Distal Spin Modulation in Two‐dimensional van der Waals VS ₂ /FePSe ₃ @Ni Heterostructure for Electrocatalytic Oxygen Reduction Reaction

ABSTRACT This study designs a novel 2D van der Waals magnetic heterojunction, VS 2 /FePSe 3 @Ni, achieving remote spin control over the oxygen reduction reaction (ORR) catalytic performance by manipulating the spin orientation of the underlying VS 2 layer. Theoretical calculations reveal that switching the ferromagnetic VS 2 layer's spin orientation from spin‐up to spin‐down induces significant shifts in the heterojunction's band edge alignment and built‐in electric field. This restructuring shifts the optimal ORR pathway: the spin‐down state favors the efficient 4e − pathway with H 2 O desorption as the rate‐determining step (energy barrier: −0.86 eV), while the spin‐up state promotes 2e − reduction where OOH hydrogenation limits the rate (energy barrier: −0.54 eV). Further analysis reveals that spin flipping significantly enhances the material's electrical conductivity and Seebeck coefficient, leading to a notable improvement in the thermoelectric figure of merit ZT, demonstrating excellent thermoelectric conversion potential. This research not only uncovers the remote‐control mechanism of spin polarization effects on the catalytic performance of heterojunctions but also provides a new paradigm for developing highly active and selective spintronic catalysts and multifunctional thermoelectric materials.