Ligand Design in Atomically Precise Copper Nanoclusters and Their Application in Electrocatalytic Reactions

Abstract

AbstractMetal nanoclusters (MNCs) are compositionally well‐defined and also structurally precise materials with unique molecule‐like properties and discrete electronic energy levels. Atomically precise ligand‐protected Cu nanoclusters (LP‐CuNCs) are one category of typical MNCs that usually demonstrate unique geometric and electronic structures to serve as electrocatalysts. However, the synthesis, application, as well as structure‐performance relationship of LP‐CuNCs are not adequately studied. Significantly, the ligands are essential to the geometric structure, crystal structure, size, and electronic structure of LP‐CuNCs, which determine their physiochemical properties and applications. In this review, significant progress in the ligand design of LP‐CuNCs, and their application in electrocatalytic reactions is introduced. The general basics of ligand‐protected MNCs (LP‐MNCs) are first introduced and the functions of ligands are emphasized. Subsequently, a series of different ligands for LP‐CuNCs including thiolates, phosphines, alkynyl, polymers, and biomolecules are highlighted. Thereafter, their applications in different electrocatalytic reactions are discussed. It is believed that this review will not only inspire the design and synthesis of novel LP‐CuNCs, but also contribute to the extension of their applications in electrocatalytic reactions and the establishment of accurate structure‐performance relationships.