Covalent organic frameworks: an ideal platform for designing ordered materials and advanced applications

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(1), P. 120 - 242

Published: Dec. 7, 2020

Covalent organic frameworks offer a molecular platform for integrating units into periodically ordered yet extended 2D and 3D polymers to create topologically well-defined polygonal lattices built-in discrete micropores and/or mesopores.

Language: Английский

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Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: March 1, 2021

Abstract Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report designed synthesis of four isostructural porphyrinic two-dimensional covalent (MPor-DETH-COF, M = H 2 , Co, Ni, Zn) and activity generation. Our results clearly show that all adopt AA stacking structures, with high crystallinity large surface area. Interestingly, incorporation different transition metals into porphyrin rings can rationally tune evolution rate corresponding frameworks, order CoPor-DETH-COF < Por-DETH-COF NiPor-DETH-COF ZnPor-DETH-COF. Based on detailed experiments calculations, this tunable performance mainly explained by tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple effective way efficient tuning activities at level, but also provides valuable insight structure design better photocatalysis.

Language: Английский

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Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 565 - 788

Published: Dec. 1, 2021

This review surveys recent progress in the chemistry of polycyclic heteroaromatic molecules with a focus on structural diversity and synthetic methodology. The article covers literature published during period 2016-2020, providing an update to our first this topic (

Language: Английский

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Optoelectronic processes in covalent organic frameworks

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(3), P. 1813 - 1845

Published: Dec. 17, 2020

Covalent organic frameworks (COFs) are crystalline porous materials constructed from molecular building blocks using diverse linkage chemistries. Their modular construction system allows not only for tailor-made design but also an immense variety of blocks, opening the door to numerous different functionalities and potential applications. As a consequence, large number that can act as light-harvesters, semiconductors, ligands, binding sites or redox centers have recently been integrated into scaffolds COFs. This unique combination reticular chemistry with control intrinsic properties paves way towards new semiconducting (opto-)electronic applications such sensors, photocatalysts -electrodes, supercapacitor battery materials, solar-harvesting devices light emitting diodes. With developments regarding motif, highly stable still tunable COFs developed even under harsh conditions. Further, stacking modes distances in investigated powerful means optical electrical characteristics these self-assembled frameworks. Advanced understanding optoelectronic processes has enabled their implementation promising real-world review highlights key concepts synthesis electro- photoactive well our frameworks, hence establishing paradigm rational well-defined novel devices.

Language: Английский

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Covalent organic frameworks

Nature Reviews Methods Primers, Journal Year: 2023, Volume and Issue: 3(1)

Published: Jan. 12, 2023

Language: Английский

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Two-dimensional conjugated metal–organic frameworks (2D c-MOFs): chemistry and function for MOFtronics

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(4), P. 2764 - 2793

Published: Jan. 1, 2021

Two-dimensional conjugated MOFs are emerging for multifunctional electronic devices that brings us “MOFtronics”, such as (opto)electronics, spintronics, energy devices.

Language: Английский

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Metal–Covalent Organic Frameworks (MCOFs): A Bridge Between Metal–Organic Frameworks and Covalent Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(33), P. 13722 - 13733

Published: April 9, 2020

Abstract Many sophisticated chemical and physical properties of porous materials strongly rely on the presence metal ions within structures. Whereas homogeneous distribution metals is conveniently realized in metal–organic frameworks (MOFs), limited stability potentially restricts their practical implementation. From that perspective, development metal–covalent organic (MCOFs) may address these shortcomings by incorporating active species atop highly stable COF backbones. This Minireview highlights examples MCOFs tackle important issues from design, synthesis, characterization to cutting‐edge applications.

Language: Английский

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Reconstructed covalent organic frameworks

Nature, Journal Year: 2022, Volume and Issue: 604(7904), P. 72 - 79

Published: April 6, 2022

Abstract Covalent organic frameworks (COFs) are distinguished from other polymers by their crystallinity 1–3 , but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions poorly reversible 4,5 . More chemistry can improve 6–9 this typically yields with poor physicochemical stability and limited application scope 5 Here we report a general scalable protocol prepare imine COFs, based on an unexpected framework reconstruction. In contrast standard approaches in which monomers initially randomly aligned, our method involves pre-organization of using removable covalent tether, followed confined polymerization. This reconstruction route produces reconstructed greatly enhanced much higher porosity means simple vacuum-free synthetic procedure. The increased improves charge carrier transport, leading sacrificial photocatalytic hydrogen evolution rates up 27.98 mmol h −1 g nanoconfinement-assisted strategy is step towards programming function materials through atomistic structural control.

Language: Английский

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Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 7104 - 7113

Published: May 3, 2021

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed recent years. However, the of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine (denoted as CoPc-PI-COF-1 CoPc-PI-COF-2) have devised prepared through solvothermal reaction tetraanhydrides 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine 4,4′-biphenyldiamine, respectively. resultant CoPc-PI-COFs four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, excellent resistance 12 M HCl aqueous solution 20 days. Current–voltage curves reveal conductivity CoPc-PI-COF-2 value 3.7 × 10–3 1.6 S m–1, Due same Co(II) electroactive sites together similar porosity CO2 adsorption capacity CoPc-PI-COFs, cathodes made up carbon black display CO2-to-CO Faradaic efficiency 87–97% at applied potentials between −0.60 −0.90 V (vs RHE) 0.5 KHCO3 solution. comparison CoPc-PI-COF-2&carbon electrode, counterpart provides larger current density (jCO) −21.2 mA cm–2 associated its higher conductivity. This cathode also high turnover number frequency, amounting 277 000 2.2 s–1 −0.70 during 40 h measurement. present result clearly discloses potential 2D porous crystalline solids electrocatalysis.

Language: Английский

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A Stable and Conductive Metallophthalocyanine Framework for Electrocatalytic Carbon Dioxide Reduction in Water

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(38), P. 16587 - 16593

Published: May 21, 2020

Transformation of carbon dioxide to high value-added chemicals becomes a significant challenge for clean energy studies. Here stable and conductive covalent organic framework was developed electrocatalytic reduction monoxide in aqueous solution. The cobalt(II) phthalocyanine catalysts are topologically connected via robust phenazine linkage into two-dimensional tetragonal that is under boiling water, acid, or base conditions. 2D lattice enables full π conjugation along x y directions as well conduction the z axis across columns. With these structural features, exhibits faradaic efficiency 96 %, an exceptional turnover number up 320 000, long-term frequency 11 412 hour-1 , which 32-fold improvement over molecular catalyst. combination catalytic activity, selectivity, efficiency, durability desirable production.

Language: Английский

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