Solvent Coordination-Induced Synergistic Phase, Facet, and Defect Engineering of CdS for Photocatalytic Hydrogen Evolution

Conventional exogenous modification strategies fail to fundamentally resolve the inherent conflict between rapid carrier recombination and severe photocorrosion in cadmium sulfide (CdS) photocatalysts. To address this issue, a solvent coordination strategy was developed for synergistic phase, facet, and defect engineering of CdS. Four CdS samples were successfully synthesized, including CdS cubic phase, nanospheres, nanowires, and nanorods. Systematic experimental characterizations combined with density functional theory (DFT) calculations reveal that ethylenediamine (EDA) selectively adsorbs on the (002) facet, inducing oriented growth along [101] and in situ sulfur vacancy (V s ) enrichment on the highly active (101) facet. The optimized CdS nanorods deliver a photocatalytic hydrogen evolution (PHE) rate 11.17 times higher than that of the CdS cubic phase and maintain high activity following 30 h of continuous illumination. This work provides new insights into the rational design of highly efficient and stable sulfide-based photocatalysts.