Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO_(2) Cycloaddition  

作　　者：YAN Shengrong ZHANG Lan SHI Songhu REN Yanyan LIU Wenhao LI Yujie DUAN Fang LU Shuanglong DU Mingliang CHEN Mingqing 

机构地区：[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

出　　处：《Chemical Research in Chinese Universities》2025年第1期121-130,共10页高等学校化学研究(英文版)

基　　金：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);High-end Training Program for Teachers’Professional Leaders in Higher Vocational Colleges of Jiangsu Province in 2023,China(No.2023GRFX045).

摘　　要：The photocatalytic CO_(2) 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 Fe^(2+) and Zr^(4+)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 CO_(2) 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 CO_(2) 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 Zr^(4+) as Lewis acid sites for the ring-opening of ECH,which is the rate-determining step for the visible light boosted chemical fixation of CO_(2) into CCs.This work might provide some insights for design and preparation of COPs with multiple active sites to modulate their photocatalytic activities.

关 键 词：Photocatalytic CO_(2)cycloaddition Cyclic carbonate Covalent organic polymer Bimetallic active site 

分 类 号：O62[理学—有机化学]