Chemical Reviews, Vol.121, No.2, 567-648, 2021
Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures
Heterogeneous catalysis involves solid-state catalysts, among which metal nanoparticles occupy an important position. Unfortunately, no two nanoparticles from conventional synthesis are the same at the atomic level, though such regular nanoparticles can be highly uniform at the nanometer level (e.g., size distribution similar to 5%). In the long pursuit of well-defined nanocatalysts, a recent success is the synthesis of atomically precise metal nanoclusters protected by ligands in the size range from tens to hundreds of metal atoms (equivalently 1-3 nm in core diameter). More importantly, such nanoclusters have been crystallographically characterized, just like the protein structures in enzyme catalysis. Such atomically precise metal nanoclusters merge the features of well-defined homogeneous catalysts (e.g., ligand-protected metal centers) and enzymes (e.g., protein-encapsulated metal clusters of a few atoms bridged by ligands). The well-defined nanoclusters with their total structures available constitute a new class of model catalysts and hold great promise in fundamental catalysis research, including the atomically precise size dependent activity, control of catalytic selectivity by metal structure and surface ligands, structure-property relationships at the atomic-level, insights into molecular activation and catalytic mechanisms, and the identification of active sites on nanocatalysts. This Review summarizes the progress in the utilization of atomically precise metal nanoclusters for catalysis. These nanocluster-based model catalysts have enabled heterogeneous catalysis research at the single-atom and single-electron levels. Future efforts are expected to achieve more exciting progress in fundamental understanding of the catalytic mechanisms, the tailoring of active sites at the atomic level, and the design of new catalysts with high selectivity and activity under mild conditions.