2D Covalent Organic Frameworks Research Articles

Needle trap devices packed with an imine-based 2D COF: An innovative tool for the sampling of polycyclic aromatic hydrocarbons in air

This study introduces a new method for sampling and microextraction of polycyclic aromatic hydrocarbons (PAHs) in the air using needle trap devices (NTDs) packed with an imine-based covalent-organic framework (COF) as an adsorbent. The NTD was coupled with gas chromatography-flame ionization detection (GC-FID) for analytes’ separation and quantification. The COF adsorbent was synthesized using a solvothermal method at room temperature and packed inside a stainless-steel needle. The adsorbent was characterized using X-ray diffraction analysis (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM-EDS) and Brunauer-Emmett-Teller (BET) analysis. The method was developed in the laboratory under various conditions and subsequently applied in the field to compare the results with those obtained using sampling and analytical method-NIOSH 5528. The desorption conditions and breakthrough volume (BtV) were optimized at recommended exposure limits concentration using response surface methodology (RSM) with a central composite design (CCD). Accordingly, the optimal values for desorption temperature and BtV were obtained 310 °C and 2840 mL, respectively. The limits of detection (LODs) and the limits of quantification (LOQs) were found to be 0.021–0.027 and 0.065–0.091 μg L−1, respectively. The repeatability and reproducibility of the method (R%) were estimated to be 4.02–6.83 % and 8.51–10.34 %, respectively. Also comparing the mean concentrations of the samples collected by the NTD and the NIOSH 5528 method, revealed no statistically significant differences between the methods (p > 0.05). Overall, the COF-packed NTD was identified as an appropriate and reliable method for sampling and extracting occupational and ambient contaminants in the workplace air.

Versatile Metal-Free Photocatalysts Based on 3D Covalent Organic Frameworks Capable of Reductive and Oxidative Organic Transformations and Polymerizations

Versatile Metal-Free Photocatalysts Based on 3D Covalent Organic Frameworks Capable of Reductive and Oxidative Organic Transformations and Polymerizations

Tuning the Topology of Two-Dimensional Covalent Organic Frameworks through Site-Selective Synthetic Strategy.

Tuning the topology of two-dimensional (2D) covalent organic frameworks (COFs) is of paramount scientific interest but remains largely unexplored. Herein, we present a site-selective synthetic strategy that enables the tuning of 2D COF topology by simply adjusting the molar ratio of an amine-functionalized dihydrazide monomer (NH2 -Ah) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (Tz). This approach resulted in the formation of two distinct COFs: a clover-like 2D COF with free amine groups (NH2 -Ah-Tz) and a honeycomb-like COF without amine groups (Ah-Tz). Both COFs exhibited good crystallinity and moderate porosity. Remarkably, the clover-shaped NH2 -Ah-Tz COF, with abundant free amine groups, displayed significantly enhanced adsorption capacities toward crystal violet (CV, 261 mg/g) and congo red (CR, 1560 mg/g) compared to the non-functionalized honeycomb-like Ah-Tz COF (123 mg/g for CV and 1340 mg/g for CR), underscoring the pivotal role of free amine functional groups in enhancing adsorption capacities for organic dyes. This work highlights that the site-selective synthetic strategy paves a new avenue for manipulating 2D COF topology by adjusting the monomer feeding ratio, thereby modulating their adsorption performances toward organic dyes.

A Visible Light Responsive Smart Covalent Organic Framework with a Bridged Azobenzene Backbone.

Condensation of 3,3'-diamino-2,2'-ethylene-bridged azobenzene with 1,2,4,5-tetrakis-(4-formylphenyl) benzene produces a visible light responsive porous 2D covalent organic framework, COF-bAzo-TFPB, with a large surface area, good crystallinity, and thermal and chemical stability. The results demonstrate that the elaborated designed linker can make azo unit on the COF-bAzo-TFPBskeleton undergo reversible photoisomerization. This work expands the application scope of covalent organic frameworks in photo-controlled release, uptake of guest molecules, dynamic photoswitching, and UV-sensitive functions.

Triple Isomerism in 3D Covalent Organic Frameworks.

Isomerism in covalent organic frameworks (COFs) has scarcely been known. Here, for the first time we show 3D COFs with three framework isomers or polymorphs constructed from the same building blocks. All isomers were obtained as large (>10 μm) crystals; although their crystal shapes were distinctly different, they showed identical FT-IR and solid-state NMR spectra. Our structural analyses revealed unprecedented triple isomerism in 3D COFs (noninterpenetrated dia, qtz, and 3-fold interpenetrated dia-c3 nets). Furthermore, this Communication reports the first known COF with qtz topology for which the structure determination was based on Rietveld analysis. We achieved triple framework isomerism by reticulating a tetrahedral building block with a flexible junction and a linear building block with PEO side chains and by varying solution compositions. Our energy calculations, along with the discovery of interisomer transition, revealed that the isomer with qtz topology was a kinetic isomer. Thus, this simple yet little-explored concept of reticulating only flexible building blocks is an effective pathway to significantly broaden the diversity of 3D COFs, which have been proposed for a myriad of applications.

