Brønsted acid mediated covalent organic framework membranes for efficient molecular separation

Wang, Hongjian; Chen, Long; Yang, Hao; Wang, Meidi; Yang, Long; Du, Haiyan; Cao, Chenliang; Ren, Yanxiong; Wu, Yingzhen; Pan, Fusheng; Jiang, Zhongyi

doi:10.1039/c9ta06924k

Cited by 64 publications

(45 citation statements)

References 48 publications

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“…All experimental patterns were consistent with the simulated ones of corresponding frameworks in reversed AA stacking via structural modeling in Material Studio (Figure S9,S10). Thec hemical structures of the synthesized COF-QAs were also characterized by solid-state 13 CNMR measurement and Fourier transform infrared spectroscopy (FTIR) analysis (Figure S12-S14), which revealed the formation of characteristic bands inside the frameworks.N 2 adsorption-desorption isotherms at 77 Kw ere examined to evaluate the porosity of COF-QAs membranes (Figure S15,S16).…”

Section: Resultsmentioning

confidence: 99%

“…[12] Among them, interfacial polymerization has been identified as most popular platform method for COFs monolayers and membranes owing to its exceptional designability,s calability and applicability.H owever,t his method is enslaved to the strong coupling between the reaction-diffusion process of precursors and assembly of as-formed COFs nanoparticles.The vigorous reaction and rapid precipitation would confer the resultant membranes with loosely,r andomly packed structures and thus large grain boundary resistance. [13] Theloose membrane structure with numerous discontinuous and noneffective ion transport paths is unfavorable for obtaining high ion conductivity due to the lack of sufficient shuttling cationic sites among COFs nanoparticles.T herefore,f abricating COFs membranes with tight structure and much lower grain boundary resistance,w hich can take full advantage of the long-range ordered framework structure and thus achieve rapid anion transport, becomes an urgent pursuit and pendent task. [14] Inspired by the interfacial synthesis of COFs,p hasetransfer polymerization based on an organic-aqueous reaction system, at wo-stage process including the preparation of colloidal suspensions followed by the assembly of COFs nanoplates,w ould establish ap latform for membrane fabrication of anion conductive COFs.…”

Section: Introductionmentioning

confidence: 99%

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Tight Covalent Organic Framework Membranes for Efficient Anion Transport via Molecular Precursor Engineering

Kong

et al. 2021

Angewandte Chemie

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Fabricating covalent organic frameworks (COFs) membranes with tight structure,w hich can fully utilizew elldefined framework structure and thus achieve superior conduction performance,r emains ag rand challenge.H erein, through molecular precursor engineering of COFs,wereported the fabrication of tight COFs membrane with the everreported highest hydroxide ion conductivity over 200 mS cm À1 at 80 8 8C, 100 %RH. Six quaternary ammonium-functionalized COFs were synthesized by assembling functional hydrazides and different aldehyde precursors.I na no rganic-aqueous reaction system, the impact of the aldehyde precursors with different size, electrophilicity and hydrophilicity on the reaction-diffusion process for fabricating COFs membranes was elucidated. Particularly,m ore hydrophilic aldehydes were prone to push the reaction zone from the interface region to the aqueous phase of the reaction system, the tight membranes were thus fabricated via phase-transfer polymerization process, conferring around 4-8 times the anion conductivity over the loose membranes via interfacial polymerization process.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tight Covalent Organic Framework Membranes for Efficient Anion Transport via Molecular Precursor Engineering

Kong

et al. 2021

Angewandte Chemie

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“…The graphene crystal is synthesized at ∼1000 °C with the assistance of a copper template . However, most COF membranes are synthesized at near room temperature by the IP method, which could be one of the reasons for the low crystallinity . The poor oxidative stability of the amine monomers is also a hurdle for high-temperature synthesis.…”

