Contributions of Internal Atoms of Atomically Precise Metal Nanoclusters to Catalytic Performances

Abstract

Every atom of a heterogeneous catalyst can play a direct or indirect role in its overall catalytic properties. However, it is extremely challenging to determine explicitly which atom(s) of a catalyst can contribute most to its catalytic performance because the observed performance usually reflects an average of all the atoms in the catalyst. The emergence of atomically precise metal nanoclusters brings unprecedented opportunities to address these central issues, as the crystal structures of such nanoclusters have been solved, and hence very fundamental understanding of nanocatalysis can be attained at an atomic level. This minireview focuses on recent efforts to reveal the contributions of the internal atoms or vacancies of nanocluster catalysts to the catalytic processes, including how the catalytic activity can be dramatically changed by the central doping of a foreign atom, how catalytic activation and inactivation can be reversibly switched by shuttling the central atom into and out of nanoclusters, and how evolution in catalytic activity can be driven by structural periodicity in the inner kernels of the nanoclusters. We anticipate that progress in this research area could represent a novel conceptual framework for understanding the crucial roles of internal atoms of the catalysts in tuning the catalytic properties.

Catalytic Conversion of CO2 over Atomically Precise Gold-Based Cluster Catalysts

“…Another important factor affecting the electrochemical activity and selectivity of the metal clusters is the heteroatom doping effect. − The contributions of the central atom doping to catalytic properties of the clusters have been reported for both heterogeneous and homogeneous chemical reacions. − Here we first discussed the electrochemical performances of the central atom doping of the Au 25 cluster like Au 24 Pd and Au 24 Pt for CO 2 reduction. The single Pd-doping Au 25 Pd 1 cluster was confirmed to drastically inhibit H 2 evolution that is a competing reaction with the CO 2 reduction reaction and reached nearly 100% faradaic efficiency of CO ranging from −0.6 to −1.2 V (vs RHE) (Figure ).…”

Programmable kernel structures of atomically precise metal nanoclusters for tailoring catalytic properties

“…[22][23][24][25][26] They have become a kind of star nanocatalysts for investigating the well-defined relationships between structure and catalytic property. [27][28][29][30][31][32][33][34][35][36][37][38][39] Metal NCs usually contain several to hundreds of metal atoms with core diameters ranging from 1 to 3 nm. [22] These metal NCs show molecularlike or non-metallic behavior due to the quantized electronic structure arising from the quantum confinement effect, thus building a bridge between molecular catalysts and conventional metal NPs.…”

A Functionalized Heterogeneous Catalyst from Atomically Precise Pd1Au8 Clusters Facilitates Carbon–Carbon Bond Construction

“…[17][18][19] Notably, such clusters can be extracted from the reaction systems after the reactions and be conveniently recycled and reused, to serve as nearly fresh catalysts, which can overcome the difficulties of homogeneous metal-based complexes. [20][21][22] Therefore, such metal clusters seem to merge the features of heterogeneous and homogeneous catalysts and thus hold promise in the heterogeneous reaction systems of applications as homogeneous catalysts, and vice versa.…”