Applications Of Covalent Organic Frameworks Research Articles

Synthesis and Biomedical Applications of Covalent Organic Frameworks for Disease Diagnosis and Therapy.

Covalent organic frameworks (COFs) have emerged as a distinguished class of porous materials. Owing to their ability to be constructed through covalent bonds involving light elements, such as hydrogen, boron, carbon, nitrogen, and oxygen, COFs offer greater stability and lower cytotoxicity than metal organic frameworks do, addressing critical limitations in in vivo applications. Their unique attributes, such as high surface area, customizable pore sizes, and versatile surface functionalities, make them ideal for various biomedical applications. This review aims to provide an overview of the recent advancements in modern COFs for biomedical uses. First, a variety of methods for the synthesis of COFs are outlined, which ensures their suitability for medical use. Next, we delve into innovative biomedical applications, emphasizing their role in disease diagnostics and therapies. Finally, challenges, such as clinical translation, biocompatibility, and controlled drug release, are critically discussed, providing comprehensive insight into the potential of COFs in revolutionizing biomedical technologies. Overall, this review offers a comprehensive overview of COFs' capabilities and future prospects in enhancing biomedical technologies.

Innovative COF@MXene composites for high performance energy applications

AbstractAs a new type of composite two-dimensional material formed by the combination of Covalent Organic Frameworks (COFs) and two- dimensional (2D) MXenes, COF/MXene heterostructures (COF@MXene) inherit the stable porous two-dimensional structure of COFs and the excellent electrochemical performance and catalytic activity of MXenes, thus attracting widespread attention. Additionally, COF@MXene possesses various elemental affinity sites, efficient ion channels, and the ability to append various functional groups, which endow them with tremendous potential in electrochemical energy storage, energy conversion, and catalysis. Currently, there is a lack of extensive literature discussing the utilization of COF@MXene. The quest for enhanced physicochemical attributes through tailored modifications and composite strategies for COF@MXene is still a noteworthy hurdle. Furthermore, discovering novel application contexts that can harness the exceptional capabilities of these materials presents a formidable task. This review initiates with an exploration of the primary methodologies for synthesizing COF and MXene composites. Subsequently, it outlines the diverse applications of COF and MXene in energy storage, energy conversion, and environmental conservation. Lastly, it discusses the primary obstacles and future trajectories within these domains.

Covalent Organic Framework-Involved Sensors for Efficient Enrichment and Monitoring of Food Hazards: A Systematic Review.

The food safety issues caused by environmental pollution have posed great risks to human health that cannot be ignored. Hence, the precise monitoring of hazard factors in food has emerged as a critical concern for the food safety sector. As a novel porous material, covalent organic frameworks (COFs) have garnered significant attention due to their large specific surface area, excellent thermal and chemical stability, modifiability, and abundant recognition sites. This makes it a potential solution for food safety issues. In this research, the synthesis and regulation strategies of COFs were reviewed. The roles of COFs in enriching and detecting food hazards were discussed comprehensively and extensively. Taking representative hazard factors in food as the research object, the expression forms and participation approaches of COFs were explored, along with the effectiveness of corresponding detection methods. Finally, the development directions of COFs in the future as well as the problems existing in practical applications were discussed, which was beneficial to promote the application of COFs in food safety and beyond.

Functionalized sp2 Carbon-Conjugated Covalent Organic Frameworks for Interfacial Modulation of Inverted Perovskite Solar Cells.

Interfacial modulation utilizing functional materials is proven to be crucial for obtaining high photovoltaic performance in lead halide perovskite solar cells (PSCs). This study investigates, for the first time, the utilization of a pyrene-based sp2 carbon-conjugated covalent organic framework (sp2c-COF) as an interfacial layer in inverted PSCs. Functionalized with cyano (-CN) Lewis base groups, the sp2c-COF exhibits a dual effect, simultaneously passivating both the NiOx and the perovskite layers. Detailed characterization results highlight the role of sp2c-COF in reducing the Ni3+ defect density in NiOx films and forming Lewis acid-base adducts with undercoordinated Pb2+ on the perovskite surfaces, thereby inhibiting interfacial redox reactions and suppressing non-radiative recombination. Moreover, sp2c-COF leads to improved crystallinity of perovskite films. Benefiting from the synergistic effects, sp2c-COF-modified devices delivered a champion efficiency of 17.64%. These findings underscore the potential of sp2c-COF as a functional interface material for PSCs, offering enhanced efficiency and stability. The study contributes to advancing the understanding and application of covalent organic frameworks in photovoltaic technologies.

