Efficient homogenous catalysis of CO2 to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

doi:10.1016/j.cjche.2022.01.009

Chinese Journal of Chemical Engineering ›› 2022, Vol. 43 ›› Issue (3): 110-115.DOI: 10.1016/j.cjche.2022.01.009

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Efficient homogenous catalysis of CO₂ to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

Zhen Lu^1,2, Jie He¹, Bogeng Guo¹, Yulai Zhao^1,2, Jingyu Cai^1,2, Longqiang Xiao^1,2, Linxi Hou^1,2,3

1. Department of Materials-Oriented Chemical Engineering, School of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. Qingyuan Innovation Laboratory, Quanzhou 362801, China;
3. Fujian Key Laboratory of Advanced Manufacturing Technology of Specialty Chemicals, Fuzhou University, Fuzhou 350116, China

Received:2021-11-12 Revised:2022-01-04 Online:2022-04-28 Published:2022-03-28
Contact: Longqiang Xiao,E-mail:xiaolq@fzu.edu.cn;Linxi Hou,E-mail:lxhou@fzu.edu.cn
Supported by:
This work was financially supported by the National Natural Science Foundation of China (21504025), the Natural Science Foundation of Fujian Province (2019J05040), Fujian Provincial Department of Education (JT180038), Key Program of Qingyuan Innovation Laboratory (00221003), Fuzhou University Testing Fund of precious apparatus(2021T022), Talent Program (GXRC-18041) and Higher Education Disciplinary Innovation Program ('111' Program) of Fuzhou University.

Efficient homogenous catalysis of CO₂ to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

Zhen Lu^1,2, Jie He¹, Bogeng Guo¹, Yulai Zhao^1,2, Jingyu Cai^1,2, Longqiang Xiao^1,2, Linxi Hou^1,2,3

1. Department of Materials-Oriented Chemical Engineering, School of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. Qingyuan Innovation Laboratory, Quanzhou 362801, China;
3. Fujian Key Laboratory of Advanced Manufacturing Technology of Specialty Chemicals, Fuzhou University, Fuzhou 350116, China

通讯作者: Longqiang Xiao,E-mail:xiaolq@fzu.edu.cn;Linxi Hou,E-mail:lxhou@fzu.edu.cn
基金资助:
This work was financially supported by the National Natural Science Foundation of China (21504025), the Natural Science Foundation of Fujian Province (2019J05040), Fujian Provincial Department of Education (JT180038), Key Program of Qingyuan Innovation Laboratory (00221003), Fuzhou University Testing Fund of precious apparatus(2021T022), Talent Program (GXRC-18041) and Higher Education Disciplinary Innovation Program ('111' Program) of Fuzhou University.

Abstract

Abstract: The cycloaddition between CO₂ and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO₂ as C1 source. The development of catalyst to mediate cycloaddition between CO₂ and epoxides at low temperature and pressure is still a challenge. Herein, a series of polypyrazoles with glass transition temperature (T_g) in the range of 42.3–52.5 ℃ were synthesized and served as catalyst to mediate the cycloaddition of CO₂ and epoxides by the assistant of tetrabutylammonium bromide. The catalytic behaviors of polypyrazole on the model cycloaddition of CO₂ to epichlorohydrin, including the reaction parameters optimization and versatility were investigated in detail, and excellent yield (99.9%) and selectivity (99%) were obtained under the optimized reaction conditions of 70 ℃ and 1.0 MPa for 6.0 h. Noteworthily, the polypyrazole acts as homogeneous catalyst during reaction (higher than T_g). And under room temperature, polypyrazoles can be easily separated and recovered, which is a promising feature of a heterogeneous catalyst. Furthermore, the reaction mechanism was proposed. The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier, which play an important role in promoting CO₂ cycloaddition.

Key words: Carbon dioxide, CO₂ conversion, Cyclic carbonate, Heterogeneous catalysis, Polypyrazole

摘要： The cycloaddition between CO₂ and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO₂ as C1 source. The development of catalyst to mediate cycloaddition between CO₂ and epoxides at low temperature and pressure is still a challenge. Herein, a series of polypyrazoles with glass transition temperature (T_g) in the range of 42.3–52.5 ℃ were synthesized and served as catalyst to mediate the cycloaddition of CO₂ and epoxides by the assistant of tetrabutylammonium bromide. The catalytic behaviors of polypyrazole on the model cycloaddition of CO₂ to epichlorohydrin, including the reaction parameters optimization and versatility were investigated in detail, and excellent yield (99.9%) and selectivity (99%) were obtained under the optimized reaction conditions of 70 ℃ and 1.0 MPa for 6.0 h. Noteworthily, the polypyrazole acts as homogeneous catalyst during reaction (higher than T_g). And under room temperature, polypyrazoles can be easily separated and recovered, which is a promising feature of a heterogeneous catalyst. Furthermore, the reaction mechanism was proposed. The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier, which play an important role in promoting CO₂ cycloaddition.

关键词: Carbon dioxide, CO₂ conversion, Cyclic carbonate, Heterogeneous catalysis, Polypyrazole

Zhen Lu, Jie He, Bogeng Guo, Yulai Zhao, Jingyu Cai, Longqiang Xiao, Linxi Hou. Efficient homogenous catalysis of CO₂ to generate cyclic carbonates by heterogenous and recyclable polypyrazoles[J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 110-115.

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Efficient homogenous catalysis of CO₂ to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

Efficient homogenous catalysis of CO₂ to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

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