Use Of Covalent Organic Frameworks Research Articles

Covalent Organic Framework (COF) Based Catalysts for Photocatalytic Cross‐Dehydrogenative Coupling Reactions

Covalent organic frameworks (COFs) are robust, porous materials with well‐defined structures that have been employed for gas separation, photoluminescence, sensing, energy storage, and heterogeneous catalysis. This review summarizes recent progress in the use of COFs as a versatile platform for heterogeneous photocatalytic cross‐dehydrogenative coupling (CDC) reactions, which are an efficient and clean methodology for the formation of C‐C or C‐P bonds. We review the synthesis of these photocatalytic COFs, correlating their catalytic performance with their structures and photoelectric properties.

Porous Azatruxene Covalent Organic Frameworks for Anion Insertion in Battery Cells.

Covalent organic frameworks (COFs) containing well-defined redox-active groups have become competitive materials for next-generation batteries. Although high potentials and rate performance can be expected, only a few examples of p-type COFs have been reported for charge storage to date with even fewer examples on the use of COFs in multivalent ion batteries. Herein, we report the synthesis of a p-type highly porous and crystalline azatruxene-based COF and its application as a positive electrode material in Li- and Mg-based batteries. When this material is used in Li-based half cells as a COF/carbon nanotube (CNT) electrode, a discharge potential of 3.9 V is obtained with discharge capacities of up to 70 mAh g-1 at a 2 C rate. In Mg batteries using a tetrakis(hexafluoroisopropyloxy)borate electrolyte, cycling proceeds with an average discharge voltage of 2.9 V. Even at a fast current rate of 5 C, the capacity retention amounts to 84% over 1000 cycles.

Spatially confined coordination platform in covalent organic framework for selective uranium adsorption from aqueous solutions

The use of covalent organic frameworks (COFs) to remove uranium from nuclear wastewater, especially capture uranium by well-defined nanopores and customizable groups, is highly desired. The development of an ideal binding site with optimal balance between adsorption capacity and selectivity has remained an attractive challenge. Herein, a staggered stacking self-assembly approach was adapted to control the pore size and confine space of dioxin-linked COF-316 with modified functional groups to achieve higher capture efficiency. EXAFS analysis suggested that COF-316-COOH and COF-316-AO both have high affinities toward U(VI) owing to inner-sphere surface complexation by two or three atoms, DFT calculations further revealed that the uranyl cation was coordinated by = NOH or –COOH groups from two adjacent COF layers. The synergistic coordination in multi-confined interlaminar position provides an ideal spatial coordination platform for uranium, and the merits of capacity, selectivity and stability underscore the potential application of COF-316-AO for efficient uranium removal.

Microwave-assisted synthesis of triazine covalent organic frameworks via friedel-crafts reaction for use in treating brackish Water

Water scarcity is becoming an ever-growing problem in society. This is all due to the rapid increase in human population, harsh changes in the weather climate. New approaches for treating and recycling brine water into freshwater instead of discharging are needed, significantly large reduction in energy usage and decreasing harmful impact to the environment must be achieved in brine recovery. This study aims to introduced green technology into the reclamation of brine water by use of covalent organic frameworks (COFs) materials which will be used as part of a novel triazine-based COFs material which can be used as a nanomembrane for desalination of brine water from water treatment plants at Umgeni Water. Current technological approaches used are inefficient and unsuitable in 3rd world, developing countries including the republic of South Africa. This work focuses on a microwave-assisted synthesis involving Friedel Crafts reaction between monomers to yield a product of a triazine-based covalent organic frameworks (COFs) membranes. To confirm the products high resolution transmission electron microscopy (HRTEM), carbon NMR (13C NMR) with peaks at chemical shifts of 131, 143 and 172 ppm respectively. Fourier-transform infrared spectroscopy (FTIR) was employed and showed N-H stretches at a region of 3396 to 3050 cm-1. The COFs that were successfully synthesised are going to be incorporated on a polymeric substrate to fabricate a nanofiltration membrane and applied for nanofiltration or ultrafiltration purposes.

Recent advances in the fabrication of organic solvent nanofiltration membranes using covalent/metal organic frameworks.

