Hierarchical Co₉S₈/CdS Hollow Nanocages for Efficient and Robust Cooperative Coupling Photoredox Synthesis

The elaborate development of photocatalysts that can maximize the utility of solar energy with simultaneous photocatalytic H 2 evolution and high‐quality chemicals production holds great promise in the field of selective photoredox synthesis. Herein, the in situ growth of CdS nanowires on the outside surface of Co 9 S 8 hollow nanocages is reported to create a hierarchical CdS/Co 9 S 8 hollow photocatalyst for efficient photochemical coupling of amines to produce imines and H 2 . This ingenious hierarchical photocatalyst has a unique hollow structure and dense interfacial contact with a type‐I band orientation, which facilitates the interfacial transfer of charge carriers. The photocatalytic activity of this hierarchical hollow catalyst is significantly enhanced in comparison to CdS and Co 9 S 8 , and distinctively exhibits excellent recycling stability. Mechanistic studies have shown that the carbon‐centered radical Ph( • CH)NH 2 is essential for the reaction. Additionally, the CdS/Co 9 S 8 hollow hybrid also exhibits outstanding performance in coupling various primary amines to the corresponding imines, highlighting the broad applicability of this photocatalyst for C−N coupling reactions. This work offers a new strategy for the efficient design of heterostructured hollow semiconductor‐based photocatalysts for the cooperative coupling of clean fuel production and fine chemical synthesis.