Metalloporphyrin based MOF-545 coupled with solid solution Zn_xCd_1-xS for efficient photocatalytic hydrogen production

The growing concern over the rapid consumption of fossil fuels has spurred scientists to seek environment-friendly and sustainable energy alternatives. The utilization of photocatalytic water splitting shows great potential in generating environmentally friendly hydrogen energy. Zirconium-based porphyrin MOF-545 has drawn extensive attention in photocatalysis since it has strong light absorption and fast electron transfer capability. A series of Zr-based metalloporphyrins containing different metals, MOF-545M (M = Co, Ni, Cu, Zn), were synthesized and assembled with solid solution Zn_xCd_1-xS (ZCS) nanoparticle to develop the corresponding of hybrid photocatalysts, ZCS/MOF-545M. Various characterizations show that introducing the porphyrin MOF-545Co not only improve the visible light response range of Zn_0.5Cd_0.5S (ZCS-0.5) but also enhance the carrier separation efficiency of ZCS-0.5. The carrier transfer direction during the reaction was confirmed by surface photovoltage spectroscopy and shows the formation of S-scheme. Under visible light irradiation, the hybrid photocatalyst ZCS-0.5/MOF-545Co exhibits a high H₂ evolution rate of 148 μmol h^-1, with increases of 52.8, 22.9 and 6.5 times than those of bare ZnS, CdS and ZCS-0.5, respectively. The present work gives a strategy for erecting S-scheme heterojunction to inhibit the photocorrosion of metal sulfides and enhancement the carrier separation efficiency.