Postsynthetic functionalization of covalent organic frameworks

Yusran, Yusran; Guan, Xinyu; Li, Hui; Fang, Qianrong; Qiu, Shilun

doi:10.1093/nsr/nwz122

Cited by 169 publications

(99 citation statements)

References 115 publications

(100 reference statements)

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“…The possibility of COFs decoration with functional electroactive groups has been widely explored. [28][29][30]52,53] This synthesis platform includes the manageable installation of reactive functional groups on the frameworks to produce electroactive COFs (Scheme 1c). A wide range of reactive functional groups has been installed in COFs, such as functional groups that contained electron-rich ionic or charged species.…”

Section: Electroactive Cofs With Reactive Functional Groupsmentioning

confidence: 99%

“…The judicious installations of redox moieties on COFs [29,52,77] and their high thermal and chemical stability, [78] make COF suitable for pseudocapacitive energy storage. Indeed, several COFs have been employed as active materials for pseudocapacitor electrodes.…”

Section: Pseudocapacitorsmentioning

confidence: 99%

“…Hence, the exploration of proton conducting materials usable for solid electrolyte membranes in PEMFCs is a top priority in this emerging field. [153] The judicious fabrication of COFs membranes and thin films [183] and the tunable functional decoration of highly ordered and define pores, [25,29,78] promise huge potential for exploration in fuel-cell technology. Indeed, COFs have been widely designed and explored for proton conduction, as we briefly discussed in the previous section.…”

Section: Electroactive Cofs For Fuel Cellsmentioning

confidence: 99%

“…[27] In addition, the synthesis of COFs allows tailoring the composition and the functionality via predesigned building blocks or postsynthetic modification of the established frameworks. [28][29][30] This synthetic flexibility includes the manageable installation of electroactive moieties on the COF skeletons. Hence, it transforms COFs into prospective electroactive materials that are applicable for energy-related applications.…”

Section: Introductionmentioning

confidence: 99%

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Electroactive Covalent Organic Frameworks: Design, Synthesis, and Applications

2020

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have been employed as promising electrochemical double-layer capacitor (EDLC) electrodes [34] and electrical conductors. [35] In the field of batteries, electrocatalysis, and fuel cells, COFs have also appeared recently. [36-38] In this review article, the recent progress in the design and synthesis of electroactive COFs and their applications in the fields of electrochemical energy storages (EES), electrochemical energy conversions and electrocatalysis are overviewed. Their performances as capacitor, battery, conductor, fuel cell, and electrocatalysis are discussed. Furthermore, the perspectives on developing electroactive COFs as future smart materials for energy storage and conversion are provided. 2. Design Principles of Electroactive COFs To enable COFs to conduct both ions and electrical charges or store electrochemical energy in capacitors and batteries requires the specific design of electroactive sites within the structure. Similarly, to execute electrocatalytic phenomena in the key electrochemical reactions (e.g., ORR, OER, and HER), COF-based electrocatalysts should possess catalytic sites that are able to undertake efficient catalytic processes and avoid overpotential. [39] Thus, careful design of electroactive COFs with abundant accessible active sites, long-term durability, and if possible, low-cost and greener technologies is pivotal. The design of electroactive COFs has been performed in various strategies. These strategies include preparing COFs with high surface areas and accessible active surfaces, incorporating electroactive sites (e.g., electron-rich species and metals) in their frameworks, and hybridizing COFs with other electroactive components to enhance their electroactivity. To make these more practical, we provide a scheme (Scheme 1) to describe how electroactive COFs were designed so far and further discuss them in the following subsections. 2.1. Electroactive Bulk and Exfoliated COFs The accessible surface areas and active sites in porous materials influence their activities. Therefore, bulk and exfoliated COFs have been prepared to improve the accessibility toward their electroactive sites (Scheme 1a). COFs have been widely prepared as bulk crystalline powder and employed in various applications. [40-43] Meanwhile, efforts in the development of bulk COFs with controlled pore size and to drive for more accessibility of the active sites were reported. For example, Jiang and co-workers prepared a high-surface-area mesoporous 2D imide-linked D TP-A NDI-COF with a pore size of 5.06 nm for the construction of Li-ion battery electrode. [44] Li and co-workers reported another 2D imide-linked PIBN-based COF with a pore size of 1.4 nm for a similar application. [45] These two electroactive COFs with distinct porosity exhibited remarkable and unique performances in the field of battery. In addition, COFs have also been prepared as bulk thin films or membranes. For example, Halder et al. synthesized flexible, self-standing, and chemically stable thick sheet (≈200 µm) TpOMe-DAQ film (where TpOMe ...

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Section: Electroactive Cofs With Reactive Functional Groupsmentioning

confidence: 99%

Section: Pseudocapacitorsmentioning

confidence: 99%

Section: Electroactive Cofs For Fuel Cellsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electroactive Covalent Organic Frameworks: Design, Synthesis, and Applications

2020

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“…[49,51] It can also be used to modulate the flexibility [52] of as tructure,t he mechanical properties, [53] and change its polarity. [54] Post-synthetic modification is mostly used to tether functional groups to the inner pore surface, [55] such as biologically active groups, [55g] ionic functional groups, [56] catalysts, [55c] and gas-releasing agents. [57] This allows the introduction of fundamentally new properties to the reticular material or the stabilization of tethered guests that would otherwise deactivate in solution.…”

Section: Internal Modificationmentioning

confidence: 99%

Beyond Frameworks: Structuring Reticular Materials across Nano‐, Meso‐, and Bulk Regimes

et al. 2020

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Reticular materials are of high interest for diverse applications, ranging from catalysis and separation to gas storage and drug delivery. These open, extended frameworks can be tailored to the intended application through crystal‐structure design. Implementing these materials in application settings, however, requires structuring beyond their lattices, to interface the functionality at the molecular level effectively with the macroscopic world. To overcome this barrier, efforts in expressing structural control across molecular, nano‐, meso‐, and bulk regimes is the essential next step. In this Review, we give an overview of recent advances in using self‐assembly as well as externally controlled tools to manufacture reticular materials over all the length scales. We predict that major research advances in deploying these two approaches will facilitate the use of reticular materials in addressing major needs of society.

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