Electronically Inverted Perovskite‐Type Co‐catalyst as a Universal Platform for Enhanced Photocatalysis

Abstract Co‐catalysts are commonly employed as catalytic centers to activate reactants and intermediates for driving redox reactions with photogenerated carriers during photocatalysis. Herein, a group of electronically inverted perovskite‐type nitrides Cu_xIn_1−xNNi₃ (0 ≤ x ≤ 1) are reported as novel and versatile co‐catalysts for the significantly enhanced photocatalytic hydrogen production performance on various photocatalysts, such as metal sulfides (CdS, ZnIn₂S₄), carbon nitride (g‐C₃N₄), and metal oxide (TiO₂), respectively. The hybrid photocatalyst Cu_0.5In_0.5NNi₃/CdS exhibits an optimal activity up to 6945 µmol g⁻¹ h⁻¹ and a remarkable enhancement factor of 6146% compared with that of pristine CdS. Besides, a high reaction stability with repetitive photocatalytic cycles is achieved. The obvious improvement of activity can be ascribed to the promoted charge separation of energetic carriers due to the metallic properties of Cu_xIn_1−xNNi₃ and abundant Ni active sites. A near‐zero Gibbs free energy of adsorbed atomic hydrogen on the Ni‐site is thermodynamically favorable for hydrogen evolution, which can be regulated by electronic states of A‐sites (Cu/In). This work not only demonstrates the great potential of perovskite‐structured nitrides as a universal platform for enhanced photocatalysis but also addresses the importance of exploring new catalytic applications for unique perovskite‐derivatives with cations/anions exchanged in coordinated sites of polyhedral.