作者：W. Li,* Y. Dang, T. Ma, J. Li, G. Liao, F. Gao, W. Duan, Xu. Wang, C. Wang*
关键字：Photocatalysis; Single-atom cocatalysis; Hydrogen evolution; Cadmium sulfide; Density functional theory
论文来源：期刊
具体来源：https://doi.org/10.1002/solr.202300110
发表时间：2023年

Single-atom (SA) cocatalysis has obvious superiority in promoting solar-to-chemical energy conversion. However, easy aggregation of SAs is very unfavorable to its catalysis for high surface energy. Herein, a photoreduction procedure was adopted to immobilize Ni SAs on CdS nanoparticles (NPs) to construct the synergistic electric metal-semiconductor interaction (EMSI) for highly promoting the simulated sunlight-driven H₂O-to-H₂ (HTH) conversion in alkaline condition (pH = 14.0) without any sacrificial agent addition, and the nanocatalyst with 1.25‰ of Ni carrying capacity (CdS-Ni_1.25‰) achieved the highest HTH conversion rate (8149.71 μmol·h^-1·g^-1, 13.0-fold greater of that of CdS NPs) and stable photostability accompanied by 27.60% of apparent quantum yield (AQY_{400 nm}). Characterizations and density functional theory calculations indicated that the EMSI on CdS-Ni_1.25‰ nanocatalyst greatly improved the light absorption capacity and promoted the orderly bulk-to-surface migration of photoexcitons, effectively suppressing their recombination kinetics for higher photoexciton utilization efficiency. Under alkaline conditions, high concentration of OH^- ions are easy to react with photogenerated holes to generate hydroxyl radicals for effectively inhibiting the oxidation half-reaction and obtaining higher HTH conversion performance owing to significantly reduced energy barriers on atomic Ni sites. This study provides an insight for improving the performance of conventional photocatalyst through non-noble metallic SAs cocatalysis.