Guided Assembly of Well-Defined Hierarchical Nanoporous Polymers by Lewis Acid–Base Interactions

Three-dimensional hierarchical nanoporous polymers and carbon nanomaterials with well-defined superstructures are of great interest for various intelligent applications, whereas a facile and versatile approach to access those materials with a high surface area, stable well-defined morphology, and ordered pores still remains a significant challenge. Herein, we report a self-regulated Lewis acid–base interaction-mediated assembly strategy for the in situ synthesis of morphology-engineered hyper-cross-linked porous polymers and carbon materials. A series of functionalized aromatic compounds (FAC) is subjected to self-cross-linking via classic Friedel–Crafts chemistry to achieve stable porous polymers with a high surface area. Varying the monomer/catalyst combination had a dramatic effect on the acid–base interaction, facilitating the tailoring of the self-assembled morphologies from nanotubes to hollow nanospheres, and even nanosheets. A mechanistic study showed that the byproducts generated during cross-linking orchestrate the interactions between the catalyst (acid) and FAC (base) and simultaneously drive the self-assembly to yield specific morphologies. Based on the rigid hollow polymer framework and intrinsic hydroxyl functionality, the hyper-cross-linked hollow nanospheres were easily transformed to an acid-functionalized catalyst for efficient biodiesel production. Moreover, high-quality porous carbonaceous nanocounterparts such as carbon nanotubes, hollow carbon nanospheres, and carbon nanosheets could also be produced by direct pyrolysis of the corresponding polymer precursors. These findings may provide guidance for the facile design of morphology-controlled functionalized polymers and carbon nanomaterials for various applications.