Rigid Nanoporous Urea-Based Covalent Triazine Frameworks for C2/C1 and CO2/CH4 Gas Separation.
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ABSTRACT:
SUBMITTER: Krishnaraj C
PROVIDER: S-EPMC8235060 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Covalent triazine frameworks (CTFs) are a class of organic polymer materials constructed by aromatic 1,3,5-triazine rings with planar π-conjugation properties. CTFs are highly stable and porous with N atoms in the frameworks, possessing semiconductive properties; thus they are widely used in gas adsorption and separation as well as catalysis. The properties of CTFs strongly depend on the type of monomers and the synthesis process. Synthesis methods including ionothermal polymerization, amino-aldehyde synthesis, trifluoromethanesulfonic acid catalyzed synthesis, and aldehyde-amidine condensation have been intensively studied in recent years. In this review, we discuss the recent advances and future developments of CTFs synthesis.
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Project description:Covalent triazine frameworks (CTFs) are normally synthesized by ionothermal methods. The harsh synthetic conditions and associated limited structural diversity do not benefit for further development and practical large-scale synthesis of CTFs. Herein we report a new strategy to construct CTFs (CTF-HUSTs) via a polycondensation approach, which allows the synthesis of CTFs under mild conditions from a wide array of building blocks. Interestingly, these CTFs display a layered structure. The CTFs synthesized were also readily scaled up to gram quantities. The CTFs are potential candidates for separations, photocatalysis and for energy storage applications. In particular, CTF-HUSTs are found to be promising photocatalysts for sacrificial photocatalytic hydrogen evolution with a maximum rate of 2647 μmol h-1 g-1 under visible light. We also applied a pyrolyzed form of CTF-HUST-4 as an anode material in a sodium-ion battery achieving an excellent discharge capacity of 467 mAh g-1 .
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Project description:Herein, we report the first synthesis of covalent triazine-based frameworks (CTFs) based on a hexanitrile monomer, namely the novel pseudo-octahedral hexanitrile 1,4-bis(tris(4'-cyano-phenyl)methyl)benzene 1 using both ionothermal reaction conditions with ZnCl2 at 400 °C and the milder reaction conditions with the strong Brønsted acid trifluoromethanesulfonic acid (TFMS) at room temperature. Additionally, the hexanitrile was combined with different di-, tri-, and tetranitriles as a second linker based on recent work of mixed-linker CTFs, which showed enhanced carbon dioxide captures. The obtained framework structures were characterized via infrared (IR) spectroscopy, elemental analysis, scanning electron microscopy (SEM), and gas sorption measurements. Nitrogen adsorption measurements were performed at 77 K to determine the Brunauer-Emmett-Teller (BET) surface areas range from 493 m2/g to 1728 m2/g (p/p0 = 0.01-0.05). As expected, the framework CTF-hex6 synthesized from 1 with ZnCl2 possesses the highest surface area for nitrogen adsorption. On the other hand, the mixed framework structure CTF-hex4 formed from the hexanitrile 1 and 1,3,5 tricyanobenzene (4) shows the highest uptake of carbon dioxide and methane of 76.4 cm3/g and 26.6 cm3/g, respectively, at 273 K.
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Project description:Covalent triazine frameworks have recently been demonstrated as promising materials for photocatalytic water splitting and are usually used in the form of suspended powder. From a practical point of view, immobilized CTFs materials are more suitable for large-scale water splitting, owing to their convenient separation and recycling potential. However, existing synthetic approaches mainly result in insoluble and unprocessable powders, which make their future device application a formidable challenge. Herein, we report an aliphatic amine-assisted interfacial polymerization method to obtain free-standing, semicrystalline CTFs film with excellent photoelectric performance. The lateral size of the film was up to 250 cm2, and average thickness can be tuned from 30 to 500 nm. The semicrystalline structure was confirmed by high-resolution transmission electron microscope, powder X-ray diffraction, grazing-incidence wide-angle X-ray scattering, and small-angle X-ray scattering analysis. Intrigued by the good light absorption, crystalline structure, and large lateral size of the film, the film immobilized on a glass support exhibited good photocatalytic hydrogen evolution performance (5.4 mmol h-1 m-2) with the presence of co-catalysts i.e., Pt nanoparticles and was easy to recycle.
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Project description:Chromoselective photocatalysis offers an intriguing opportunity to enable a specific reaction pathway out of a potentially possible multiplicity for a given substrate by using a sensitizer that converts the energy of incident photon into the redox potential of the corresponding magnitude. Several sensitizers possessing different discrete redox potentials (high/low) upon excitation with photons of specific wavelength (short/long) have been reported. Herein, we report design of molecular structures of two-dimensional amorphous covalent triazine-based frameworks (CTFs) possessing intraband states close to the valence band with strong red edge effect (REE). REE enables generation of a continuum of excited sites characterized by their own redox potentials, with the magnitude proportional to the wavelength of incident photons. Separation of charge carriers in such materials depends strongly on the wavelength of incident light and is the primary parameter that defines efficacy of the materials in photocatalytic bromination of electron rich aromatic compounds. In dual Ni-photocatalysis, excitation of electrons from the intraband states to the conduction band of the CTF with 625 nm photons enables selective formation of C‒N cross-coupling products from arylhalides and pyrrolidine, while an undesirable dehalogenation process is completely suppressed.
