Stability Of Covalent Organic Frameworks Research Articles

Rigid covalent organic frameworks with thiazole linkage to boost oxygen activation for photocatalytic water purification

Owing to their capability to produce reactive oxygen species (ROS) under solar irradiation, covalent organic frameworks (COFs) with pre-designable structure and unique architectures show great potentials for water purification. However, the sluggish charge separation, inefficient oxygen activation and poor structure stability in COFs restrict their practical applications to decontaminate water. Herein, via a facile one-pot synthetic strategy, we show the direct conversion of reversible imine linkage into rigid thiazole linkage can adjust the π-conjugation and local charge polarization of skeleton to boost the exciton dissociation on COFs. The rigid linkage can also improve the robustness of skeleton and the stability of COFs during the consecutive utilization process. More importantly, the thiazole linkage in COFs with optimal C 2p states (COF-S) effectively increases the activities of neighboring benzene unit to directly modulate the O2-adsorption energy barrier and improve the ROS production efficiency, resulting in the excellent photocatalytic degradation efficiency of seven toxic emerging contaminants (e.g. degrading ~99% of 5 mg L−1 paracetamol in only 7 min) and effective bacterial/algal inactivation performance. Besides, COF-S can be immobilized in continuous-flow reactor and in enlarged reactor to efficiently eliminate pollutants under natural sunlight irradiation, demonstrating the feasibility for practical application.

Irreversible bonds for higher stability of COF materials in photocatalytic reactions

Covalent organic frameworks (COFs), one of a multitude of advanced mainstream materials in photocatalysts, are crystalline porous materials with tunable topology and high porosity and are connected by dynamic covalent bonds. We sought to achieve efficient photocatalytic yields, making the stability of the bond energy crucial. Stable bond energy will enable our products to be more economically efficient. At present, the main photocatalysts are reversible imine bonds and other 2D COFs, but irreversibly stable COFs are seldom involved. Therefore, this review surveys the relevant literature to explore the stability of irreversible bond energy, elaborating the synthesis schemes of irreversible bonds. Irreversibly connected bonds will improve the stability and durability of our synthesized catalyst in practical applications, so we seek to explore the stability of bond energy for our practical applications. In this review, we offer a detailed summary of the irreversible bonding pattern, explore the stability of COFs, and summarize classic highly crystalline ordered semiconductor COFs with irreversible bonding methods.

TpBD/UiO-66-NH2 micro-mesoporous hybrid material as a stationary phase for open tubular capillary electrochromatography.

The excellent stability of covalent organic frameworks (COFs) and the diversity of metal organic frameworks (MOFs) make MOF/COF hybrid materials promising candidates for chromatographic stationary phases. In this paper, a TpBD/UiO-66-NH2 hybrid material was synthesized through a Schiff-base reaction between TpBD COFs and UiO-66-NH2 MOFs; characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy; and bonded to a capillary to prepare a TpBD/UiO-66-NH2-bonded open tubular capillary electrochromatography (OT-CEC) column. Results suggested that the hybrid material had the crystal morphology of a single COF and MOF, a micro-mesoporous structure, and good thermal stability. The inner surface of the OT-CEC column was tightly and uniformly distributed with the stationary phase (∼1.5 μm). The baseline separation of 13 amino acids and three families (4 acidic antibiotics, 4 preservatives and 6 sulfonamides) of emerging pollutant mixtures was achieved due to the synergistic effect of TpBD and UiO-66-NH2 in the stationary phase. The OT-CEC column showed good reproducibility and stability with relative standard deviations of migration time and resolutions in the range of 1.17-3.93% and 1.79-4.31%, respectively.

Quantitative Construction of Boronic-Ester Linkages in Covalent Organic Frameworks for the Carbon Dioxide Reduction.

Covalent organic frameworks (COFs) have been utilized for catalyzing the reduction of carbon dioxide (CO2RR) due to their atomic metal centers and controllable pore channels, which are facilitated by different covalent bonds. However, the exploration of boron-based linkages in these catalytic COFs has been limited owing to potential instability. Herein, we present the construction of boronic ester-linked COFs through nucleophilic substitution reactions in order to catalyze the CO2 RR. The inclusion of abundant fluorine atoms within the frameworks enhances their hydrophobicity and subsequently improves water tolerance and chemical stability of COFs. The content of boron atoms in the COF linkages was carefully controlled, with COFs featuring a higher density of boron atoms exhibiting increased electronic conductivity, enhanced reductive ability, and stronger binding affinity towards CO2 . Consequently, these COFs demonstrate improved activity and selectivity. The optimized COFs achieve the highest activity, achieving a turnover frequency of 1695.3 h-1 and a CO selectivity of 95.0 % at -0.9 V. Operando synchrotron radiation measurements confirm the stability of Co (II) atoms as catalytically active sites. By successfully constructing boronic ester-linked COFs, we not only address potential instability concerns but also achieve exceptional catalytic performance for CO2 RR.

