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

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.

Key words： CO₂ cycloaddition reaction; covalent organic frameworks; cyclic carbonate; vinylene-linked; synergetic effects

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was financially supported by the Guangdong Basic and Applied Basic Research Foundation (Grant No. 2022A1515011606) and the Haihe Laboratory of Sustainable Chemical Transformations.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-023-2369-x and is accessible for authorized users.

References

1 Huang C H , Tan C S . A review: CO₂ utilization. Aerosol and Air Quality Research, 2014, 14(2): 480–499

2 Hepburn C , Adlen E , Beddington J , Carter E A , Fuss S , Dowell N M , Minx J C , Smith P , Williams C K . The technological and economic prospects for CO₂ utilization and removal. Nature, 2019, 575(7781): 87–97

3 De S , Dokania A , Ramirez A , Gascon J . Advances in the design of heterogeneous catalysts and thermocatalytic processes for CO₂ utilization. Science Advances, 2020, 10(23): 14147–14185

4 Tian S , Yan F , Zhang Z , Jiang J . Calcium-looping reforming of methane realizes in situ CO₂ utilization with improved energy efficiency. ACS Catalysis, 2019, 5: eaav5077

5 Chai J , Liu Z , Zhang J , Sun J , Tian Z , Ji Y , Tang K , Zhou X , Cui G . A superior polymer electrolyte with rigid cyclic carbonate backbone for rechargeable lithium ion batteries. ACS Applied Materials & Interfaces, 2017, 9(21): 17897–17905

6 Dick G R , Komarova A O , Luterbacher J S . Controlling lignin solubility and hydrogenolysis selectivity by acetal-mediated functionalization. Green Chemistry, 2022, 24(3): 1285–1293

7 Alves M , Grignard B , Mereau R , Jerome C , Tassaing T , Detrembleur C . Organocatalyzed coupling of carbon dioxide with epoxides for the synthesis of cyclic carbonates: catalyst design and mechanistic studies. Catalysis Science & Technology, 2017, 7(13): 2651–2684

8 Zhang W , Dai J , Wu Y C , Chen J X , Shan S Y , Cai Z , Zhu J B . Highly reactive cyclic carbonates with a fused ring toward functionalizable and recyclable polycarbonates. ACS Macro Letters, 2022, 11(2): 173–178

9 Monica F D , Kleij A W . Mechanistic guidelines in nonreductive conversion of CO₂: the case of cyclic carbonates. Catalysis Science & Technology, 2020, 10(11): 3483–3501

10 Liu Q , Wu L , Jackstell R , Beller M . Using carbon dioxide as a building block in organic synthesis. Nature Communications, 2015, 6(1): 5933

11 Jiang B , Liu J , Yang G , Zhang Z . Efficient conversion of CO₂ into cyclic carbonates under atmospheric by halogen and metal-free poly (ionic liquids). Chinese Journal of Chemical Engineering, 2023, 55: 202–211

12 Song H , Wang Y , Xiao M , Liu L , Liu Y , Liu X , Gai H . Design of novel poly (ionic liquids) for the conversion of CO₂ to cyclic carbonates under mild conditions without solvent. ACS Sustainable Chemistry & Engineering, 2019, 7(10): 9489–9497

13 Guo L , Lamb K J , North M . Recent developments in organocatalysed transformations of epoxides and carbon dioxide into cyclic carbonates. Green Chemistry, 2021, 23(1): 77–118

14 Andrea K A , Butler E D , Brown T R , Anderson T S , Jagota D , Rose C , Lee E M , Goulding S D , Murphy J N , Kerton F M . . Iron complexes for cyclic carbonate and polycarbonate formation: selectivity control from ligand design and metal-center geometry. Inorganic Chemistry, 2019, 58(16): 11231–11240

15 Wu Y , Song X , Xu S , Chen Y , Oderinde O , Gao L , Wei R , Xiao G . Chemical fixation of CO₂ into cyclic carbonates catalyzed by bimetal mixed MOFs: the role of the interaction between Co and Zn. Dalton Transactions, 2020, 49(2): 312–321

16 Dhankhar S S , Ugale B , Nagaraja C M . Co-catalyst-free chemical fixation of CO₂ into cyclic carbonates by using metal-organic frameworks as efficient heterogeneous catalysts. Chemistry, an Asian Journal, 2020, 15(16): 2403–2427

17 Sarkar S , Ghosh S , Islam S M A . Zn(II)-functionalized COF as a recyclable catalyst for the sustainable synthesis of cyclic carbonates and cyclic carbamates from atmospheric CO₂. Organic & Biomolecular Chemistry, 2022, 20(8): 1707–1722

18 Haque N , Biswas S , Ghosh S , Chowdhury A H , Khan A , Islam S M . Zn(II)-embedded nanoporous covalent organic frameworks for catalytic conversion of CO₂ under solvent-free conditions. ACS Applied Nano Materials, 2021, 4(8): 7663–7674

19 Li J , Han Y , Ji T , Wu N , Lin H , Jiang J , Zhu J . Porous metallosalen hypercrosslinked ionic polymers for cooperative CO₂ cycloaddition conversion. Industrial & Engineering Chemistry Research, 2020, 59(2): 676–684

20 Zhang W , He Q , Chen Y , Luo R , Zhou X , Ji H . A metal-free hydroxyl functionalized quaternary phosphine type ionic liquid polymer for cycloaddition of CO₂ and epoxides. Dalton Transactions, 2022, 51(4): 1303–1307

