Fabrication of Nitrogen-Doped Mesoporous Carbon With Tunable Pore Size via Self-Assembly of Poly(4-Vinylpyridine)-Block-Poly(2,2,2-Trifluoroethyl Methacrylate).

Abstract

Precise control of pore structures of nitrogen-doped mesoporous carbon (NMC) is still challenging. In this study, we address this issue by developing a soft-template approach based on the molecular design of block copolymers, enabling systematic tuning of nanostructures. Specifically, we synthesized poly(4-vinylpyridine)-block-poly(2,2,2-trifluoroethyl methacrylate) (P4VP-b-PTFEMA) via reversible addition-fragmentation chain-transfer (RAFT) polymerization and employed it as a soft template for fabricating NMCs. The P4VP block selectively interacts with phenol-formaldehyde resol, enabling retention of microphase-separated morphology during carbonization, while the fluorine-containing PTFEMA block enhances phase separation through strong segmental repulsion. Ordered morphologies, including cylindrical structures, are formed upon blending with resol. These morphologies are preserved during thermal treatment at 900°C, leading to the formation of NMCs with well-defined porous structures. The resulting NMCs exhibit tunable pore diameters ranging from 5.5 to 21.3 nm, controlled by the degree of polymerization of the PTFEMA block. These results highlight the potential of block copolymer design for achieving predictable mesopore architectures, offering a scalable platform for the development of functional porous materials.