Molecular structure and application of Covalent Organic Frameworks (COFs) in tumor therapy

Molecular structure and application of Covalent Organic Frameworks (COFs) in tumor therapy

Construction of chiral crown ethers in robust covalent organic frameworks for electrochromatographic enantioseparation

ABSTRACT Capillary electrochromatography (CEC) is a rapidly emerging separation technique that merges the high separation efficiency of capillary electrophoresis with the exceptional selectivity of liquid chromatography. However, it remains a synthetic challenge to design functional chiral stationary phases (CSPs) with high chemical stability against acid and base in CEC enantioseparation. Here we demonstrate that incorporating chiral crown ethers into stable covalent organic frameworks (COFs) enables efficient and stable separations of racemates by CEC. This facilitates the crafting of two three-dimensional (3D) chiral COFs by polycondensation of a chiral 1,1'-binaphyl-20-crown-6-derived dialdehyde and tetraamines with diisopropyl substituents. Both feature an 11-fold interpenetrated diamond framework, characterized by tubular open channels decorated with chiral crown ethers serving as enantioselective recognition and binding sites. These frameworks demonstrate excellent stability in water, acid and base, thanks to the presence of bulky isopropyl groups that shield the dynamic imine linkages. Moreover, the precisely defined COF channels enhanced the accessibility of the enclosed crown ethers to the analytes while providing strong protection against harsh environments, rendering them suitable for CSPs in CEC separations. They can effectively separate some important enantiomers, including ketones, epoxides and alkaline substances, when utilized as coatings on chiral columns, particularly facilitating the chiral separation of drugs. This study advances the application of COFs in electrochromatographic separations, expanding the scope of porous materials design and engineering to create COFs with targeted enantioselective properties.

Covalent Organic Framework Nanoarchitectonics: Recent Advances for Precious Metal Recovery.

The recovery of precious metals (PMs) from secondary resources has garnered significant attention due to environmental and economic considerations. Covalent organic frameworks (COFs) have emerged as promising adsorbents for this purpose, owing to their tunable pore size, facile functionalization, exceptional chemical stability, and large specific surface area. This review provides an overview of the latest research progress in utilizing COFs to recover PMs. Firstly, the design and synthesis strategies of chemically stable COF-based materials, including pristine COFs, functionalized COFs, and COF-based composites, are delineated. Furthermore, the application of COFs in the recovery of gold, silver, and platinum group elements is delved into, emphasizing their high adsorption capacity and selectivity as well as recycling ability. Additionally, various interaction mechanisms between COFs and PM ions are analyzed. Finally, the current challenges faced by COFs in the field of PM recovery are discussed, and potential directions for future development are proposed, including enhancing the recyclability and reusability of COF materials and realizing the high recovery of PMs from actual acidic wastewater. With the targeted development of COF-based materials, the recovery of PMs can be realized more economically and efficiently in the future.

Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly-Efficient Rechargeable Batteries.

Alkali metals (Li, Na, and K) and multivalent metals (Zn, Mg, Ca, and Al) have become star anodes for developing high-energy-density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid-state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.

Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly‐Efficient Rechargeable Batteries

AbstractAlkali metals (e.g. Li, Na, and K) and multivalent metals (e.g. Zn, Mg, Ca, and Al) have become star anodes for developing high‐energy‐density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid‐state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.

