A Silver-Chalcogenide Nanomaterial Enveloped with a Carborane-Thiolate Shell for the Electroreduction of CO₂ to CO

Electrocatalytic CO 2 reduction using atomically precise nanomaterials has garnered significant research interest, owing to their controllable molecular structures. Here, we have synthesized an electrocatalyst composed of single crystals having a one-dimensional assembly of silver atoms bridged by sulfur atoms of meta -carborane-9-thiolates. The molecular structure of the framework was further characterized through high-resolution ESI-MS, which exhibited silver- and carborane-thiolate-containing ions originating from the fragmentation of the framework. This thermally stable solid acted as an efficient catalyst for the electrocatalytic conversion of CO 2 to CO with a Faradaic efficiency of 85 ± 3%. In situ Raman studies provided experimental verification of binding of CO 2 to the framework. First-principles density functional theory calculations confirmed the feasible adsorption of CO 2 with the Ag chains, highlighting its favorable interaction with the catalyst. Furthermore, free energy calculations revealed the rate-determining step of the conversion process to be the formation of *COOH. This study presents an efficient electrocatalyst featuring a one-dimensional silver-chalcogenide framework.