situ characterization and theoretical calculation results, it was established that the synergistic effect of the photothermal conditions acted on the (002) crystal surface of ZnO to stimulate the growth of zinc vacancies, which resulted in the formation of defect energy levels, adsorption sites, and an adjusted Fermi level. As a result, the electron transfer behavior between adsorbed CO or H2 and the crystal surface varied, which further affected the photocatalytic behavior. The results show that the effect of photothermal synergy may not only produce the expected kinetic energy, but more importantly, produce energy that can change the activation mode of the reactant gas. This study provides a new understanding of the CO catalytic oxidation and reduction processes over semiconductor materials.