Construction of Multivariate Hierarchical Metal–Organic Framework/Polymer Composites by Redox Concomitant Reconstitution Method for Photothermal Catalytic CO2 Conversion

Abstract The rational design of metal–organic framework/polymer (MOF/polymer) composites featuring integrated architectures and synergistic functionalities represents an effective strategy for developing advanced materials whose emergent properties outperform those of individual components. Herein, we report a Redox Concomitant Reconstitution (RCR) strategy that enables the concomitant structural reconstitution of metastable MOFs and in situ polymer functionalization, resulting in hierarchical MOF/polymer composites with structure-function synergy. Upon exposure to a mixed methanol/pyrrole vapor, the metastable CuCo-PC precursor is structurally reconstituted into hierarchical CuCo-MOF-74 enriched with Cu(0)/Cu(I)/Cu(II)/Co(II) multimetallic sites, while pyrrole is concomitantly oxidatively polymerized into a conformal polypyrrole (PPy) layer, yielding CuCo-MOF-74/PPy composites with integrated architecture and functionality. Benefiting from the synergy among the multimetallic catalytic sites, hierarchical porosity, and PPy photothermal layer, the composite achieves a 96% yield in the photothermal catalytic CO2 cycloaddition using sterically hindered long-chain epoxides and maintains robust stability over 10 consecutive cycles. This work establishes the RCR strategy as a versatile platform for constructing advanced multifunctional MOF/polymer composites with tailored architectures and synergistic functionalities, opening new opportunities for solar-driven CO2 valorization and the rational design of next-generation MOF-based hybrid materials.