Organic solvent nanofiltration (OSN) has evolved as a vital technological frontier with paramount significance in the separation and purification of organic solvents. Its implication is particularly prominent in industries such as pharmaceuticals, petrochemicals, and environmental remediation. This comprehensive review, meticulously navigates through the current state of research in OSN membranes, unveiling both the critical challenges and promising opportunities that beckon further exploration. The central focus of this review is on the unique utilization of covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) in OSN membrane design, leveraging their distinctive structural attributes-tunable porosity, robust chemical stability, and molecular sieving capabilities. These qualities position them as exceptional candidates for crafting membranes tailored to the intricacies of organic solvent environments. Our investigation extends into the fundamental principles that render COFs and MOFs adept in OSN applications, dissecting their varied fabrication methods while offering insights into the advantages and limitations of each. Moreover, we address environmental and sustainability considerations in the use of COF and MOF-based OSN membranes. Furthermore, we meticulously present the latest advancements and innovations in this burgeoning field, charting a course toward potential future directions and emerging research areas. By underscoring the challenges awaiting exploration, this review not only provides a panoramic view of the current OSN landscape but also lays the groundwork for the evolution of efficient and sustainable OSN technologies, specifically harnessing the unique attributes of COFs and MOFs.

COFs as porous organic materials for the separation and purification of ethylene from C2 hydrocarbons.

With rapid societal development, there has been a significant increase in the demand for chemicals. Ethylene, as the most widely used basic chemical, is now subject to increasingly stringent quality and purity standards. The separation and purification of ethylene from C2 hydrocarbons via covalent organic frameworks (COFs) are a fascinating and challenging area of research. Compared with conventional separation techniques, COFs have demonstrated the capacity to efficiently separate and purify analogues while simultaneously reducing energy consumption. As a result, it is urgent to conduct a study on COF applications in separating and purifying ethylene from C2 hydrocarbons to foster greater advancement in this field. This review provides an overview of research on ethylene separation, discusses the results and effective strategies reported for the use of COFs in ethylene separation to date, and presents challenges encountered in the current development process. The aim of this review is to inspire the design of COFs for ethylene separation and facilitate further development in this emerging field.

Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy

AbstractNanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) are crystalline organic porous materials with several benefits for cancer therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs in cancer therapy from the perspective of reticular chemistry and function‐oriented materials design. First, the modification sites and functionalization methods of COFs are discussed, followed by their potential as multifunctional nanoplatforms for tumor targeting, imaging, and therapy by integrating functional components. Finally, some challenges in the clinical translation of COFs are presented with the hope of promoting the development of COF‐based anticancer nanomedicines and bringing COFs closer to clinical trials.

Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy.

Nanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) are crystalline organic porous materials with several benefits for cancer therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs in cancer therapy from the perspective of reticular chemistry and function-oriented materials design. First, the modification sites and functionalization methods of COFs are discussed, followed by their potential as multifunctional nanoplatforms for tumor targeting, imaging, and therapy by integrating functional components. Finally, some challenges in the clinical translation of COFs are presented with the hope of promoting the development of COF-based anticancer nanomedicines and bringing COFs closer to clinical trials.

Covalent organic frameworks as catalyst support: A case study of thermal, hydrothermal, and mechanical pressure stability of β-ketoenamine-linked TpBD-Me2

Covalent organic frameworks (COFs) are crystalline, ordered networks, that, due to their high surface areas and the opportunity for periodic placement of catalytically active sites, are interesting materials for catalysis. Despite the great interest in the use of COFs for this application, there is currently a lack of fundamental understanding on how catalytically relevant conditions affect the integrity of the materials. To gain insight into the stability of COFs as catalyst supports, we herein subjected a β-ketoenamine-linked COF to thermal treatment at high temperatures, to autogenous pressure in water at different temperatures, and to mechanical pressure during pelletizing, after which the materials were thoroughly characterized to gain insight into the structural changes occurring during these catalytically relevant treatments. The COF was largely stable under all hydrothermal conditions studied, highlighting the applicability of β-ketoenamine-linked COFs under aqueous and vapor conditions. On the other hand, thermal and pressure treatments led to a rapid decline in the surface area already at the lowest temperatures and pressures studied. Theoretical calculations indicated this loss to stem from interlayer rearrangement or buckling of the COF layers induced by the applied conditions. This study demonstrates the suitability of β-ketoenamine-linked COFs for use under hydrothermal conditions, and sheds light on the degradation pathways under thermal and pressure treatments, opening the path to the design of COFs with increased stability under such conditions.