A panoramic perspective of recent progress in 2D and 3D covalent organic frameworks for drug delivery

AbstractThe development of efficient drug delivery systems is essential for improving the efficacy and safety of cancer drugs, particularly for aggressive and difficult‐to‐treat cancers. Covalent organic frameworks (COFs) are emerging as innovative porous nanomaterials in drug delivery systems (DDS), due to their unique properties, including the metal‐free organic skeleton, predetermined structures and pore geometries, high porosity, large surface area, facile surface modification potential, and good biocompatibility. These characteristics make COFs excellent candidates for improving drug delivery by enhancing drug loading capacity and enabling precise encapsulation. This review emphasizes the importance of donor‐acceptor‐based COFs, which provide channels for charge transportation, and we also explore how the π‐conjugated skeleton of COFs enhances its long‐acting fluorescent properties and facilitates drug uptake via cell endocytosis. While this review primarily focuses on recent advancements in COF‐based targeted DDS, it also acknowledges the challenges posed by the diverse pore geometries in porous materials and discusses potential solutions. Further, it underlines the potential of developing future drug carriers that can successfully and specifically target cancer cells, improving treatment efficiency while reducing adverse side effects.

Atomically dispersed Ni active sites on covalent organic frameworks for heterogeneous metallaphotocatalytic C–N cross-coupling

Covalent organic frameworks (COFs) have been acknowledged as a potential platform for heterogeneous photoredox cross-coupling due to their excellent chemical stability, admirable controllability, and extremely prominent surface area. However, synthesizing COFs with bidentate ligand units and utilizing active sites remain a grand challenge. Herein, we report a promising new family of 2,6-pyridinedicarboxaldehyde-bis-(p-aminophenylimine)-based two-dimensional (2D) COFs (PP-COF) using an amine monomer and classic tri-aldehydes. On this basis, dispersed Ni single-atom sites were immobilized on three-types imine-based bi-coordinated 2D COFs (Ni SAS-PP-COF) as heterogeneous dual photoredox catalysts for photo/Ni dual-catalyzed C–N cross-coupling between aryl bromides and alkyl/sulfo amines. Under solar energy irradiation, PP-COF could absorb light to generate electrons and holes, then the photogenerated electrons are transferred to Ni sites to reduce divalent nickel to monovalent nickel. Monovalent nickel is necessary to drive the nickel catalytic cycle. Due to the increased charge separation and abundant active sites, the state-of-the-art Ni SAS-PP-COFs catalyst achieves excellent catalytic performance in comparison of pristine PP-COF. The heterogeneous Ni SAS-PP-COF catalytic system not only confirms the prospect of COFs as potential photoredox/transition-metal dual catalysts, but also provides in-depth insights into the synthesis of functional COFs toward practical metallaphotocatalytic application.

Terahertz Conductivity of Free-Standing 3D Covalent Organic Framework Membranes Fabricated via Triple-Layer-Dual Interfacial Approach.

Processable covalent organic framework membranes (COFM) are emerging as potential semiconducting materials for device applications. Nevertheless, the fabrication of crystalline and free-standing 3D COFMs is challenging. In this work, a unique time and solvent-efficient triple-layer-dual interfacial (TLDI) approach for the simultaneous synthesis of two 3D COFMs from a single system is developed. Besides, for the first time, the optical conductivity of these free-standing 3D COFMs is analyzed using terahertz (THz) spectroscopy in transmission mode. Interestingly, these membranes show excellent transmittance at THz frequencies with very high intrinsic THz conductivities. The evaluated scattering time and plasma frequency of the free carriers of the COFMs are highly promising for future applications in optoelectronic devices in THz frequencies.

The thermoelastic properties of monolayer covalent organic frameworks studied by machine-learning molecular dynamics.

