Nanoarchitectonics toward Full Coverage of CdZnS Nanospheres by Layered Double Hydroxides for Enhanced Visible‐Light‐Driven H2 Evolution

Abstract Nanoarchitectonics of semiconductors shed light on efficient photocatalytic hydrogen evolution by precisely controlling the surface microenvironment of cocatalysts. Taking cadmium zinc sulfide (CZS) nanoparticles as a target, the spontaneous modifications are conducted by interactions between surface Cd 2+ /Zn 2+ atoms and thiol groups in thioglycolic acid. The capping ligand impacts the semiconductor surface with a negative electronic environment, contributing to the full coverage of CZS by nickel‐cobalt hydroxides (NiCo‐LDHs) cocatalysts. The obtained core‐shell CZS@NiCo‐LDHs, possessing a shell thickness of ≈20 nm, exhibits a distinguished topology (S BET = 87.65m 2 g −1 ), long surface carrier lifetime, and efficient charge‐hole separation. Further photocatalytic hydrogen evaluation demonstrates an enhanced H 2 evolution rate of 18.75 mmol g −1 h −1 with an apparent quantum efficiency of 16.3% at 420 nm. The recorded catalytic performance of the core‐shell sample is 44.6 times higher than that of pure CZS nanospheres under visible light irradiation. Further density functional theory simulations indicate that sulfur atoms play the role of charge acceptor and surface Ni/Co atoms are electron donors, as well as a built‐in electric field effect can be established. Altogether, this work takes advantage of strong S affinity from surface metal atoms, revealing the interfacial engineering toward improved visible‐light‐driven photocatalytic hydrogen evolution (PHE) activity.