Asymmetric Electron Transport‐Induced Formation of High‐Valent IrOx in NiFeOOH Heterostructure for Efficient Water Oxidation

Abstract Metal oxyhydroxides (MOOHs) as the active phase of transition metal‐oxide (TMOs) electrodes in the oxygen evolution reaction (OER) are limited by unsatisfactory electrochemical activity and stability during high‐current conditions. Herein, the heterostructure of high‐valent IrO x (Ir n+ , n>4) combined with FeNi 3 OOH via asymmetric electron transport is deliberately designed on carbon cloth (IrO x ‐FeNi 3 OOH/CC) as a promising OER electrocatalyst for industrial deployments. Experimental and DFT calculations reveal that the asymmetric electron transfer from Ir to the low‐spin orbital of Fe/Ni sites via bridged O 2− sites (Ir─O─Ni/Fe bonds) at IrO x ‐FeNi 3 OOH heterostructure interfaces induces the formation of high‐valent Ir species. This process tailors the d‐band center of Ir sites, thereby reducing the energy barrier of the rate‐determining step from O * to OOH * in OER. The elevated activity of high‐valent Ir enables IrO x ‐FeNi 3 OOH/CC to achieve an ultra‐low overpotential of 241 mV at 200 mA cm −2 , along with remarkable stability for 160 h under large current conditions (outperforming commercial IrO 2 /CC). This work offers a basis for rationally designing and analyzing the potential role of precious‐metal‐based oxyhydroxides as electrocatalysts for the OER and related processes.