Anion Modulation of Ag-Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO 2 Reduction.

How to achieve CO 2 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 Ag 4 L 4 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=NO 3 , ClO 4 , BF 4 ) via anion template effect. Notably, Ag-MOC-NO 3 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-ClO 4 and Ag-MOC-BF 4 with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO 2 -to-CO conversion. The density functional theory calculations suggest that the adsorption of CO 2 on unsaturated Ag-site is stabilized by C-H⋅⋅⋅O hydrogen-bonding of CO 2 in a microenvironment surrounded by three benzimidazole rings, and the activation of CO 2 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 CO 2 reduction to CO which is a key intermediate in chemical industry process.