Cu₂₆ Nanoclusters with Quintuple Ligand Shells for CO₂ Electrocatalytic Reduction

Abstract

Copper nanostructures represent an important class of materials in CO2 electrocatalytic reduction (CO2ER) 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 [Cu26(DPPE)3(CF3CO2)8(CH3O)2(tBuCC)4H11]+ (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 CO2ER to CO reaction.

Thiacalix[4]arene Etching of an Anisotropic Cu70H22 Intermediate for Accessing Robust Modularly Assembled Copper Nanoclusters

“…Of note, the PhCC – and CF 3 COO – ligands regioselectively cover both sides of the Cu 70 NC, showing an anisotropic distribution similar to the packing of Cu atoms, which is different from the reported symmetrical distribution of organic components in mixed-ligand-protected metal NCs. , Specifically, nine CF 3 COO – bridge Cu atoms of the Cu 21 bowl, and the 12 PhCC – ligands bound to three Cu 6 units of the Cu 22 propeller, which are evenly distributed at the equatorial region. This wavy configuration array provides forceful support for the formation of the quasi - C 3 -axis (Figure S12).…”

Carboxylate-Protected “Isostructural” Cu20 Nanoclusters as a Model System: Carboxylate Effect on Controlling Catalysis

“…In consideration of the high abundance, low price, low environmental footprint, and unique catalytic properties of copper, great interest has been sparked for copper nanoclusters in recent years. ,,,,,,,,,− Several groups of Liu, Bakr, Zang, Sun, Hyeon, Hayton, and Zheng have successfully crystallized out a handful of copper nanoclusters by advanced synthetic strategies, which include [Cu 20 H 11 (S 2 P­(O i Pr) 2 ) 9 ], [Cu 32 H 20 {S 2 P­(O i Pr) 2 } 12 ], [Cu 23 (PhSe) 16 (Ph 3 P) 8 (H) 6 ] + , [Cu 61 (S t Bu) 26 S 6 Cl 6 H 14 ], Cu 8 (H)­(L1) 6 (L1 = 9 H -carbazole-9-carbodithioate), Cu 18 H­(PET) 14 (Ph 3 P) 6 (NCS) 3 (PET = phenylethanethiolate), [Cu 36 H 10 (PET) 24 (PPh 3 ) 6 Cl 2 ], [Cu 20 (CCPh) 12 (OAc) 6 )], [Cu 25 H 22 (PPh 3 ) 12 ]­Cl, and [Cu 25 H 10 (SPhCl 2 ) 18 ] 3– . ,,,,,,,,, The atomically precise copper nanoclusters are highly active, enabling driving a family of chemical reactions under mild conditions. The well-documented copper nanocluster for organic catalysis refers to Cu 6 H 6 (PPh 3 ) 6 , which is promising in conjugate reduction reactions. , In several pioneering reports, copper nanoclusters have also been used as catalysts for driving thermal catalysis (click chemistry and hydrogenation of ketones), electrocatalysis (CO 2 reduction), and photocatalysis (C–N Coupling and CO 2 reduction). ,,− Notably, the key role of surface coordination ligands in controlling the catalytic performance has also been observed in copper cluster nanocatalysts . To gain insights into the underlying mechanism of the “ligand effect” and help control the copper cluster catalysis, it is thus desirable to obtain isostructural copper nanoclusters for direct structural and catalytic comparison.…”

Atomically precise metal nanoclusters as catalysts for electrocatalytic CO2 reduction

“…32 328 Furthermore, [Cu 26 (CF 3 CO 2 ) 8 (CH 3 O) 2 (CuC t Bu) 4 (DPPE) 3 H 11 ] + is also reported to be a catalyst exhibiting high CO selectivity. 329 Regarding the templated Cu NCs, [Cu 4 Ti 9 O 9 (BC) 18 (O i Pr) 3 (CuC t Bu)(CH 3 CN)] (BC = benzoic acid) exhibited high selectivity and good catalytic activity for the electrocatalytic reduction of CO 2 to C 2 H 4 at 400 mA cm −2 (FE C 2 H 4 : 47.6 ± 3.4%). 330 From these reports, the CRR products of Cu NCs are often not only CO but also HCOOH, CH 4 , and C2 compounds.…”