A Sequential One-Pot Block Copolymer Synthesis: Toward Mesoporous Carbon Materials for Selective CO2 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 PAN209-b-P(AN207-co-BA149)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 CO2 adsorption capacity (2.52 mmol g- 1), rapid desorption kinetics, and high selectivity over N2. This work establishes a streamlined platform to produce functional carbon architectures for environmental remediation.