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Covalent organic frameworks (COFs) are highly promising as heterogeneous photocatalysts due to their tunable structures and optoelectronic properties. Though COFs have been used as heterogeneous photocatalysts, they have mainly been employed in water splitting, carbon dioxide reduction, and hydrogen evolution reactions. A few examples in organic synthesis using metal-anchored COF photocatalysts were reported. Herein, we report highly stable ß-keto-enamine-based COFs as photocatalysts for metal-free C-B bond formation reactions. Three different COFs have been availed for this purpose. Their photocatalysis performances have been monitored for 12 different substrates, like quinolines, pyridines, and pyrimidines. All the COFs showcase moderate-to-high yields (up to 96%) depending upon the substrate's molecular functionality. High crystallinity, a large surface area, a low band gap, and a suitable band position result in the highest catalytic activity of TpAzo COF. The thorough mechanistic investigation further highlights the crucial role of light-harvesting capacity, charge separation efficiency, and current density during catalysis. The light absorbance capacity of the COF plays a critical role during catalysis as yields are maximized near the COF's absorption maxima. The high photostability of the as-synthesized COFs offers their reusability for several (>5) catalytic cycles.
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Few-layer organic nanosheets are becoming increasingly attractive as two-dimensional (2D) materials due to their precise atomic connectivity and tailor-made pores. However, most strategies for synthesizing nanosheets rely on surface-assisted methods or top-down exfoliation of stacked materials. A bottom-up approach with well-designed building blocks would be the convenient pathway to achieve the bulk-scale synthesis of 2D nanosheets with uniform size and crystallinity. Herein, we have synthesized crystalline covalent organic framework nanosheets (CONs) by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines. The bent geometry of thianthrene in THT retards the out-of-plane stacking, while the flexible diamines introduce dynamic characteristics into the framework, facilitating nanosheet formation. Successful isoreticulation with five diamines with two to six carbon chain lengths generalizes the design strategy. Microscopic imaging reveals that the odd and even diamine-based CONs transmute to different nanostructures, such as nanotubes and hollow spheres. The single-crystal X-ray diffraction structure of repeating units indicates that the odd-even linker units of diamines introduce irregular-regular curvature in the backbone, aiding such dimensionality conversion. Theoretical calculations shed more light on nanosheet stacking and rolling behavior with respect to the odd-even effects.
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Water has been recognized as an excellent solvent for maneuvering both the catalytic activity and selectivity, especially in the case of heterogeneous catalysis. However, maintaining the active catalytic species in their higher oxidation states (IV/V) while retaining the catalytic activity and recyclability in water is an enormous challenge. Herein, we have developed a solution to this problem using covalent organic frameworks (COFs) to immobilize the (Et4N)2[FeIII(Cl)bTAML] molecules, taking advantage of the COF's morphology and surface charge. By using the visible light and [CoIII(NH3)5Cl]Cl2 as a sacrificial electron acceptor within the COF, we have successfully generated and stabilized the [(bTAML)FeIV-O-FeIV(bTAML)]- species in water. The COF backbone simultaneously acts as a porous host and a photosensitizer. This is the first time that the photochemically generated Fe2IV-µ-oxo radical cation species has demonstrated high catalytic activity with moderate to high yield for the selective oxidation of the unactivated C-H bonds, even in water. To enhance the catalytic activity and achieve good recyclability, we have developed a TpDPP COF film by transforming the TpDPP COF nanospheres. We have achieved the regio- and stereoselective functionalization of unactivated C-H bonds of alkanes and alkenes (3°:2° = 102:1 for adamantane with the COF film), which is improbable in homogeneous conditions. The film exhibits C-H bond oxidation with higher catalytic yield (32-98%) and a higher degree of selectivity (cis/trans = 74:1; 3°:2° = 100:1 for cis-decalin).
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Covalent organic nanotubes (CONTs) are porous one-dimensional frameworks connected through imine bonds via Schiff base condensation between aldehydes and amines. The presence of two amine groups at the ortho position in the structurally demanding tetraaminotriptycene (TAT) building block leads to multiple reaction pathways between the ditopic aldehyde and the tetratopic amine. We have synthesized five different monomers of CONT-1 by the Schiff base condensation reaction between TAT and o-anisaldehyde. The conversion of imine to imidazole bonding in a monomer is probed using NMR, mass spectrometry, and X-ray diffraction techniques. Solid-state NMR provide insights into the CONTs' structural connectivity. A theoretical investigation suggests that the π-π stacking could be the driving force for rapid imine to imidazole conversion within the CONT-1. Microscopic imaging sheds further light on the self-assembly process of the CONTs, indicating both head-to-head and side-by-side assembly.
