Orchestrating Ti─S and Ni─S Bonding Interfaces for Accelerated Charge Transfer in a S‐Scheme Photocatalyst

Abstract Precise engineering of interfacial electron transfer is pivotal for advancing photocatalytic performance. Herein, a TiO 2 /CdS/Ni (CSTNi) core–shell photocatalyst featuring orchestrated interfacial charge transport is designed. Oxygen vacancies in TiO 2 serve as electron reservoirs, while interfacial Ti─S bonds accelerate carrier transfer across the TiO 2 /CdS (CST) interface. Simultaneously, Ni nanoparticles function as active sites, promoting rapid electron migration via Ni─S interfacial bonding. Notably, the d ‐orbital hybridization of transition metals (Ti and Ni) with the p orbitals of sulfur modulates the local electronic structure, synergistically enhancing interfacial electron dynamics. X‐ray absorption spectroscopy confirms the formation of Ti─S and Ni─S bonds with strong electronic coupling, while X‐ray photoelectron spectroscopy and density functional theory (DFT) calculations reveal directed charge migration at the CST and CdS/Ni interfaces. Femtosecond transient absorption (fs‐TA) spectroscopy demonstrates a marked acceleration of interfacial electron transfer, with CSTNi exhibiting a rate constant of 2.0 × 10 9 s −1 , significantly surpassing CdS/Ni (6.7 × 10 8 s −1 ). Benefiting from the engineered interfacial pathways, CSTNi achieves superior photocatalytic degradation of microplastics, concurrently delivering a remarkable H 2 evolution rate. This work introduces an strategy for coupling interfacial chemical bonding with cocatalyst engineering, offering new insights for the rational design of high‐efficiency photocatalytic systems.