Xinran Sun, Baoxin Ge, Ruru Huang, Junhua Zhang, Jiayi Chen, Weiren Cheng, Guigang Zhang, Sibo Wang, Xue Feng Lu
ABSTRACT Surmounting the high kinetic barrier of water dissociation is a prerequisite for efficient alkaline hydrogen evolution reaction (HER). Herein, we present a nitrogen‐doping strategy for CeO 2‐x supports to tailor the interfacial water microenvironment at supported Pt sites. By leveraging distinct ligand‐directed metal–organic framework precursors, we construct well‐defined Pt−N/O−Ce interfacial coordination motifs. Nitrogen doping not only stabilizes ultrafine Pt clusters via enhanced metal–support interactions but also triggers pronounced interfacial electronic redistribution. Crucially, operando surface‐enhanced Raman spectroscopy reveals that the Pt−N/O−Ce interface promotes the accumulation of weakly hydrogen‐bonded K + ·H 2 O species, which disrupts the rigid interfacial water network and accelerates the rate‐determining water dissociation step. Consequently, the obtained catalyst with Pt−N/O−Ce interface delivers a remarkable mass activity of 13.6 A mg −1 Pt at 100 mV overpotential for HER, representing a 7.6‐fold enhancement over its N‐free counterpart. Demonstrating industrial viability, the Pt/N‐CeO 2‐x @NC achieves 1 A cm −2 at 1.73 V in a large‐area (25 cm 2 ) anion‐exchange membrane water electrolyzer, maintaining exceptional durability over 1600 h at 80°C (degradation rate of 87.5 µV h −1 ). This work elucidates the critical role of N‐mediated interfacial engineering in breaking the water dissociation bottleneck for robust industrial‐scale alkaline electrolysis.