Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Язык: Английский

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Boosting Ethane/Ethylene Separation by MOFs through the Amino‐Functionalization of Pores

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(48)

Опубликована: Окт. 7, 2022

Adsorption technology based on ethane-selective materials is a promising alternative to energy-intensive cryogenic distillation for separating ethane (C2 H6 ) and ethylene H4 ). We employed pore engineering strategy tune the environment of metal-organic framework (MOF) through organic functional groups boosted C2 /C2 separation MOF. Introduction amino (-NH2 into Tb-MOF-76 not only decreased sizes but also facilitated multiple guest-host interactions in confined pores. The NH2 -functionalized Tb-MOF-76(NH2 has increased uptakes selectivity. results experimental simulated transient breakthroughs reveal that significantly improved one-step performance mixtures with high (>99.95 %) productivity 17.66 L kg-1 compared 7.53 by Tb-MOF-76, resulting from suitable confinement accessible -NH2 surfaces.

Язык: Английский

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In Situ Growth of Covalent Organic Framework Nanosheets on Graphene as the Cathode for Long‐Life High‐Capacity Lithium‐Ion Batteries

Advanced Materials, Год журнала: 2022, Номер 34(37)

Опубликована: Июль 29, 2022

The poor electronic and ionic conductivities of covalent organic frameworks (COFs) severely restrict the development COF-based electrodes for practical rechargeable batteries, therefore inspiring more research interest from direction both material synthesis technology. Herein, a dual-porous COF, USTB-6, with good crystallinity rich redox-active sites is conceived fabricated by polymerization 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino [2,3-a:2',3'-c]phenazine 2,7-diaminopyrene-4,5,9,10-tetraone. In particular, heterogeneous same starting materials in presence graphene affords uniformly dispersed COF nanosheets thickness 8.3 nm on conductive carbon substrate, effectively enhancing conductivity electrode. Such graphene-supported USTB-6 cathode when used lithium-ion battery exhibits specific capacity 285 mA h g-1 at current density 0.2 C excellent rate performance prominent 188 10 C. More importantly, 170 retained using after 6000 cycles charge discharge measurement 5

Язык: Английский

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Conjugated Three-Dimensional High-Connected Covalent Organic Frameworks for Lithium–Sulfur Batteries

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(37), С. 17209 - 17218

Опубликована: Сен. 9, 2022

Developing conjugated three-dimensional (3D) covalent organic frameworks (COFs) still remains an extremely difficult task due to the lack of enough 3D building blocks. Herein, condensation between 8-connected pentiptycene-based D2h block (DMOPTP) and 4-connected square-planar linkers affords two COFs (named 3D-scu-COF-1 3D-scu-COF-2). A combination homoaromatic structure former with 2D latter linking units enables π-electron delocalization over whole both COFs, endowing them excellent conductivities 3.2-3.5 × 10-5 S cm-1. In particular, rigid quadrangular prism shape DMOPTP guides formation a twofold interpenetrated scu topology high-connected permanent porosity large Brunauer-Emmett-Teller (BET) surface area 2340 1602 m2 g-1 for 3D-scu-COF-2, respectively, ensuring effective small molecule storage mass transport characteristics. This, in their good charge properties, renders promising sulfur host materials lithium-sulfur batteries (LSBs) high capacities (1035-1155 mA h at 0.2 C, 1 C = 1675 g-1), rate capabilities (713-757 5.0 C), superior cycling stability (71-83% capacity retention 2.0 after 500 cycles), surpassing most LSB cathodes reported thus far.

Язык: Английский

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Construction of Covalent Organic Frameworks via Multicomponent Reactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(3), С. 1475 - 1496

Опубликована: Янв. 16, 2023

Multicomponent reactions (MCRs) combine at least three reactants to afford the desired product in a highly atom-economic way and are therefore viewed as efficient one-pot combinatorial synthesis tools allowing one significantly boost molecular complexity diversity. Nowadays, MCRs no longer confined organic have found applications materials chemistry. In particular, can be used prepare covalent frameworks (COFs), which crystalline porous assembled from monomers exhibit broad range of properties applications. This synthetic approach retains advantages small-molecule MCRs, not only strengthening skeletal robustness COFs, but also providing additional driving forces for their crystallization, has been series robust COFs with diverse The present perspective article provides general background discusses types employed COF date, addresses related critical challenges future perspectives inspire MCR-based design new promote further progress this emerging field.

