Probing and Leveraging the Structural Heterogeneity of Nanomaterials for Enhanced Catalysis

[Image: see text] The marriage between nanoscience and heterogeneous catalysis has introduced transformative opportunities for accessing better nanocatalysts. However, the structural heterogeneity of nanoscale solids stemming from distinct atomic configurations makes it challenging to realize atomic-level engineering of nanocatalysts in the way that is attained for homogeneous catalysis. Here, we discuss recent efforts in unveiling and exploiting the structural heterogeneity of nanomaterials for enhanced catalysis. Size and facet control of nanoscale domains produce well-defined nanostructures that facilitate mechanistic studies. Differentiation of surface and bulk characteristics for ceria-based nanocatalysts guides new thoughts toward lattice oxygen activation. Manipulating the compositional and species heterogeneity between local and average structures allows regulation of catalytically active sites via the ensemble effect. Studies on catalyst restructurings further highlight the necessity to assess the reactivity and stability of nanocatalysts under reaction conditions. These advances promote the development of novel nanocatalysts with expanded functionalities and bring atomistic insights into heterogeneous catalysis.