Charge Dynamics in A Donor–Acceptor Covalent Organic Framework with Periodically Ordered Bicontinuous Heterojunctions

Jin, Shangbin; Ding, Xuesong; Feng, Xiao; Supur, Mustafa; Furukawa, Ko; Takahashi, Seiya; Addicoat, Matthew A.; El‐Khouly, Mohamed E.; Nakamura, Toshikazu; Irle, Stephan; Fukuzumi, Shunichi; Nagai, Atsushi; Jiang, Donglin

doi:10.1002/anie.201209513

Cited by 283 publications

(198 citation statements)

References 39 publications

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“…1,2 Depending on their topology and functionality, these reticular materials are promising candidates for various applications, such as gas adsorption, 3,4 separation, 5,6 catalysis, 7,8 proton conduction, 9 energy storage, 10 and optoelectronics. 11−15 …”

Section: Introductionmentioning

confidence: 99%

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

et al. 2016

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Crystallinity and porosity are of central importance for many properties of covalent organic frameworks (COFs), including adsorption, diffusion, and electronic transport. We have developed a new method for strongly enhancing both aspects through the introduction of a modulating agent in the synthesis. This modulator competes with one of the building blocks during the solvothermal COF growth, resulting in highly crystalline frameworks with greatly increased domain sizes reaching several hundreds of nanometers. The obtained materials feature fully accessible pores with an internal surface area of over 2000 m2 g–1. Compositional analysis via NMR spectroscopy revealed that the COF-5 structure can form over a wide range of boronic acid-to-catechol ratios, thus producing frameworks with compositions ranging from highly boronic acid-deficient to networks with catechol voids. Visualization of an −SH-functionalized modulating agent via iridium staining revealed that the COF domains are terminated by the modulator. Using functionalized modulators, this synthetic approach thus also provides a new and facile method for the external surface functionalization of COF domains, providing accessible sites for post-synthetic modification reactions. We demonstrate the feasibility of this concept by covalently attaching fluorescent dyes and hydrophilic polymers to the COF surface. We anticipate that the realization of highly crystalline COFs with the option of additional surface functionality will render the modulation concept beneficial for a range of applications, including gas separations, catalysis, and optoelectronics.

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Section: Introductionmentioning

confidence: 99%

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

et al. 2016

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“…Covalent organic frameworks (COFs) are ac lass of porousorganic polymers that have attracted tremendous interest in various fields, such as gas adsorption and storage, [20, 21a,b] catalysis, [22] sensing, [23] and photovoltaics. [24] They do not only exhibit exceptional properties (such as permanent porosity,h igh surface areas, and easily-tunablef rameworks) but also, their fully organic nature may result in an improved filler-polymeri nteraction, avoiding the formation of nonselectived efects upon MMM preparation. [25] Despite the fact that many reportso n gas storage using COFs have been published, [21a, 20, 26] only af ew reports on the application of COFs in membranes for gas separation can be found.…”

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confidence: 99%

Azine‐Linked Covalent Organic Framework (COF)‐Based Mixed‐Matrix Membranes for CO₂/CH₄ Separation

Shan

Seoane

Rozhko

et al. 2016

Chemistry A European J

172

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Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO2 from an equimolar CO2 /CH4 mixture. The COF-based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.

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“…[3][4][5][6] COFs have attracted al ot of interest for their diverse applications,i ncluding gas separation and storage, [7,8] catalysis, [9,10] and optoelectronic devices. [4,11] On the other hand, the reversible reactions can lead to instability of the COF structure. Thus,r ational design and optimizationo ft he linkages in COFs have become af ocus for researchi nt he field to enhance COF stability.…”

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confidence: 99%

Reconstruction of Covalent Organic Frameworks by Dynamic Equilibrium

Gao

Bai

Zeng

et al. 2015

Chemistry A European J

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Covalent organic frameworks (COFs) are periodic two- or three-dimensional polymeric networks with high surface areas, low density, and designed structures. Because COFs are normally prepared based on reversible formation of covalent bonds with relatively weak stability, their structures can be easily broken or damaged due to changes in the surrounding environment. Thus, developing strategies to realize the reconstruction of COFs in order to extend their usage lifetime is crucial for practical applications. In addition, exploring the kinetics of COF growth under varied reaction conditions is important for better understanding the nucleation and growth processes of COFs. In this work, the reformation mechanism of an imine-based COF using an ex situ characterization method was investigated, disclosing an interesting COF reconstruction progress from disorder to order. The present study shows the regeneration ability of COFs, and the developed method could be generalized for broader use in the field.

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Charge Dynamics in A Donor–Acceptor Covalent Organic Framework with Periodically Ordered Bicontinuous Heterojunctions

Cited by 283 publications

References 39 publications

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

Azine‐Linked Covalent Organic Framework (COF)‐Based Mixed‐Matrix Membranes for CO₂/CH₄ Separation

Reconstruction of Covalent Organic Frameworks by Dynamic Equilibrium

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Charge Dynamics in A Donor–Acceptor Covalent Organic Framework with Periodically Ordered Bicontinuous Heterojunctions

Cited by 283 publications

References 39 publications

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks—A Modulation Approach

Azine‐Linked Covalent Organic Framework (COF)‐Based Mixed‐Matrix Membranes for CO2/CH4 Separation

Reconstruction of Covalent Organic Frameworks by Dynamic Equilibrium

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Product

Resources

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Azine‐Linked Covalent Organic Framework (COF)‐Based Mixed‐Matrix Membranes for CO₂/CH₄ Separation