Molecular metal nanoclusters for ORR, HER and OER: Achievements, opportunities and challenges

With the rapid development of economy, the past decades have experienced more and more severe energy depletion and environmental pollution issues, hence it is urgent to develop more environmental-friendly energy devices, such as fuel cells, metal-air batteries, water electrolysis and so on. However, such devices have long been suffering from the sluggish reaction kinetics and high energy barriers, plus the conventional electrocatalysts used in these devices mostly are noble-metal-based materials, such as Pt/C, IrO2, and RuO2. These noble-metal-based electrocatalysts possess significant disadvantages such as high price, limited reserves, and undesirable stability, and these factors together hinder their large-scale industrial application and the inhomogeneity of the catalyst structure at the atomic level also impose great challenges to disclose the underlying catalytic mechanism. Noble metal nanoclusters, as a promising type of electrocatalyst with definitive composition and structure, have been attracting increasingly research efforts. This review aims to summarize the recent achievements of molecular metal nanoclusters employed in electrocatalytic processes, with particular elaboration on oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), oxygen evolution reaction (OER), as well as to unravel the catalytic mechanism and establish the relationship between its structure and functionality. Specifically, the size effect, the metal core configuration, charge effect, size effect, ligand effect, and metal-ligand binding motifs of the metal clusters that would impact the electrocatalytic performance are comprehensively discussed. In the end, the outlook and perspective including challenges and opportunities are proposed. We anticipate this review would be beneficial for gaining a deeper understanding of engineering nanoclusters for electrocatalysis and to expand its application in electrocatalysis.