Unlocking Synthesis of Polyhedral Oligomeric Silsesquioxane-Based Three-Dimensional Polycubane Covalent Organic Frameworks DOI
Guanyu Qiao, Xiaoxue Wang, Xiao Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3373 - 3382

Published: Jan. 25, 2024

Reticular chemistry effectively yields porous structures with distinct topological lattices for a broad range of applications. Polyhedral oligomeric silsesquioxane (POSS)-based octatopic building blocks rare Oh symmetric configuration and attracting inorganic features have great potential creating three-dimensional (3D) covalent organic frameworks (COFs) new topologies. However, the intrinsic flexibility intensive motion cubane-type POSS molecules make construction 3D regular challenging. Herein, by fastening three or four cores per aromatic rigid linker from rational steric directions, we successfully developed serial crystalline COFs unpresented "the" scu Both experimental theoretical results proved formation target POSS-based COFs. The resultant hybrid networks designable chemical skeletons high surface areas maintain superiorities both components, such as their compatibility salts, abundant periodic electroactive sites, excellent thermal stability, open multilevel nanochannels. Consequently, polycubane could serve outstanding solid electrolytes ionic conductivity 1.23 × 10–4 S cm–1 lithium-ion transference number 0.86 at room temperature. This work offers pathway to generate ordered multiconnected flexible cube motifs enrich topologies

Language: Английский

Metalated covalent organic frameworks: from synthetic strategies to diverse applications DOI
Qun Guan, Lele Zhou, Yu‐Bin Dong

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

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

Language: Английский

Citations

214
Boosting Ethane/Ethylene Separation by MOFs through the Amino‐Functionalization of Pores DOI

Gang‐Ding Wang,

Rajamani Krishna, Yong‐Zhi Li

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Oct. 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.

Language: Английский

Citations

124
In Situ Growth of Covalent Organic Framework Nanosheets on Graphene as the Cathode for Long‐Life High‐Capacity Lithium‐Ion Batteries DOI
Xiaolin Liu, Yucheng Jin, Hailong Wang

et al.

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(37)

Published: July 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

Language: Английский

Citations

117
Construction of Covalent Organic Frameworks via Multicomponent Reactions DOI
Qun Guan, Lele Zhou, Yu‐Bin Dong

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(3), P. 1475 - 1496

Published: Jan. 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.

Language: Английский

Citations

112
Conjugated Three-Dimensional High-Connected Covalent Organic Frameworks for Lithium–Sulfur Batteries DOI
Wenbo Liu, Lei Gong, Zhixin Liu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 17209 - 17218

Published: Sept. 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.

Language: Английский

Citations

107
Research Progress in Donor−Acceptor Type Covalent Organic Frameworks DOI Open Access
Yeqing Xia, Weifeng Zhang, Shuai Yang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(48)

Published: April 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.

Language: Английский

Citations

102
Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries DOI
Wenbo Liu, Kang Wang,

Xiaoning Zhan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8141 - 8149

Published: March 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.

Language: Английский

Citations

101
A Microporous Metal‐Organic Framework with Unique Aromatic Pore Surfaces for High Performance C2H6/C2H4 Separation DOI

Yingxiang Ye,

Yi Xie, Yanshu Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 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.

Language: Английский

Citations

87
Rationally fabricating 3D porphyrinic covalent organic frameworks with scu topology as highly efficient photocatalysts DOI Creative Commons
Fazheng Jin, En Lin,

Tonghai Wang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(11), P. 3064 - 3080

Published: Aug. 19, 2022

Language: Английский

Citations

82
A Metal‐Organic Framework with Nonpolar Pore Surfaces for the One‐Step Acquisition of C2H4from a C2H4and C2H6Mixture DOI
Zhengyi Di, Caiping Liu, Jiandong Pang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 17, 2022

Because C2 H4 plays an essential role in the chemical industry, economical and energy-efficient separation of ethylene (C2 ) from ethane H6 is extremely important. With exception energy-intensive cryogenic distillation, there are few one-step methods to obtain polymer-grade (≥99.95 % pure) /C2 mixtures. Here we report a highly stable metal-organic-framework (MOF) FJI-H11-Me(des) (FJI-H=Hong's group Fujian Institute Research on Structure Matter) which features one-dimensional hexagonal nonpolar pore surfaces constructed by aromatic rings alkyl groups. This adsorbs rather than between 273 303 K. Practical breakthrough experiments with containing 1 have shown that can realize acquisition polymer-grade, 99.95 pure under various conditions including different gas flow rates, temperatures relative humidity.

Language: Английский

Citations

78