Boosting the Electroreduction of CO2 to CO by Ligand Engineering of Gold Nanoclusters.

The electrochemical CO2 reduction reaction (CO2RR) has been widely studied as a promising means to convert anthropogenic CO2 into valuable chemicals and fuels. In this process, the alkali metal ions present in the electrolyte are known to significantly influence the CO2RR activity and selectivity. In this study, we report a strategy for preparing efficient electrocatalysts by introducing a cation‐relaying ligand, namely 6‐mercaptohexanoic acid (MHA), into atom‐precise Au25 nanoclusters (NCs). The CO2RR activity of the synthesized Au25(MHA)18 NCs was compared with that of Au25(HT)18 NCs (HT=1‐hexanethiolate). While both NCs selectively produced CO over H2, the CO2‐to‐CO conversion activity of the Au25(MHA)18 NCs was significantly higher than that of the Au25(HT)18 NCs when the catholyte pH was higher than the pKa of MHA, demonstrating the cation‐relaying effect of the anionic terminal group. Mechanistic investigations into the CO2RR occurring on the Au25 NCs in the presence of different catholyte cations and concentrations revealed that the CO2‐to‐CO conversion activities of these Au25 NCs increased in the order Li+<Na+<K+<Cs+, and are gated by the cation‐coupled electron transfer step. These results were confirmed by the Nernstian shifts of the polarization curves at different cation concentrations. [ABSTRACT FROM AUTHOR]