Optimizing Edge Active Sites via Intrinsic In‐Plane Iridium Deficiency in Layered Iridium Oxides for Oxygen Evolution Electrocatalysis

Abstract Improving catalytic activity of surface iridium sites without compromising catalytic stability is the core task of designing more efficient electrocatalysts for oxygen evolution reaction (OER) in acid. This work presents phase transition of a bulk layered iridate Na2IrO3 in acid solution at room temperature, and subsequent exfoliation to produce 2D iridium oxide nanosheets with around 4 nm thickness. The nanosheets consist of OH‐terminated, honeycomb‐type layers of edge‐sharing IrO6 octahedral framework with intrinsic in‐plane iridium deficiency. The nanosheet material is among the most active Ir‐based catalysts reported for acidic OER and gives an iridium mass activity improvement up to a factor of 16.5 over rutile IrO2 nanoparticles. The material also exhibits good catalytic and structural stability and retains the catalytic activity for more than 1300 h. The combined experimental and theoretical results demonstrate that edge Ir sites of the layer are active centers for OER, with structural hydroxyl groups participating in the catalytic cycle of OER via a non‐traditional adsorbate evolution mechanism. The existence of intrinsic in‐plane iridium deficiency is the key to building a unique local environment of edge active sites that have optimal surface oxygen adsorption properties and thereby high catalytic activity.