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

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 TiO2 magnetic composite photocatalyst (CoNiP@TiO2), 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@TiO2.