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A novel bifunctional metalloporphyrin-based hyper-crosslinked ionic polymer as heterogeneous catalyst for efficiently converting CO2 into cyclic carbonates

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Abstract

The rapid development of industrialization generated an urgent requirement for the catalytic conversion of CO2 into high-value-added chemical products. Herein, a class of novel bifunctional metalloporphyrin-based hyper-crosslinked ionic polymer (ImHCP-Co) was synthesized via one-pot Friedel–Crafts alkylation and quaternization reactions. The obtained bifunctional ImHCP-Co showed a high BET surface area and sufficient CO2 adsorption capacity. Relying on the synergistic effect of the electrophilic and nucleophilic functionalities, the as-prepared ImHCP-Co showed an excellent performance in CO2 cycloaddition using epichlorohydrin as the substrate (99% conversion and 99% selectivity) and can be carried out without any solvents or cocatalysts to afford a high turnover number. Importantly, it could also convert various epoxide substrates into the corresponding cyclic carbonates and can maintain 82.5% of its catalytic ability after 5 cycles. The catalytic mechanism was systematically explained by DFT calculation and proved the cooperative effect of Co2+ centers and nucleophilic Cl− in the catalytic process. This study provides a new avenue for the design and preparation of HCP-based multifunctional catalysts used for the treatment of greenhouse gases.

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Acknowledgements

This work was supported by the Key research and development guidance projects in Heilongjiang province (grant number GZ(2021)0034); the Opening Foundation of Heilongjiang Province Key Laboratory of Polymeric Composition material (CLKFKT(2021)B6); the National Natural Science Foundation of China (grant number 52173202); and the Heilongjiang Science Foundation Project (grant number YQ(2022)E043). The Spartan software used for the calculation was provided by Prof. Toshiki Aoki, Niigata University, Japan.

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Authors and Affiliations

  1. Technology Innovation Center of Industrial Hemp for State Market Regulation, College of Chemistry and Chemical Engineering, Qiqihar University, Wenhua Street 42, Qiqihar, 161006, Heilongjiang, China

    Jianjun Wang, Jiaqi Chen & Zhichun Shi

  2. Heilongjiang Province Key Laboratory of Polymeric Composition Material, College of Materials Science and Engineering, Qiqihar University, Wenhua Street 42, Qiqihar, 161006, Heilongjiang, China

    Jianjun Wang, Dongning Li, Jiao Liu & Yu Zang

  3. Analysis and Testing Center, Qiqihar University, Wenhua Street 42, Qiqihar, 161006, Heilongjiang, China

    Liang Xu

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Contributions

JC did the experiment and investigation; JW was involved in conceptualization and writing, reviewing and editing; DL helped with the experiment and data analysis; ZS contributed to software and funding acquisition; JL edited the manuscript and analyzed the data; LX participated in writing, reviewing and editing; and YZ was responsible for supervision and drafting revision.

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Correspondence to Jianjun Wang or Yu Zang.

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Wang, J., Chen, J., Li, D. et al. A novel bifunctional metalloporphyrin-based hyper-crosslinked ionic polymer as heterogeneous catalyst for efficiently converting CO2 into cyclic carbonates. J Mater Sci 59, 1235–1252 (2024). https://doi.org/10.1007/s10853-023-09280-y

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