Self-catalyzed cycloaddition of CO2 and epoxides over covalent organic frameworks without adding solvent and co-catalyst

doi:10.1016/j.cjche.2025.05.026

中国化学工程学报 ›› 2025, Vol. 87 ›› Issue (11): 10-18.DOI: 10.1016/j.cjche.2025.05.026

Self-catalyzed cycloaddition of CO₂ and epoxides over covalent organic frameworks without adding solvent and co-catalyst

Jingwen Yang¹, Zhengyan Qu¹, Jiuxuan Zhang¹, Hong Jiang¹, Zhenchen Tang^1,2, Weihong Xing^1,2, Rizhi Chen^1,2

1. State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
2. Suzhou Laboratory, Suzhou 215000, China

收稿日期:2025-04-14 修回日期:2025-05-15 接受日期:2025-05-15 出版日期:2025-11-28 发布日期:2025-07-08
通讯作者: Zhenchen Tang,E-mail:z.tang@njtech.edu.cn;Rizhi Chen,E-mail:rizhichen@njtech.edu.cn
基金资助:
The authors are grateful for the financial support from the National Key Research and Development Program (2022YFB3805504), the National Natural Science Foundation (22208149, 22278209, 22178165, 21921006, 22208144), and the Natural Science Foundation of Jiangsu Province (BK20220354, BK20211262, BK20220346) of China.

Self-catalyzed cycloaddition of CO₂ and epoxides over covalent organic frameworks without adding solvent and co-catalyst

Jingwen Yang¹, Zhengyan Qu¹, Jiuxuan Zhang¹, Hong Jiang¹, Zhenchen Tang^1,2, Weihong Xing^1,2, Rizhi Chen^1,2

1. State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
2. Suzhou Laboratory, Suzhou 215000, China

Received:2025-04-14 Revised:2025-05-15 Accepted:2025-05-15 Online:2025-11-28 Published:2025-07-08
Contact: Zhenchen Tang,E-mail:z.tang@njtech.edu.cn;Rizhi Chen,E-mail:rizhichen@njtech.edu.cn
Supported by:
The authors are grateful for the financial support from the National Key Research and Development Program (2022YFB3805504), the National Natural Science Foundation (22208149, 22278209, 22178165, 21921006, 22208144), and the Natural Science Foundation of Jiangsu Province (BK20220354, BK20211262, BK20220346) of China.

摘要/Abstract

摘要： The cycloaddition of CO₂ and epoxides to synthesize cyclic carbonates is a key strategy for CO₂ utilization, though heterogeneous catalysts often suffer from instability. Covalent organic frameworks (COFs) present a compelling alternative due to their excellent textural properties and abundant Lewis basic sites. Herein, triazine-based COFs (PC-COFs) were synthesized by optimizing reaction time and temperature and were applied to catalyze the CO₂ cycloaddition with epichlorohydrin (ECH) under solvent-free conditions, Instead of necessity of adding homogeneous co-catalyst, this study reveals a synergistic self-catalysis mechanism, where the carbonate product adsorbed on the Lewis basic PC-COF surface forms catalytic pairs with Lewis acidic carbonates, significantly accelerating the reaction. After five cycles, catalytic activity increased by 35% from 56.2% to 91.4%, and stabilizing over seven cycles. Under optimal reaction conditions, PC-COF-50-30 demonstrated outstanding catalytic performance, with a 98.7% ECH conversion, 97.6% selectivity to ECH carbonate and a CO₂ conversion rate of 9.0 g·g^-1·h^-1. This work provides a valuable example of high-performance CO₂ cycloaddition catalysts and a strategy to achieve enhanced catalytic efficiency through product-catalyst synergy.

关键词: Covalent organic framework (COF), CO₂ cycloaddition, Self-catalysis, Cyclic carbonate

Abstract: The cycloaddition of CO₂ and epoxides to synthesize cyclic carbonates is a key strategy for CO₂ utilization, though heterogeneous catalysts often suffer from instability. Covalent organic frameworks (COFs) present a compelling alternative due to their excellent textural properties and abundant Lewis basic sites. Herein, triazine-based COFs (PC-COFs) were synthesized by optimizing reaction time and temperature and were applied to catalyze the CO₂ cycloaddition with epichlorohydrin (ECH) under solvent-free conditions, Instead of necessity of adding homogeneous co-catalyst, this study reveals a synergistic self-catalysis mechanism, where the carbonate product adsorbed on the Lewis basic PC-COF surface forms catalytic pairs with Lewis acidic carbonates, significantly accelerating the reaction. After five cycles, catalytic activity increased by 35% from 56.2% to 91.4%, and stabilizing over seven cycles. Under optimal reaction conditions, PC-COF-50-30 demonstrated outstanding catalytic performance, with a 98.7% ECH conversion, 97.6% selectivity to ECH carbonate and a CO₂ conversion rate of 9.0 g·g^-1·h^-1. This work provides a valuable example of high-performance CO₂ cycloaddition catalysts and a strategy to achieve enhanced catalytic efficiency through product-catalyst synergy.

Key words: Covalent organic framework (COF), CO₂ cycloaddition, Self-catalysis, Cyclic carbonate

Jingwen Yang, Zhengyan Qu, Jiuxuan Zhang, Hong Jiang, Zhenchen Tang, Weihong Xing, Rizhi Chen. Self-catalyzed cycloaddition of CO₂ and epoxides over covalent organic frameworks without adding solvent and co-catalyst[J]. 中国化学工程学报, 2025, 87(11): 10-18.

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Self-catalyzed cycloaddition of CO₂ and epoxides over covalent organic frameworks without adding solvent and co-catalyst

Self-catalyzed cycloaddition of CO₂ and epoxides over covalent organic frameworks without adding solvent and co-catalyst

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