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The future of water-derived hydrogen as the "sustainable energy source" straightaway bets on the success of the sluggish oxygen-generating half-reaction. The endeavor to emulate the natural photosystem II for efficient water oxidation has been extended across the spectrum of organic and inorganic combinations. However, the achievement has so far been restricted to homogeneous catalysts rather than their pristine heterogeneous forms. The poor structural understanding and control over the mechanistic pathway often impede the overall development. Herein, we have synthesized a highly crystalline covalent organic framework (COF) for chemical and photochemical water oxidation. The interpenetrated structure assures the catalyst stability, as the catalyst's performance remains unaltered after several cycles. This COF exhibits the highest ever accomplished catalytic activity for such an organometallic crystalline solid-state material where the rate of oxygen evolution is as high as â¼26,000 µmol L-1 s-1 (second-order rate constant k ≈ 1650 µmol L s-1 g-2). The catalyst also proves its exceptional activity (k ≈ 1600 µmol L s-1 g-2) during light-driven water oxidation under very dilute conditions. The cooperative interaction between metal centers in the crystalline network offers 20-30-fold superior activity during chemical as well as photocatalytic water oxidation as compared to its amorphous polymeric counterpart.
Assuntos
Estruturas Metalorgânicas , Água , Hidrogênio , Oxigênio/química , Complexo de Proteína do Fotossistema II/química , Água/químicaRESUMO
Covalent organic nanotubes (CONTs) are one-dimensional porous frameworks constructed from organic building blocks via dynamic covalent chemistry. CONTs are synthesized as insoluble powder that restricts their potential applications. The judicious selection of 2,2'-bipyridine-5,5'-dicarbaldehyde and tetraaminotriptycene as building blocks for TAT-BPy CONTs has led to constructing flexible yet robust and self-standing fabric up to 3 µm thickness. The TAT-BPy CONTs and TAT-BPy CONT fabric have been characterized by solid-state one-dimensional (1D) 13C CP-MAS, two-dimensional (2D) 13C-1H correlation NMR, 2D 1H-1H DQ-SQ NMR, and 2D 14N-1H correlation NMR spectroscopy. The mechanism of fabric formation has been established by using high-resolution transmission electron microscopy and scanning electron microscopy techniques. The as-synthesized viscoelastic TAT-BPy CONT fabric exhibits high mechanical strength with a reduced modulus (Er) of 8 (±3) GPa and hardness (H) of 0.6 (±0.3) GPa. Interestingly, the viscoelastic fabric shows time-dependent elastic depth recovery up to 50-70%.
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Heterogeneous catalysis in water has not been explored beyond certain advantages such as recyclability and recovery of the catalysts from the reaction medium. Moreover, poor yield, extremely low selectivity, and active catalytic site deactivation further underrate the heterogeneous catalysis in water. Considering these facts, we have designed and synthesized solution-dispersible porous covalent organic framework (COF) nanospheres. We have used their distinctive morphology and dispersibility to functionalize unactivated C-H bonds of alkanes heterogeneously with high catalytic yield (42-99%) and enhanced regio- and stereoselectivity (3°:2° = 105:1 for adamantane). Further, the fabrication of catalyst-immobilized COF nanofilms via covalent self-assembly of catalytic COF nanospheres for the first time has become the key toward converting the catalytically inactive homogeneous catalysts into active and effective heterogeneous catalysts operating in water. This unique covalent self-assembly occurs through the protrusion of the fibers at the interface of two nanospheres, transmuting the catalytic spheres into films without any leaching of catalyst molecules. The catalyst-immobilized porous COF nanofilms' chemical functionality and hydrophobic environment stabilize the high-valent transient active oxoiron(V) intermediate in water and restricts the active catalytic site's deactivation. These COF nanofilms functionalize the unactivated C-H bonds in water with a high catalytic yield (45-99%) and with a high degree of selectivity (cis:trans = 155:1; 3°:2° = 257:1, for cis-1,2-dimethylcyclohexane). To establish this approach's "practical implementation", we conducted the catalysis inflow (TON = 424 ± 5) using catalyst-immobilized COF nanofilms fabricated on a macroporous polymeric support.
