A tunable ionic covalent organic framework platform for efficient CO<sub>2</sub> catalytic conversion

doi:10.1007/s11705-023-2369-x

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (1) : 3 https://doi.org/10.1007/s11705-023-2369-x

RESEARCH ARTICLE

A tunable ionic covalent organic framework platform for efficient CO₂ catalytic conversion

Ting Li^1,², Ji Xiong^1,², Minghui Chen^1,², Quan Shi^1,², Xiangyu Li^1,², Yu Jiang^1,², Yaqing Feng^1,², Bao Zhang^1,^2,³(

)

¹. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
². Guangdong Laboratory of Chemistry and Fine Chemical Industry Jieyang Center, Jieyang 522000, China
³. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

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Abstract

The cycloaddition reaction between epoxides and CO₂ is an effective method to utilize CO₂ resource. Covalent organic frameworks (COFs) provide a promising platform for the catalytic CO₂ transformations on account of their remarkable chemical and physical properties. Herein, a family of novel vinylene-linked ionic COFs named TE-COFs (TTE-COF, TME-COF, TPE-COF, TBE-COF) has been facilely synthesized from N-ethyl-2,4,6-trimethylpyridinium bromide and a series of triphenyl aromatic aldehydes involving different numbers of nitrogen atoms in the central aromatic ring. The resulting catalyst TTE-COF with excellent adsorption capacity (45.6 cm³·g^–1, 273 K) exhibited outstanding catalytic performance, remarkable recyclability and great substrate tolerance. Moreover, it was also observed that the introduction of nitrogen atom in the precursor led to a great improvement in the crystallinity and CO₂ adsorption capacity of TE-COFs, thus resulting to a progressively improved catalytic performance. This work not only illustrated the influence of monomer nitrogen content on the crystallinity and CO₂ adsorption capacity of TE-COFs but also provided a green heterogeneous candidate for catalyzing the cycloaddition between CO₂ and epoxides, which shed a light on improving the catalytic performance of the CO₂ cycloaddition reaction by designing the covalent organic frameworks structures.

Keywords CO₂ cycloaddition reaction covalent organic frameworks cyclic carbonate vinylene-linked synergetic effects

Corresponding Author(s): Bao Zhang

About author:

Peng Lei and Charity Ngina Mwangi contributed equally to this work.

Just Accepted Date: 06 September 2023 Issue Date: 07 November 2023

Cite this article:

Ting Li,Ji Xiong,Minghui Chen, et al. A tunable ionic covalent organic framework platform for efficient CO₂ catalytic conversion[J]. Front. Chem. Sci. Eng., 2024, 18(1): 3.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2369-x
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I1/3

Fig.1 Design and synthesis of the TE-COFs.

Fig.2 PXRD patterns of (a) TTE-COF, (b) TME-COF, (c) TPE-COF, and (d) TBE-COF.

Fig.3 (a) Solid-state ¹³C CP-MAS NMR spectra of TE-COFs; (b) FTIR spectra of TE-COFs.

Fig.4 (a) XPS survey spectrum of TTE-COF; (b) high-resolution N 1s XPS spectrum of TTE-COF; (c) high-resolution Br 3d spectrum of TTE-COF.

Fig.5 N₂ sorption isotherm and pore size distribution of (a) TTE-COF, (b) TME-COF, (c) TPE-COF, and (d) TBE-COF.

Fig.6 (a, b) CO₂ sorption isotherms of the TE-COFs at 273 and 298 K.

Fig.7 SEM images of (a) TTE-COF, (b) TME-COF, (c) TPE-COF, and (d) TBE-COF.

Fig.8 The catalytic kinetics of TE-COFs. Conditions: (a) epichlorohydrin 12.8 mmol, TE-COFs 20 mg, 60 °C, 0.1 MPa, and 20 h; (b) epichlorohydrin 12.8 mmol, TE-COFs 20 mg, 80 °C, 0.1 MPa, and 20 h; (c) epichlorohydrin 12.8 mmol, TE-COFs 20 mg, 100 °C, 0.1 MPa, and 20 h.

Fig.9 (a) Effect of reaction temperature: epichlorohydrin (12.8 mmol), TTE-COF (20 mg), 0.1 MPa, 24 h; (b) effect of reaction time: epichlorohydrin (12.8 mmol), TTE-COF (20 mg), 100 °C, 0.1 MPa; (c) effect of TTE-COF loading: epichlorohydrin (12.8 mmol), 100 °C, 0.1 MPa, 20 h. The yields were determined by ¹H NMR.

Tab.1 CO₂ cycloaddition reaction with different epoxides^a)

Fig.10 (a) Recyclability of the TTE-COF catalyst. Conditions: epichlorohydrin 12.8 mmol, TTE-COF 20 mg, 100 °C, 0.1 MPa, and 20 h; (b) N₂ sorption isotherm and pore size distribution at 77 K of TTE-COF after 5 cycles of the reaction; (c) PXRD of TTE-COF before and after 5 cycles of the reaction; (d) FTIR spectra of TTE-COF before and after 5 cycles of the reaction.

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[1]	Jiaxin Li, Chengguang Yue, Wenhao Ji, Bangman Feng, Mei-Yan Wang, Xinbin Ma. Recent advances in cycloaddition of CO₂ with epoxides: halogen-free catalysis and mechanistic insights[J]. Front. Chem. Sci. Eng., 2023, 17(12): 1879-1894.

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