<i>In Situ</i> Characterization Reveals a Favorable Reconstruction of BiVO₄ in Thermal catalysis

Reconstruction of catalysts, widely acknowledged in electrocatalysis, has rarely been explored in thermal catalysis. This study demonstrates a dynamic favorable reconstruction of BiVO4 in thermal selective oxidation of benzylic C–H of toluene using in situ techniques. BiVO4 undergoes reconstruction during high-temperature H2 reduction, wherein Bi dissolves and aggregates into metallic Bi particle to form Bi/BiVO4. Bi/BiVO4 undergoes secondary reconstruction through high-temperature O2 oxidation in thermal catalysis, wherein Bi migrates toward metallic Bi particle to form Bi2O3/BiVO4. Bi2O3/BiVO4 exhibits good adsorption performance on toluene and O2, and promotes charge transport to generate more abundant active species. Therefore, a toluene conversion of 26,300.00 μmol·gcat–1·h–1 and product yield of 410.00 mmol·gcat–1 were achieved, giving the highest reported product yield for thermal selective oxidation of the benzylic C–H bond of toluene. Based on this, Bi2O3/BiVO4 catalysts with high-performance can be synthesized by a one-step hydrothermal method, opening up new avenues for thermal catalyst design.