Oxygen-modulated engineering of Cu<sup>0</sup>-Cu<sup>+</sup> interfaces for CO<sub>2</sub>-to-C<sub>2</sub>H<sub>4</sub> photoreduction.

Ren, Yuqi; Cheng, Miao; He, Hongbin; You, Changjun; Duan, Lunbo; Sun, Zhenkun; Peng, Ruoxuan; Zhu, Yuan-Hao et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

CO<sub>2</sub>-to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O<sub>2</sub> partial pressures and sluggish C<sub>2</sub>-product formation. Herein, Ru<sub>0.6</sub>Cu<sub>1</sub>(Cu<sup>0</sup>-Cu<sup>1+</sup>)/CeO<sub>2</sub> catalysts with adaptive O<sub>2</sub> tolerance are prepared by O<sub>2</sub>-mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H<sub>2</sub>O dissociation. Photothermal effect promotes O<sub>2</sub>-driven self-assembly of Cu<sup>0</sup>-Cu<sup>1+</sup> charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of <sup>*</sup>CHOCO intermediates and restructuring the C-C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C<sub>1</sub> to C<sub>2</sub>, as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g<sup>-1</sup> C<sub>2</sub>H<sub>4</sub> with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency-25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.