In Situ Reconstruction of a Highly Integrated Cu/Cu2O/MoO2 Dual Heterojunctions for High-Performance CO2 Photothermal Catalysis.

During heterogeneous photothermal catalysis, catalysts are prone to undergo random and disordered structural evolution, which poses a severe challenge to the construction of advanced photothermal catalytic systems integrating photoexcited charge carrier separation, molecular activation, and active-site engineering. In this work, we employ an in situ reconstruction strategy to fabricate a highly integrated Cu/Cu2O/MoO2 composite catalyst using Cu3Mo2O9 as the precursor under a CO2/H2 reaction atmosphere. The as-constructed Cu/Cu2O Schottky junction and Cu2O/MoO2 p-n junction form a dual-heterojunction structure, enabling efficient separation of photogenerated charge carriers. Meanwhile, amorphous MoO2 with abundant oxygen vacancies and Cu/Cu2O provide functionally complementary activation sites for CO2 activation and H2 dissociation/spillover, respectively. Benefiting from the efficient synergistic interplay among the three components (Cu, Cu2O, and MoO2), the Cu/Cu2O/MoO2 catalyst enables the efficient conversion of CO2 via the photothermal reverse water-gas shift (RWGS) reaction, delivering a superior CO production rate of 14.65 mmol g-1 h-1 alongside ultra-long stability, retaining high activity across an impressive 215-h continuous reaction run. This study offers a new avenue for the construction of integrated functional photothermal catalysts with high performance via an in situ reconstruction approach.