高等学校化学学报

高等学校化学学报

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噻二唑基稀土金属有机骨架高效催化CO2环加成反应

郭井鹏1,张航川1,魏娜1,王舒1,姜宏波1,赵震1,2   

  1. 1. 沈阳师范大学化学化工学院 2. 中国石油大学(北京), 重质油国家重点实验室

  • 收稿日期:2025-07-14 修回日期:2025-08-19 网络首发:2025-08-20 发布日期:2025-08-20
  • 通讯作者: 魏娜 E-mail:wwweina@126.com
  • 基金资助:
    国家自然科学基金（批准号：22002095）和辽宁省高校基本科研项目（批准号：LJ212510166006）资助

Thiadiazole-Based Rare-Earth Metal-Organic Frameworks for Efficient Catalysis of CO2 cycloaddition reactions

Guo Jingpeng1, Zhang Hangchuan1, Wei Na1, Wang Shu1, Jiang Hongbo1, Zhao Zhen1,2

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收稿日期: 2021-XX-XX. 网络首发日期: 2021-XX-XX.

联系人简介: 魏娜, 女, 博士, 讲师, 主要从事金属有机框架材料催化性能的研究. E-mail: wwweina@126.com

赵震, 男, 博士, 教授, 主要从事环境催化、稀土催化、石油炼制与化工催化及催化新材料等方面的研究.

E-mail: zhenzhao@cup.edu.cn

基金项目:国家自然科学基金（批准号：22002095）资助.

Supported by the National Natural Science Foundation of China (No. 22002095).

  

  1. 1. School of Chemistry and Chemical Engineering, Shenyang Normal University 2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum

  • Received:2025-07-14 Revised:2025-08-19 Online First:2025-08-20 Published:2025-08-20
  • Contact: WEI Na E-mail:wwweina@126.com
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. 22002095) and Liaoning Provincial Education Department Basic Research Projects for Universities (No. LJ212510166006).

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摘要： 本文利用含有噻二唑基团的四羧酸配体, 5,5’-(苯并噻二唑-4,7-二取代)-间苯二甲酸(H4BTDI), 与稀土金属硝酸盐通过溶剂热法合成了一系列异质同晶的新型三维稀土金属有机骨架(MOFs)材料, [RE4(BTDI)3(DMF)4]?solv (RE-BTDI, RE = Er, Dy, Y). 通过Py-IR和NH3-TPD测试定性定量的证实了RE-BTDI结构的稀土金属节点可作为Lewis酸性位点, 同时通过配体引入的噻二唑基团作为极性位点可提升材料的CO2吸附性能, 在二者的协同下, RE-BTDI对CO2和一系列环氧化物的环加成反应展示出良好的催化活性. 在80 oC, 1MPa CO2条件下, 0.1 mol%的Er-BTDI催化CO2与氧化苯乙烯的环加成反应5小时, 苯乙烯环状碳酸酯的产率均可达到90%, 并且在循环催化5轮后, 催化活性和催化剂结构均没有明显改变. 此外, 对于其他环氧化物, RE-BTDI在较温和的条件下催化，相应环状碳酸酯产物的产率可达到92.5%-99%.

关键词: 金属有机骨架, 稀土, 噻二唑, 非均相催化, 二氧化碳环加成

Abstract: A series of novel isostructural three-dimensional rare-earth metal-organic frameworks (MOFs), [RE(BTDI)3(H2O)4]·4H2O·solv (RE-BTDI, RE = Er, Dy, Y) were synthesized by solvothermal method using tetracarboxylic acid ligand containing thiadiazole groups, 5,5'-(benzothiadiazole-4,7-diyl)diisophthalic acid (H4BTDI) and rare earth metal nitrates. The rare earth metal nodes on the frameworks of RE-BTDI are Lewis acidic sites which was confirmed qualitatively and quantitatively by Py-IR and NH3-TPD. Meanwhile, the thiadiazole groups introduced by ligands can be used as polar sites to enhance the CO2 adsorption performance of these materials. Under the synergy of the Lewis acidic sites and thiadiazole groups, RE-BTDI show good catalytic activity for the cycloaddition reaction of CO2 and a series of epoxides. Under the condition of 80 ℃, 1MPa CO2, 0.1 mol% RE-BTDI catalyzed the cycloaddition reaction of CO2 and styrene oxide for 5 hours, the yield of styrene cyclic carbonate can reach 90%, and after 5 rounds of cyclic catalysis, the catalytic activity and catalyst structure are maintained well. In addition, for other epoxides, the yields of the corresponding cyclic carbonate products can reach 92.5% to 99% catalyzed by RE-BTDI under relatively mild conditions.

Key words: Metal Organic Frameworks, Rare-earth, Thiadiazole, Heterogeneous catalysis, CO2 cycloaddition

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