Multication and Structure Regulation: Utilizing X‐Doped (X = Co, Mn, Cu) ZnS/CoO Hollow Composites to Spatially Propel the Charge for Superior Solar Hydrogen Evolution

Abstract

Developing polyhedral hollow structures with a concise and flexible method is intensively pursued to construct the high‐efficiency photocatalytic system. Herein, a general ion exchange‐induced strategy is developed to synthesize various hollow X‐doped (X = Co, Mn, Cu) ZnS with tunable interior components. To make the reactivity superior, abundant CoO nanoparticles are integrated into doped ZnS hollow microstar as visible‐light‐responsive photocatalysts for efficient H2 evolution. This distinct heterostructure gives full play to the following structural and compositional virtues: (i) multifacet light reflections in cavity offer massive photoexcited active centers for water photosplitting; (ii) the built‐in electric field (formed at the p‐n junction) accelerates interfacial charge separation and enhance the reducibility of photogenerated electrons, which endows the doped ZnS/CoO composite superior H2 evolution rate (1763.17 μmol h−1 g−1) and stable cyclability without needing any cocatalyst. More importantly, the formation of the potential barrier at the p‐n nanointerface and essential hydrogen evolution reaction steps are investigated to gain insight into the catalytic mechanism of the doped ZnS/CoO system.