Single-Atom Tailored Atomically-Precise Nanoclusters for Enhanced Electrochemical CO2 Reduction Activity

Abstract The development of facile tailoring approach to adjust the intrinsic activity and stability of atomically-precise metal nanoclusters (NCs) catalysts is of great interest but remians challenging. Herein, the well-defined Au8 NCs modified by single-atom (SA) sites were rationally synthesized via a co-eletropolymerization strategy, in which uniformly dispersed metal NC and SA co-entrenched on the poly-carbazole matrix. Systematic characterization and theoretical modeling reveal that functionalizing SAs enable altering the electronic structures of Au8 clusters, which amplifies their electrocatalytic CO2 reduction reaction (CO2RR) activity by ~18.07 fold compared to isolated Au8 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 CO2RR. Moreover, this strategy fixing NCs and SAs 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.