Magnetic Field-Driven Spin State Transformation in Promoting the Catalytic Activity of Doped Single-Atom for Hydrogen Evolution Reaction.

Wang, Chenjing; Yang, Yuquan; Zheng, Jinlong; Yuan, Yanru; Pang, Dawei; Liu, Jiajia; Wu, Hongjing; Liu, Naiyan et al. · Adv Mater · 2026

basic_science · Level V

Where this comes from

Abstract

Developing efficient electrocatalysts for the hydrogen evolution reaction (HER) requires innovative strategies to modulate electronic structures and reaction kinetics. Herein, a ferromagnetic Ru<sub>SAs</sub>/Ni<sub>2</sub>P@Fe<sub>3</sub>O<sub>4</sub> core-shell catalyst is designed, which synergizes Ru single-atoms (SAs) doping and external magnetic field excitation. Under a 0.3 T magnetic field, Ru<sub>SAs</sub>/Ni<sub>2</sub>P@Fe<sub>3</sub>O<sub>4</sub>-0.3 T achieves a remarkably low overpotential of 38.9 mV at 10 mA cm<sup>-2</sup> and a Tafel slope of 39.5 mV dec<sup>-1</sup> in alkaline media, outperforming its counterparts without magnetic stimulation. Advanced characterization (XANES, Mössbauer, EPR, SQUID) and density functional theory calculations reveal that the magnetic field induces a spin-state transition in Fe<sup>3+</sup> (from low-spin to high-spin), enhancing interfacial charge transfer and enriching electron density around Ru SAs. These effects optimize hydrogen adsorption free energy (ΔG<sub>H*</sub>) and reaction kinetics. The Ru SAs serve as the dominant active sites, while the spin-state reconfiguration of the Fe<sub>3</sub>O<sub>4</sub> core under magnetic fields stabilizes the structure and accelerates electron transfer. This work unveils a dual-regulation mechanism combining atomic doping and spin engineering, offering a novel pathway for designing high-performance catalysts via electronic and magnetic synergy.