Thermal Transformation of Polyacrylonitrile Accelerated by the Formation of Ultrathin Nanosheets in a Metal-Organic Framework.

In this study, polyacrylonitrile (PAN) nanosheets with unimolecular thickness were successfully synthesized by cross-linking polymerization in the 2D nanospaces of a metal-organic framework. In contrast to 1D and 3D analogues, crystallization could be inhibited by the topological constraint of the ultrathin 2D network structure, allowing for an efficient thermal transformation reaction of PAN. The amorphous nature of the PAN nanosheets led to an increase in the access of oxygen molecules to the polymer chains, facilitating the thermal dehydroaromatization reactions to yield a ladder polymer structure with a highly extended conjugated system. Notably, further carbonization of this ladder polymer afforded graphitic carbon with a highly ordered structure because of the well-defined precursor structure.