3D Covalent Organic Frameworks Based on Polycyclic Aromatic Hydrocarbons for Reversible Oxygen Capture

Zhang, Minghao; Fang, Jing; Liu, Yaozu; Wang, Yujie; Liao, Libin; Tang, Lu; Zhu, Lei; Qiu, Shilun; Fang, Qianrong

doi:10.1002/sstr.202000108

Cited by 17 publications

(9 citation statements)

References 26 publications

(26 reference statements)

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“…Anthracene or naphthalene, two typical PAHs, were employed in building 3D PAH-functionalized COFs (JUC-575 and JUC-576, Figure 4c). 54 Featuring reversible singlet oxygen capture and release between the parent COFs and endoperoxide COFs (EPO-COFs) through UV−vis irradiation switching, these functional 3D COFs were potential molecular carriers in biology and organic synthesis.…”

Section: Bottom-up Synthesis Of Functional 3d Cofs With Active Buildi...mentioning

confidence: 99%

“…With the existence of polyoxometalate moieties, CPOFs were employed as anode materials for lithium-ion batteries (LIBs) (Figure b) and displayed high reversible capacity (as high as 550 mA h g –1 ), rate performance, and cycling stability (up to 500 cycles). Anthracene or naphthalene, two typical PAHs, were employed in building 3D PAH-functionalized COFs (JUC-575 and JUC-576, Figure c) . Featuring reversible singlet oxygen capture and release between the parent COFs and endoperoxide COFs (EPO-COFs) through UV–vis irradiation switching, these functional 3D COFs were potential molecular carriers in biology and organic synthesis.…”

Section: Functional Regulation Of 3d Cofsmentioning

confidence: 99%

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Functional Regulation and Stability Engineering of Three-Dimensional Covalent Organic Frameworks

et al. 2022

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Metrics & MoreArticle Recommendations CONSPECTUS: As one of the most attractive members in the porous materials family, covalent organic frameworks (COFs) have been reported thousands of times since their first discovery in 2005, covering their design, synthesis, and applications. However, an overwhelming majority of these COFs are based on two-dimensional (2D) topologies while three-dimensional (3D) COFs are numbered fewer than 100 up to date. In fact, baring enhanced specific surface area, interconnected channels, well-exposed functional moieties, and highly adjustable structures, 3D COFs are often more competitive in various application fields like adsorption, separation, chemical sensing, and heterogeneous catalysis compared with their 2D counterparts. However, significant crystallization problems and poor chemical stabilities, which might be attributed to the highly void frameworks and the absence of π−π stacking, have raised severe limitations over the research and application of 3D COFs. To solve these problems, more elaborate synthesis regulations or more moderate functionalization conditions are required. More importantly, the strategies for enhancing chemical stabilities of 3D COFs are of vital importance for their further development and practical applications.In this Account, we review the design principles, functional approaches, and stability regulation methods toward functional 3D COFs. We begin the discussion with some essential elements in the construction of 3D COF structures, including topologies, interpenetrations, linkages, and synthetic methods. After that, we focus on several strategies for the functionalization of 3D COFs, including in situ approaches (utilizing in situ generated COF linkages as the active sites), bottom-up synthesis (embedding functional moieties from predesigned building blocks), and postsynthesis modification (covalent modification or metalation of pristine frameworks). At last, we highlight some approaches toward the durable amplification of 3D COFs, which is highly important for framework functionalization and practical application. This target could be achieved through not only the introduction of some extra strengthening force, such as hydrophobic effects, coulomb repulsion, and steric hindrance effects, but also the utilization of robust linkages, which could enhance the stability from material nature. Due to their high surface area, various interpenetrated channels, multifarious functionalities, and promising stabilities, 3D COFs demonstrated excellent performance and have great potential in a wide range of application fields including adsorption and separation, heterogeneous catalysis, energy storage, and so on. Although the development of these materials has been limited by serious crystallization problems and stability restriction, great efforts have been devoted by researchers in the past decade, and a mass of strategies have been developed in synthesis control, functionalization regulation, and stability enhancement for 3D COFs. We expect 3D COFs to be practi...

