In Situ Reconstruction of Helical Iron Borophosphate Precatalyst toward Durable Industrial Alkaline Water Electrolysis and Selective Oxidation of Alcohols

Abstract Iron‐based (pre)catalysts have attracted enormous attention for various electrooxidation reactions due to the low cost, high abundance, and multiple accessible redox states of iron. Herein, a well‐defined helical iron borophosphate (LiFeBPO) is developed as an electro(pre)catalyst for the oxygen evolution reaction (OER) and selective alcohol oxidation. When deposited on nickel foam (NF), LiFeBPO exhibits an exceptional OER performance at ambient conditions attaining a current density of 100 mA cm⁻² at ≈276 mV overpotential in 1 m KOH. Notably, this anode sustains durable alkaline water electrolysis at 500 mA cm⁻² for over 330 h under industrial conditions (6 m KOH and 85 °C). In –situ and ex situ investigations reveal a deep reconstruction of LiFeBPO during OER, which transforms into a 3D open porous skeleton assembled by ultrasmall, low‐crystalline α‐FeOOH nanoparticles (interfacing with NiOOH of NF). This structure contributes to exposing accessible surface active sites, as well as accelerating mass transport and bubble detachment. Moreover, this electrode also catalyzes the electrooxidation of alcohols (methanol, ethylene glycol, and glycerol) to formic acid (FA) with high selectivity and full conversion. This study provides promising solutions for designing suitable anodes for the simultaneous production of green hydrogen fuel and value–added FA from electrooxidation reactions.