Enhanced CO2 Reactive Capture and Conversion Using Aminothiolate Ligand–Metal Interface

Metallic catalyst modification by organic ligands is an emerging catalyst design in enhancing the activity and selectivity of electrocatalytic carbon dioxide (CO₂) reactive capture and reduction to value-added fuels. However, a lack of fundamental science on how these ligand-metal interfaces interact with CO₂ and key intermediates under working conditions has resulted in a trial-and-error approach for experimental designs. With the aid of density functional theory calculations, we provided a comprehensive mechanism study of CO₂ reduction to multicarbon products over aminothiolate-coated copper (Cu) catalysts. Our results indicate that the CO₂ reduction performance was closely related to the alkyl chain length, ligand coverage, ligand configuration, and Cu facet. The aminothiolate ligand-Cu interface significantly promoted initial CO₂ activation and lowered the activation barrier of carbon-carbon coupling through the organic (nitrogen (N)) and inorganic (Cu) interfacial active sites. Experimentally, the selectivity and partial current density of the multicarbon products over aminothiolate-coated Cu increased by 1.5-fold and 2-fold, respectively, as compared to the pristine Cu at -1.16 V_RHE, consistent with our theoretical findings. This work highlights the promising strategy of designing the ligand-metal interface for CO₂ reactive capture and conversion to multicarbon products.