Enhanced Oxygen Evolution and Zinc‐Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts

Abstract Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe 2 O 4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH − and O 2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm −2 . Besides, rechargeable zinc‐air batteries based on Ni/MnFe 2 O 4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin‐selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next‐generation OER catalysts with boosted performance.