A review on covalent organic frameworks for rechargeable zinc-ion batteries

In recent years, rechargeable zinc-ion batteries (ZIBs) are considered to be a promising alternative to lithium-ion batteries owing to their high safety and theoretical capacity with low cost. Nevertheless, the in-depth development of rechargeable zinc-ion batteries is restricted by a sequence of issues, such as the dissolution and structure collapse of cathode materials, the formation of by-products, severe anode corrosion, passivation, and the growth of zinc dendrites. The covalent organic frameworks (COFs) can solve the above problems to a certain extent owing to their ideal characteristics, such as rigid structure, insolubility, high porosity, and abundant active sites. COFs, as advanced materials for ZIBs, have attracted researchers’ attention. In this review, we systematically summarized the synthesis methods of COFs and discussed the application of several advanced characterization technologies in COFs, which would provide a reference for the in-depth research of COFs. In addition, we elucidated the use of COFs as cathode materials and anode protective layers in rechargeable ZIBs. Finally, we discussed the challenges and solutions in the development of COF materials, which would provide constructive insights into the future direction of COFs.

Flexible all-organic nanocomposite films interlayered with in situ synthesized covalent organic frameworks for electrostatic energy storage

Poly(vinylidene fluoride)-based terpolymers, known for having the largest dielectric constant among the existing dielectric polymers, are attractive materials for electrostatic film capacitors used in lightweight electrification systems. However, the potential of these terpolymers in film capacitor applications remains constrained by their low electrical insulating and mechanical strengths. To address these limitations, we introduced rigid covalent organic framework (COF) nanospheres into the thin films of soft terpolymers via in situ synthesis and a facile layer-by-layer solution casting method, whereby multilayer films consisting of two polymer outer layers and a COF-containing middle layer were readily obtained. The resultant all-organic thin films exhibit simultaneously high dielectric constant, enhanced breakdown strength, superior energy density (∼25 J cm–3) at efficiencies over 80%, along with greatly improved mechanical self-supporting capability and excellent mechanical flexibility. This work demonstrates the unprecedented use of COF for electrostatic energy storage, uncovering its potential for flexible electronic applications operating under high electric fields.

Recent Advances in the Use of Covalent Organic Frameworks as Heterogenous Photocatalysts in Organic Synthesis.

Organic photochemistryisintensely developed in the 1980s, in which the nature of excited electronic states and the energy and electron transfer processes arethoroughly studied and finally well-understood. This knowledge from molecular organic photochemistry can be transferred to the design of covalent organic frameworks (COFs) as active visible-light photocatalysts. COFs constitute a new class of crystalline porous materials with substantial application potentials. Featured with outstanding structural tunability, large porosity, high surface area, excellent stability, and unique photoelectronic properties, COFs are studied as potential candidates in various research areas (e.g., photocatalysis). This review aims to provide the state-of-the-art insights into the design of COF photocatalysts (pristine, functionalized, and hybrid COFs) for organic transformations. The catalytic reaction mechanism of COF-based photocatalysts and the influence of dimensionality and crystallinity on heterogenous photocatalysis performance are also discussed, followed by perspectives and prospects on the main challenges and opportunities in future research of COFs and COF-based photocatalysts.

Covalent Organic Frameworks for Atmospheric Water Harvesting

Atmospheric water harvesting using reticular materials is an innovation that has the potential to change the world. Using covalent organic frameworks (COFs) for capturing water holds great promise because COFs are metal-free, stable under working conditions, and their structure can be intentionally designed to meet the requirements for this application. To promote the chemistry and use of COFs for atmospheric water harvesting, important features for synthesizing suitable water-harvesting COFs are discussed. The achievements of using COFs as water harvesters are then highlighted, showing how the water harvesting properties are related to the structural design. Finally, perspectives and research directions for further studies in COF chemistry are provided.

Engineering Covalent Organic Frameworks as Heterogeneous Photocatalysts for Organic Transformations.

Covalent organic frameworks (COFs) are an emerging category of organic polymers with highly porous crystalline structures. In the last decade, reports on the use of COFs as heterogeneous photocatalysts for organic transformations have shown significant progress. Still, comprehensive reviews on the mechanisms of the photocatalytic organic transformations using COFs are lacking. This Review provides a comprehensive and systematic overview of COF-based photocatalysts for organic transformations. Firstly, we discuss the photophysical properties and the characterization methods of COF-based photocatalysts. Then, the general photocatalytic mechanism, the advantages, and the strategies to improve the photocatalytic efficiency of COF-based photocatalysts are summarized. After that, advanced examples of COF-based photocatalysts for organic transformations are analyzed with regard to the underlying mechanisms. The Review ends with a critical perspective on the challenges and prospects.