Recent progress of covalent organic frameworks in high selective separation of radionuclides

The utilization of nuclear energy power and nuclear weapon tests not only releases large amounts of radionuclides into environment, but also needs 235U as nuclear fuel for nuclear energy generation. Covalent organic frameworks (COFs) have the advantages of tunable porous structures, adjustable active sites and enough special functional groups, which assure the high selective preconcentration of target radionuclides from complex solutions. In this perspective, the selective extraction of radionuclides (U(VI) as representative cationic ion, Tc(VII) as representative anionic ion, I2 as gaseous nuclide and other nuclides) by COFs through sorption, and photocatalytic strategies are described, and the results show the high efficiency of COFs in target radionuclides removal. The perspective and challenges for the real applications of COFs in future are discussed in the end.Graphical

In-situ construction of covalent organic frameworks membrane via interfacial polymerization and crosslinking modification using trimesoyl chloride for organic solvent nanofiltration

Organic solvent nanofiltration (OSN) is a modern technology for separating and purifying organic solvents. It has the advantages of both low energy consumption and low environmental pollution. In this work, we utilized an oligomer triggered interfacial polymerization (OT-IP) method and followed by a post-IP modification using trimesoyl chloride (TMC) to synthesize a kind of covalent organic frameworks (COFs)/TMC membrane. This process involves pre-mixing both COFs monomers in a same organic solvent to form oligomers, followed by conducting an IP reaction at the interface between the organic solvent phase and an aqueous phase solution containing acetic acid as a catalyst. Subsequently, a surface modification is conducted using TMC n-hexane solution, which effectively manipulates the surface hydrophilicity, average size, solute rejection, solvent permeance and solvent resistance of the membrane. Afterward, crosslinking and solvent activation are performed to improve its solvent resistance and separation permeance. The optimized OSN membrane exhibits an ethanol permeance of 72.5 L m−2 h−1 MPa−1 with an RDB rejection of 98.4 %. Its surface roughness is as low as 3.4 nm. Furthermore, it has high permeance for both polar solvents (MeOH permeance of 176.7 L m−2 h−1 MPa−1) and weakly polar solvents (EtOAc permeance of 183.0 L m−2 h−1 MPa−1). Moreover, the optimized OSN membrane demonstrates excellent solvent resistance and excellent catalyst recovery performance. Therefore, this work presents a promising avenue for the application of COFs in OSN membranes.

Unveiling the Potential of Highly Porous Covalent Organic Frameworks for Water-Jet Rewritable Papers.

The massive use of paper has resulted in significant negative impacts on the environment. Fortunately, recent progress has been made in the field of rewritable paper, which has great potential in solving the increasing demand for paper while minimizing its environmental footprint. In this work, we report a green and economic strategy to develop ink-free rewritable paper by introducing hydrochromic covalent organic frameworks (COFs) in paper and using water as the sole trigger. When exposed to water or acidic solvents, two kinds of imino COFs change their colors reversibly from red to black. Additionally, a new visible absorption band appears, indicating that it can be transformed into another structure reversibly. This reversibility may be due to the isomerization from the diiminol to an iminol/cisketoenamine and its inability to doubly tautomerize to a diketoenamine. Specifically, we prepared the rewritable paper by loading these two COFs onto filter paper by using the decompression filtration method. When exposed to water, the paper undergoes a color change from red to black, which shows promising potential for applications in water-jet printing. Additionally, there is no significant performance degradation after 20 uses and 10 days between, further highlighting their potential as rewritable papers. To further improve its uniformity, we take the interface polymerization strategy to yield highly crystalline and more compact membranes, which are then transferred to paper to prepare writable papers. Our research has opened up a way for the application of COFs as a water-based printing material.

Recent Advancements in the Applications of Covalent Organic Frameworks for Cancer Therapeutics: A Review

Covalent organic frameworks (COFs) have gained significant attention in recent years as efficient cancer therapeutics owing to their uniform porosity, biocompatibility, diversified structures and stability in the biological medium. This review aimed to explore different synthetic strategies to obtain COFs for biomedical applications. Several synthetic procedures viz. solvothermal synthesis, ionothermal synthesis, microwave synthesis, mechanochemical synthesis, sonochemical synthesis have discussed been in terms of their applications in cancer therapy. The cancer therapeutics involves cancer drug delivery, photodynamic therapy (PDT), photo thermal therapy (PTT) and sonodynamic therapy (SDT). In some instances, single therapeutics treatments appear as inadequate effect and thus necessitate combination therapies for effective cancer termination with minimal side effects. The current study covers all the main synthetic techniques and uses of COFs in various cancer therapeutic treatments.

