We synthesized a two-dimensional (2D) crystalline covalent organic framework (spc-COF) that was designed to be fully π-conjugated and constructed from all sp carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both and directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The spc-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.
We have demonstrated a hydroquinone stitched β-ketoenamine COF acting as an efficient organic cathode in an aqueous rechargeable zinc ion battery.
Development of porous materials combining stability and high performance has remained a challenge. This is particularly true for proton-transporting materials essential for applications in sensing, catalysis and energy conversion and storage. Here we report the topology guided synthesis of an imine-bonded (C=N) dually stable covalent organic framework to construct dense yet aligned one-dimensional nanochannels, in which the linkers induce hyperconjugation and inductive effects to stabilize the pore structure and the nitrogen sites on pore walls confine and stabilize the H 3 PO 4 network in the channels via hydrogen-bonding interactions. The resulting materials enable proton super flow to enhance rates by 2-8 orders of magnitude compared to other analogues. Temperature profile and molecular dynamics reveal proton hopping at low activation and reorganization energies with greatly enhanced mobility.
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), 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 meso pores in COF-GO foams. Considering the rheological features of the precursor hydrogel, we could integrate crystalline and porous COF-GO foams into self-supported 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.
Covalent organic frameworks (COFs) have attracted surging interest lately due to their wide potential in several frontline application areas like gas storage, sensing, photovoltaics, fuel cells, active catalyst supports, and so on. However, only very few reports are available for the metal-free electrocatalysis over COFs. Herein, we developed a new thiadiazole-based COF, C4-SHz COF, through the reaction between 1,3,5-tris(4-formylphenyl)benzene and 2,5-dihydrazinyl-1,3,4-thiadiazole that possesses a very high specific surface area of 1224 m 2 g −1 , unique molecular architecture, high porosity, and abundant active sites. The as-synthesized C4-SHz COF displayed superior electrocatalytic oxygen evolution reaction (OER) activity and excellent long-term durability. The electrocatalytic performance of the C4-SHz COF achieved a current density of 10 mA/cm 2 at an overpotential of 320 mV. The higher activity of the C4-SHz COF could be attributed to the high Brunauer−Emmett−Teller surface area, porosity, and network structure of the π-conjugated organic building blocks, which allowed fast charge and mass transport processes. This work validates the promising potential of a metal-free COF electrocatalyst toward the OER and its capability to replace carbon-based electrocatalysts.
In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C2‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4′‐bis(diethylphosphonomethyl)biphenyl with C3‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (Eg=2.2 eV) and 2D‐PPQV2 (Eg=2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog (2D‐C=N‐PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction.
Photoelectrochemical (PEC) water reduction, which can convert solar energy into clean, storable hydrogen fuel, has attracted considerable attention to address energy and environmental issues. [1-3] A PEC water splitting cell is an innovative H 2-production device consisting of solar energy collection (semiconductors) and water electrolysis (catalysts) units. [4-6] Principally, the semiconductors need to comply with several requirements for efficient PEC applications, such as a wide-range light harvesting ability, efficient charge transfer, corrosion stability, and a higher-lying lowest unoccupied molecular orbital (LUMO) energy level than the reduction potential of the proton (H + /H 2). [1,7] 2D covalent organic frameworks (2D COFs), as crystalline, layer-stacked, 2D porous polymers, have emerged as a promi sing class of materials for photocatalysis and PEC applications recently. [3,8-12] Their energy bandgaps, positions of the frontier orbitals, and active centers can be facilely tailored by bottom-up organic synthesis with abundant building blocks, linkages, and topologies. [6,13,14] In particular, 2D π-conjugated COFs, which belong to the class of 2D conjugated polymers, show notable advantages for PEC applications due to the π-stacked columns Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene-bridged donor-acceptorbased 2D sp 2-carbon-linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron-accepting building block 2,3,8,9,14,15-hexa(4-formylphenyl) diquinoxalino[2,3a:2′,3′-c]phenazine (HATN-6CHO) and the first electron-donating linker 2,2′-([2,2′-bithiophene]-5,5′-diyl)diacetonitrile (ThDAN) provides the 2D CCP-HATNThDAN (2D CCP-Th). Compared with the corresponding biphenyl-bridged 2D CCP-HATN-BDAN (2D CCP-BD), the bithiophenebased 2D CCP-Th exhibits a wide light-harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital-lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP-Th a promising candidate for PEC water reduction. As a result, 2D CCP-Th presents a superb H 2-evolution photocurrent density up to ≈7.9 µA cm −2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09-6.0 µA cm −2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H 2. The ORCID identification number(s) for the author(s) of this article can be found under
Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuliresponsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans−cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans−cis−trans photoisomerization could be reversibly controlled by alternating UV-and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.
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