Strong Synergy between Pd Single Atom and Zn Vacancy Boosts Photocatalytic Pure Water Splitting

Single‐atom and vacancy‐engineered photocatalysts have shown their remarkable strengths in improving carrier transfer dynamics, yet constructing the integration of single atoms and vacancies as the active site is still challenging. Herein, an icing‐assisted photochemical strategy has been employed to anchor Pd single atoms in Zn vacancies on Cd x Zn 1− x S nanorods to form a Pd–S 4 tetrahedron coordination structure, enabling exceptional photocatalytic water splitting performance in the absence of any sacrificial agents. Under visible light irradiation, the H 2 evolution rate of Pd/Cd 0.1 Zn 0.9 S reaches 608.2 μmol g −1 h −1 , which is around 229, 6.7, 6.1, and 2 times to that of ZnS, Cd 0.1 Zn 0.9 S, Pd/ZnS, and Pd NPs/Cd 0.1 Zn 0.9 S, respectively. Detailed experimental and theoretical analyses confirm that Pd–S hybridized electronic states and Pd single atoms are beneficial for enhancing the charge separation/transfer, accelerating the formation of H* and the release of H 2 .