biostudies-literatureShingyouchi YJapan Society for the Promotion of Science LondonTakahashi Industrial and Economic Research FoundationYazaki Memorial Foundation for Science and TechnologyScientific Research on Innovative Areas "Aquatic Functional Materials"Kumagai Foundation for Science and TechnologyScientific Research on Innovative AreasIwatani Naoji FoundationJoint Usage/Research Center for CatalysisJapan Society for the Promotion of Sciencee2409910https://www.ebi.ac.uk/biostudies/studies/S-EPMC12019909biostudies-literatureUnknown21(16)The electrochemical CO₂ reduction reaction (CO₂RR) has been extensively studied because it can be leveraged to directly convert CO₂ into valuable hydrocarbons. Among the various catalysts, copper nanoclusters (Cu NCs) exhibit high selectivity and efficiency for producing CO₂RR products owing to their unique geometric/electronic structures. However, the influence of protective ligands on the CO₂RR 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 Cu₁₄ NCs in the CO₂RR. Notably, Cu₁₄ 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 CO₂ reduction.Small (Weinheim an der Bergstrasse, Germany)Ligand-Dependent Intracluster Interactions in Electrochemical CO<sub>2</sub> Reduction Using Cu<sub>14</sub> Nanoclusters.PMC1201990922AY005622K1901222H0456224K0145923AY018923H00289Ikeda KNegishi YHossain SMetha GFBiswas SOsborn DJTanaka TYoshigoe YKawawaki TOgami MShingyouchi YKamiyama MfalseLigand-Dependent Intracluster Interactions in Electrochemical CO<sub>2</sub> Reduction Using Cu<sub>14</sub> Nanoclusters.The electrochemical CO₂ reduction reaction (CO₂RR) has been extensively studied because it can be leveraged to directly convert CO₂ into valuable hydrocarbons. Among the various catalysts, copper nanoclusters (Cu NCs) exhibit high selectivity and efficiency for producing CO₂RR products owing to their unique geometric/electronic structures. However, the influence of protective ligands on the CO₂RR 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 Cu₁₄ NCs in the CO₂RR. Notably, Cu₁₄ 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 CO₂ reduction.2025-01-01T00:00:00Z2025 Apr2025-06-26T03:05:31.038Z2025-06-26T03:05:31.038ZS-EPMC120199093963237610.1002/smll.202409910