The heterogeneous and multifunctional charged polymers have broad application prospects in modern catalysis. One of the valid methods of synthesizing multifunctional charged polymers is incorporating metalloporphyrins with halide anions. Herein, a series of zinc(II)porphyrin-based porous ionic polymers [PIP-ZnTIPP/DVB (1:m) (m = 20, 40, 60, 80)] were synthesized by combining imidazolium-functionalized Zn-porphyrin (ZnTIPP) and divinylbenzene (DVB) through the free-radical copolymerization by a solvothermal method. The rigid PIPs have many physical advantages such as spatial separation of Zn-porphyrin sites, high thermal stability, hierarchical pore structures, high specific surface area, and abundant imidazolium (Br − ) group in the polymeric skeletons, which exhibit fantastic catalytic activity for the coupling reaction of epoxides and CO 2 without any solvent or cocatalyst. In particular, the catalyst PIP-ZnTIPP/DVB (1:20) displayed the highest catalytic activity with a yield of 99% and a turnover frequency (TOF) of 759 h −1 and could be recycled six times without the loss of activity. The excellent catalytic activity results from a synergistic effect between zinc sites and nucleophilic bromide anions.

The design and synthesis of efficient heterogeneous catalysts for catalytic conversion of CO2 are an important challenge. The novel zinc porphyrin polymer reported herein, [ZnPy+CPP‐BTA]I−, is synthesized from trans‐A2B2 porphyrin precursor 5,15‐(4‐carboxyphenyl)‐10,20‐(pyridyl)‐porphyrin (PyCPP) and 1,2,4,5‐benzenetetramine tetrahydrochloride (BTA), employing a sequential post‐synthetic methylation and metalation strategy. The newly synthesized zinc porphyrin polymer was well characterized by Fourier transform infrared spectroscopy (FT‐IR), Ultraviolet–visible spectroscopy (UV–vis), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal gravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). As bifunctional heterogeneous catalyst incorporated zinc porphyrin and nucleophile I−, [ZnPy+CPP‐BTA]I− shows good catalytic activity and recyclability for the cycloaddition reactions of epoxides and CO2 under lower CO2 initial pressure and cocatalyst‐free conditions.

A zinc(II)porphyrin‐based ion porous organic polymer (ZnTPyPBr4‐iPOP) is successfully synthesized from newly designed pyridinium‐functionalized cationic Zn‐porphyrin monomer (ZnTPyPBr4) by free radical self‐polymerization, and is employed as an efficient bifunctional heterogeneous catalyst for CO2 cycloaddition reaction with epoxides. The ZnTPyPBr4‐iPOP exhibits excellent catalytic performance and good substrate expansion in CO2 cycloaddition reaction under solvent‐free and cocatalyst‐free conditions with a TOF as high as 15,500 h−1 for the cycloaddition of CO2 and epichlorohydrin. The synergistic effect of zinc(II)porphyrin as the Lewis acidic site and the Br− anion as the nucleophile in ZnTPyPBr4‐iPOP responds to the high catalytic activity. Moreover, ZnTPyPBr4‐iPOP can easily be recovered and reused at least seven times without the loss of activity. This work provides a valuable approach for the synthesis of novel and efficient heterogeneous catalyst for CO2 cycloaddition.