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.