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

doi:10.1016/j.cjche.2022.01.009

中国化学工程学报 ›› 2022, Vol. 43 ›› Issue (3): 110-115.DOI: 10.1016/j.cjche.2022.01.009

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

收稿日期:2021-11-12 修回日期:2022-01-04 出版日期:2022-03-28 发布日期:2022-04-28
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.

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:2022-03-28 Published:2022-04-28
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.

摘要/Abstract

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

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

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]. 中国化学工程学报, 2022, 43(3): 110-115.

参考文献

[1] Q. Yi, T.T. Liu, X.B. Wang, Y.Y. Shan, X.Y. Li, M.G. Ding, L.J. Shi, H.B. Zeng, Y.C. Wu, One-step multiple-site integration strategy for CO₂ capture and conversion into cycli*c carbonates under atmospheric and cocatalyst/metal/solvent-free conditions, Appl. Catal. B Environ. 283 (2021) 119620. http://dx.doi.org/10.1016/j.apcatb.2020.119620
[2] Z.H. Wu, Y. Nan, Y. Zhao, X.Y. Wang, S.Y. Huang, J.F. Shi, Immobilization of carbonic anhydrase for facilitated CO₂ capture and separation, Chin. J. Chem. Eng. 28 (11) (2020) 2817-2831. http://dx.doi.org/10.1016/j.cjche.2020.06.002
[3] W. Zhou, Q.W. Deng, G.Q. Ren, L. Sun, L. Yang, Y.M. Li, D. Zhai, Y.H. Zhou, W.Q. Deng, Enhanced carbon dioxide conversion at ambient conditions via a pore enrichment effect, Nat. Commun. 11 (2020) 4481. https://www.nature.com/articles/s41467-020-18154-9
[4] F.F. Li, F. Mocci, X.P. Zhang, X.Y. Ji, A. Laaksonen, Ionic liquids for CO₂ electrochemical reduction, Chin. J. Chem. Eng. 31 (2021) 75-93. http://dx.doi.org/10.1016/j.cjche.2020.10.029
[5] Y.Y. Zhang, G.W. Yang, R. Xie, L. Yang, B. Li, G.P. Wu, Scalable, durable, and recyclable metal-free catalysts for highly efficient conversion of CO₂ to cyclic carbonates, Angew. Chem. Int. Ed. 59 (51) (2020) 23291-23298. https://doi.org/10.1002/anie.202010651
[6] W.Z. Sun, M.C. Wang, Y.Q. Zhang, W.L. Ding, F. Huo, L. Wei, H.Y. He, Protic vs aprotic ionic liquid for CO₂ fixation:a simulation study, Green Energy Environ. 5 (2) (2020) 183-194. http://dx.doi.org/10.1016/j.gee.2020.04.004
[7] Y.X. Wu, Y.C. Ding, J.H. Xu, Y.D. Wang, K. Mumford, G.W. Stevens, W.Y. Fei, Efficient fixation of CO₂ into propylene carbonate with[BMIM]Br in a continuous-flow microreaction system, Green Energy Environ. 6 (2) (2021) 291-297. http://dx.doi.org/10.1016/j.gee.2020.04.016
[8] J.W. Lan, Y. Qu, P. Xu, J.M. Sun, Novel HBD-Containing Zn (dobdc) (datz) as efficiently heterogeneous catalyst for CO₂ chemical conversion under mild conditions, Green Energy Environ. 6 (1) (2021) 66-74. http://dx.doi.org/10.1016/j.gee.2019.12.005
[9] J. Liu, G.Q. Yang, Y. Liu, D.J. Zhang, X.B. Hu, Z.B. Zhang, Efficient conversion of CO₂ into cyclic carbonates at room temperature catalyzed by Al-salen and imidazolium hydrogen carbonate ionic liquids, Green Chem. 22 (14) (2020) 4509-4515. https://doi.org/10.1039/d0gc00458h
[10] K. Naveen, H. Ji, T.S. Kim, D. Kim, D.H. Cho, C3-symmetric zinc complexes as sustainable catalysts for transforming carbon dioxide into mono- and multi-cyclic carbonates, Appl. Catal. B Environ. 280 (2021) 119395. http://dx.doi.org/10.1016/j.apcatb.2020.119395
[11] N. Patil, S. Bhoopathi, V. Chidara, N. Hadjichristidis, Y. Gnanou, X.S. Feng, Recycling a borate complex for synthesis of polycarbonate polyols:towards an environmentally friendly and cost-effective process, ChemSusChem 13 (18) (2020) 5080-5087. https://doi.org/10.1002/cssc.202001395
[12] A.J. Kamphuis, F. Picchioni, P.P. Pescarmona, CO₂-fixation into cyclic and polymeric carbonates:principles and applications, Green Chem. 21 (3) (2019) 406-448. https://doi.org/10.1039/c8gc03086c
[13] R. Babu, A.C. Kathalikkattil, R. Roshan, J. Tharun, D.W. Kim, D.W. Park, Dual-porous metal organic framework for room temperature CO₂ fixation via cyclic carbonate synthesis, Green Chem. 18 (1) (2016) 232-242. https://doi.org/10.1039/c5gc01763g
[14] T.K. Pal, D. De, P.K. Bharadwaj, Metal-organic frameworks for the chemical fixation of CO₂ into cyclic carbonates, Coord. Chem. Rev. 408 (2020) 213173. http://dx.doi.org/10.1016/j.ccr.2019.213173
[15] K.A. Andrea, F.M. Kerton, Triarylborane-catalyzed formation of cyclic organic carbonates and polycarbonates, ACS Catal. 9 (3) (2019) 1799-1809. https://doi.org/10.1021/acscatal.8b04282
