A facile and one-pot synthesis of metalloporphyrin-based ionic porous organic polymers (M-iPOPs) was performed through a typical Yamamoto-Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al-based materials (Al-iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO capture capacity. If we consider the particular physicochemical properties, heterogeneous Al-iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent- and additive-free synthesis of cyclic carbonates from various epoxides and CO with an excellent activity and good recyclability under mild conditions. Interestingly, these CO -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO in N , v/v) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin-based porous materials is regarded as a promising new strategy for the chemical conversion of CO .

A series of metalloporphyrin‐based hyper‐crosslinked polymers (M‐HCPs: M=Al, Co, Fe, Mn) has been directly synthesized through Friedel–Crafts alkylation reactions. The M‐HCPs afforded abundant permanent nanopores, high Brunauer–Emmett–Teller (BET) surface area, and exceptional CO2/N2 adsorptive selectivity. The experimental results suggested that the hollow tubular Al‐HCP exhibited extraordinary catalytic performance in the solvent‐free synthesis of cyclic carbonates from epoxides and CO2 by using tetrabutylammonium bromide as a cocatalyst under mild conditions, which was clearly superior to the corresponding homogeneous analogue. Surprisingly, a high turnover frequency (TOF) value of 14 880 h−1 was achieved with propylene oxide at 100 °C and 3.0 MPa, which was a promising result for industrial production compared with previously reported heterogeneous catalysts. More interestingly, Al‐HCP could smoothly catalyze the cycloaddition reaction, producing the corresponding cyclic carbonates by using simulated flue gas (15 % CO2 and 85 % N2 in volume) as the raw material under ambient conditions. Moreover, Al‐HCP could be readily recycled and efficiently reused more than ten times, exhibiting excellent stability.

Multifunctionalization of organic polymers for acting synergistically on substrate is of wide interest in the field of modern catalysis, but it is still a significant challenge. Herein, two novel bifunctional polymers were first designed and synthesized by combining ionic liquids (ILs) with zinc(II) porphyrin through simple and reversible Schiff base reactions. The fabricated polymers with flexible structures and nitrogen-rich environments presented high affinity toward CO 2 molecules at ambient conditions. Owing to the cooperative nature of intercalated ILs and Lewis acidic metal sites, these materials could serve as efficient heterogeneous catalysts for the insertion of CO 2 into epoxides to produce cyclic carbonates. As expected, these polymers exhibited good catalytic performance, robust constancy, excellent recyclability, and good substrate expansibility for this reaction in the absence of cocatalyst under mild or even ambient conditions. Notably, the selected catalyst SYSU-Zn@IL2 could directly convert diluted CO 2 (15% CO 2 in N 2 ) into cyclic carbonate at 80 °C and 3.0 MPa, further offering the great application potential for recycling real-world carbon resource.

Based on the concept of function-oriented synthesis, we pertinently developed a series of new functional ionic polymers, which exhibited good catalytic performance, robust constancy, and excellent substrate expansibility for sustainable catalysis of CO2-involved reactions.