Functional Regulation and Stability Engineering of Three-Dimensional Covalent Organic Frameworks DOI
Xinyu Guan, Qianrong Fang, Yushan Yan

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(14), P. 1912 - 1927

Published: June 27, 2022

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

Language: Английский

Covalent Organic Frameworks: Design, Synthesis, and Functions DOI
Keyu Geng, Ting He, Ruoyang Liu

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(16), P. 8814 - 8933

Published: Jan. 22, 2020

Covalent organic frameworks (COFs) are a class of crystalline porous polymers with permanent porosity and highly ordered structures. Unlike other polymers, significant feature COFs is that they structurally predesignable, synthetically controllable, functionally manageable. In principle, the topological design diagram offers geometric guidance for structural tiling extended polygons, polycondensation reactions provide synthetic ways to construct predesigned primary high-order Progress over past decade in chemistry these two aspects undoubtedly established base COF field. By virtue availability units diversity topologies linkages, have emerged as new field materials offer powerful molecular platform complex tailor-made functional development. Here we target comprehensive review field, historic overview survey advances topology reactions, illustrate features diversities, scrutinize development potential various functions through elucidating structure–function correlations based on interactions photons, electrons, holes, spins, ions, molecules, discuss key fundamental challenging issues need be addressed, predict future directions from chemistry, physics, perspectives.

Language: Английский

Citations

2904

Covalent organic frameworks: an ideal platform for designing ordered materials and advanced applications DOI Open Access
Ruoyang Liu, Ke Tian Tan, Yifan Gong

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(1), P. 120 - 242

Published: Dec. 7, 2020

Covalent organic frameworks offer a molecular platform for integrating units into periodically ordered yet extended 2D and 3D polymers to create topologically well-defined polygonal lattices built-in discrete micropores and/or mesopores.

Language: Английский

Citations

759

Design and applications of three dimensional covalent organic frameworks DOI
Xinyu Guan, Fengqian Chen, Qianrong Fang

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(5), P. 1357 - 1384

Published: Jan. 1, 2020

We summarize in this review the current state-of-the-art development of three dimensional covalent organic frameworks.

Language: Английский

Citations

721

Orderly Porous Covalent Organic Frameworks-based Materials: Superior Adsorbents for Pollutants Removal from Aqueous Solutions DOI Creative Commons
Xiaolu Liu,

Hongwei Pang,

Xuewei Liu

et al.

The Innovation, Journal Year: 2021, Volume and Issue: 2(1), P. 100076 - 100076

Published: Jan. 10, 2021

Covalent organic frameworks (COFs) are a new type of crystalline porous polymers known for chemical stability, excellent structural regularity, robust framework, and inherent porosity, making them promising materials capturing various types pollutants from aqueous solutions. This review thoroughly presents the recent progress advances COFs COF-based as superior adsorbents efficient removal toxic heavy metal ions, radionuclides, pollutants. Information about interaction mechanisms between summarized macroscopic microscopic standpoints, including batch experiments, theoretical calculations, advanced spectroscopy analysis. The adsorption properties assessed compared with other widely used adsorbents. Several commonly strategies to enhance materials' performance relationship property sorption ability also discussed. Finally, summary perspective on opportunities challenges proposed provide some inspiring information designing fabricating environmental pollution management.

Language: Английский

Citations

543

Opportunities of Covalent Organic Frameworks for Advanced Applications DOI Creative Commons
Yanpei Song, Qi Sun, Briana Aguila

et al.

Advanced Science, Journal Year: 2018, Volume and Issue: 6(2)

Published: Nov. 12, 2018

Abstract Covalent organic frameworks (COFs) are an emerging class of functional nanostructures with intriguing properties, due to their unprecedented combination high crystallinity, tunable pore size, large surface area, and unique molecular architecture. The range properties characterized in COFs has rapidly expanded include those interest for numerous applications ranging from energy environment. Here, a background overview is provided, consisting brief introduction porous materials the design feature COFs. Then, recent advancements as designer platform plethora emphasized together discussions about strategies principles involved. Finally, challenges remaining this type material real outlined.

Language: Английский

Citations

516

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built‐In Functions DOI
Xinyi Chen, Keyu Geng, Ruoyang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(13), P. 5050 - 5091

Published: May 30, 2019

Abstract A new approach has been developed to design organic polymers using topology diagrams. This strategy enables covalent integration of units into ordered topologies and creates a polymer form, that is, frameworks. is breakthrough in chemistry because it sets molecular platform for synthesizing with predesignable primary high‐order structures, which central aim over century but unattainable traditional principles. field its own features are distinct from conventional polymers. Review summarizes the fundamentals as well major progress by focusing on used including principles, synthetic strategies, control methods. We scrutinize built‐in functions specific structures revealing various interplays mechanisms involved expression function. propose fundamental issues be addressed future directions physics, materials, application perspectives.

