Tailoring the Porous Structure of Carbon for Enhanced Oxidative Cleavage and Esterification of C(CO)‐C Bonds

The cleavage and functionalization of carbon-carbon bonds are crucial for the reconstruction and upgrading of organic matrices, particularly in the valorization of biomass, plastics, and fossil resources. However, the inherent kinetic inertness and thermodynamic stability of C-C σ bonds make this process challenging. Herein, we fabricated a glucose-derived defect-rich hierarchical porous carbon as a heterogeneous catalyst for the oxidative cleavage and esterification of C(CO)-C bonds. Systematic investigations revealed that the hierarchical porous structure enhances the adsorption of O₂ and ketones, thereby boosting the catalytic efficiency of defects. This catalyst exhibits performance comparable to that of the reported nitrogen-doped or metal nanoparticle-supported carbon materials, as well as transition metal-based homogeneous catalytic systems. This work deepens our understanding of the reaction process underlying this transformation and provides insights for designing efficient carbon-based materials for oxidative transformations.