Unveiling Anodic Reconstruction of Electroless‐Deposited Dual‐Sided <scp>NiFeP</scp> Catalyst‐Coated Membranes for Efficient Anion Exchange Membrane Water Electrolysis

This study presents a unique strategy for fabricating electroless‐deposited dual‐sided NiFeP catalyst‐coated membranes (CCMs), with the dual‐sided catalyst layers serving as cathode and anode for anion‐exchange membrane (AEM) water electrolysis. The electroless‐deposited dual‐sided CCM enables ionomer‐free integration and enhanced membrane‐catalyst adhesion, providing structural simplicity and scalability for practical AEM water electrolysis. The Ni 0.72 Fe 0.14 P 0.14 anode delivers current densities of 0.5 and 1.0 A cm −2 with low overpotentials of 398 and 440 mV, respectively, and remains stable for >100 h at 0.5 A cm −2 , with a small decay rate of 0.6 mV h −1 . The enhanced performance originates from the reconstruction process facilitated by the optimal Fe and P content during the oxygen evolution reaction (OER). In situ Raman spectroscopy demonstrates that formation of FeOOH effectively promotes the generation of highly active β‐NiOOH and shows a synergistic effect with β‐NiOOH for enhanced OER catalytic performance. Ex situ characterizations and in situ Raman spectroscopy suggest that a NiFe‐layered double hydroxide/Ni 0.72 Fe 0.14 P 0.14 heterostructure with a modulated electronic structure is formed upon cessation of the initial OER, which is beneficial for the subsequent OER. This study provides new insights into the design and mechanistic analysis of ionomer‐free CCMs for the development of industrial AEM water electrolysis systems.