LAUSR

Abstract Achieving structure optimizing and component regulation simultaneously in the ZnIn2S4‐based photocatalytic system is an enormous challenge in improving its hydrogen evolution performance. 3D hollow‐structured photocatalysts have been intensively studied due to their obvious advantages in solar energy conversion reactions. The synthesis of 3D hollow‐structured ZnIn2S4, however, is limited by the lack of suitable template or synthesis methods, thereby restricting the wide application of ZnIn2S4 in the field of photocatalysis. Herein, Ce‐doped ZnIn2S4 photocatalysts with hollow nanocages are obtained via one‐step hydrothermal method with an ordered large‐pore tetrakaidecahedron cerium‐based metal–organic frameworks (Ce‐MOFs) as template and Ce ion source. The doping of Ce and the formation of ZnIn2S4 tetrakaidecahedron hollow nanocages with ultrathin nanosheet subunits are simultaneously induced by the Ce‐MOFs, making this groundbreaking work. The Ce‐doped ZnIn2S4 with a nonspherical 3D hollow nanostructure inherit the tetrakaidecahedron shape of the Ce‐MOF templates, and the shell is composed of ultrathin nanosheet subunits. Both theoretical and experimental results indicate that the doping of Ce and the formation of hollow nanocages increase light capture and the separation of photogenerated charge carriers.