New in-sights into the engineering of reactive oxygen species with boosting photothermal catalytic selectivity for dihydroxyacetone by synergistic Cu/ Ce bimetallic active center over BiVO4

The low selectivity and conversion rate of dihydroxyacetone (DHA) by glycerol oxidation over catalysts due to their poor reactive oxygen species (ROS) regulation, which still seriously limits the practical application. Engineering of ROS, especially singlet oxygen (1O2), by constructing oxygen vacancies (OVs) can tune surface/bulk electronic structure and improve surface active sites of catalytic oxidation with desired selectivity and reactivity. Herein, we report the preparation of DHA by photothermal catalysis (PTC) of glycerol over Cu/Ce-BiVO4 ternary system with unique Ce nanoisland structure on the surface of BiVO4 substrate for effectively anchoring Cu. The forming Ce-O-Cu asymmetric oxygen vacancies can both promote the electron transfer to form superoxide anion (.O2 ) and also improve the efficiency of energy transfer to generate 1O2. Furthermore, the synergistic Ce and Cu bimetal active sites can regulate the microelectron structure of Ce3+/Ce4+ and Cu0/Cu+redox centers, leading an outstanding yield of 41.1% and a boosting selectivity reached to 59.7%..O2 can enhance the conversion of glycerol oxidation, while 1O2 can boost the selectivity to directionally form DHA. The synergistic effect of 1O2 and .O2 is the key to improve catalytic efficiency. First-principles calculations indicate that the most reasonable reaction pathway for 1O2 production is O2 -> Cu/Ce-BVO -> 1O2. This study explores the relationship between asymmetric oxygen vacancy and singlet oxygen production, and provides a basis for designing new highperformance catalysts.