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.

Blue light photocatalytic oxidation of sulfides to sulfoxides with oxygen over a thiazole-linked 2D covalent organic framework

With permanent porosity and intrinsic crystallinity, covalent organic frameworks (COFs) have great potential for solar energy conversions. However, the crystallinity of COFs necessitates reversible linkages like imine, leading to inadequate chemical stability of COFs as photocatalysts. To overcome this inadequacy, post-synthetic modifications (PSMs) transform an imine-linked COF, TTI-COF, into a thiazole-linked COF, TTT-COF. The morphology and crystallinity of TTT-COF are similar to that of TTI-COF. Compared to TTI-COF, TTT-COF secures evident amelioration of stability and optoelectronic properties supported by both experiments and theoretical calculations. Consequently, these two COFs are exploited for the photocatalytic oxidation of organic sulfides. Under blue light-emitting diode irradiation, TTI-COF marginally impels the reaction. In contrast, TTT-COF emerges with significantly better activity for selective oxidation of organic sulfides with oxygen in ethanol. This work sheds light on the transformative power of PSMs for tailoring COFs in visible light photocatalysis for oxidations.

Bottom-Up Synthesis of Covalent Organic Frameworks with Quasi-Three-Dimensional Integrated Architecture via Interlayer Cross-Linking.

Developing strategies to enhance the structural robustness of covalent organic frameworks (COFs) is of great importance. Here, we rationally design and synthesize a class of cross-linked COFs (CCOFs), in which the two-dimensional (2D) COF layers are anchored and connected by polyethylene glycol (PEG) or alkyl chains through covalent bonds. The bottom-up fabrication of these CCOFs is achieved by the condensation of cross-linked aldehyde monomers and tritopic amino monomers. All the synthesized CCOFs possess high crystallinity and porosity, and enhanced structural robustness surpassing the typical 2D COFs, which means that they cannot be exfoliated under ultrasonication and grinding due to the cross-linking effect. Furthermore, the cross-linked patterns of PEG units are uncovered by experimental results and Monte Carlo molecular dynamics simulations. It is found that all CCOFs are dominated by vertical cross-layer (interlayer) connections (clearly observed in high-resolution transmission electron microscopy images), allowing them to form quasi-three-dimensional (quasi-3D) structures. This work bridges the gap between 2D COFs and 3D COFs and provides an efficient way to improve the interlayered stability of COFs.

Fluorine-Containing Covalent Organic Frameworks: Synthesis and Application.

Covalent organic frameworks (COFs) are a type of crystalline porous polymers that possess ordered structures and eternal pores. Because of their unique structural characteristics and diverse functional groups, COFs have been used in various application fields, such as adsorption, catalysis, separation, ion conduction, and energy storage. Among COFs, the fluorine-containing COFs (fCOFs) have been developed for special applications by virtue of special physical and chemical properties resulting from fluorine element, which is a nonmetallic halogen element and possesses strong electronegativity. In the organic chemistry field, introducing fluorine into chemicals enables those chemicals to exhibit many interesting properties, and fluorine chemistry increasingly plays an important role in the history of chemical development. The introduction of fluorine in COFs can enhance the crystallinity, porosity, and stability of COFs, making COFs having superior performances and some new applications. In this review, the synthesis and application of fCOFs are systematically summarized. The application involves photocatalytic production of hydrogen peroxide, photocatalytic water splitting, electrocatalytic CO2 reduction, adsorption for different substances (H2 , pesticides, per-/polyfluoroalkyl substances, polybrominated diphenyl ethers, bisphenols, and positively charged organic dye molecules), oil-water separation, energy storage (e.g., zinc-ion batteries, lithium-sulfur batteries), and proton conduction. Perspectives of remaining challenges and possible directions for fCOFs are also discussed.

An imine-linked covalent organic framework for renewable and sensitive determination of antibiotic

Lanthanide-functionalized porous organic materials have been the promising candidates in the chemical and biological sensing. Considering the superior thermal and solvent stability of covalent organic frameworks (COFs), the development of lanthanide ions-functionalized COFs based sensing platform is meaningful, while remains to be a challenge. In this work, a new imine-linked COF which provides suitable coordination sites for Tb3+ was constructed via the Schiff base reaction between P-phenylenediamine (Pda) and 2,6-Diformylpyridine (Dfp). Benefiting from its high signal-to-noise, the COF@Tb shows excellent ability to determinate ciprofloxacin (CIP) with a detection limit of 3.01 nM. The measurement can maintain good stability in the presence of potential interference or in actual sample. Being washed with ethanol after each measurement, COF@Tb can be recycled for five times. This work provides a novel alternative strategy for efficient construction of lanthanide-grafted COFs and may promote the development of porous organic materials based chemical sensing.

