Ligand‐Dependent Intracluster Interactions in Electrochemical CO<sub>2</sub> Reduction Using Cu<sub>14</sub> Nanoclusters
Yamato Shingyouchi, Masaki Ogami, Sourav Biswas, Tomoya Tanaka, Maho Kamiyama, Kaoru Ikeda, Sakiat Hossain, Yusuke Yoshigoe, D. J. Osborn, Gregory F. Metha, Tokuhisa Kawawaki, Yuichi Negishi
Abstract
Abstract The electrochemical CO 2 reduction reaction (CO 2 RR) has been extensively studied because it can be leveraged to directly convert CO 2 into valuable hydrocarbons. Among the various catalysts, copper nanoclusters (Cu NCs) exhibit high selectivity and efficiency for producing CO 2 RR products owing to their unique geometric/electronic structures. However, the influence of protective ligands on the CO 2 RR performance of Cu NCs remains unclear. In this study, it is shown that different thiolate ligands, despite having nearly identical geometries, can substantially affect the electrochemical stability of Cu 14 NCs in the CO 2 RR. Notably, Cu 14 NCs protected by 2‐phenylethanethiolate exhibit greater stability and achieve a relatively higher selectivity (≈40%) for formic acid production compared with the cyclohexanethiolate‐protected counterpart. These insights are crucial for designing Cu NCs that are both stable and highly selective, enhancing their efficacy for electrochemical CO 2 reduction.