Synergizing Electronic‐Structure Modulation With Magnetic‐Field‐Assisted Charge Dynamics for Enhanced Photocatalytic Hydrogen Evolution

ABSTRACT Optimizing adsorption thermodynamics inevitably introduces deep‐level defects that aggravate carrier recombination, making it challenging to simultaneously regulate surface reaction thermodynamics and suppress recombination kinetics within a single catalytic system. Herein, we develop a CoNiP‐modified TiO 2 magnetic composite photocatalyst (CoNiP@TiO 2 ), employing a strategy that combines intrinsic electronic structure regulation with an external magnetic field to address this issue. The electronic interaction between Co and Ni modulates the d‐band centers, reduces the reaction barriers, and improves H* adsorption/desorption thermodynamics. Simultaneously, the applied magnetic field promotes photogenerated charge separation and interfacial charge transfer while suppressing carrier recombination. As a result, this synergistic mechanism yields an ultrahigh hydrogen evolution rate of 5041.30 µmol g −1 h −1 , nearly an order of magnitude higher than that under non‐magnetic conditions. Our findings provide compelling evidence that coupling intrinsic electronic‐structure modulation with external magnetic field regulation enables the decoupling and synergistic optimization of surface reaction thermodynamics and charge transport kinetics in CoNiP@TiO 2 .