Anion Modulation of Ag‐Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction

How to achieve CO₂ electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal-organic cages with multiple metal sites, tunable active centers, and well-defined microenvironments may provide a promising catalyst model. Here, we report self-assembly of Ag₄L₄ type cuboctahedral cages from coordination dynamic Ag⁺ ion and triangular imidazolyl ligand 1,3,5-tris(1-benzylbenzimidazol-2-yl) benzene (Ag-MOC-X, X=NO₃, ClO₄, BF₄) via anion template effect. Notably, Ag-MOC-NO₃ achieves the highest CO faradaic efficiency in pH-universal electrolytes of 86.1 % (acidic), 94.1 % (neutral) and 95.3 % (alkaline), much higher than those of Ag-MOC-ClO₄ and Ag-MOC-BF₄ with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO₂-to-CO conversion. The density functional theory calculations suggest that the adsorption of CO₂ on unsaturated Ag-site is stabilized by C-H⋅⋅⋅O hydrogen-bonding of CO₂ in a microenvironment surrounded by three benzimidazole rings, and the activation of CO₂ is dependent on the coordination dynamics of Ag-centers modulated by the hosted anions through Ag⋅⋅⋅X interactions. This work offers a supramolecular electrocatalytic strategy based on Ag-coordination geometry and host-guest interaction regulation of MOCs as high-efficient electrocatalysts for CO₂ reduction to CO which is a key intermediate in chemical industry process.