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Project description:The development of covalent organic frameworks (COFs) with nodes and spacers, designed to maximize their functional properties, is a challenge. Triazines exhibit better electron affinity than benzene-based aromatic rings; therefore, structures based on 1,3,5-substituted triazine-centered nodes are more stable than those from 1,3,5-benzene-linked COFs. Compared to COFs prepared from flat, rigid sp2 carbon-linked triazine nodes, the O-linked flexible tripodal triazine-based COF demonstrates several unpredictable properties such as an increase in crystallinity and cavity size. In this study, the COF prepared from O-linked flexible 2,4,6-tris(p-formylphenoxy)-1,3,5-triazine serves as an excellent absorbent for removing methylene blue from water. Our results demonstrate that COF is highly stable in water and functions as a robust adsorbent. Its adsorption isotherm is consistent with the Langmuir model and its adsorption kinetics follows a pseudo-second order model. Moreover, the COF was characterized using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, solid-state ultraviolet-visible spectroscopy, and X-ray diffraction. It exhibited permanent porosity, a high specific surface area (279.5 m2·g-1), and was chemically and thermally stable. Photophysical studies revealed that the COF exhibits a low bandgap energy value of 3.07 eV, indicating its semiconducting nature.
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Project description:Despite extensive efforts, only three main strategies have been developed to synthesize covalent triazine-based frameworks (CTFs) thus far. We report herein a totally new synthetic strategy which allows C-C bonds in the CTFs to be formed through aromatic nucleophilic substitution reactions. The as-synthesized CTF-1 and CTF-2 exhibited photocatalytic water splitting activity comparable to the CTFs made using ionothermal or Brønsted acid-catalyzed polymerization. Interestingly, CTF-2 distinguished itself by its two-photon fluorescence (emission at ∼530 nm under irradiation at either 400 nm or 800 nm).
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Project description:Oxygen activation is a critical step in ubiquitous heterogeneous oxidative processes, most prominently in catalysis, electrolysis, and pharmaceutical applications. We present here our findings on metal-free O2 activation on covalent triazine frameworks (CTFs) as an important class of N-rich materials. The O2 activation process was studied for the formation of aldehydes, ketones and imines. A detailed mechanistic study of O2 activation and the role of nitrogen heteroatoms were comprehensively investigated. The electron paramagnetic resonance (EPR) and control experiments provide strong evidence for the reaction mechanism proving the applicability of the CTFs to activate oxygen into superoxide species. This report highlights the importance of a self-templating procedure to introduce N functionalities for the development of metal-free catalytic materials. The presented findings reveal an important step toward the use of CTFs as inexpensive and high-performance alternatives to metal-based materials not only for catalysis but also for biorelated applications dealing with O2 activation.
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Project description:Covalent triazine frameworks, which are crosslinked porous polymers with two-dimensional molecular structures, are promising materials for heterogeneous catalysts. However, the application of the frameworks as electrocatalysts has not been achieved to date because of their poor electrical conductivity. Here we report that platinum-modified covalent triazine frameworks hybridized with conductive carbon nanoparticles are successfully synthesized by introducing carbon nanoparticles during the polymerization process of covalent triazine frameworks. The resulting materials exhibit clear electrocatalytic activity for oxygen reduction reactions in acidic solutions. More interestingly, the platinum-modified covalent triazine frameworks show almost no activity for methanol oxidation, in contrast to commercial carbon-supported platinum. Thus, platinum-modified covalent triazine frameworks hybridized with carbon nanoparticles exhibit selective activity for oxygen reduction reactions even in the presence of high concentrations of methanol, which indicates potential utility as a cathode catalyst in direct methanol fuel cells.
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Project description:The synthesis of porous electrode materials is often linked with the generation of waste that results from extensive purification steps and low mass yield. In contrast to porous carbons, covalent triazine frameworks (CTFs) display modular properties on a molecular basis through appropriate choice of the monomer. Herein, the synthesis of a new pyridine-based CTF material is showcased. The porosity and nitrogen-doping are tuned by a careful choice of the reaction temperature. An in-depth structural characterization by using Ar physisorption, X-ray photoelectron spectroscopy, and Raman spectroscopy was conducted to give a rational explanation of the material properties. Without any purification, the samples were applied as symmetrical supercapacitors and showed a specific capacitance of 141 F g-1 . Residual ZnCl2 , which acted formerly as the porogen, was used directly as the electrolyte salt. Upon the addition of water, ZnCl2 was dissolved to form the aqueous electrolyte in situ. Thereby, extensive and time-consuming washing steps could be circumvented.
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