21 Liu K , Xu Z X , Huang H , Zhang Y D , Liu Y , Qiu Z H , Tong M M , Long Z Y , Chen G J . In situ synthesis of pyridinium-based ionic porous organic polymers with hydroxide anions and pyridinyl radicals for halogen-free catalytic fixation of atmospheric CO₂. Green Chemistry, 2022, 24(1): 136–141

22 Wang H , Wang H , Wang Z , Tang L , Zeng G , Xu P , Chen M , Xiong T , Zhou C , Li X . . Covalent organic framework photocatalysts: structures and applications. Chemical Society Reviews, 2020, 49(12): 4135–4165

23 Wang Z , Zhang S , Chen Y , Zhang Z , Ma S . Covalent organic frameworks for separation applications. Chemical Society Reviews, 2020, 49(3): 708–735

24 Yang Z Z , Zhao Y , Ji G , Zhang H , Yu B , Gao X , Liu Z . Fluoro-functionalized polymeric ionic liquids: highly efficient catalysts for CO₂ cycloaddition to cyclic carbonates under mild conditions. Green Chemistry, 2014, 16(8): 3724–3728

25 Chen J , Zhong M , Tao L , Liu L , Jayakumar S , Li C , Li H , Yang Q . The cooperation of porphyrin-based porous polymer and thermal-responsive ionic liquid for efficient CO₂ cycloaddition reaction. Green Chemistry, 2018, 20(4): 903–911

26 Zhao Y , Zhao Y , Qiu J , Li Z , Wang H , Wang J . Facile grafting of imidazolium salt in covalent organic frameworks with enhanced catalytic activity for CO₂ fixation and the Knoevenagel reaction. ACS Sustainable Chemistry & Engineering, 2020, 8(50): 18413–18419

27 Cao J , Shan W , Wang Q , Ling X , Li G , Lyu Y , Zhou Y , Wang J . Ordered porous poly(ionic liquid) crystallines: spacing confined ionic surface enhancing selective CO₂ capture and fixation. ACS Applied Materials & Interfaces, 2019, 11(6): 6031–6041

28 Zhang Y , Yang D H , Qiao S , Han B H . Synergistic catalysis of ionic liquid-decorated covalent organic frameworks with polyoxometalates for CO₂ cycloaddition reaction under mild conditions. Langmuir, 2021, 37(34): 10330–10339

29 Zhong H , Gao J , Sa R , Yang S , Wu Z , Wang R . Carbon dioxide conversion upgraded by host-guest cooperation between nitrogen-rich covalent organic framework and imidazolium-based ionic polymer. ChemSusChem, 2020, 13(23): 6050

30 Chang G , Yang L , Yang J , Huang Y , Cao K , Ma J , Wang D . A nitrogen-rich, azaindole-based microporous organic network: synergistic effect of local dipole-π and dipole-quadrupole interactions on carbon dioxide uptake. Polymer Chemistry, 2016, 7(37): 5768–5772

31 Zhu Y , Zhang W . Reversible tuning of pore size and CO₂ adsorption in azobenzene functionalized porous organic polymers. Chemical Science, 2014, 5(12): 4957–4961

32 Meng F , Bi S , Sun Z , Jiang B , Wu D , Chen J S , Zhang F . Synthesis of ionic vinylene-linked covalent organic frameworks through quaternization-activated Knoevenagel condensation. Angewandte Chemie International Edition, 2021, 60(24): 13614–13620

33 Vyas V S , Haase F , Stegbauer L , Savasci G , Podjaski F , Ochsenfeld C , Lotsch B V . A tunable azine covalent organic framework platform for visible light-induced hydrogen generation. Nature Communications, 2015, 6(1): 8508

34 Xu Z X , Liu K , Huang H , Zhang Y D , Long Z Y , Tong M M , Chen Q J . Quaternization-induced catalyst-free synthesis of viologen-linked ionic polyacetylenes towards heterogeneous catalytic CO₂ fixation. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2022, 10(10): 5540–5549

35 Zhi Y F , Shao P P , Feng X , Xia H , Zhang Y M , Shi Z , Mu Y , Liu X M . Covalent organic frameworks: efficient, metal-free, heterogeneous organocatalysts for chemical fixation of CO₂ under mild conditions. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(2): 374–382

36 Zhang Y W , A S , Zou Y , Luo X , Li Z , Xia H , Liu X , Mu Y . Gas uptake, molecular sensing and organocatalytic performances of a multifunctional carbazole-based conjugated microporous polymer. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(33): 13422–13430

37 Bhunia S , Bhanja P , Das S K , Sen T , Bhaumik A . Triazine containing N-rich microporous organic polymers for CO₂ capture and unprecedented CO₂/N₂ selectivity. Journal of Solid State Chemistry, 2017, 247: 113–119

38 Dey S , Bhunia A , Breitzke H , Groszewicz P B , Buntkowsky G , Janiak C . Two linkers are better than one: enhancing CO₂ capture and separation with porous covalent triazine-based frameworks from mixed nitrile linkers. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2017, 5(7): 3609–3620

39 Coates G W , Moore D R . Discrete metal-based catalysts for the copolymerization of CO₂ and epoxides: discovery, reactivity, optimization, and mechanism. Angewandte Chemie International Edition, 2004, 43(48): 6618–6639

40 Klaus S , Lehenmeier M W , Anderson C E , Rieger B . Recent advances in CO₂/epoxide copolymerization-new strategies and cooperative mechanisms. Coordination Chemistry Reviews, 2011, 255(13-14): 1460–1479

41 Chen G J , Zhang Y D , Liu K , Liu X Q , Wu L , Zhong H , Dang X J , Tong M M , Long Z Y . In situ construction of phenanthroline-based cationic radical porous hybrid polymers for metal-free heterogeneous catalysis. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2021, 9(12): 7556–7565