Decoupling of Spin and Non‐Spin Effects From Electronic Structure Modulation for Oxygen Electrocatalysis
Yingliang Zhao, Zhen Ji, X.L. Xiao, Zhi Fang, Yanglong Hou
Abstract
Abstract The aggravation of global warming and environmental degradation amplifies the demand for green energy technologies, where oxygen‐involved reactions, including oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), play pivotal roles in energy conversion. However, they suffer from inherent spin‐related kinetic bottlenecks due to the spin transitions between singlet H 2 O and triplet O 2 . While the modulation strategies (built‐in electric fields, built‐in magnetic fields, crystal fields and ligand fields) advance electronic structure engineering for catalyst design. Nevertheless, they inevitably co‐regulate spin effects (spin state/polarization) and non‐spin effects (d‐band center shifts, valence tuning, etc.), making it difficult to distinguish the individual contributions to catalytic performance. This review systematically distinguishes the influence of spin/non‐spin factors in electronic structure‐modulated OER/ORR, aiming to clarify their regulatory mechanisms, contribution ratios, and synergistic effects. Statistical analyses indicate that spin‐related and non‐spin‐related effects exhibit comparable importance, with synergistic regulation yielding superior OER performance. Further analyzing their distinct roles in dynamics (adsorption/desorption) and kinetics (spin flip/selective electron transfer), this work proposes a deeply decoupling approach to disentangle these effects, providing new perspectives for rational design of spin‐controlled electrocatalysts and optimizing catalytic performance beyond traditional constraints.