Amino-functional magnetic covalent organic framework as an effective adsorbent for the determination of neonicotinoids in food samples.

Recently, covalent organic frameworks have gained popularity in sample pretreatment. However, the application of covalent organic frameworks in the enrichment of hydrophilic compounds remains a challenge. Thus, a functionalized magnetic covalent organic framework equipped with amino groups was constructed using a bottom-up functionalization strategy. Considering the advantages of this novel adsorbent such as high porosity, large adsorption capacity, and hydrophilic surface, a sensitive magnetic solid-phase extraction coupled with high-performance liquid chromatography-tandem mass spectrometry method was established for the effective determination of neonicotinoids. This method exhibited good linearities with correlation coefficients ranging from 0.9983 to 0.9995, low detection limits in the range 0.003-0.009 ng g-1 and 0.001-0.013 ng mL-1, and limits of quantification in the range 0.010-0.031 ng g-1 and 0.004-0.044 ng mL-1. Furthermore, satisfactory repeatability with relative standard deviations ≤ 6.7% and spiked recoveries between 82.3 and 99.8% were obtained. This work not only provided a promising adsorbent for the sensitive determination of trace-level neonicotinoids but also represented a unique insight for effective enrichment of super hydrophilic hazards.

SERS substrate based on COF@Ag for detecting amoxicillin in honey and lake water

This study presents the design of a Surface-enhanced Raman scattering (SERS) substrate, COF@Ag, for the sensitive detection of Amoxicillin (AMX) in lake water and honey. Furthermore, the study investigates the role of covalent organic frameworks (COFs) in SERS detection. The characterization results demonstrate the capability of COFs to efficiently enrich Ag nanoparticles (AgNPs), resulting in a more concentrated distribution of hotspots and an enhanced electromagnetic field on the substrate. By employing density functional theory (DFT) simulation, the frontier electronic orbitals of COFs and AMX were analyzed, and the chemical bonds and weak interactions in the system were examined using the Interaction Region Indicator (IRI) method to propose potential enhancement mechanisms. In aqueous solutions, the linear range is 1 μg/L-30 μg/L, with a limit of detection (LOD) 0.279 μg/L. In lake water, the linear range span from 100 μg/L to 500 μg/L, with a detection limit of 8.244 μg/L. For honey, the linear range extend from 20 ng/g to 100 ng/g, with a detection limit of 2.917 ng/g. This method holds key significance in facilitating the rapid detection of amoxicillin and advancing the application of COFs in SERS.

Covalent organic frameworks: spotlight on applications in the pharmaceutical arena.

Covalent organic frameworks (COFs) have much potential in the field of analytical separation research due to their distinctive characteristics, including easy modification, low densities, large specific surface areas and permanent porosity. This article provides a historical overview of the synthesis and broad perspectives on the applications of COFs. The use of COF-based membranes in gas separation, water treatment (desalination, heavy metals and dye removal), membrane filtration, photoconduction, sensing and fuel cells is also covered. However, these COFs also demonstrate great promise as solid-phase extraction sorbents and solid-phase microextraction coatings. In addition to various separation applications, this work aims to highlight important advancements in the synthesis of COFs for chiral and isomeric compounds.

Fabrication of p-n Heterostructured Photocatalysts with Triazine-Based Covalent Organic Framework and CuInS2 for High-Efficiency CO2 Reduction.

The application of covalent organic frameworks (COFs) for the photocatalytic reduction of CO2 is mostly limited by severe charge recombination and low sunlight utilization. Herein, a triazine-based COF with an electron-rich and large π-conjugated system (TCOF) was employed as a building block and integrated with CuInS2 (CIS) to construct a noble-metal-free and high-efficiency photocatalyst for CO2 reduction. The in situ growth of CIS nanosheets on TCOF creates a p-n heterojunction, named CIS@TCOF. Compared with TCOF, the CIS@TCOF heterostructure exhibits a dramatically boosted photocatalytic performance in the reduction of CO2. The produced HCOOH yield over 10 wt % CIS@TCOF can be up to 171.2 μmol g-1 h-1 under visible light irradiation with good reproducibility, which is about 3 times as high as that over TCOF. Further in-depth studies indicate that the introduction of CIS not only enhances the visible light utilization but also restrains the recombination of photogenerated electron-hole pairs efficiently and facilitates the photoinduced charge transfer via the p-n heterojunction system due to the unique structural and compositional features. This research shows the great potential of COFs as efficient photocatalytic carbon fixation materials and provides a versatile route to construct semiconductor-COF heterostructures for photocatalysis.