Effect of Covalent Organic Frameworks Containing Different Groups on Properties of Sulfonated Poly(ether ether ketone) Matrix Proton Exchange Membranes.

The rich −SO3H groups enable sulfonated poly (ether ether ketone) (SPEEK) to possess excellent proton conductivities in proton exchange membrane (PEM), but cause excessive water absorption, resulting in the decline of dimensional stability. It is a challenge to resolve the conflict between conductivity and stability. Owing to its unique structural designability, covalent organic frameworks (COFs) have been used to regulate the performances of PEMs. The authors propose the use of COFs with acidic and basic groups for meeting the requirements of proton conductivity and dimensional stability. Herein, COFs containing different groups (sulfoacid, pyridine, and both) were uniformly dispersed into the SPEEK matrix by in situ synthesis, and the effects on the properties of SPEEK matrix PEMs were revealed. The sulfoacid group significantly improves proton conductivities. At 60 °C, under 95% RH, the conductivity of the SPEEK/TpPa−SO3H-20 composite membrane was 443.6 mS·cm−1, which was 3.3 times that of the pristine SPEEK membrane. The pyridine group reduced the swelling ratio at 50 °C from 220.7% to 2.4%, indicating an enhancement in dimensional stability. Combining the benefits of sulfoacid and pyridine groups, SPEEK/TpPa−(SO3H-Py) composite membrane has a conductivity of 360.3 mS·cm−1 at 60 °C and 95% RH, which is 1.86 times that of SPEEK, and its swelling ratio is 11.8%, about 1/20 of that of SPEEK membrane. The method of in situ combination and regulation of groups open up a way for the development of SPEEK/COFs composite PEMs.

Covalent Organic Framework (COF): A Drug and Carrier to Attenuate Retinal Ganglion Cells Death in an Acute Glaucoma Mouse Model

Purpose: We aim to investigate the use of covalent organic framework (COF) nanoparticles in the local treatment of glaucoma, both as a means of protecting retinal ganglion cells (RGCs), and as a carrier for delayed release of the medication rapamycin following a single intravitreal injection. Methods: a water-dispersible COF, and a COF-based nanoplatform for rapamycin release (COF-Rapa) was constructed. C57BL/6J mice were randomly divided into four groups: intravitreal injection of 1.5 µL normal saline (NS), COF (0.67 ng/µL), rapamycin (300 µM) or COF-Rapa (0.67 ng/µL-300 µM), respectively. The ischemia–reperfusion (I/R) model was established to mimic high intraocular pressure (IOP)-induced retinal injury in glaucoma. Labeling of RGCs by Fluoro-Gold and retinal electroretinogram were used to evaluate retinal function. Immunohistochemistry and Western blotting analyses of retinas were performed. Results: COF nanoparticles were delivered in vitro and in vivo. Six weeks after the COF injection, the number of RGCs was unaffected. In addition, the number of RBPMS-positive RGCs, GFAP-positive astrocytes and Iba1-positive microglia did not differ from the normal control. COF could effectively reduce RGCs death, improve phototransduction function and alleviate the overactivation of microglia compared to NS control after retinal I/R injury. Within six weeks, the mammalian target of rapamycin complex 1 (mTORC1) signaling pathway in the retinas could be inhibited by a single intravitreal injection of COF-Rapa. Compared with single COF administration, COF-Rapa significantly reduced the inflammatory reaction after retinal I/R injury. Conclusions: COF may act as both an RGC protection agent and a carrier for prolonged rapamycin release. This research may lead to the development of novel RGC protection agents and drug delivery techniques, as well as the creation of multifunctional COF-based biomaterials for glaucoma retinopathy.

