Manipulating Spin Exchange Interactions and Spin‐Selected Electron Transfers of 2D Metal Phosphorus Trisulfide Crystals for Efficient Oxygen Evolution Reaction

Abstract Because oxygen molecules in the ground state favor a triplet spin configuration, spin‐polarized electrons at electrocatalysts may promote the generation of parallel spin‐aligned oxygen atoms, enhancing oxygen evolution reaction (OER) kinetics. In this study, a significant enhancement of OER performance is demonstrated by controlling the spin‐exchange interaction and spin‐selected electron transfer of 2D Co_xFe_1−xPS₃ (x = 0–0.45) van der Waals (vdW) single crystals through Co doping. The pristine FePS₃ exhibits antiferromagnetic orbital ordering, while the Co‐doped FePS₃ exhibits the emergence of interatomic ferromagnetism due to doping‐mediated magnetic exchange interactions. The coupling between Fe and Co ions in the Co‐doped FePS₃ crystal allows the formation of efficient spin‐selective electron transfer channels compared to the pristine FePS₃. The correlation of spin‐exchange interactions and spin‐selected electron transfers of 2D Co‐doped FePS₃ crystals with a superior OER performance is further revealed by superconducting quantum interference device magnetometer, in situ X‐ray absorption near edge spectra and density functional theory simulations. The result suggests that manipulating the spin‐exchange interactions of 2D vdW crystals to enhance the spin‐selected electron transfer efficiencies through doping is an effective strategy to boost their OER catalytic performances.