Delamination of Layered Covalent Organic Frameworks

Berlanga, Isadora; Ruiz‐González, M. Luisa; González‐Calbet, José M.; Fierro, J.L.G.; Mas‐Ballesté, Rubén; Zamora, Félix

doi:10.1002/smll.201002264

Cited by 252 publications

(182 citation statements)

References 16 publications

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“…69,[75][76][77][78][79][80][81] For example, through the sublimation of monomer 1 under ultrahigh vacuum, surface covalent organic frameworks (SCOFs-1) with near-complete monolayer has successfully been obtained on Ag (111) (Fig. 13).…”

Section: Solvothermal Synthesismentioning

confidence: 97%

Covalent organic frameworks (COFs): from design to applications

2013

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Covalent organic frameworks (COFs) represent an exciting new type of porous organic materials, which are ingeniously constructed with organic building units via strong covalent bonds. The well-defined crystalline porous structures together with tailored functionalities have offered the COF materials superior potential in diverse applications, such as gas storage, adsorption, optoelectricity, and catalysis. Since the seminal work of Yaghi and co-workers in 2005, the rapid development in this research area has attracted intensive interest from researchers with diverse expertise. This critical review describes the state-of-the-art development in the design, synthesis, characterisation, and application of the crystalline porous COF materials. Our own opinions on further development of the COF materials are also presented for discussion (155 references).

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Section: Solvothermal Synthesismentioning

confidence: 97%

Covalent organic frameworks (COFs): from design to applications

2013

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“…[4] Covalent organic nanosheets (CONs) are a new member of this family of 2D materials. CONs are generally synthesized by exfoliating their bulk counterparts, such as covalent organic frameworks (COFs) [5] or covalent triazene frameworks (CTFs), [6] through mechanical delamination, [7] solvent-assisted exfoliation, [8] and self-exfoliation. [9] However, controlling the layer thickness of exfoliated CONs is a challenging task and requires significant attention.…”

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confidence: 99%

Chemically Delaminated Free‐Standing Ultrathin Covalent Organic Nanosheets

et al. 2016

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Covalent organic nanosheets (CONs) are a new class of porous thin two-dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene-based covalent organic framework (COF) to N-hexylmaleimide-functionalized CONs, to yield centimeter-sized free-standing thin films through layer-by-layer CON assembly at the air-water interface. The thin-layer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.

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“…Porous, template-free COPs with uniform tube morphology have been used for device manufacturing [16] and catalysis, [17,18] but reports of the synthesis and application of this type of material remain scarce. Studies of covalent nanosheets are more prevalent, but, this type of material is obtained by either liquid phase exfoliation [19] or mechanical delamination, [20] and these two methods often result in low surface areas because the mechanical forces involved often cause pore blockage. In short, syntheses that rely on mechanical techniques for isolating nanosheets tend to be expensive and non-scalable and produce materials that have limited adsorption efficiency.…”

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confidence: 99%

Morphological Diversity in Nanoporous Covalent Organic Materials Derived from Viologen and Pyrene

Das¹,

Škorjanc²,

Sharma

et al. 2017

ChemNanoMat

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Adjustment of the morphology of covalent organic nanomaterials is a challenge but can be achieved by perturbing the planarity of the monomers used as core moieties in these polymers. Here we describe a templatefree Zincke reaction for the synthesis of covalent organic nanosheets (CONs) that stack several layers thick and of covalent organic tubes (COTs). Both materials contain the same viologen linker but different pyrene-based cores. Both polymeric materials are nanoporous, cationic, and highly stable in water, even in the presence of acid (1 M HCl) or base (1 M NaOH). Their porosity and ionic surfaces are responsible for high affinities and adsorption capacities for iodine vapor.Porous covalent organic polymers (COPs) are well known for their diverse applications in fields such as gas storage and separation, [1][2][3][4] catalysis, [5][6][7][8] sensing, [9,10] drug delivery, [11] and environmental remediation. [12] In order to design COPs with improved functionality, considerable research has been undertaken to understand the relationship between the morphologies and properties of these materials. [13][14][15] It has been observed that the morphology of COPs can be tuned by changing the symmetry of their constituent building blocks, but precise regulation of COP nanostructure remains a challenging task.Syntheses of covalent organic hollow tubes (COTs) and nanosheets (CONs) are of interest because their large surface areas facilitate the adsorption of small molecule guests. Porous, template-free COPs with uniform tube morphology have been used for device manufacturing [16] and catalysis, [17,18] but reports of the synthesis and application of this type of material remain scarce. Studies of covalent nanosheets are more prevalent, but, this type of material is obtained by either liquid phase exfoliation [19] or mechanical delamination, [20] and these two methods often result in low surface areas because the mechanical forces involved often cause pore blockage. In short, syntheses that rely on mechanical techniques for isolating nanosheets tend to be expensive and non-scalable and produce materials that have limited adsorption efficiency. Designing an efficient and green approach to the large-scale synthesis of porous CONs stacked several (or fewer) layers thick is an open challenge. [21] In general, porous COPs are synthesized from neutral building blocks, which limits the range of application for the materials. For example, neutral COPs are not optimal for the uptake of charged species, including toxic ionic guest molecules. To address this issue, we have begun to develop charged COPs that incorporate redox-active viologens and are capable of adsorbing iodine vapor, toxic dyes, and metal ions by anion exchange. [22,23] Despite their great potential, viologen-based COPs are still rarely documented in the literature, though Li et al. [24] have reported supramolecular organic frameworks (SOFs) that contain viologen struts and form in water.Herein, we report a one-pot, template-free solvothermal synthesis ...

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Delamination of Layered Covalent Organic Frameworks

Cited by 252 publications

References 16 publications

Covalent organic frameworks (COFs): from design to applications

Covalent organic frameworks (COFs): from design to applications

Chemically Delaminated Free‐Standing Ultrathin Covalent Organic Nanosheets

Morphological Diversity in Nanoporous Covalent Organic Materials Derived from Viologen and Pyrene

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