LAUSR

The coordination compounds in the oxygen evolution reaction (OER) have been researched extensively. However, their poor durability (mostly < 100 h) and controversial reconstruction mechanism restrict their practical applications. Herein, a new‐type polyoxomolybdate‐organic complex (POMo) via wet‐chemistry synthesis with fixed coordination between metal centers (Ni2+ and [Mo8O26]4−) and 2‐Methylimidazole ligand is introduced. After introducing iron, a series of Fe‐doped Ni‐POMo with porous and amorphous structures are fabricated. These features accelerate the diffusion‐leaching processes of ligands and anions, resulting in rapid and complete phase reconstruction during alkaline OER. As a result, nickel‐iron (oxy)hydroxides with rich vacancies and poly‐/low‐crystalline features are in situ generated through dissolution‐redeposition, and serve as the OER‐active species. The optimized Fe0.052Ni‐POMo array pre‐catalyst has excellent activity and sustains ultrastable catalysis for 545 h. The complete reconstruction of POMo enables high catalytic durability (230 h) and stable active phase under realistic conditions (30 wt% KOH, 60.9 °C). Accordingly, the completely reconstructed catalysts with unique structures and ultrastable catalysis have the potential to be applied in industry.