Accelerating Hydrogen Spillover on Cu δ+ /Ru δ+ ‐O v ‐Ce 3+
Qianxi Liu, Mang Zheng, Xiang Li, Fanqi Luo, Qi Li, Chengwu Yang, Shuting Zhang, Xudong Xiao, Baojiang JiangABSTRACT
Photothermal CO 2 methanation represents a promising strategy for sustainable fuel synthesis under mild conditions, yet its efficiency remains constrained by the kinetic mismatch between CO 2 activation and active H delivery. Herein, we constructed atomically dispersed Cu δ+ /Ru δ+ tandem sites anchored on the oxygen‐vacancy‐rich CeO 2 (111) surface. Advanced characterizations verify the coordination of both metals within the CeO 2 lattice, forming a well‐defined dual‐site configuration. Under simulated solar irradiation, the optimized catalyst achieves a remarkable CH 4 production rate of 4.92 mmol·g cat −1 ·h −1 at a moderate surface temperature of 349.6°C while maintaining excellent long‐term stability. Through a combination of in situ spectroscopic studies, catalytic evaluations, and density functional theory calculations, we elucidate a synergistic tandem mechanism, in which Cu δ+ sites facilitate CO 2 adsorption and primary activation, while adjacent Ru δ+ sites promote H 2 dissociation and subsequent hydrogen spillover. This spatially coupled process ensures efficient transfer of active hydrogen species to the reaction intermediates, dramatically accelerating the cleavage of the C─O bond and the intermediates hydrogenation. This work offers atomistic insights into bifunctional synergy, establishing a design paradigm for efficient CO 2 conversion photothermal catalysts.