A Sequential One‐Pot Block Copolymer Synthesis: Toward Mesoporous Carbon Materials for Selective CO 2 Adsorption

ABSTRACT Polymer‐derived porous carbon nanomaterials are pivotal for addressing global challenges, particularly in energy storage as well as carbon capture, utilization, and storage (CCUS). Herein, we report a facile one‐pot synthetic route to block copolymer (BCP) precursors for mesoporous carbons using a photo‐iniferter reversible addition‐fragmentation chain transfer (PI‐RAFT) polymerization. This scalable approach yields well‐defined polyacrylonitrile‐ block ‐poly(acrylonitrile‐ co ‐ n ‐butyl acrylate) (PAN‐ b ‐P(AN‐ co ‐BA)) block copolymers with molecular weights up to 286 kg mol − 1 , alongside other common PAN BCPs. The characteristics of the BCPs are confirmed exemplary for PAN 209 ‐ b ‐P(AN 207 ‐ co ‐BA 149 ) 41.2 by differential scanning calorimetry, evidenced by two glass transition temperatures (91.5 °C and −13.7 °C) and by atomic force microscopy, which confirmed distinct phase separation of thin films. Also, the robustness of the polymerization was demonstrated by synthesizing multiple sets of BCPs and a numbering‐up experiment with 10 samples, showing an average size of 49.8 ± 2.3 kg mol −1 with a dispersity Đ of 1.22 ± 0.01. Subsequent electrospinning and carbonization transformed BCP into a nitrogen‐doped (11 at.%) hierarchical porous carbon membrane. This membrane exhibited promising CCUS performance, characterized by high CO 2 adsorption capacity (2.52 mmol g − 1 ), rapid desorption kinetics, and high selectivity over N 2 . This work establishes a streamlined platform to produce functional carbon architectures for environmental remediation.