Single-atom tailored atomically-precise nanoclusters for enhanced electrochemical reduction of CO<sub>2</sub>-to-CO activity.

Wang, Yi-Man; Yan, Fang-Qin; Wang, Qian-You; Du, Chen-Xia; Wang, Li-Ya; Li, Bo; Wang, Shan; Zang, Shuang-Quan · Nat Commun · 2024

basic_science · Level V

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Abstract

The development of facile tailoring approach to adjust the intrinsic activity and stability of atomically-precise metal nanoclusters catalysts is of great interest but remians challenging. Herein, the well-defined Au<sub>8</sub> nanoclusters modified by single-atom sites are rationally synthesized via a co-eletropolymerization strategy, in which uniformly dispersed metal nanocluster and single-atom co-entrenched on the poly-carbazole matrix. Systematic characterization and theoretical modeling reveal that functionalizing single-atoms enable altering the electronic structures of Au<sub>8</sub> clusters, which amplifies their electrocatalytic reduction of CO<sub>2</sub> to CO activity by ~18.07 fold compared to isolated Au<sub>8</sub> metal clusters. The rearrangements of the electronic structure not only strengthen the adsorption of the key intermediates *COOH, but also establish a favorable reaction pathway for the CO<sub>2</sub> reduction reaction. Moreover, this strategy fixing nanoclusters and single-atoms on cross-linked polymer networks efficiently deduce the performance deactivation caused by agglomeration during the catalytic process. This work contribute to explore the intrinsic activity and stability improvement of metal clusters.