Polymer Brush-Grafted Metal–Organic Framework Nanoplates for Enhanced Catalysis of CO2 Cycloaddition with Epoxides

The catalytic performance of 2D nanostructure-based heterogeneous catalysts is highly dependent on their dispersibility and stability. This work presents the grafting of polymer brushes onto 2D Cu-based metal-organic framework (MOF) nanoplates via a versatile UV-induced radical polymerization approach for CO2 fixation through the cycloaddition reaction with epoxides. The polymer brushes are selectively anchored to the external surfaces of the nanoplates, which greatly improves the long-term dispersibility and stability in solvents while preserving their intrinsic porosity and crystalline structures. The poly(N,N-dimethylaminoethyl methacrylate)-grafted 2-aminoterephthalic acid copper (CuBDC-NH2@PDMAEMA) nanoplates, with an optimized polymer brush thickness, achieve a maximum yield of 81.2% in the cycloaddition of CO2 with styrene oxide, which is a 1.6-fold improvement over that of the unmodified CuBDC-NH2 nanoplates. The grafted nanoplates also exhibit excellent recyclability with a slight decrease in yield after multiple consecutive cycles. The versatility of this approach is further demonstrated by its application to other polymers and epoxide substrates, where polymer-grafted catalysts consistently outperform their pristine counterparts. Our strategy provides a feasible and efficient route to synthesize MOF/polymer hybrid nanomaterials for sustainable CO2 utilization and green chemistry applications.