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The induction of macro and mesopores into two-dimensional porous covalent organic frameworks (COFs) could enhance the exposure of the intrinsic micropores toward the pollutant environment, thereby, improving the performance. However, the challenge is to build a continuous hierarchically porous macro-architecture of crystalline organic materials in the bulk scale. In this regard, we have strategized a novel synthetic method to create hierarchically porous COF foams consisting of ordered micropores (2-2.2 nm) and disordered meso and macropores (50 nm to 200 µm) as well as ordered macropores (1.5 mm to 2 cm). Herein, graphene oxide was used for creating disordered macro and mesopores in COF-GO foams. Considering the rheological features of the precursor hydrogel, we could integrate crystalline and porous COF-GO foams into self-supported three-dimensional (3D)-printed objects with the desired shapes and sizes. Therefore, we have engineered the 3D macro-architecture of COF-GO foams into complex geometries keeping their structural order and continuous porosity intact over a range of more than a million (10-9 m to 10-3 m). The interconnected 3D openings in these COF-GO foams further enhance the rapid and efficient uptake of organic and inorganic pollutants from water (>95% removal within 30 s). The abundant distribution of interconnected macroporous volume (55%) throughout the COF-GO foam matrix enhances the flow of water (1.13 × 10-3 m·s-1) which results in efficient mass transport and adsorption.
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The key factor responsible for fast diffusion and mass transfer through a porous material is the availability of a widely open pore interior having complete accessibility from their surface. However, because of their highly stacked nature, ordered two-dimensional (2D) materials fail to find real-world applicability, as it is difficult to take advantage of their complete structure, especially the inner cores. In this regard, three-dimensional (3D) nanostructures constructed from layered two-dimensional crystallites could prove to be advantageous. However, the real challenge is to cultivate a porous nanostructure with ordered pores where the pores are surrounded by crystalline walls. Herein, a simple yet versatile in situ gas-phase foaming technique has been employed to address these cardinal issues. The use of baking soda leads to the continuous effervescence of CO2 during the crystallization of foam, which creates ripples and fluctuations on the surface of the 2D crystallites. The induction of ordered micropores within the disordered 3D architecture synergistically renders fast diffusion of various guests through the interconnected pore network. The high-density defects in the hierarchically porous structure help in ultrafast adsorption (<10 s) of various pollutants (removal efficiency of 99%) from water, all of which would lead to significant environmental benefit. The pseudo-second-order rate constant for the BPA pollutant is 182.3 g mg-1 min-1, which is the highest among all the literature reports to date. The high removal efficiency (highest efficiency of 94% and average efficiency of 70%) of a persistent organic pollutant has been attended for the first time.
Assuntos
Estruturas Metalorgânicas/química , Nanoestruturas/química , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Microscopia Confocal , Estrutura Molecular , Tamanho da Partícula , Porosidade , Propriedades de Superfície , Poluentes Químicos da Água/químicaRESUMO
The reaction of SIPr, [1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1), with C6 F6 led to the formation of an unprecedented mesoionic compound (2). The formation of 2 is made accessible by deprotonation of the SIPr backbone with simultaneous elimination of HF. The C-F bond para to the imidazolium ring in 2 is only of 1.258(4)â Å, which is the one of the shortest structurally authenticated C-F bonds known to date. The liberation of HF during the reaction is unequivocally proved by the addition of one more equivalent of SIPr, which leads to the imidazolium salt with the HF2 - anion. To functionalize 2, the latter reacted with B(C6 F5 )3 to give an unusual donor-acceptor compound, where the fluoride atom from the C6 F5 moiety coordinates to B(C6 F5 )3 and the carbanion moiety remains unaffected. Such coordination susceptibility of the fluoride atom of a nonmetallic system to a main-group Lewis acid (Fnon-metal âBR3 ) is quite unprecedented.
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Porous solids that can be switched between different forms with distinct physical properties are appealing candidates for separation, catalysis, and host-guest chemistry. In this regard, porous organic cages (POCs) are of profound interest because of their solution-state accessibility. However, the application of POCs is limited by poor chemical stability. Synthesis of an exceptionally stable imine-linked (4+6) porous organic cage (TpOMe-CDA) is reported using 2,4,6-trimethoxy-1,3,5-triformyl benzene (TpOMe) as a precursor aldehyde. Introduction of the -OMe functional group to the aldehyde creates significant steric and hydrophobic characteristics in the environment around the imine bonds that protects the cage molecules from hydrolysis in the presence of acids or bases. The electronic effect of the -OMe group also plays an important role in enhancing the stability of the reported POCs. As a consequence, TpOMe-CDA reveals exceptional chemical stability in neutral, acidic and basic conditions, even in 12 m NaOH. Interestingly, TpOMe-CDA exists in three different porous and non-porous polymorphic forms (α, ß, and γ) with respect to differences in crystallographic packing and the orientation of the flexible methoxy groups. All of the polymorphs retain their crystallinity even after treatment with acids and bases. All the polymorphs of TpOMe-CDA differ significantly in their properties as well as morphology and could be reversibly switched in the presence of an external stimulus.
