In Situ Regulating Cobalt/Iron Oxide‐Oxyhydroxide Exchange by Dynamic Iron Incorporation for Robust Oxygen Evolution at Large Current Density

Abstract The key dilemma for green hydrogen production via electrocatalytic water splitting is the high overpotential required for anodic oxygen evolution reaction (OER). Co/Fe‐based materials show superior catalytic OER activity to noble metal‐based catalysts, but still lag far behind the state‐of‐the‐art Ni/Fe‐based catalysts probably due to undesirable side segregation of FeOOH with poor conductivity and unsatisfied structural durability under large current density. Here, a robust and durable OER catalyst affording current densities of 500 and 1000 mA cm −2 at extremely low overpotentials of 290 and 304 mV in base is reported. This catalyst evolves from amorphous bimetallic FeOOH/Co(OH) 2 heterostructure microsheet arrays fabricated by a facile mechanical stirring strategy. Especially, in situ X‐ray photoelectron spectroscopy (XPS) and Raman analysis decipher the rapid reconstruction of FeOOH/Co(OH) 2 into dynamically stable Co 1‐x Fe x OOH active phase through in situ iron incorporation into CoOOH, which perform as the real active sites accelerating the rate‐determining step supported by density functional theory calculations. By coupling with MoNi 4 /MoO 2 cathode, the self‐assembled alkaline electrolyzer can deliver 500 mA cm −2 at a low cell voltage of 1.613 V, better than commercial IrO 2 (+) ||Pt/C (‐) and most of reported transition metal‐based electrolyzers. This work provides a feasible strategy for the exploration and design of industrial water‐splitting catalysts for large‐scale green hydrogen production.