Two-dimensional (2D) covalent organic frameworks (COFs) are emerging as promising 2D polymeric materials with broad applications owing to their unique properties, among which the mechanical properties are quite important for various applications. However, the mechanical properties of 2D COFs have not been systematically studied yet. Herein, a machine-learned neuroevolution potential (NEP) was developed to study the elastic properties of two representative monolayer 2D COFs, namely COF-1 and COF-5. The trained NEP enables one to study the elastic properties of 2D COFs in realistic situations (e.g., finite size and temperature) and possesses greatly improved computational efficiency when compared with density functional theory calculations. With the aid of the obtained NEP, molecular dynamics (MD) simulations together with a strain-fluctuation method were employed to evaluate the elastic constants of the considered 2D COFs at different temperatures. The elastic constants of COF-1 and COF-5 monolayers were found to decrease with an increase in the temperature, though they were almost isotropic irrespective of the temperature. The thermally induced softening of 2D COFs below a critical temperature was observed, which is mainly attributed to their inherent ripple configurations at finite temperatures, while above the critical temperature, the damping effect of anharmonic vibrations became the dominant factor. Based on the proposed mechanisms, analytical models were developed for capturing the temperature dependence of elastic constants, which were found to agree with the MD simulation results well. This work provides an in-depth insight into the thermoelastic properties of monolayer COFs, which can guide the development of 2D COF materials with tailored mechanical behaviors for enhancing their performance in various applications.

Bifunctional oxygen reduction/evolution reaction electrocatalysts achieved by axial ligand modulation on two-dimensional porphyrin frameworks.

Exploring efficient and low-cost oxygen reduction and oxygen evolution reaction (ORR/OER) bifunctional catalysts is essential for the development of energy storage and conversion devices. Herein, enlightened by the experimentally synthesized cobalt(II) meso-tetraethynylporphyrins (Co-TEP) molecule, we designed a novel 2D covalent organic framework (COF), namely a 2D Co-TEP monolayer, by dimensional expansion. The 2D Co-TEP monolayer, with Co atoms distributed separately and stabilized by uniform pyrrolic-N coordination, features metal-nitrogen-carbon single-atom catalyst activity and shows tunable catalytic activity for the electrochemical ORR/OER by axial ligand (O, OH, Cl, CN, CH3, NO, F) modulation. By means of the state-of-the-art constant-potential first-principles computations and microkinetic simulations, we demonstrated that 2D Co-TEP-CN exhibits good ORR/OER performance in both acidic and alkaline conditions. The difference between the onset-potential for the OER and the half-wave potential for the ORR is only 0.85 V at pH = 1, smaller than that of Pt/IrO2 electrocatalysts. The good electrocatalytic performance is maintained by replacing the center metal atoms with Mn, Fe and/or Ni. Our investigation highlights the role of the pyrrolic-N coordination and the ligands in improving the catalytic activity of 2D COFs and provides new insights into the rational design of efficient bifunctional ORR/OER catalysts.

Two-dimensional covalent organic framework-based hybrid nanosheets for electrochemical detection of 5-fluorouracil and uracil in biofluids

A 2D covalent organic framework (COF), supramolecule cucurbit[8]uril, and an AuNP-based electrochemical sensor for simultaneous detection of 5-fluorouracil and uracil, in concentrated biofluids, holding promise for practical sensing.

In-plane Polarity Boosts Photocatalytic Overall Water Splitting in Two-Dimensional Covalent Organic Frameworks with Polarized Linkages

Benefiting from the modular nature and tunable optoelectronic properties, two-dimensional (2D) covalent organic frameworks (COFs) emerge as promising candidates for photocatalytic overall water splitting (OWS). However, the rapid recombination of...

A cobalt-modified covalent organic framework enables highly efficient degradation of 2,4-dichlorophenol in high concentrations through peroxymonosulfate activation.

The development of covalent organic frameworks (COFs) which can rapidly degrade high concentrations of 2,4-dichlorophenol is of great significance for its practical application. In this work, we report a cobalt-doped two-dimensional (2D) COF (JLNU-307-Co) for the ultra-efficient degradation of high concentration 2,4-dichlorophenol (2,4-DCP) by activating peroxymonosulfate (PMS). The JLNU-307-Co/PMS system takes only 3 min to degrade 100% of 50 mg L-1 2,4-DCP and shows excellent catalytic stability in real water. The superoxide radical (O2˙-) and singlet oxygen (1O2) play a major role in the system through capture experiments and electron spin resonance (ESR) tests. Compared to most previously reported catalysts, JLNU-307-Co/PMS showed the highest efficiency to date in degrading 2,4-DCP. This work not only demonstrates the potential of COFs as a catalyst for water environmental treatment, but also provides unprecedented insights into the degradation of organic pollutants.

Effect of interlayer slipping on the geometric, thermal and adsorption properties of 2D covalent organic frameworks: a comprehensive review based on computational modelling studies.

