Dual Electric Field Coupling with Tunable Schottky Barrier Synergistically Regulating Electronic Configuration in CoP@Ni‐CdS Heterojunction for Efficient Photocatalytic H2 Evolution

Abstract Designing and exploiting visible‐light‐responsive materials that converts solar into chemical energy is promising in achieving green energy sustainability, but addressing low electron–hole separation efficiency and sluggish surface kinetic process remains formidable challenges. Herein, a novel CoP@Ni‐CdS Schottky junction composed of Ni‐doped CdS nanorods and quasi‐metallic CoP nanoparticles is constructed via a simple hydrothermal–calcination method. Experiments and theoretical calculations demonstrate that magnetic Ni‐doping not only induces a spin‐polarized electric field and enhances the built‐in interfacial electric field strength, but also rises the Schottky barrier height at the heterointerface, which synergistically accelerates the separation efficiency of photoinduced charges and modulates the electronic configuration of the active site to optimize the adsorption–desorption behaviors for H 2 O molecules and H* intermediates. Therefore, the designed CoP@Ni‐CdS catalyst exhibits an exceptional photocatalytic performance with H 2 evolution rate of 42.14 mmol g −1 h −1 with the apparent quantum efficiencies of 16.8% at 420 nm, which is 14.14 and 2.21 times higher than that of pristine CdS and Ni‐CdS, respectively. This work provides in‐depth insights into fabricating dual electric fields, tuning the Schottky barrier and modulating the electronic configuration of active sites in Schottky heterojunction for ameliorative photocatalytic activity.