Dynamically Stable CuCu Pair Sites Based on In Situ-Exsolved Cu Nanoclusters on CaCO for Efficient CO Electroreduction.

Copper-based catalysts are the choice for producing multi-carbon products (C) during CO electroreduction (CORR), where the CuCu pair sites are proposed to be synergistic hotspots for C-C coupling. Maintaining their dynamic stability requires precise control over electron affinity and anion vacancy formation energy, posing significant challenges. Here, we present an in situ reconstruction strategy to create dynamically stable CuCuOCa motifs at the interface of exsolved Cu nanoclusters and CaCO nanospheres (Cu/CaCO). In situ XAFS analysis confirmed the low-valency state of Cu during CORR. DFT calculations demonstrated that the nanocluster size arises from the balance between metal-support interactions and Cu-Cu cohesive energy, while the dynamic stability of rich interfacial Cu sites is attributed to their low electron affinity and high CO vacancy formation energy, which collectively contribute to reduced reducibility. The transformed Cu/CaCO exhibits an impressive C Faradaic efficiency of 83.7 % at a partial current density of 393 mA cm, facilitated by adsorption of *CO with varying electronegativity at heterogeneous copper sites that lowers the C-C coupling energy barrier. Our findings establish insoluble carbonate as an effective anion pairing for CuCu sites, highlighting the effectiveness of the in situ reconstitution strategy in producing a high density of dynamically stable CuCu pair sites.