Linking atomic to mesoscopic scales in multilevel structural tailoring of single-atom catalysts for peroxide activation†

A key challenge in designing single-atom catalysts (SACs) with multiple and synergistic functions is to optimize their structure across different scales, as each scale determines specific material properties. We advance the concept of a comprehensive optimization of SACs across different levels of scale, from atomic, microscopic to mesoscopic scales, based on interfacial kinetics control on the coupled metal-dissolution/polymer-growth process in SAC synthesis. This approach enables us to manipulate the multilevel interior morphologies of SACs, such as highly porous, hollow, and double-shelled structures, as well as the exterior morphologies inherited from the metal oxide precursors. The atomic environment around the metal centers can be flexibly adjusted during the dynamic metal-oxide consumption and metal–polymer formation. We show the versatility of this approach using mono- or bi-metallic oxides to access SACs with rich microporosity, tunable mesoscopic structures and atomic coordinating compositions of oxygen and nitrogen in the first coordination-shell. The structures at each level collectively optimize the electronic and geometric structure of the exposed single-atom sites and lower the surface *O formation barriers for efficient and selective peroxidase-type reaction. The unique spatial geometric configuration of the edge-hosted active centers further improves substrate accessibility and substrate-to-catalyst hydrogen overflow due to tunable structural heterogeneity at mesoscopic scales. This strategy opens up new possibilities for engineering more multilevel structures and offers a unique and comprehensive perspective on the design principles of SACs.