Cu₂₆ Nanoclusters with Quintuple Ligand Shells for CO₂ Electrocatalytic Reduction

Copper nanostructures represent an important class ofmaterialsin CO2 electrocatalytic reduction (CO2ER) reactions,but deciphering their molecular structures, especially those withmultiple and irregular organic-inorganic interfaces, remainsa grand challenge. Through comprehensive characterization of a 26-nucleicopper nanocluster of [Cu-26(DPPE)(3)(CF3CO2)(8)(CH3O)(2)((BuC)-Bu-t VC)(4)H-11](+) (DPPE is 1,2-bis(diphenylphosphino)ethane),which is stabilized by quintuple ligand shells of phosphine, carboxylicacid, alcohol, alkynyl, and hydride, we demonstrate in this work theefficiency of hybrid ligands in controlling geometrical arrangements,electronic structures, and catalytic performance of copper nanoclusters.The diverse ligands in the cluster endow it with a peculiar geometricstructure and distinct electronic structure and, more importantly,a delicate surface structure. As a result, the cluster displays highperformance in CO2ER to CO reaction.