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Easy and bulk-scale syntheses of two-dimensional (2D) covalent organic frameworks (COFs) represent an enduring challenge in material science. Concomitantly, the most critical aspect is to precisely control the porosity and crystallinity of these robust structures. Disparate complementary approaches such as solvothermal synthesis have emerged recently and are fueled in part by the usage of different modulators and acids that have enriched the COF library. Yet, the fundamental understanding of the integral processes of 2D COF assembly, including their growth from nucleating sites and the origin of periodicity, is an intriguing chemical question that needs to be answered. To address these cardinal questions, a green and easy-to-perform approach of COF formation has been delineated involving acid-diamine salt precursors. The role of hydrogen bonding [ dav(Namine-H···Oacid); dav signifies the average Namine-H···Oacid distances, i.e., the average distance from the H atom of the amine to the O atom of the acid] present in the acid-diamine salts in improving the COFs' crystallinity and porosity has further been decoded by thorough crystallographic analyses of the salt molecules. What is particularly noteworthy is that we have established the hydrogen-bonding distances dav(Namine-H···Oacid) in the acid-diamine salts that are pivotal in maintaining the reversibility of the reaction, which mainly facilitates highly crystalline and porous COF formation. Moreover, this reactant-structure to the product-quality relationship has further been utilized for the synthesis of highly crystalline and porous COFs that are unattainable by other synthetic means.
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Covalent organic frameworks (COFs) have emerged as promising electrode materials in supercapacitors (SCs). However, their insoluble powder-like nature, poor capacitive performance in pristine form, integrated with inferior electrochemical stability is a primary concern for their long-term use in electrochemical devices. Keeping this in perspective, herein we report a redox active and hydrogen bonded COF with ultrahigh stability in conc. H2SO4 (18 M), conc. HCl (12 M) and NaOH (9 M). The as-synthesized COF fabricated as thin sheets were efficiently employed as a free-standing supercapacitor electrode material using 3 M aq. H2SO4 as an electrolyte. Moreover, the pristine COF sheet showcased outstanding areal capacitance 1600 mF cm-2 (gravimetric 169 F g-1) and excellent cyclic stability (>100â¯000) without compromising its capacitive performance or Coulombic efficiency. Moreover, as a proof-of-concept, a solid-state supercapacitor device was also assembled and subsequently tested.
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A rapid and scalable synthesis of six new imine-linked highly porous and crystalline COFs is presented that feature exceptionally high chemical stability in harsh environments including conc. H2 SO4 (18 m), conc. HCl (12 m), and NaOH (9 m). This is because of the presence of strong interlayer C-Hâ â â N hydrogen bonding among the individual layers, which provides significant steric hindrance and a hydrophobic environment around the imine (-C=N-) bonds, thus preventing their hydrolysis in such an abrasive environment. These COFs were further converted into porous, crystalline, self-standing, and crack-free COF membranes (COFMs) with extremely high chemical stability for their potential applications for sulfuric acid recovery. The as-synthesized COFMs exhibit unprecedented permeance for acetonitrile (280â Lm-2 h-1 bar-1 ) and acetone (260â Lm-2 h-1 bar-1 ).
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Poor mechanical stability of the polymer electrolyte membranes remains one of the bottlenecks towards improving the performance of the proton exchange membrane (PEM) fuel cells. The present work proposes a unique way to utilize crystalline covalent organic frameworks (COFs) as a self-standing, highly flexible membrane to further boost the mechanical stability of the material without compromising its innate structural characteristics. The as-synthesized p-toluene sulfonic acid loaded COF membranes (COFMs) show the highest proton conductivity (as high as 7.8×10-2 â S cm-1 ) amongst all crystalline porous organic polymeric materials reported to date, and were tested under real PEM operating conditions to ascertain their practical utilization as proton exchange membranes. Attainment of 24â mW cm-2 power density, which is the highest among COFs and MOFs, highlights the possibility of using a COF membrane over the other state-of-the-art crystalline porous polymeric materials reported to date.
