Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO2 Cycloaddition

doi:10.1007/s40242-025-4202-1

Chemical Research in Chinese Universities ›› 2025, Vol. 41 ›› Issue (1): 121-130.doi: 10.1007/s40242-025-4202-1

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Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO₂ Cycloaddition

YAN Shengrong^1,2,3, ZHANG Lan¹, SHI Songhu¹, REN Yanyan¹, LIU Wenhao¹, LI Yujie¹, DUAN Fang¹, LU Shuanglong¹, DU Mingliang¹, CHEN Mingqing¹

1. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, P. R. China;
2. School of Environmental and Biological Engineering, Nantong College of Science and Technology, Nantong 226007, P. R. China;
3. Jiangsu Engineering Research Center of Environmental Functional Materials and Pollution Control, Nantong 226007, P. R. China

Received:2024-10-06 Online:2025-02-01 Published:2025-01-18
Contact: DUAN Fang,duanfang@jiangnan.edu.cn;CHEN Mingqing,mqchen@jiangnan.edu.cn E-mail:duanfang@jiangnan.edu.cn;mqchen@jiangnan.edu.cn
Supported by:
This work was supported by the National Key Research and Development Program of China (No. 2022YFA1203600), the National Natural Science Foundation of China (No. 52173201), the Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (No. KYCX18_1808), and High-end Training Program for Teachers' Professional Leaders in Higher Vocational Colleges of Jiangsu Province in 2023, China (No. 2023GRFX045).

Abstract

Abstract: The photocatalytic CO₂ cycloaddition to prepare high value-added chemicals, such as cyclic carbonates (CCs) under mild conditions is an effective strategy to realize carbon neutrality. Herein, through a three-step reaction, the porphyrin-based covalent organic polymer with bimetallic active sites (Fe-COP-Zr) is successfully obtained by coordinating Fe²⁺ and Zr⁴⁺ with porphyrin and bipyridine (Bpy), respectively. Owing to excellent photosensitivity of porphyrin moieties, Fe-COP-Zr exhibits outstanding visible light absorption, which is very important for the production of photogenerated carriers. Consequently, Fe-COP-Zr shows high photocatalytic performance towards CO₂ cycloaddition with a yield of 12.1 mmol/h, which is 6 times higher than that of pure covalent organic polymer (COP) and 3 times higher than that of monometallic Fe-COP. The reason for this excellent photocatalytic CO₂ cycloaddition performance may be ascribed to the synergistic effect of Fe and Zr sites. The photogenerated electrons are easily injected into epichlorohydrin (ECH) through Fe—O bonds to form affluent electron transition state, and interact with Zr⁴⁺ as Lewis acid sites for the ring-opening of ECH, which is the rate-determining step for the visible light boosted chemical fixation of CO₂ into CCs. This work might provide some insights for design and preparation of COPs with multiple active sites to modulate their photocatalytic activities.

Key words: Photocatalytic CO₂ cycloaddition, Cyclic carbonate, Covalent organic polymer, Bimetallic active site

YAN Shengrong, ZHANG Lan, SHI Songhu, REN Yanyan, LIU Wenhao, LI Yujie, DUAN Fang, LU Shuanglong, DU Mingliang, CHEN Mingqing. Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO₂ Cycloaddition[J]. Chemical Research in Chinese Universities, 2025, 41(1): 121-130.

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Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO₂ Cycloaddition

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