| Abstract | The electrochemical reduction of CO₂ into valuable chemicals presents a promising strategy for carbon utilization; however, it remains challenging due to low activity, poor selectivity and stability of existing catalysts. In this study, we report the fabrication of free‐standing silver single‐atom catalysts (Ag SACs) designed for the efficient conversion of CO₂ to carbon monoxide (CO) at high current densities in a bicarbonate electrolyzer. The Ag single atoms dispersed within a carbon matrix, forming Ag⎯N₃ active sites for the electrocatalytic CO₂ reduction reaction (CO₂ RR). The catalytic activity and stability of the free‐standing Ag SACs are evaluated at a current density of 100 mA cm⁻², demonstrating prolonged electrolysis with consistent Faradaic efficiency for CO production. Density functional theory calculations revealed that the Ag⎯N₃ active site significantly lowers the energy barriers for the CO₂ absorption step compared to Ag⎯Ag and Ag⎯Ni sites, facilitating CO₂ activation and contributing to enhanced catalytic activity and stability during CO₂ reduction. Detailed analysis of the electronic structure and coordination environment further validates the superior performance of the Ag⎯N₃ site in the free‐standing Ag SACs, underscoring their effectiveness in CO₂ electroreduction. These findings highlight the potential of the free‐standing Ag SACs to advance CO₂ reduction technologies, offering enhanced efficiency and selectivity for CO₂ conversion. |
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