No 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.

An effective strategy is developed to synthesize a novel and stable layered Cu nanocluster in one pot reduction method. The cluster, with molecular formula of [Cu14(tBuS)3(PPh3)7H10]BF4 which has been unambiguously...

A novel alkynyl-stabilized silver-copper alloy nanocluster with the composition of [Ag13-xCu6+x(tBuC6H4C≡C)14(PPh3)6](SbF6)3 was prepared by (PPh3)2CuBH4-mediated reduction approach. The nanocluster featured a centred disordered-octahedral Ag7Cu6 kernel, which was protected by hybrid...

Manipulating the interfacial/surface structure of ligand-stabilized atomically precise metal nanoclusters (NCs) is one of the central tasks in nanoscience because surface motifs are directly related to key properties of nanomaterials. Although great progress has been made in engineering the surface of gold and silver nanoclusters, parallel studies on lighter copper analogues hitherto remain unexplored. In this work, we report the design, synthesis, and structure of a new class of copper nanoclusters featuring virtually identical kernels but different surface motifs. The four Cu29 nanoclusters share the same Cu13 kernel with unprecedented anticuboctahedral architecture. Finely modulating synthetic parameters endows the Cu13 core with diverse surface structures, thus affording the Cu29 series with labile surface coatings. More interestingly, the slight surface modification results in distinct optical and catalytic properties of the cluster compounds, highlighting the importance of the surface structure in shaping the behaviors of copper nanomolecules. This work not only exemplifies the efficiency of surface engineering for controlling properties of well-defined copper nanoclusters but also provides a new family of Cu materials with a clear molecular structure and controlled surface motifs that hold great promise in studying structure–property relationships.

Illustrating molecualr strucure of metal nanoclusters with the protection of multiple ligands is the prequisite to understand strucure-property relationships of nano or bulk materials with hybrid interfaces. Reported herein is...