Elucidating the intrinsic core-shell structure of carbon nanospheres from glucose hydrothermal carbonization

This study explores the core-shell structure formation mechanisms of primary carbon nanospheres (PCNs) through hydrothermal carbonization (HTC) of glucose at 200 °C, focusing on key phase-change polymerization reactions. Colloidal carbon nanoparticles in the aqueous phase filtrate self-assembled into secondary carbon nanospheres (SCNs) with intrinsic hollow structures during room temperature storage. FTIR results revealed similar functional groups on PCNs and SCNs surfaces due to esterification reactions during HTC cooling. XPS and 13 C NMR analyses identified HMF aldol condensation and etherification as dominant reactions for PCNs, while esterification and aldol condensation with levulinic acid were dominant for SCNs. The hypothesis suggests that PCNs initially formed hollow microframeworks but collapsed due to consumption of encapsulated organics, resulting in hydrophobic cores. These cores grew through aggregation (linear) and surface reactions (exponential), internalizing hydrophilic surfaces into hydrophobic cores, forming the final core-shell structure of PCNs.