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User:GBen3535/Covalent organic framework

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Covalent organic frameworks (COFs) are a class of materials that form two- or three- dimensional structures through reactions between organic precursors resulting in strong, covalent bonds to afford porous, stable, and crystalline materials. COFs emerged as a field from the overarching domain of organic materials as researchers optimized both synthetic control and precursor selection.[1] These improvements to coordination chemistry enabled non-porous and amorphous organic materials such as organic polymers to advance into the construction of porous, crystalline materials with rigid structures that granted exceptional material stability in a wide range of solvents and conditions.[1][2] Through the development of reticular chemistry, precise synthetic control was achieved and resulted in ordered, nano-porous structures with highly preferential structural orientation and properties which could be synergistically enhanced and amplified.[3] With judicious selection of COF secondary building units (SBUs), or precursors, the final structure could be predetermined, and modified with exceptional control enabling fine-tuning of emergent properties.[4] This level of control facilitates the COF material to be designed, synthesized, and utilized in various applications, many times with metrics on scale or surpassing that of the current state-of-the-art approaches.

History

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Structure

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Secondary Building Units

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Reticular Synthesis

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Reticular synthesis enables facile bottom-up synthesis of the framework materials to introduce precise perturbations in chemical composition, resulting in the highly controlled tunability of framework properties.[4][5][6] Through a bottom-up approach, a material is built from atomic or molecular components synthetically as opposed to a top-down approach, which forms a material from the bulk through approaches such as exfoliation, lithography, or other varieties of post-synthetic modification.[3][7] The bottom-up approach is especially advantageous with respect to materials such as COFs because the synthetic methods are designed to directly result in an extended, highly crosslinked framework that can be tuned with exceptional control at the nanoscale level.[3][8][9] Geometrical and dimensional principles govern the framework’s resulting topology as the SBUs combine to form predetermined structures.[10][11] This level of synthetic control has also been termed “molecular engineering”, abiding by the concept termed by Arthur R. von Hippel in 1956.[12]

 
Through the use of reticular synthesis, topological control is enabled through judicious selection of precursors that result in bonding directionality in the final resulting network. This figure has been adapted from Jiang and coworkers chapter on Two- and Three-dimensional Covalent Organic Frameworks (COFs) in Comprehensive Supramolecular Chemistry II.[13]

It has been established in the literature that, when integrated into an isoreticular framework, such as a COF, properties from monomeric compounds can be synergistically enhanced and amplified.[3] COF materials possess the unique ability for bottom-up reticular synthesis to afford robust, tunable frameworks that synergistically enhance the properties of the precursors, which, in turn, offers many advantages in terms of improved performance in different applications. As a result, the COF material is highly modular and tuned efficiently by varying the SBUs’ identity, length, and functionality depending on the desired property change on the framework scale.[14] Ergo, there exists the ability to introduce diverse functionality directly into the framework scaffold to allow for a variety of functions which would be cumbersome, if not impossible, to achieve through a top-down method. such as lithographic approaches or chemical-based nanofabrication. Through reticular synthesis, it is possible to molecularly engineer modular, framework materials with highly porous scaffolds that exhibit unique electronic, optical, and magnetic properties while simultaneously integrating desired functionality into the COF skeleton.

Synthetic Chemistry

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Reticular synthesis was used by Yaghi and coworkers in 2005 to construct the first two COFs reported in the literature: COF-1, using a dehydration reaction of benzenediboronic acid (BDBA), and COF-5, via a condensation reaction between hexahydroxytriphenylene (HHTP) and BDBA.[15] These framework scaffolds were interconnected through the formation of boroxine and boronate linkages, respectively, using solvothermal synthetic methods.[15]

Solvothermal Synthesis

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The solvothermal approach is the most common used in the literature but typically requires long reaction times due to the insolubility of the organic SBUs in nonorganic media and the time necessary to reach thermodynamic COF products.[16]

 
Reversible reactions for COF formation featuring nitrogen to form a variety of linkages (imine, hydrazone, azine, squaraine, phenazine, imide, triazine).

COF Linkages

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Reversible reactions for COF formation featuring boron to form a variety of linkages (boronate, boroxine, and borazine).
 
Reversible reactions for COF formation featuring a variety of atoms to form different linkages (a double stage connecting boronate ester and imine linkages, alkene, silicate, nitroso).

Since Yaghi and coworkers’ seminal work in 2005, COF synthesis has expanded to include a wide range of organic connectivity such as boron-, nitrogen-, other atom-containing linkages.[2][17][18][19] The linkages in the figures shown are not comprehensive as other COF linkages exist in the literature, especially for the formation of 3D COFs.







Templated Synthesis

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Morphological control on the nanoscale is still limited as COFs lack synthetic control in higher dimensions due to the lack of dynamic chemistry during synthesis. To date, researchers have attempted to establish better control through different synthetic methods such as solvothermal synthesis, interface-assisted synthesis, solid templation as well as seeded growth.[14][20][21] First on of the precursors are deposited onto the solid support followed by the introduction of the second precursor in vapor form. This results in the deposition of the COF as a thin film on the solid support.[22]

Figure 5: Solid-vapor assisted templation consists of forming a COF on a surface by depositing one precursor on a solid surface and exposing the surface to the other SBU, which is in the vapor phase, resulting in a COF thin film.

