Spin‐Related Electron Transfer and Orbital Interactions in Oxygen Electrocatalysis

Abstract Oxygen evolution and reduction reactions play a critical role in determining the efficiency of the water cycling (H 2 O ⇔ H 2 + O 2 ), in which the hydrogen serves as the energy carrier. That calls for a comprehensive understanding of oxygen electrocatalysis for efficient catalyst design. Current opinions on oxygen electrocatalysis have been focused on the thermodynamics of the reactant/intermediate adsorption on the catalysts. Because the oxygen molecule is paramagnetic, its production from or its reduction to diamagnetic hydroxide/water involves spin‐related electron transfer. Both electron transfer and orbital interactions between the catalyst and the reactant/intermediate show spin‐dependent character, making the reaction kinetics and thermodynamics sensitive to the spin configurations. Herein, a brief introduction on the spintronic explanation of the catalytic phenomena on oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is given. The local spin configurations and orbital interactions in the benchmark transition‐metal‐based catalysts for OER and ORR are analyzed as examples. To further understand the spintronic oxygen electrocatalysis and to develop more efficient spintronic catalysts, the challenges are summarized and future opportunities proposed. Spin electrocatalysis may emerge as an important topic in the near future and help integrate a comprehensive understanding of oxygen electrocatalysis.