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Section: Bottom-up Synthesis Of Functional 3d Cofs With Active Buildi...mentioning

confidence: 99%

Section: Functional Regulation Of 3d Cofsmentioning

confidence: 99%

Functional Regulation and Stability Engineering of Three-Dimensional Covalent Organic Frameworks

et al. 2022

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“…In contrast, the frameworks in 3D COFs are extended through hypersymmetric building blocks, featuring high specific surface area, which is especially promising in the gas storage and supercapacitors. [ 76 ]…”

Section: Structural Diversity and Controlmentioning

confidence: 99%

Covalent organic frameworks: From materials design to electrochemical energy storage applications

et al. 2021

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Covalent organic frameworks (COFs), with large surface area, tunable porosity, and lightweight, have gained increasing attention in the electrochemical energy storage realms. In recent years, the development of high‐performance COF‐based electrodes has, in turn, inspired the innovation of synthetic methods, selection of linkages, and design of the topological structures. This review aims to present an overview of the recent advances in designing COF materials for various energy storage technologies. The fundamentals of COF materials, including synthetic chemistry, linkage diversity, and structure design, are first introduced. An in‐depth understanding of the charge storage mechanism and the structure‐property relationships of the COF electrodes is subsequently provided, highlighting their designing strategies in the latest energy storage applications. The last section of this review discusses the challenges COFs are facing and outlines new directions that could advance COF research in emerging energy technologies.

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“…Covalent organic frameworks (COFs) are an emerging class of crystalline porous materials, formed by linking organic building units into predictable structures through strong covalent bonds. [ 6 ] Since the pioneering work by Yaghi in 2005, [ 7 ] COFs have flourished due to their characteristic features, such as low density, regular pore structure, large specific surface area, and tunable function, which endow them great application potential in gas adsorption and separation, chemical sensing, heterogeneous catalysis, proton conduction, and drug delivery. [ 8 ] Moreover, COFs have been proven to be an excellent photocatalyst for various photocatalytic reactions, including water splitting, CO 2 reduction, pollution degradation, and organic transformations, due to the following reasons: i) the abundant organic building units provide great opportunities for COFs with tunable bandgaps; ii) the extensive п‐conjugated skeleton in COFs can ensure the mobility of photo‐generated carriers; iii) the large specific surface area of COFs enables the reactant transportation.…”

Section: Introductionmentioning

confidence: 99%

Construction of Core–Shell MOF@COF Hybrids with Controllable Morphology Adjustment of COF Shell as a Novel Platform for Photocatalytic Cascade Reactions

et al. 2021

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Recently, novel core-shell MOF@COF hybrids display excellent performance in various fields because of their inherited advantages from their parent MOFs and/or COFs. However, it is still a grand challenge to adjust the morphology of MOFs and/or COFs for consequent performance improvement. Herein, a Ti-MOF@TpTt hybrid coated with ultra-thin COF nanobelt, which is different from the fibrillar-like parent COF, is successfully synthesized through a sequential growth strategy. The as-obtained Pd decorated Ti-MOF@TpTt catalyst exhibits much higher photocatalytic performance than those of Ti-MOF, TpTt-COF, and Ti-MOF@TpTt hybrids with fibrillar-like COF shell for the photocatalytic cascade reactions of ammonia borane (AB) hydrolysis and nitroarenes hydrogenation. These can be attributed to its high BET surface area, core-shell structure, and type II heterojunction, which offers more accessible active sites and improves the separation efficiency of photo-generated carriers. Finally, the possible mechanisms of the cascade reaction are also proposed to well explain the improved performance of this photocatalytic system. This work presents a constructive route for designing core-shell MOF@COF hybrids with controllable morphology adjustment of COF shell, leading to the improved photocatalytic ability to broaden the applications of MOF/COF hybrid materials.

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3D Covalent Organic Frameworks Based on Polycyclic Aromatic Hydrocarbons for Reversible Oxygen Capture

Cited by 17 publications

References 26 publications

Functional Regulation and Stability Engineering of Three-Dimensional Covalent Organic Frameworks

Functional Regulation and Stability Engineering of Three-Dimensional Covalent Organic Frameworks

Covalent organic frameworks: From materials design to electrochemical energy storage applications

Construction of Core–Shell MOF@COF Hybrids with Controllable Morphology Adjustment of COF Shell as a Novel Platform for Photocatalytic Cascade Reactions

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