Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties

Abstract

Improving the knowledge of the relationship between structure and properties is fundamental in catalysis. Recently, researchers have developed a variety of well-controlled methods to synthesize atomically precise metal nanoclusters (NCs). NCs have shown high catalytic activity and unique selectivity in many catalytic reactions, which are related to their ultrasmall size, abundant unsaturated active sites, and unique electronic structure different from that of traditional nanoparticles (NPs). More importantly, because of their definite structure and monodispersity, they are used as model catalysts to reveal the correlation between catalyst performance and structure at the atomic scale. Therefore, this review aims to summarize the recent progress on NCs in catalysis and provide potential theoretical guidance for the rational design of high-performance catalysts. First a brief summary of the synthetic strategies and characterization methods of NCs is provided. Then the primary focus of this reviewthe model catalyst role of NCs in catalysisis illustrated from theoretical and experimental perspectives, particularly in electrocatalysis, photocatalysis, photoelectric conversion, and catalysis of organic reactions. Finally, the main challenges and opportunities are examined for a deep understanding of the key catalytic steps with the goal of expanding the catalytic application range of NCs.

Theoretical Analysis of the Mackay Icosahedral Cluster Pd55(PiPr3)12(μ3‐CO)20: An Open‐Shell 20‐Electron Superatom

“…Finally, note that the present study is also relevant to catalysis as Pd 55 clusters are close to the optimal cluster size for maximum catalytic activity of Pd clusters and small nanoparticle catalysts. [59][60][61]…”

Photo/electrocatalysis and photosensitization using metal nanoclusters for green energy and medical applications

“…Recent synthetic innovations have allowed the fabrication of atomically precise metal nanoclusters (NCs). [8][9][10][11][12][13][14][15][16][17][18] These metal NCs contain a few to hundreds of metal atoms that are protected by organic ligands (e.g., thiolate, phosphine, small molecules, synthetic polymers, and biomolecules). Particularly, thiolate-protected metal NCs and their alloy NCs can be prepared with atomic precision as M n (SR) m (M ¼ gold (Au), silver (Ag), cupper (Cu), platinum (Pt), palladium (Pd), or other element; SR ¼ thiolate ligand) in a wide range of sizes by varying the n and m values.…”

“…Recently, several excellent reviews have discussed the syntheses of metal NCs, 13 photoluminescence, 14 and their biomedical [15][16][17] and catalytic applications. 18 However, to the best of our knowledge, there are no publications focusing on the photo/electrocatalytic and photosensitizing characteristics of metal NCs for applications in the green energy and medical elds. Therefore, a survey of recent progress, with a view to improving the photo/ electrocatalytic and photosensitizing capability of metal NCs is needed.…”

Unraveling the single-atom electrocatalytic activity of transition metal-doped phosphorene

“…TOC GRAPHICS KEYWORDS: Single atom catalyst, Activity screening, Phosphorene, Overpotential, Chemical degradation Endeavors to curb the catalyst loading without dwindling the activity has been a far-reaching goal in the area of heterogeneous catalysis. [1][2][3] Attempts towards realization of this goal along with the development of nanotechnology have explored catalysts of different dimensions such as nanoclusters, nanowires, 2D sheets and so on. The very recent decades have witnessed the emergence of single atom catalysts (SACs), where the atomically dispersed metals catalyzing the reactions and thereby turned out to be the quintessential examples for the green chemistry concept of 'atom economy'.…”