Section: Crystal Engineeringmentioning

confidence: 99%

Engineering Covalent Organic Framework Membranes

Zhang

Jiang

2021

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Membrane technology plays an increasingly important role for sustainable development of our society owing to its huge capability to tackle the energy crisis, water scarcity, environmental pollution, and carbon neutrality. To fully unlock the potential of membranes, it is in high demand to develop advanced membrane materials that significantly outperform conventional polymer membrane materials in separation performance and longterm stability. The emergent covalent organic frameworks (COFs) have been deemed as potent membrane materials because of their unique structure and properties in comparison with polymers, zeolites, and metal organic frameworks (MOFs). (i) First, the highly tunable and ordered crystalline pore structure, high porosity, and excellent stability render COFs an ideal membrane material.COFs are more stable than MOFs and, in some cases, are even more stable than zeolite. Moreover, it is easier to introduce functional groups into the COF nanochannels compared with zeolite and MOFs. Further, COFs are ideally suitable for constructing ordered nanochannels with size in the range of 0.6−3 nm which is difficult to be realized by other materials. (ii) Second, along with the unremitting discovery of diverse platform chemistries such as reticular chemistry, the in-depth understanding of nucleation/growth mechanisms of COFs as well as the rapid progress of manufacturing technologies and various routes to fabricating COF membranes with favorable physical and chemical structures inside the nanochannels are being actively exploited. COFs generally show better membrane-formation ability owing to their abundant 2D structures, which make it easier to fabricate ultrathin membranes compared with zeolite and MOFs. (iii) Last, a great number of COF membranes exhibit exceptionally high separation performance and stability, establishing their position as the next-generation membranes.In this Account, we discuss three types of engineering toward COF membranes based on Schiff base reaction for high-efficiency molecules/ion separations, i.e., reticular engineering, crystal engineering, and nanochannel engineering. First, we discuss the reticular engineering of COF membranes with a focus on the bond types, chemical structure, and architecture design. The membraneformation ability and methods of COFs are also analyzed. Second, we discuss the crystal engineering of COF membranes with a focus on the key thermodynamical and kinetic factors to drive the disorder-to-order transition where we attempt to dig deeper into the crystallization habit of COF membranes. Third, we discuss nanochannel engineering of COF membranes with a focus on the construction and modulation of the physical and chemical microenvironments of nanochannels for efficient and selective transport of molecules/ions. Last, we conclude with a perspective on the opportunities and major challenges in the R&D of COF membranes, targeting at identifying the future directions.

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“…Small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) can also be used to evaluate the crystallinity or the crystalline phase orientation of such membranes [162,163]. Additionally SAXS can measure the particle size of the nanocrystals, which could be provide useful information to improve the preparation processes [164].…”

Section: Characterisation Of Structural Propertiesmentioning

confidence: 99%

“…The Brunauer-Emmett-Teller (BET) surface area was calculated from N 2 adsorption isotherms measured at 77 K. The experimental data derived from these measurements allowed the determination of the pore size distribution by the application of different models as a function of the pore geometry. The isotherm shape also gives some information about the pore size [87,162,163].…”

Section: Textural Characterisation Of the Membrane Surfacementioning

confidence: 99%

Metal and Covalent Organic Frameworks for Membrane Applications

2020

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Better and more efficient membranes are needed to face imminent and future scientific, technological and societal challenges. New materials endowed with enhanced properties are required for the preparation of such membranes. Metal and Covalent Organic Frameworks (MOFs and COFs) are a new class of crystalline porous materials with large surface area, tuneable pore size, structure, and functionality, making them a perfect candidate for membrane applications. In recent years an enormous number of articles have been published on the use of MOFs and COFs in preparation of membranes for various applications. This review gathers the work reported on the synthesis and preparation of membranes containing MOFs and COFs in the last 10 years. Here we give an overview on membranes and their use in separation technology, discussing the essential factors in their synthesis as well as their limitations. A full detailed summary of the preparation and characterization methods used for MOF and COF membranes is given. Finally, applications of these membranes in gas and liquid separation as well as fuel cells are discussed. This review is aimed at both experts in the field and newcomers, including students at both undergraduate and postgraduate levels, who would like to learn about preparation of membranes from crystalline porous materials.

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Brønsted acid mediated covalent organic framework membranes for efficient molecular separation

Abstract: A Brønsted acid mediated one-step assembly method is designed to fabricate COF-JLU2 membranes for molecule separation, where the partition coefficient of Brønsted acid affects the structure–performance relationship of membranes.

Cited by 64 publications

References 48 publications

Tight Covalent Organic Framework Membranes for Efficient Anion Transport via Molecular Precursor Engineering

Tight Covalent Organic Framework Membranes for Efficient Anion Transport via Molecular Precursor Engineering

Engineering Covalent Organic Framework Membranes

Metal and Covalent Organic Frameworks for Membrane Applications

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