Progress on application of covalent organic frameworks for advanced lithium metal batteries

Since Li metal batteries (LMBs) theoretically possess high energy density, they are the most concerned rechargeable batteries at present. Whereas, poor safety and short cycling lives of the LMBs originate from various problems of LMBs components including cathode/anode materials, electrolytes, and separators have impeded their practical application. Covalent organic frameworks (COFs), which feature diverse structures, flexible frameworks, and versatile functions, have been extensively investigated as potential alternatives for above mentioned key components of LMBs. With the rational design and pre-/postsynthesis functionalization, COFs can be precisely customized for targeted functionalities, which can tackle the issues of LMBs. The current status of the application of COFs in LMBs, which covers working principles and strategies for improving electrochemical performance, will be discussed in this review. What's more, the challenges and potential directions for further developments of COFs in LMBs are presented in the final section.

A graft-modified sponge with COFs for wastewater treatment and iodine adsorption

Azo dyes, used in large quantities in drinks, have become a threat to human health. In the treatment of dyes, the method of chemical adsorption is often used due to its simple and efficient features. Covalent organic frameworks (COFs) material with the characteristics of stability and porosity has great potential for the adsorption of azo dyes. However, the application of COFs is severely limited by their poor mechanical properties and hard recovery. By the strategy of in situ growth using the original functional groups of the sponge, COFs are successfully grafted onto melamine sponges to give rise to a porous sponge@COFs material. The material can adsorb up to 621 mg g−1 of Congo red, a common azo dye. In addition, it exhibits strong adsorption of iodine solution with the saturated adsorption of 1504.76 mg g−1. More importantly, sponge@COFs can selectively adsorb azo dyes with S–O- bond. The adsorption mechanism is inferred as the connect of S–O- in the Congo red molecule with O atom of sponge@COFs. Also, the mechanism of iodine adsorption is explained to be due to the coordination of C atoms in COFs with I atom. In addition, as an adsorbent, the material is recoverable, stable and heat resistant. Relying on the stronger performance and lower cost, sponge@COFs is expected to be developed as a new adsorbent.

Precise local functionalization of covalent organic framework for efficient carrier separation in photocatalytic H2 evolution

Improving carrier transport rate and suppressing carrier recombination are two huge challenges in the photocatalytic applications of covalent organic frameworks (COFs)-based semiconductors. In this study, we propose a strategy to enhance carrier transport efficiency by regulating the local microenvironment of the electronic characteristics in the acceptors through structural modification. Three different functional group-modified fluorenone-based COFs were successfully synthesized through precise design. The results demonstrate that the photocatalytic hydrogen evolution activities of COFs modified with electron-donating functional groups are significantly higher than that of COFs modified by electron-withdrawing functional groups. Specifically, the photocatalytic hydrogen evolution performance of phenyl-modified FOOPh-COF could reach 228.5 mmol h−1g−1, which is 11.8 times higher than that of Br atom-modified FOOBr-COF (19.3 mmol h−1g−1). Femtosecond time-resolved transient absorption spectroscopy (fs-TAS) results reveal that introducing phenyl groups into the acceptor significantly enhances its inhibitory effect on the carrier recombination. Density functional theory calculations further prove that modifying the acceptor by electron-donating functional groups can achieve the increased electron density in the CO active center. The electrons in the CO region in the phenyl-modified fluorenone structure are more enriched and delocalized, which can enhance the speed of electron migration, shorten the migration distance, and inhibit carrier recombination. After loading Pt, it has the lowest H* adsorption-free energy among three samples. This work clarifies the importance of the functionalization modification of COFs’ acceptors in regulating the local electronic environment and further provides new insights into the structure–activity relationship of fluorenone-based COF-based photocatalysts.