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

Abstract

Electrocatalytic CO2 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 CO2 to CO with a Faradaic efficiency of 85 ± 3%. In situ Raman studies provided experimental verification of binding of CO2 to the framework. First-principles density functional theory calculations confirmed the feasible adsorption of CO2 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. © 2025 American Chemical Society.