Language: Английский

Citations

502

Optoelectronic processes in covalent organic frameworks DOI Open Access
Niklas Keller, Thomas Bein

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(3), P. 1813 - 1845

Published: Dec. 17, 2020

Covalent organic frameworks (COFs) are crystalline porous materials constructed from molecular building blocks using diverse linkage chemistries. Their modular construction system allows not only for tailor-made design but also an immense variety of blocks, opening the door to numerous different functionalities and potential applications. As a consequence, large number that can act as light-harvesters, semiconductors, ligands, binding sites or redox centers have recently been integrated into scaffolds COFs. This unique combination reticular chemistry with control intrinsic properties paves way towards new semiconducting (opto-)electronic applications such sensors, photocatalysts -electrodes, supercapacitor battery materials, solar-harvesting devices light emitting diodes. With developments regarding motif, highly stable still tunable COFs developed even under harsh conditions. Further, stacking modes distances in investigated powerful means optical electrical characteristics these self-assembled frameworks. Advanced understanding optoelectronic processes has enabled their implementation promising real-world review highlights key concepts synthesis electro- photoactive well our frameworks, hence establishing paradigm rational well-defined novel devices.

Language: Английский

Citations

398

Recent Progress in Metal‐Free Covalent Organic Frameworks as Heterogeneous Catalysts DOI
Yongfeng Zhi,

Zongrui Wang,

Hao‐Li Zhang

et al.

Small, Journal Year: 2020, Volume and Issue: 16(24)

Published: May 17, 2020

Abstract Covalent organic frameworks (COFs), connecting different units into one system through covalent bonds, are crystalline porous materials with 2D or 3D networks. Compared conventional such as inorganic zeolite, active carbon, and metal‐organic frameworks, COFs a new type of well‐designed pore structure, high surface area, outstanding stability, easy functionalization at the molecular level, which have attracted extensive attention in various fields, energy storage, gas separation, sensing, photoluminescence, proton conduction, magnetic properties, drug delivery, heterogeneous catalysis. Herein, recent advances metal‐free versatile platform for catalysis wide range chemical reactions presented synthetic strategy promising catalytic applications COF‐based catalysts (including photocatalysis) summarized. According to types reactions, this review is divided following five parts discussion: achiral catalysis, chiral conversion, photocatalytic conversion water splitting reduction carbon dioxide), pollutant degradation. Furthermore, remaining challenges prospects also presented.

Language: Английский

Citations

307

2D and 3D Porphyrinic Covalent Organic Frameworks: The Influence of Dimensionality on Functionality DOI
Yi Meng, Yi Luo, Ji‐Long Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(9), P. 3624 - 3629

Published: Nov. 27, 2019

Abstract The construction of 2D and 3D covalent organic frameworks (COFs) from functional moieties for desired properties has gained much attention. However, the influence COFs dimensionality on their functionalities, which can further assist in COF design, never been explored. Now, by selecting designed precursors topology diagrams, porphyrinic (2D‐PdPor‐COF 3D‐PdPor‐COF) are synthesized. By model building Rietveld refinement powder X‐ray diffraction, 2D‐PdPor‐COF crystallizes as sheets while 3D‐PdPor‐COF adopts a five‐fold interpenetrated pts topology. Interestingly, compared with 2D‐PdPor‐COF, showed interesting properties, including 1) higher CO 2 adsorption capacity; 2) better photocatalytic performance; 3) size‐selective photocatalysis. Based this study, we believe that incorporation moieties, definitely functionalities.

Language: Английский

Citations

304

Unveiling Electronic Properties in Metal–Phthalocyanine-Based Pyrazine-Linked Conjugated Two-Dimensional Covalent Organic Frameworks DOI
Mingchao Wang, Marco Ballabio, Mao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(42), P. 16810 - 16816

Published: Sept. 26, 2019

π-Conjugated two-dimensional covalent organic frameworks (2D COFs) are emerging as a novel class of electroactive materials for (opto)electronic and chemiresistive sensing applications. However, understanding the intricate interplay between chemistry, structure, conductivity in π-conjugated 2D COFs remains elusive. Here, we report detailed characterization electronic properties two samples consisting Zn- Cu-phthalocyanine-based pyrazine-linked COFs. These synthesized by condensation metal-phthalocyanine (M = Zn Cu) pyrene derivatives. The obtained polycrystalline-layered p-type semiconductors both with band gap ∼1.2 eV. A record device-relevant mobility up to ∼5 cm2/(V s) is resolved dc limit, which represents lower threshold induced charge carrier localization at crystalline grain boundaries. Hall effect measurements (dc limit) terahertz (THz) spectroscopy (ac combination density functional theory (DFT) calculations demonstrate that varying metal center from Cu phthalocyanine moiety has negligible (∼5 × 10-7 S/cm), (∼1012 cm-3), scattering rate (∼3 1013 s-1), effective mass (∼2.3m0) majority carriers (holes). Notably, transport found be anisotropic, hole mobilities being practically null in-plane finite out-of-plane these

Language: Английский

Citations

290