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Research on covalent organic frameworks (COFs) has recently gathered significant momentum by the virtue of their predictive design, controllable porosity, and long-range ordering. However, the lack of solvent-free and easy-to-perform synthesis processes appears to be the bottleneck toward their greener fabrication, thereby limiting their possible potential applications. To alleviate such shortcomings, we demonstrate a simple route toward the rapid synthesis of highly crystalline and ultraporous COFs in seconds using a novel salt-mediated crystallization approach. A high degree of synthetic control in interlayer stacking and layer planarity renders an ordered network with a surface area as high as 3000 m2 g-1. Further, this approach has been extrapolated for the continuous synthesis of COFs by means of a twin screw extruder and in situ processes of COFs into different shapes mimicking the ancient terracotta process. Finally, the regular COF beads are shown to outperform the leading zeolites in water sorption performance, with notably facile regeneration ability and structural integrity.
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Translating the performance of covalent organic frameworks (COFs) from laboratory to macroscopic reality demands specific morphologies. Thus, the advancement in morphological modulation has recently gained some momentum. A clear understanding of nano- to macroscopic architecture is critical to determine, optimize, and improve performances of this atomically precise porous material. Along with their chemical compositions and molecular frameworks, the prospect of morphology in various applications should be discussed and highlighted. A thorough insight into morphology versus application will help produce better-engineered COFs for practical implications. 2D and 3D frameworks can be transformed into various solids such as nanospheres, thin films, membranes, monoliths, foams, etc., for numerous applications in adsorption, separation photocatalysis, the carbon dioxide reduction, supercapacitors, and fuel cells. However, the research on COF chemistry mainly focuses on correlating structure to property, structure to morphology, and structure to applications. Here, critical insights on various morphological evolution and associated applications are provided. In each case, the underlying role of morphology is unveiled. Toward the end, a correlation between morphology and application is provided for the future development of COFs.
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Carbon nanotubes, and synthetic organic nanotubes more generally, have in recent decades been widely explored for application in electronic devices, energy storage, catalysis and biosensors. Despite noteworthy progress made in the synthesis of nanotubular architectures with well-defined lengths and diameters, purely covalently bonded organic nanotubes have remained somewhat challenging to prepare. Here we report the synthesis of covalently bonded porous organic nanotubes (CONTs) by Schiff base reaction between a tetratopic amine-functionalized triptycene and a linear dialdehyde. The spatial orientation of the functional groups promotes the growth of the framework in one dimension, and the strong covalent bonds between carbon, nitrogen and oxygen impart the resulting CONTs with high thermal and chemical stability. Upon ultrasonication, the CONTs form intertwined structures that go on to coil and form toroidal superstructures. Computational studies give some insight into the effect of the solvent in this assembly process.
Assuntos
Técnicas Biossensoriais , Nanotubos de Carbono , Aminas , Catálise , Nanotubos de Carbono/química , PorosidadeRESUMO
Flexible supercapacitors in modern electronic equipment require light-weight electrodes, which have a high surface area, precisely integrated redox moieties, and mechanically strong flexible free-standing nature. However, the incorporation of the aforementioned properties into a single electrode remains a great task. Herein, we could overcome these challenges by a facile and scalable synthesis of the convergent covalent organic framework (COF) free-standing flexible thin sheets through solid-state molecular baking strategy. Here, redox-active anthraquinone (Dq) and π-electron-rich anthracene (Da) are judiciously selected as two different linkers in a ß-ketoenamine-linked two-dimensional (2D) COF. As a result of precisely integrated anthraquinone moieties, COF thin sheet exhibits redox activity. Meanwhile, π-electron-rich anthracene linker assists to improve the mechanical property of the free-standing thin sheet through the enhancement of noncovalent interaction between crystallites. This binder-free strategy offers the togetherness of crystallinity and flexibility in 2D COF thin sheets. Also, the synthesized porous crystalline convergent COF thin sheets are benefited with crack-free uniform surface and light-weight nature. Further, to demonstrate the practical utility of the material as an electrode in energy-storage systems, we fabricated a solid-state symmetrical flexible COF supercapacitor device using a GRAFOIL peeled carbon tape as the current collector.
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The remarkable effect of anions on the transition from supramolecular gels to crystalline phases has been described. An amino acid-based metallohydrogel was transformed into different metal-organic frameworks through the selective picking of anions. The metallohydrogel and the resulting metal-organic frameworks (MOFs) were thoroughly characterized. The results demonstrated controlled access over the binding of a particular anion to selectively form a particular MOF.