Light-Driven Hydrogen Evolution Assisted by Covalent Organic Frameworks

Covalent organic frameworks (COFs) are crystalline porous organic polymers built from covalent organic blocks that can be photochemically active when incorporating organic semiconducting units, such as triazine rings or diacetylene bridges. The bandgap, charge separation capacity, porosity, wettability, and chemical stability of COFs can be tuned by properly choosing their constitutive building blocks, by extension of conjugation, by adjustment of the size and crystallinity of the pores, and by synthetic post-functionalization. This review focuses on the recent uses of COFs as photoactive platforms for the hydrogen evolution reaction (HER), in which usually metal nanoparticles (NPs) or metallic compounds (generally Pt-based) act as co-catalysts. The most promising COF-based photocatalytic HER systems will be discussed, and special emphasis will be placed on rationalizing their structure and light-harvesting properties in relation to their catalytic activity and stability under turnover conditions. Finally, the aspects that need to be improved in the coming years will be discussed, such as the degree of dispersibility in water, the global photocatalytic efficiency, and the robustness and stability of the hybrid systems, putting emphasis on both the COF and the metal co-catalyst.

An Ultrastable Crystalline Acylhydrazone-Linked Covalent Organic Framework for Efficient Removal of Organic Micropollutants from Water.

As an important member of crystalline porous polymers, acylhydrazone-linked covalent organic frameworks (COFs) have gained much attention in recent years. However, the low structural stability imparts a limit on their practical applications. To tackle this problem, we report a simple strategy to increase the chemical stability of acylhydrazone-linked COFs by incorporating azobenzene groups in the conjugated framework. Through reinforcing the π-π stacking interactions between the adjacent layers with increased π-surface, it is surprising to find that the resulting materials exhibit extreme stability in harsh environments, such as in strong acid, strong base, aqueous educing agent and boiling water, even exposed to air for one year. As a proof-of-concept, such frameworks have been used to remove various organic micropollutants such as antibiotics, plastic components, endocrine disruptors, and carcinogens from water with high capacity, fast speed and excellent reusability over a wide pH range at environmentally relevant concentrations. The results provide a new avenue to significantly enhance the stability of COFs for practical applications.

Robust crystalline aromatic imide-linked two-dimensional covalent organic frameworks confining ruthenium nanoparticles as efficient hydrogen evolution electrocatalyst

The hydrogen evolution reaction (HER) is the crucial step in electrochemical water splitting. To succeed in real applications, one of the major challenges faced by HER is the development of robust and efficiency electrocatalysts. Herein, robust highly crystalline aromatic imide-based two-dimensional covalent organic frameworks (COFs) were prepared through a high temperature solvothermal process, taking advantage of the uniform pore size and specialized pore environment, efficient HER catalyst Cryst-2D-PMPI-Ru were synthesized in which ruthenium (Ru) nanoclusters are uniform dispersed with small particle size (less than 2 nm). In alkaline media, Cryst-2D-PMPI-Ru requires overpotential of only 35.1 mV to afford a current density of 10 mA/cm2, which outperforms the benchmark 20% Pt/C catalyst (37.3 mV). The excellent performance of was presumably attributed to the uniform and ultrasmall Ru nanoclusters with a satisfied dispersion, which provides the massive active sites for HER. In acid solution, the overpotential of Cryst-2D-PMPI-Ru (55.3 mV) is close to Pt/C (40.3 mV). The Tafel slope of PMDA/MA-Ru-180-800 is 36.5 mV/dec and the mechanism of the reaction is of the Volmer-Heyrovsky type. Besides, compared with their counterpart with low degree of crystllinity, the Cryst-2D-PMPI-Ru electrocatalyst also exhibits superior performance stability due to the stability of COF. The results provide important evidence that high crystallinity and robust aromatic structure of the polymeric frameworks precursors can substantially enhance their electrocatalytic performance and stability.

