Inspired by the rich morphology of ZnO and cation-exchange technology, regular dodecahedron-like CeO 2 /ZnO was obtained by the calcination of Ce doped ZIF-8 precursor in this study, and CeO 2 /ZnS was obtained by the in-situ vulcanization of CeO 2 /ZnO. This design not only maintained the morphology of ZIF-8, but also enhanced the oxidation-reduction capacity of the catalyst. When the Ce content was 10 wt %, 10-CeO 2 /ZnS sample showed the best photocatalytic hydrogen production performance in all XÀ CeO 2 /ZnS samples. Loading of co-catalysts can effectively enhance the surface hydrogen reduction in photocatalytic water splitting by introducing a positive Schottky barrier. CuS was regarded as a promising cocatalyst to replace the noble metals due to its low cost and equivalent or even better performance. The in-situ cation exchange method was used to load co-catalyst CuS on the 10-CeO 2 /ZnS composites to obtain the 10-CeO 2 /ZnS-CuS composites which had the large specific surface area, regular dodecahedral structure and much excellent photolysis of water to produce hydrogen characters. This work provided a new strategy for the advantages combining of co-catalyst, p-n junction as well as the porous structure to enhance the photocatalytic characters.

SnO2 is a wide band gap semiconductor which has no photocatalysis under visible light. In this study, the disordered porous SnO2 precursor was constructed which showed obvious photocatalysis under visible light irradiation. Its degradation rate to RhB was 51.66% after 100 min, and the amount of hydrogen produced could reach 11.13 mmol⋅g−1 after 3.5 h under visible light irradiation. And then, In2O3 was used as sensitizer to increase the specific surface area of porous SnO2 matrix. The specific surface area of porous SnO2 was increased from 167.355 m2⋅g−1 to 544.394 m2⋅g−1 when the doping amount of In2O3 was 1.5 wt.%. The photocatalytic properties of the porous SnO2 matrix was also vastly increased. The highest photocatalytic activity was observed for the In2O3/SnO2‐1.5 sample, the degradation rate of RhB was 93.50% after 100 min which was 1.85 times of the SnO2 matrix, and the hydrogen production rate could reach 21.51 mmol⋅g−1 after 3.5 h which was 1.94 times of the SnO2 matrix under visible light irradiation. The catalyst had a much higher stability which could be recycled utilize.