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

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.