Язык: Английский

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Research Progress in Donor−Acceptor Type Covalent Organic Frameworks

Advanced Materials, Год журнала: 2023, Номер 35(48)

Опубликована: Апрель 24, 2023

Covalent organic frameworks (COFs) are new porous materials constructed by covalent bonds, with the advantages of pre-designable topology, adjustable pore size, and abundant active sites. Many research studies have shown that COFs exhibit great potential in gas adsorption, molecular separation, catalysis, drug delivery, energy storage, etc. However, electrons holes intrinsic COF prone to compounding transport, carrier lifetime is short. The donor-acceptor (D-A) type COFs, which synthesized introducing D A units into backbone, combine separated electron hole migration pathway, tunable band gap optoelectronic properties D-A polymers unique made progress related recent years. Here, synthetic strategies first outlined, including rational design linkages as well functionalization approaches. Then applications catalytic reactions, photothermal therapy, electronic systematically summarized. In final section, current challenges, directions for development presented.

Язык: Английский

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Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8141 - 8149

Опубликована: Март 29, 2023

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) exhibited great potential sulfur hosts LSBs to solve such problem. Herein, pentiptycene-based D2h symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized building block toward preparing COFs. Condensation DMOPTP with 4-connected tetrakis(4-aminophenyl)methane affords an expanded [8 + 4] connected network 3D-flu-COF, flu topology. The non-interpenetrated nature topology endows 3D-flu-COF high Brunauer-Emmett-Teller surface area 2860 m2 g-1, large octahedral cavities, cross-linked tunnels in framework, enabling loading capacity (∼70 wt %), strong LiPS adsorption capability, facile ion diffusion. Remarkably, when used host LSBs, delivers 1249 mA h g-1 at 0.2 C (1.0 = 1675 g-1), outstanding rate capability (764 5.0 C), excellent stability, representing one best results among thus far reported COF-based materials being competitive state-of-the-art inorganic materials.

Язык: Английский

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A Microporous Metal‐Organic Framework with Unique Aromatic Pore Surfaces for High Performance C₂H₆/C₂H₄ Separation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 20, 2023

Developing adsorptive separation processes based on C2 H6 -selective sorbents to replace energy-intensive cryogenic distillation is a promising alternative for H4 purification from /C2 mixtures, which however remains challenging. During our studies two isostructural metal-organic frameworks (Ni-MOF 1 and Ni-MOF 2), we found that 2 exhibited significantly higher performance than Ni-MOF-1, as clearly established by gas sorption isotherms breakthrough experiments. Density-Functional Theory (DFT) showed the unblocked unique aromatic pore surfaces within induce more stronger C-H⋅⋅⋅π with over while suitable spaces enforce its high uptake capacity, featuring one of best porous materials this very important separation. It generates 12 L kg-1 polymer-grade product equimolar mixtures at ambient conditions.

Язык: Английский

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Rationally fabricating 3D porphyrinic covalent organic frameworks with scu topology as highly efficient photocatalysts

Chem, Год журнала: 2022, Номер 8(11), С. 3064 - 3080

Опубликована: Авг. 19, 2022

Язык: Английский

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Porous framework materials for energy & environment relevant applications: A systematic review

Green Energy & Environment, Год журнала: 2023, Номер 9(2), С. 217 - 310

Опубликована: Янв. 3, 2023

Carbon peaking and carbon neutralization trigger a technical revolution in energy & environment related fields. Development of new technologies for green production storage, industrial saving efficiency reinforcement, capture, pollutant gas treatment is highly imperious demand. The emerging porous framework materials such as metal–organic frameworks (MOFs), covalent organic (COFs) hydrogen-bonded (HOFs), owing to the permanent porosity, tremendous specific surface area, designable structure customizable functionality, have shown great potential major energy-consuming processes, including sustainable catalytic conversion, energy-efficient separation storage. Herein, this manuscript presents systematic review global comprehensive applications, from macroscopic application perspective.

Язык: Английский

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