The electronic structure of active sites is critically important for electrochemical reactions. Here, the authors report a facile approach to independently regulate the electronic structure of Fe in Ni_0.75Fe_0.25Se₂ by P doping. The resulting electrode exhibits superior catalytic performance for the oxygen evolution reaction (OER) showing a low overpotential (238 mV at 100 mA cm⁻², 185 mV at 10 mA cm⁻²) and an impressive durability in an alkaline medium. Additionally, the mass activity of 328.19 A g⁻¹ and turnover frequency (TOF) of 0.18 s⁻¹ at an overpotential of 500 mV are obtained for P─Ni_0.75Fe_0.25Se₂ which is much higher than that of Ni_0.75Fe_0.25Se₂ and RuO₂. This work presents a new strategy for the rational design of efficient electrocatalysts for OER.

An in-depth understanding of electrocatalytic mechanisms is essential for advancing electrocatalysts for the oxygen evolution reaction (OER). The emerging oxide pathway mechanism (OPM) streamlines direct O–O radical coupling, circumventing the formation of oxygen vacancy defects featured in the lattice oxygen mechanism (LOM) and bypassing additional reaction intermediates (*OOH) inherent to the adsorbate evolution mechanism (AEM). With only *O and *OH as intermediates, OPM-driven electrocatalysts stand out for their ability to disrupt traditional scaling relationships while ensuring stability. This review compiles the latest significant advances in OPM-based electrocatalysis, detailing design principles, synthetic methods, and sophisticated techniques to identify active sites and pathways. We conclude with prospective challenges and opportunities for OPM-driven electrocatalysts, aiming to advance the field into a new era by overcoming traditional constraints.

This study achieved dendrite-free Zn metal anodes for Zn-ion batteriesviaanin situgenerated gradient organic/inorganic hybrid solid–electrolyte interphase enabled by a eutectic electrolyte.