Fabrication of nitrogen-doped mesoporous carbon with a three-dimensional bicontinuous double gyroid structure via P4VP-b-PTFEMA/resol self-assembly

Double gyroid-structured porous carbons are attractive because their bicontinuous networks provide efficient transport pathways. However, the fabrication of such structures remains challenging owing to the narrow compositional window of the double gyroid phase and the difficulty in preserving the morphology during carbonization. In this study, nitrogen-doped mesoporous carbon (NMC) with a double gyroid structure was fabricated through the self-assembly of poly(4-vinylpyridine)- block -poly(2,2,2-trifluoroethyl methacrylate) (P4VP- b -PTFEMA) and phenol-formaldehyde resol. By systematically varying the resol content, morphology transitions from lamellar to double gyroid and cylindrical structures were observed, enabling access to the otherwise narrow double gyroid-forming region. The double gyroid morphology was retained after carbonization at 900 °C, yielding NMCs with ordered bicontinuous nanostructures. Furthermore, the optimized composition was scaled up while maintaining the double gyroid framework, yielding a mesoporous NMC with a pore diameter of 7.1 nm. More importantly, the results of the present study demonstrate that the selective incorporation of low-molecular-weight resol can effectively manipulate the self-assembled morphology of block copolymer systems, enabling access to the double gyroid phase and stabilization of the bicontinuous nanostructure during carbonization. These findings provide new insights into morphology control in block copolymer/additive systems and demonstrate how self-assembled polymer nanostructures can be translated into complex porous carbon architectures.