Cu₂₆ Nanoclusters with Quintuple Ligand Shells for CO₂ Electrocatalytic Reduction

Copper nanostructures represent an important class of materials in CO 2 electrocatalytic reduction (CO 2 ER) reactions, but deciphering their molecular structures, especially those with multiple and irregular organic–inorganic interfaces, remains a grand challenge. Through comprehensive characterization of a 26-nuclei copper nanocluster of [Cu 26 (DPPE) 3 (CF 3 CO 2 ) 8 (CH 3 O) 2 ( t BuC≡C) 4 H 11 ] + (DPPE is 1,2-bis(diphenylphosphino)ethane), which is stabilized by quintuple ligand shells of phosphine, carboxylic acid, alcohol, alkynyl, and hydride, we demonstrate in this work the efficiency 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 geometric structure and distinct electronic structure and, more importantly, a delicate surface structure. As a result, the cluster displays high performance in CO 2 ER to CO reaction.