Crystallinity and stability of covalent organic frameworks

Covalent organic frameworks (COFs) are a class of organic porous polymers with high crystallinity, and their structures can be precisely tailored via topology design. Owing to the characteristics of permanent pores, periodic structures and rich building blocks, COFs have triggered tremendous attention in the past fifteen years and are extensively investigated in various fields. Crystallinity and stability are two crucial features for practical applications. In general, these two features are contradictory for COFs formed via dynamic covalent chemistry (DCC). High thermodynamic reversibility is usually required to attain exceptional crystallinity of COFs, often resulting in limited stability. The first two reported COFs are based on the boroxine and boronate ester linkages, which are unstable in water and even in humid conditions. Therefore, many researchers doubt the stability of COFs for real applications. Actually, in these years, various novel linkages have been developed for the construction of COFs, and numerous newly synthesized COFs are robust towards strong acid/base and even some of them can resist the attack of strong oxidizing and reducing agents. In this review, we focus on the linkage chemistry of the COFs in terms of crystallinity and stability, further extending it to the investigation in the mechanisms of the crystal growth and the overall regulation of the contradiction between stability and crystallinity. The strategies for improving the crystallinity, including selecting building units, introducing non-covalent interactions and slowing nucleation and growth rate, are described in the third section, while the methodologies for increasing the stability from the viewpoints of chemical modification and non-covalent interactions are summarized in the fourth section. Finally, the challenges and perspectives are presented.

In situ growth of COF-rLZU1 on the surface of silica sphere as stationary phase for high performance liquid chromatography

The composite materials consist of Covalent Organic Frameworks (COFs) and silica have been regarded as a kind of promising stationary phases due to combination of the large specific surface area and good mechanical strength of porous silica microspheres and the porous structure and the excellent stability of COFs. Herein, a novel COFs-silica composite (SiO2@rLZU1, reduced Lan Zhou University-1) was prepared via an in-situ growth strategy with a 32 nm-thick COFs layer on the surface of silica and a 2.2 nm-thick COFs layer on the inner surface of the mesopores of spherical silica (5 μm, 120 Å). With secondary amine and phenyl groups, the novel stationary phase provided hydrophilic, hydrophobic and π-π interactions when used in HPLC, showing different selectivity from typical reversed-phase stationary phases. Probe molecules with aromatic moieties varying in polarity, including acidic (phenol, pyrocatechol, and pyrogallol), basic (aniline, 4-chloroaniline, and 4-nitroaniline) and neutral (benzene homologues) compounds, were all baseline separated on the SiO2@rLZU1 column, indicating its excellent separation performance. Besides, the SiO2@rLZU1 column also exhibited great repeatability with intraday RSDs of the retention time of three anilines less than 0.31% (n = 6) and peak area less than 1.63% (n = 6). On the SiO2@rLZU1 column, satisfied results were achieved in the separation of real samples such as fullerenes and coking wastewater, suggesting the great potential of the as-synthesized stationary phase in HPLC applications.

Cyanine-Assisted Exfoliation of Covalent Organic Frameworks in Nanocomposites for Highly Efficient Chemo-Photothermal Tumor Therapy.

Covalent organic frameworks (COFs) have received considerable interest because of their advanced applications. However, their low dispersibility and aqueous stability are intractable issues limiting their biomedical application. To address the issue, water-dispersible nanocomposites (COF@IR783) produced through the assembly of cyanines and COFs are proposed and prepared. Therefore, a strategy of "killing three birds with one stone" is developed. First, the nanocomposites exhibit superior dispersibility and aqueous stability compared to COFs. The nanocomposites have a nanosized morphology and negative charges, which are in favor of improving the blood circulation and enhanced permeability and retention-mediated tumor-targeting delivery therapy for in vivo application. Second, the nanocomposites have enhanced photothermal therapy (PTT) ability in the near-infrared region compared to cyanines. The nanocomposites also have a photoacoustic imaging ability, which can guide the antitumor therapy in vivo. Lastly, the nanocomposites can be further used as drug-delivery carriers for loading the anticancer cis-aconityl-doxorubicin (CAD) prodrug. In comparison with individual PTT or chemotherapy, the combination of PTT and chemotherapy achieved with COF@IR783@CAD synergistically induced the death of cancer cells in vitro, and an intravenous injection of COF@IR783@CAD in mice resulted in significant tumor ablation. This work indicates that the dispersibility and aqueous stability of COFs can be appropriately overcome through a rational design and can further expand the biomedical applications of COFs.

Hydrolytic Stability of Boronate Ester‐Linked Covalent Organic Frameworks

AbstractThe stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester‐linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron‐deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester‐linked COF‐5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4‐phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF‐5 crystals.

Hydrogen adsorption sites and energies in 2D and 3D covalent organic frameworks

Covalent organic frameworks (COF) are nano porous structures constructed solely from strong covalent bonds. Due to the high thermal stability, very low density and high surface area, they generate significant interest for their potential application as hydrogen storage materials. Molecular dynamics simulations were applied to check the stability of COFs under hydrogen pressure and to determine the position of preferential hydrogen sites in 2D and 3D COFs. We find that the most favoured adsorption site of H2 is on benzene rings in the organic linkers as well as the H2 can adsorb near boron–oxygen networks. The adsorption interaction energy for COFs is found to be ∼3.0kJ/mol.