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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Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1861 - 1871

Published: Jan. 20, 2022

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion single-cluster catalyst is challenging. In this work, for first time, we present versatile strategy uniformly dispersed polyoxometalates (POMs) covalent organic frameworks (COFs) through confining POM cluster into regular nanopores COF by linkage. These COF-POM composites combine properties light absorption, electron transfer, and suitable catalytic active sites; as result, they exhibit outstanding activity artificial photosynthesis: that is, CO2 photoreduction with H2O donor. Among them, TCOF-MnMo6 achieved highest CO yield (37.25 μmol g-1 h-1 ca. 100% selectivity) gas-solid reaction system. Furthermore, mechanism study based on density functional theory (DFT) calculations demonstrated photoinduced transfer (PET) process occurs from to POM, then reduction oxidation occur COF, respectively. This work developed method single which also shows potential using materials photocatalysis.

Language: Английский

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Integration of metal-organic frameworks and covalent organic frameworks: Design, synthesis, and applications

Matter, Journal Year: 2021, Volume and Issue: 4(7), P. 2230 - 2265

Published: July 1, 2021

Language: Английский

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Hybrid Porous Crystalline Materials from Metal Organic Frameworks and Covalent Organic Frameworks

Advanced Science, Journal Year: 2021, Volume and Issue: 8(20)

Published: Aug. 19, 2021

Abstract Two frontier crystalline porous framework materials, namely, metal‐organic frameworks (MOFs) and covalent organic (COFs), have been widely explored owing to their outstanding physicochemical properties. While each type of has its own intrinsic advantages shortcomings for specific applications, combining the complementary properties two materials allows engineering new classes hybrid with superior individual components. Since first report MOF/COF in 2016, it rapidly evolved as a novel platform diverse applications. The state‐of‐art advances various synthetic approaches hybrids are hereby summarized, together applications different areas. Perspectives on main challenges future opportunities also offered order inspire multidisciplinary effort toward further development chemically diverse, multi‐functional materials.

Language: Английский

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Covalent Organic Frameworks and Their Derivatives for Better Metal Anodes in Rechargeable Batteries

ACS Nano, Journal Year: 2021, Volume and Issue: 15(8), P. 12741 - 12767

Published: Aug. 5, 2021

Metal anodes based on a plating/stripping electrochemistry such as metallic Li, Na, K, Zn, Ca, Mg, Fe, and Al are recognized promising anode materials for constructing next-generation high-energy-density rechargeable metal batteries owing to their low electrochemical potential, high theoretical specific capacity, superior electronic conductivity, etc. However, inherent issues chemical reactivity, severe growth of dendrites, huge volume changes, unstable interface largely impede practical application. Covalent organic frameworks (COFs) derivatives emerging multifunctional have already well addressed the in past several years due abundant metallophilic functional groups, special inner channels, controllable structures. COFs can solve by interfacial modification, homogenizing ion flux, acting nucleation seeds, reducing corrosion anodes, so on. Nevertheless, related reviews still absent. Here we present detailed review batteries. Meanwhile, some outlooks opinions put forward. We believe catch eyes relevant researchers supply inspiration future research.

Language: Английский

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Hydrogen Bonding Regulated Flexibility and Disorder in Hydrazone-Linked Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(2), P. 1359 - 1366

Published: Jan. 4, 2023

Covalent organic framework (COF) chemistry is experiencing unprecedented development in recent decades. The current studies on COF are mainly focused the discovery of novel covalent linkages, new topological structures, synthetic methodologies, and potential applications. However, despite fact that noncovalent interactions ubiquitous chemistry, relatively little attention has been given to role bonds structures their properties. In this work, a series hydrazone-linked COFs involving hydrogen have constructed, where hydrogen-bonding interaction plays critical roles crystallinity structures. regulation structural flexibility, reversible transition between order disorder, variety host-guest demonstrated succession for first time COFs. results obtained by hydrogen-bonding-regulated strategy may also be extendable other interactions, such as π-π metal coordination Lewis acid-base etc. These findings will inspire future developments design, synthesis, regulation, applications manipulating interactions.

Language: Английский

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A sulfonate-functionalized covalent organic framework for record-high adsorption and effective separation of organic dyes

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 464, P. 142706 - 142706

Published: March 31, 2023

Language: Английский

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Constructing chemical stable 4-carboxyl-quinoline linked covalent organic frameworks via Doebner reaction for nanofiltration

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 12, 2022

Covalent linkages are the key component of covalent organic frameworks (COFs). The development stable and functional is essential to expand COFs family broaden their application prospects. In this work, we report synthesis crystalline chemical 4-carboxyl-quinoline linked (QL-COFs) via Doebner reactions in both one-pot (OP) post-synthetic modification (PSM) methods. Both methods can be universally applied most reported imine bottom-up construction or linkage conversion. Owing contractive pore size, more hydrophilic structure better stability than conventional endowed by linkage, QL-COFs supposed possess a wider range. We further demonstrate nanofiltration membrane (NFM) based on QL-COF exhibited desirable separation capacity with high rejection for small dye molecules (> 90%), water permeance (850 L m-2 h-1 MPa-1) tolerance extreme conditions (1 M HCl/NaOH), which were benefitted from enhanced properties QL-COFs. Additionally, efficient ion sieving also achieved membrane. anticipate that work opens up way robust materials practical applications.

Language: Английский

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Construction of Crystalline Nitrone-Linked Covalent Organic Frameworks Via Kröhnke Oxidation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15465 - 15472

Published: July 7, 2023

Developing diverse synthetic routes to prepare various crystalline covalent organic frameworks (COFs) and enrich the family of COFs is very important highly desirable. In this research, we demonstrate that Kröhnke oxidation (originally developed carbonyl compounds) can be employed as an efficient method construct two nitrone-linked (CityU-1 CityU-2) through ingenious design polynitroso-containing precursors well exquisite control polymerization conditions. The formation structure nitrone-based linkage units have been confirmed a mode reaction. as-obtained characterized by Fourier transform infrared X-ray photoelectron spectroscopy, powder diffraction patterns, scanning electron microscopy. Notably, CityU-1 exhibits BET specific surface area 497.9 m2g-1 with I2 capture capacity 3.0 g g-1 at 75 °C. Our research would provide more chances for applications.

Language: Английский

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The order–disorder conundrum: a trade-off between crystalline and amorphous porous organic polymers for task-specific applications

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(33), P. 17077 - 17121

Published: Jan. 1, 2022

The review unravels the order–disorder conundrum in porous organic polymers view of task-specific applications through a comparative deliberation.

Language: Английский

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