Two-dimensional covalent organic frameworks (2D-COFs) are a class of crystalline porous organic polymers, consisting of 2D-planar sheets stacked together perpendicularly via noncovalent forces. Since their discovery, 2D-COFs have attracted extensive attention for optoelectronic and adsorption applications. Owing to the layer stacking nature of 2D COFs, various new slipped structures that are energetically favourable can be designed. These interlayer slipped structures are actively responsible for tuning (mostly enhancing) the optoelectronic properties, thermal properties, and mechanical strength of 2D COFs. This review summarizes the effect of interlayer slipping on the energetic stability, electronic behaviour and gas adsorption properties of 2D layered COFs, which is explained through computational modelling simulations. Since computational modelling offers a deep insight into electronic behaviour at the atomic scale, which is potentially impossible through experimental techniques, the introduction and role of computational techniques in such studies have also been described.

Hexagonal 2D covalent organic frameworks from nonpolar and symmetric electron-accepting substituents for electron transport layers in near-infrared PeLEDs

High-throughput screening and NAMD calculations indicate that nonpolar and symmetric electron-absorbing substituents in 2D Tp-DAAQ can suppress e–h nonradiative recombination.

Extending 2D covalent organic frameworks by inserting anthracene for promoted white-light-mediated photocatalysis

A novel anthracene-based covalent organic framework was synthesized, with potential application for white light-induced oxidative coupling of amines and selective oxidation of sulfides, both of which yielded remarkable conversion and selectivity.

Imine-linked 2D covalent organic frameworks based on benzotrithiophene for visible-light-driven selective aerobic sulfoxidation

An imine-linked covalent organic framework based on benzotrithiophene generates superoxide and singlet oxygen to carry out blue-light-driven selective aerobic sulfoxidation.

POPs to COFs by post-modification: CO2 chemisorption and dissolution.

Porous organic polymers (POPs) and covalent organic frameworks (COFs) are hierarchical nano materials with variable applications. To our knowledge, this is the first report of a post-modified, non-renewable, DMSO-soluble M-POP/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) upon atmospheric H2O/CO2 trapping after 48 h, forming a DBUH+·HCO3- adduct, as verified by solution carbon-13 nuclear magnetic resonance (13C NMR) spectroscopy. The success of the post-modification resulting from aldehyde enriched POPs was proven spectroscopically. The accessible functional group was reacted with excess monoethanolamine (MEA) resulting in the formation of M-POP. Away from CO2 physisorption, only few examples have been reported on the chemisorption process. One such example is the ethylene diamine-functionalized E-COF, capable of capturing CO2via carbamation. This was evidenced by several qualitative measurements including colorimetry and conductivity, which showed an unprecedented water solubility for a 2D COF material. The crystallinity of COFs as a result of post-modification was proven by powder X-ray diffraction (PXRD).

Novel three-dimensional fibrous covalent organic frameworks constructed via silver amalgam bridging for efficient organic dye adsorption and removal.

The construction of covalent organic frameworks (COFs) with unique structures has great significance in exploring the structure-function relationship and extending their potential applications. Fibrous COFs have demonstrated superior performance in specific application scenarios owing to the distinctive three-dimensional (3D) structure. Herein, we report a facile strategy for the fabrication of 3D COF nanofiber by exploiting silver amalgam as a bridging agent to assemble one-dimensional-extended PA-COF modules into a tubular structure. Dimensions of the obtained 3D COF nanofiber were predicted by DFT calculations, and the nanofiber was endowed with the merits of favorable uniformity and high stability. Due to the enhanced exposure of conjugatable binding sites for dye retention offered by the novel 3D architecture, the PA-COF nanofiber exhibits fast adsorption (within 5 min) and superior adsorption capacity to various organic dyes, e.g., 1717 mg g-1 for methylene blue (MB) and 978.3 mg g-1 for methyl orange (MO). Moreover, the PA-COF nanofiber shows excellent reusability in dye adsorption, which makes it a potential medium for removing dye pollutants from wastewater. This work presents an effective strategy to construct COF materials with unique architecture and potential prospects in the fields of separation and wastewater treatment.

Tailored Design of a Water-Based Nanoreactor Technology for Producing Processable Sub-40Nm 3D COF Nanoparticles at Atmospheric Conditions.

Covalent organic frameworks (COFs) are crystalline materials with intrinsic porosity that offer a wide range of potential applications spanning diverse fields. Yet, the main goal in the COF research area is to achieve the most stable thermodynamic product while simultaneously targeting the desired size and structure crucial for enabling specific functions. While significant progress is made in the synthesis and processing of 2D COFs, the development of processable 3D COF nanocrystals remains challenging. Here, a water-based nanoreactor technology for producing processable sub-40nm 3D COF nanoparticles at ambient conditions is presented. Significantly, this technology not only improves the processability of the synthesized 3D COF, but also unveils exciting possibilities for their utilization in previously unexplored domains, such as nano/microrobotics and biomedicine, which are limited by larger crystallites.