[16] J.A. Castro-Osma, K.J. Lamb, M. North, Cr(salophen) complex catalyzed cyclic carbonate synthesis at ambient temperature and pressure, ACS Catal. 6 (8) (2016) 5012-5025. https://doi.org/10.1021/acscatal.6b01386
[17] R.R. Shaikh, S. Pornpraprom, V. D'Elia, Catalytic strategies for the cycloaddition of pure, diluted, and waste CO₂ to epoxides under ambient conditions, ACS Catal. 8 (1) (2018) 419-450. http://dx.doi.org/10.1021/acscatal.7b03580
[18] D.G. Jia, L. Ma, Y. Wang, W.L. Zhang, J. Li, Y. Zhou, J. Wang, Efficient CO₂ enrichment and fixation by engineering micropores of multifunctional hypercrosslinked ionic polymers, Chem. Eng. J. 390 (2020) 124652. http://dx.doi.org/10.1016/j.cej.2020.124652
[19] M.W. Hussain, V. Bhardwaj, A. Giri, A. Chande, A. Patra, Multifunctional ionic porous frameworks for CO₂ conversion and combating microbes, Chem. Sci. 11 (2020)7910-7920
[20] W. Hui, X.M. He, X.Y. Xu, Y.M. Chen, Y. Zhou, Z.M. Li, L.Q. Zhang, D.J. Tao, Highly efficient cycloaddition of diluted and waste CO₂ into cyclic carbonates catalyzed by porous ionic copolymers, J. CO₂ Util. 36 (2020) 169-176. http://dx.doi.org/10.1016/j.jcou.2019.11.003
[21] Y.C. Guo, L. Feng, C.C. Wu, X.M. Wang, X. Zhang, Confined pyrolysis transformation of ZIF-8 to hierarchically ordered porous Zn-N-C nanoreactor for efficient CO₂ photoconversion under mild conditions, J. Catal. 390 (2020) 213-223. http://dx.doi.org/10.1016/j.jcat.2020.07.037
[22] Z.Y. Fan, J.J. Wang, W.J. Wang, S. Burger, Z. Wang, Y.M. Wang, C. Wöll, M. Cokoja, R.A. Fischer, Defect engineering of copper paddlewheel-based metal-organic frameworks of type NOTT-100:implementing truncated linkers and its effect on catalytic properties, ACS Appl. Mater. Interfaces 12 (34) (2020) 37993-38002. https://doi.org/10.1021/acsami.0c07249
[23] G.R. Cai, M.L. Ding, Q.Y. Wu, H.L. Jiang, Encapsulating soluble active species into hollow crystalline porous capsules beyond integration of homogeneous and heterogeneous catalysis, Natl. Sci. Rev. 7 (1) (2020) 37-45. https://doi.org/10.1093/nsr/nwz147
[24] Q.H. Yang, C.C. Yang, C.H. Lin, H.L. Jiang, Metal-organic-framework-derived hollow N-doped porous carbon with ultrahigh concentrations of single Zn atoms for efficient carbon dioxide conversion, Angew. Chem. Int. Ed Engl. 58 (11) (2019) 3511-3515. https://pubmed.ncbi.nlm.nih.gov/30569535/
[25] Q. Guo, S.G. Xia, X.B. Li, Y. Wang, F. Liang, Z.S. Lin, C.H. Tung, L.Z. Wu, Flower-like cobalt carbide for efficient carbon dioxide conversion, Chem. Commun. 56 (57) (2020) 7849-7852. https://doi.org/10.1039/d0cc01091j
[26] P.Z. Li, X.J. Wang, J. Liu, J.S. Lim, R.Q. Zou, Y.L. Zhao, A triazole-containing metal-organic framework as a highly effective and substrate size-dependent catalyst for CO₂ conversion, J. Am. Chem. Soc. 138 (7) (2016) 2142-2145. http://dx.doi.org/10.1021/jacs.5b13335
[27] J. Liang, Y.Q. Xie, X.S. Wang, Q. Wang, T.T. Liu, Y.B. Huang, R. Cao, An imidazolium-functionalized mesoporous cationic metal-organic framework for cooperative CO₂ fixation into cyclic carbonate, Chem. Commun. 54 (4) (2018) 342-345. https://doi.org/10.1039/c7cc08630j
[28] Z. Lu, B.G. Guo, Y.L. Zhao, L.X. Hou, L.Q. Xiao, One-step synthesis of cyclic polypyrazole and the self-assembly vesicles driven by hydrogen bond, Chin. Chem. Lett. (2021) http://dx.doi.org/10.1016/j.cclet.2021.07.033
[29] X.F. Zhang, H.T. Liu, P.F. An, Y.N. Shi, J.Y. Han, Z.J. Yang, C. Long, J. Guo, S.L. Zhao, K. Zhao, H.J. Yin, L.R. Zheng, B.H. Zhang, X.P. Liu, L.J. Zhang, G.D. Li, Z.Y. Tang, Delocalized electron effect on single metal sites in ultrathin conjugated microporous polymer nanosheets for boosting CO₂ cycloaddition, Sci. Adv. 6 (17) (2020) eaaz4824. https://pubmed.ncbi.nlm.nih.gov/32426463/
[30] Y.P. Song, Q. Sun, P.C. Lan, S.Q. Ma, Secondary sphere effects on porous polymeric organocatalysts for CO₂ transformations:subtle modifications resulting in superior performance, ACS Appl. Mater. Interfaces 12 (29) (2020) 32827-32833. https://doi.org/10.1021/acsami.0c08817
[31] Y.F. Sang, J.H. Huang, Benzimidazole-based hyper-cross-linked poly(ionic liquid)s for efficient CO₂ capture and conversion, Chem. Eng. J. 385 (2020) 123973. http://dx.doi.org/10.1016/j.cej.2019.123973

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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