Nitrogen-Doped CeO_2-x Supports Accelerate Interfacial Water Dissociation at Surface Pt Sites for Durable Industrial...

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⁺·H₂O 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 cm²) 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.