Amidoxime-functionalized covalent organic framework as simultaneous luminescent sensor and adsorbent for organic arsenic from water

Organoarsenic compounds are widely used as feed additives in the poultry industry. However, the release of organoarsenic-containing wastewater can cause serious poisoning to the ecosystem. For this reason, detection and adsorption of organic arsenic from wastewater is crucial but also very challenging. Here, the use of covalent organic frameworks (COFs) as fluorescence sensors and adsorbents for the detection and adsorption of organic arsenic from water has been investigated for the first time. Two isoreticular crystalline and highly porous sp2 carbon-conjugated COFs were synthesized, and amidoxime-functionalized via post-synthetic modification (PSM). The long-range order and π-conjugated system ensure that both COFs act as fluorescent sensors for detecting the representative organic arsenic, roxarsone (ROX). The fluorescence quenching efficiencies of ROX on both COFs are over 98%. The limits of detection (LOD) for ROX by both COFs are estimated to be 6.5 and 12.3 nM. Additionally, the regular pores and the abundantly decorated amidoxime moiety exhibit extraordinary accessibility, which facilitates the adsorption of ROX. High adsorption capacities were obtained for both materials which amounts are up to 732 and 787 mg g−1. After five times of recycling, a negligible decrease in the adsorption capacity was noted, which reveals the excellent regeneration ability of those two amidoxime-functionalized COFs. These results indicate that the state-of-the-art sp2 carbon-conjugated amidoxime-functionalized COFs exhibit a high potential for the practical detection and adsorption of organoarsenic compounds from wastewater.

Cationic Covalent Organic Framework as an Ion Exchange Material for Efficient Adsorptive Separation of Biomolecules.

Although covalent organic frameworks (COFs) have earned significant interest in separation applications, the use of COFs in biomolecule separation remains unexplored. We examined the ionic COF Py-BPy2+-COF as an ion exchange material for biomolecule separation. After characterizing the properties of the synthesized COF with a variety of techniques, binding experiments with both large and small biomolecules were performed. High adsorption capacities of amino acids with different hydrophobicity and charge, as well as proteins of different isoelectric points and molecular weights, were determined in batch equilibrium experiments. Desorption experiments with mixtures of model proteins demonstrated an ability to successfully separate one protein from another with the selectivity hypothesized to be a combination of the isoelectric point, hydrophobicity, and ability to penetrate the crystalline material. Overall, the results demonstrated that Py-BPy2+-COF can be exploited as a robust crystalline anion exchange biomolecule separation material.

Photocatalytic Oxidation Reactions Mediated by Covalent Organic Frameworks and Related Extended Organic Materials

Covalent Organic Frameworks (COFs) and related extended organic materials have been widely used as photocatalysts in the last few years. Such interest arises from the wide range of covalent linkages employed in their construction, which offer many possibilities to design extended frameworks and to link photoactive building blocks. Thus, the potential utility of predesigned organic photoactive fragments can be synergistically added to the inherent advantages of heterogeneous catalysis, such as recyclability and easy separation of catalyst. In this overview, the current state of the art on the design of organic materials for photocatalytic oxidation reactions will be presented. The designing process of these materials is usually conditioned by the generally accepted concept that crystallinity and porosity defines the quality of the heterogeneous catalysts obtained. The care for the structural integrity of materials obtained is understandable because many properties and applications are intimately related to these features. However, the catalytic activity does not always directly depends on these characteristics. A critical compilation of the available literature is performed in order to offer a general perspective of the use of COFs and Covalent Triazine Frameworks (CTFs) in photocatalytic oxidation processes, including water oxidation, which constitute an important outcome relevant to artificial photosynthesis.

A Perspective on the Application of Covalent Organic Frameworks for Detection and Water Treatment.

Global population growth and water resource scarcity are significant social problems currently being studied by many researchers focusing on finding new materials for water treatment. The aim is to obtain quality water suitable for drinking and industrial consumption. In this sense, an emergent class of crystalline porous materials known as Covalent-Organic Frameworks (COFs) offers a wide range of possibilities since their structures can be designed on demand for specific applications. Indeed, in the last decade, many efforts have been made for their use in water treatment. This perspective article aims to overview the state-of-the-art COFs collecting the most recent results in the field for water detection of pollutants and water treatment. After the introduction, where we overview the classical design strategies on COF design and synthesis for obtaining chemically stable COFs, we summarize the different experimental methodologies used for COFs processing in the form of supported and free-standing membranes and colloids. Finally, we describe the use of COFs in processes involving the detection of pollutants in water and wastewater treatment, such as the capture of organic compounds, heavy metals, and dyes, the degradation of organic pollutants, as well as in desalination processes. Finally, we provide a perspective on the field and the potential technological use of these novel materials.