Properties

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Porosity

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A defining advantage of COFs is the exceptional porosity that results from the substitution of analogous SBUs of varying sizes. Pore sizes range from 7-23 Å and feature a diverse range of shapes and dimensionalities that remain stable during the evacuation of solvent.[9] The rigid scaffold of the COF structure enables the material to be evacuated of solvent and retain its structure, resulting in high surface areas as seen by the Brunauer–Emmett–Teller analysis.[23] This high surface area to volume ratio and incredible stability enables the COF structure to serve as exceptional materials for gas storage and separation.

Crystallinity

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There are several COF single crystals synthesized to date.[24] There are a variety of techniques employed to improve crystallinity of COFs. The use of modulators, monofunctional version of precursors, serve to slow the COF formation to allow for more favorable balance between kinetic and thermodynamic control, hereby enabling crystalline growth. This was employed by Yaghi and coworkers for 3D imine-based COFs (COF-300, COF 303, LZU-79, and LZU-111).[24] However, the vast majority of COFs are not able to crystallize into single crystals but instead are insoluble powders. The improvement of crystallinity of these polycrystalline materials can be improved through tuning the reversibility of the linkage formation to allow for corrective particle growth and self-healing of defects that arise during COF formation.[25]

Conductivity

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In a fully conjugated 2D COF material such as those synthesized from metallophthalocyanines and highly conjugated organic linkers, charge transport is increased both in-plane, as well as through the stacks, resulting in increased conductivity.

Integration of SBUs into a covalent framework results in the synergistic emergence of conductivities much greater than the monomeric values. The nature of the SBUs can improve conductivity. Through the use of highly conjugated linkers throughout the COF scaffold, the material can be engineered to be fully conjugated, enabling high charge carrier density as well as through- and in-plane charge transport. For instance, Mirica and coworkers synthesized a COF material (NiPc-Pyr COF) from nickel phthalocyanine (NiPc) and pyrene organic linkers that had a conductivity of 2.51 x 10-3 S/m, which was several orders of magnitude larger than the undoped molecular NiPc, 10-11 S/m.[26] A similar COF structure made by Jiang and coworkers, CoPc-Pyr COF, exhibited a conductivity of 3.69 x 10-3 S/m.[27] In both previously mentioned COFs, the 2D lattice allows for full π-conjugation in the x and y directions as well as π-conduction along the z axis due to the fully conjugated, aromatic scaffold and π-π stacking, respectively.[26][27] Emergent conductivity in COF structures are especially important for applications such as catalysis and energy storage where quick, and efficient charge transport is required for optimal performance.

Characterization

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There exists a wide range of characterization methods for COF materials. There are several COF single crystals synthesized to date. For these highly crystalline materials, X-ray diffraction (XRD) is a powerful tool capable of determining COF crystal structure.[28] The majority of COF materials suffer from decreased crystallinity so powder X-ray diffraction (PXRD) is used. In conjunction with simulated powder packing models, PXRD can determine COF crystal structure.[29]

In order to verify and analyze COF linkage formation, various techniques can be employed such as infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy.[28] Precursor and COF IR spectra enables comparison between vibrational peaks to ascertain that certain key bonds present in the COF linkages appear and that peaks of precursor functional groups disappear. In addition, solid state NMR enables probing of linkage formation as well and is well suited for large, insoluble materials like COFs. Gas adsorption-desorption studies quantify the porosity of the material via calculation of the Brunauer–Emmett–Teller (BET) surface area and pore diameter from gas adsorption isotherms.[28] Electron imagine techniques such as scanning electron microscopy (SEM), and transmission electron microscopy (TEM) can resolve surface structure and morphology, and microstructural information, respectively.[28] Scanning tunneling microscopy (STM) and atomic force microscopy (AFM) have also been used to characterize COF microstructural information as well.[28] Additionally, methods like X-ray photoelectron Spectroscopy (XPS), inductively coupled plasma mass spectroscopy (ICP-MS), and combustion analysis can be used to identify elemental composition and ratios.[28]

Applications

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Gas Storage and Separation

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Due to the exceptional porosity of COFs, they have been used extensively in the storage and separation of gases such as hydrogen, methane, etc.___(insert portion already written on wiki page) In addition to storage, COF materials are exceptional at gas separation. For instance, COFs like imine-linked COF LZU1 and azine-linked COF ACOF-1 were used as a bilayer membrane for the selective separation of the following mixtures: H2/CO2, H2/N2, and H2/CH4.[30] The COFs outperformed molecular sieves due to the inherent thermal and operational stability of the structures.[30] It has also been shown that COFs inherently act as adsorbents, adhering to the gaseous molecules to enable storage and separation.[31]

Sensing

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Due to defining molecule-framework interactions, COFs can be used as chemical sensors in a wide range of environments and applications. Properties of the COF change when their functionalities interact with various analytes enabling the materials to serve as devices in various conditions: as chemiresistive sensors,[26] as well as electrochemical sensors for small molecules.[32]

Catalysis

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Due to the ability to introduce diverse functionality into COFs’ structure, catalytic sites can be fine-tuned in conjunction with other advantageous properties like conductivity and stability to afford efficient and selective catalysts. COFs have been used as heterogeneous catalysts in organic,[33] electrochemical,[27][34] as well as photochemical reactions.[16]

Energy Storage

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A few COFs possess the stability and conductivity necessary to perform well in energy storage applications like lithium ion batteries,[35][36] and various different metal-ion batteries and cathodes.[37][38]

GBen3535 (talk) 22:56, 24 February 2021 (UTC)

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