CeOx-Induced Spatial and Electronic Modulation for General Direct Oxo Coupling in Transition Metal Hydroxides.
Electrochemical water splitting has emerged as a sustainable paradigm for hydrogen generation, where sluggish kinetics of the oxygen evolution reaction (OER) catalyzed by transition metal-based materials remain the critical bottleneck. Herein, we present a strategy that anchors CeOx nanoparticles (∼2 nm) onto two-dimensional Ni(OH)2 nanosheets, enabling dual modulation of spatial configuration and electronic states to accelerate O-O coupling. Spatially, interfacial lattice distortion between CeOx and Ni(OH)2 optimizes Ni-Ni dual-metal sites with reduced interatomic spacing. Electronically, dynamic modulation through reversible Ce3+/Ce4+ redox cycling positions Ce as an electronic regulation hub, stabilizing Ni species at the catalytically favorable +3 oxidation state through Ce─O─Ni interactions. This synergistic effect shifts the pathway from adsorbate evolution mechanism (AEM) to oxide pathway mechanism (OPM). The prepared CeOx@Ni(OH)2 achieves an overpotential of 152 mV at 10 mA cm-2 and operates continuously over 2000 h with limited performance decay. When integrated into an alkaline anion exchange membrane water electrolyzer (AEMWE), it requires 1.91 V to attain 1 A cm-2 and maintains stable operation for 450 h. This OPM activation strategy shows potential applicability across CeOx-loaded transition metal hydroxides, including Ni(OH)2, Co(OH)2, NiCo, and NiFe layered double hydroxides, offering a promising approach for alkaline OER enhancement.