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Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks.

ABSTRACT: Covalent organic frameworks (COFs) have served as a family of porous crystalline molecules for various promising applications. However, controllable synthesis of COFs with uniform morphology is paramount yet still remains quite challenging. Herein, we report self-templated synthesis of uniform and unique hollow spheres based on highly conjugated three-dimensional (3D) COFs with diameters of 500-700?nm. A detailed time-dependent study reveals the continuous transformation from initial nano sphere-like particles into uniform hollow spherical structures with Ostwald ripening mechanism. Particularly, the resulting 3D COF (3D-Sp-COF) is prone to transport ions more efficiently and the lithium-ion transference number (t+) of 3D-Sp-COF reaches 0.7, which even overwhelms most typical PEO-based polymer electrolytes. Inspiringly, the hollow spherical structures show enhanced capacitance performance with a specific capacitance of 251?F?g-1 at 0.5?A?g-1, which compares favorably with the vast majority of two-dimensional COFs and other porous electrode materials.

SUBMITTER: Liu YY

PROVIDER: S-EPMC7642269 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks.

Liu Yuan-Yuan YY Li Xiang-Chun XC Wang Shi S Cheng Tao T Yang Huiyan H Liu Chen C Gong Yanting Y Lai Wen-Yong WY Huang Wei W

Nature communications 20201103 1

Covalent organic frameworks (COFs) have served as a family of porous crystalline molecules for various promising applications. However, controllable synthesis of COFs with uniform morphology is paramount yet still remains quite challenging. Herein, we report self-templated synthesis of uniform and unique hollow spheres based on highly conjugated three-dimensional (3D) COFs with diameters of 500-700 nm. A detailed time-dependent study reveals the continuous transformation from initial nano sphere ...[more]

PMID: 33144580

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Project description:Covalent organic frameworks (COFs) define a versatile structural paradigm combining attractive properties such as crystallinity, porosity, and chemical and structural modularity which are valuable for various applications. For the incorporation of COFs into optoelectronic devices, efficient charge carrier transport and intrinsic conductivity are often essential. Here, we report the synthesis of two imine-linked two-dimensional COFs, WTA and WBDT, featuring a redox-active Wurster-type motif based on the twisted tetragonal N,N,N',N'-tetraphenyl-1,4-phenylenediamine node. By condensing this unit with either terephthalaldehyde (TA) or benzodithiophene dialdehyde (BDT), COFs featuring a dual-pore kagome-type structure were obtained as highly crystalline materials with large specific surface areas and mesoporosity. In addition, the experimentally determined high conduction band energies of both COFs render them suitable candidates for oxidative doping. The incorporation of a benzodithiophene linear building block into the COF allows for high intrinsic macroscopic conductivity. Both anisotropic and average isotropic electrical conductivities were determined with van der Pauw measurements using oriented films and pressed pellets, respectively. Furthermore, the impact of different dopants such as F4TCNQ, antimony pentachloride and iodine on the conductivities of the resulting doped COFs was studied. By using the strong organic acceptor F4TCNQ, a massive increase of the radical cation density (up to 0.5 radicals per unit cell) and long-term stable electrical conductivity as high as 3.67 S m-1 were achieved for the anisotropic transport in an oriented film, one of the highest for any doped COF to date. Interestingly, no significant differences between isotropic and anisotropic charge transport were found in films and pressed pellets. This work expands the list of possible building nodes for electrically conducting COFs from planar systems to twisted geometries. The achievement of high and stable electrical conductivity paves the way for possible applications of new COFs in organic (opto)electronics.

Project description:We use first-principles calculations to show that the square symmetry of two-dimensional (2D) metal-organic frameworks (MOFs) made from octaamino-substituted phthalocyanines and square planar Ni2+ ions, which enable strong conjugation of π electrons, has a critical impact on the magnetic properties of the lattice. In particular, we predict the unexpected emergence of a rare high-temperature ferromagnetic half-metallic ground state in one case. Among charge neutral MOFs made from (2,3,9,10,16,17,23,24)-octaiminophthalocyanine (OIPc) metallated with divalent first-row transition metal ions (M-OIPc; M = Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) and connected through square planar Ni-bisphenylenediimine moieties, NiMn-OIPc exhibits a half-metallic and ferromagnetic ground state with a large exchange energy resulting from the unique strong hybridization between the d/π orbitals of Mn, the Pc ring, and the Ni-bisphenylenediimine nodes. Notably, we show that for NiMn-OIPc there is a considerable difference between the ferromagnetic ordering temperature (Tc) predicted by a 2D Ising model, which exceeds 600 K, and a Tc of 170 K predicted by our more realistic Monte Carlo simulation that includes magnetic anisotropy. Critically, our simulations adopt two spin models that incorporate magnetic anisotropy in the form of exchange anisotropy and single-ion anisotropy. We further show that in the bulk, 2D layers of NiMn-OIPc adopt a slipped-parallel stacking configuration, and exhibit interlayer magnetic coupling that is sensitive to the relative in-plane displacement between adjacent layers. These results highlight the critical role of magnetic anisotropy in modeling the properties of 2D magnetic systems. More generally, it demonstrates that strong hybridization between open-shell ions and delocalized aromatic π systems with appropriate symmetry, combined with large magnetic anisotropy, will be an effective design strategy to realize ferromagnetic 2D MOFs with high Tc.

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Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks.

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Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks.

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