Framework nanoarchitectonics of fullerene-derived catalyst

In this review article, we examine the significance of developing catalysts via nanoarchitectonics by focusing on fullerenes as the primary material and frameworks as the nanoscale structural motif. Nanoscale frameworks such as C 60 , MOFs, and 2D carbon networks enable a precise arrangement and dispersion of single-atom metal catalysts or nanoparticles. By controlling the electronic environment and spatial configuration of catalytic active sites, framework nanoarchitectonics enables the rational design of catalysts with enhanced activity and selectivity, providing a route beyond conventional empirical materials screening. This review discusses novel examples such as metal-organic frameworks on fullerene (MOFOF)-an innovative material developed by our group-and the contribution of atomic-level framework control, specifically the catalytic functionality of carbon pentagon structures. The MOFOF architecture allows precise control over morphology, composition, and the spatial arrangement of functional sites, representing an essential approach for creating high-performance multifunctional catalytic materials-achieving capabilities that are difficult with conventional MOFs or carbon materials. Pentagon defects induce local electron redistribution and bandgap narrowing, greatly enhancing binding affinity and electrochemical reactivity as catalytic active sites. Introducing pentagon defects into C 60 -derived carbon nanomaterials yields excellent ORR performance, and synergy with nitrogen, chlorine, phosphorus, and oxygen doping substantially improves catalytic activity, H₂O₂ selectivity, and stability. Taken together, framework nanoarchitectonics could provide a basis for moving catalyst development from empirical materials screening toward rational design, in which framework geometry, defect structures, and electronic/spin states are deliberately engineered to control reaction pathways and selectivity.