Construction of a Three-dimensional Covalent Organic Framework via the Linker Exchange Strategy

Cui, Yumeng; Miao, Zhuang; Liu, Qi; Jin, Fenchun; Zhai, Yufeng; Zhang, Lingyan; Wang, Wenli; Wang, Ke; Liu, Guiyan; Zeng, Yongmei

doi:10.1007/s40242-021-1295-z

Cited by 8 publications

(10 citation statements)

References 56 publications

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“…For example, 3D COF-1 with hydroxy groups, 3D COF-2 with methoxy groups, and JNU-5 with amino groups were all successfully prepared following this strategy, while only amorphous solids could be acquired via direct synthesis. [9][10][11] Devitrification is another approach to convert amorphous polymers to crystalline COFs. Rosseinsky and co-workers prepared novel covalent amide frameworks (CAFs) by devitrification of amorphous polyamide networks under high temperature and pressure, which allowed linkage reversibility and facilitated error-checking.…”

Section: Crystallization Methodsmentioning

confidence: 99%

“…Linker replacement is regarded as helpful for frameworks with pendant groups which may hinder the crystallization. For example, 3D COF‐1 with hydroxy groups, 3D COF‐2 with methoxy groups, and JNU‐5 with amino groups were all successfully prepared following this strategy, while only amorphous solids could be acquired via direct synthesis [9–11] . Devitrification is another approach to convert amorphous polymers to crystalline COFs.…”

Section: Synthesismentioning

confidence: 99%

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Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

et al. 2022

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Three-dimensional covalent organic frameworks (3D COFs) with spatially periodic networks demonstrate significant advantages over their 2D counterparts, including enhanced specific surface areas, interconnected channels, and more sufficiently exposed active sites. Nevertheless, research on these materials has met an impasse due to serious problems in crystallization and stability, which must be solved for practical applications. In this Minireview, we first summarize some strategies for preparing functional 3D COFs, including crystallization techniques and functionalization methods. Hereafter, applications of these functional materials are presented, covering adsorption, separation, catalysis, fluorescence, sensing, and batteries. Finally, the future challenges and perspectives for the development of 3D COFs are discussed.

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Section: Crystallization Methodsmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

et al. 2022

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“…Additionally, the exchange of building blocks (linker exchange) in already existing, crystalline frameworks opens the possibility to synthesize COFs with improved crystallinity or make COFs accessible that were not accessible via condensation of the respective building blocks. , Qian et al reported the first COF-to-COF linker exchange by replacing 1,4-phenylenediamine (PA) with benzidine (BD) in an imine-linked COF, which yielded an almost complete transformation . The linker-exchange strategy was applied to achieve, among others, different COF linkages, ,− changes in the pore hierarchy and size by different linker symmetries, − the transformation of linear polymers into COFs , or 3D into 2D COFs, and the introduction of functional groups into the framework …”

Section: Introductionmentioning

confidence: 99%

“…16 The linker-exchange strategy was applied to achieve, among others, different COF linkages, 14,17−20 changes in the pore hierarchy and size by different linker symmetries, 21−23 the transformation of linear polymers into COFs 24,25 or 3D into 2D COFs, 26 and the introduction of functional groups into the framework. 27 Being a primary greenhouse gas, CO 2 plays an important role in climate change. Strategies to mitigate global warming included the reduction of CO 2 emissions via carbon capture and storage.…”

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Aromatic Amine-Functionalized Covalent Organic Frameworks (COFs) for CO₂/N₂ Separation

Dautzenberg

Smet

2023

ACS Appl. Mater. Interfaces

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CO 2 is a prominent example for an exhaust gas, and it is known for its high impact on global warming. Therefore, carbon capture from CO 2 emissions of industrial processes is increasingly important to halt and prevent the disruptive consequences of global warming. Covalent organic frameworks (COFs) as porous nanomaterials have been shown to selectively adsorb CO 2 in high quantities and with high CO 2 /N 2 selectivity. Interactions with amines are recognized to selectively adsorb CO 2 and help capture it from exhaust emissions. Herein, a novel COF (Me 3 TFB-(NH 2 ) 2 BD), which was not accessible via a direct condensation reaction, was synthetized by dynamic linker exchange starting with Me 3 TFB-BD. Despite the linker exchange, the porosity of the COF was largely maintained, resulting in a high BET surface area of 1624 ± 89 m 2 /g. The CO 2 and N 2 adsorption isotherms at 273 and 295 K were studied to determine the performance in carbon capture at flue gas conditions. Me 3 TFB-(NH 2 ) 2 BD adsorbs 1.12 ± 0.26 and 0.72 ± 0.07 mmol/g of CO 2 at 1 bar and 273 and 295 K, respectively. The COF shows a high CO 2 /N 2 IAST selectivity under flue gas conditions (273 K:83 ± 11, 295 K: 47 ± 11). The interaction of the aromatic amine groups with CO 2 is based on physisorption, which is expected to make the regeneration of the material energy efficient.

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Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid–Liquid Interface

et al. 2023

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Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well‐organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular covalent organic frameworks (COFs). Herein, for the first time, we have manifested a facile room‐temperature DCC‐directed transformation of discrete organic imine cage‐to‐COF film at the liquid–liquid interface. The unfolding of the cage leading to the generation of imine intermediates, followed by their interface‐assisted preorganization and subsequent growth of the COF film, are elucidated through detailed spectroscopic and microscopic investigations. The interfacial cage‐to‐COF transformation provides a facile route for the faster fabrication of free‐standing COF films with high porosity and crystallinity, demonstrating excellent performance towards molecular sieving and high solvent permeance. Thus, the current study opens up a new route for structural interconversion between two crystalline entities with diverse dimensionality employing DCC at the confined interface.

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Construction of a Three-dimensional Covalent Organic Framework via the Linker Exchange Strategy

Cited by 8 publications

References 56 publications

Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Aromatic Amine-Functionalized Covalent Organic Frameworks (COFs) for CO₂/N₂ Separation

Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid–Liquid Interface

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Construction of a Three-dimensional Covalent Organic Framework via the Linker Exchange Strategy

Cited by 8 publications

References 56 publications

Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Three‐Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Aromatic Amine-Functionalized Covalent Organic Frameworks (COFs) for CO2/N2 Separation

Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid–Liquid Interface

Contact Info

Product

Resources

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Aromatic Amine-Functionalized Covalent Organic Frameworks (COFs) for CO₂/N₂ Separation