Reticular Design and Synthesis of Covalent Organic Frameworks with Irregular Hexagonal Tiling

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because strict constraints on tile lengths and angles. Guided by reticular chemistry, we deconstructed type III hexagonal into a combination D2h + monomers achieved first successful synthesis 2D COFs such with hit topology. By tuning crystal growth conditions, obtained set isomers, COF-hit COF-bex, distinct structures. Powder X-ray diffraction high-resolution transmission electron microscopy were employed to precisely characterize their topology demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design using opens new avenue diversify structural types topological varieties promote chemistry.

Язык: Английский

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Two-dimensional salen-based covalent organic frameworks with highly electronegative groups as separators for high stability lithium–sulfur batteries

Polymer Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The salen-based Salen-TAPT-COF was prepared and used as a modified separator for boosting the performance of Li–S batteries.

Язык: Английский

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Rolling two-dimensional covalent organic framework (COF) sheets into one-dimensional electronic and proton-conductive nanotubes

Proceedings of the National Academy of Sciences, Год журнала: 2025, Номер 122(16)

Опубликована: Апрель 16, 2025

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) nanotubes (CNTs), herein we report in situ transformation 2D π-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly sheets at solvent interfaces. The facile “roll-sheets” resulted coaxial with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not corresponding pyrene COF, although both possess similar chemical structures. Upon replacing atoms 2,7-positions nitrogen, contrasting optical electronic properties were realized, reflecting rolled structure conjugated sheets. exhibited concerted electronic- proton-conducting nature stable conducting pathways ambient conditions. nitrogen centers act simultaneously as site charge carrier doping proton acceptors, evidenced by high photo- electrical conductivity, well record conductivity (σ = 1.98 S cm −1 ) results. present COF serves a unique materials platform conduction wall core, respectively.

Язык: Английский

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Porphyrin-Based Covalent Organic Framework Encapsulating Multiwalled Carbon Nanotubes: A High-Performance Electrocatalyst for Oxygen Reduction Reaction

Langmuir, Год журнала: 2025, Номер unknown

Опубликована: Апрель 17, 2025

The development of efficient and cost-effective oxygen reduction reaction (ORR) catalysts is crucial for advancing fuel cell technologies, given the limitations platinum-based catalysts. Here, we present a novel nanocomposite, cobalt-based porphyrinic covalent organic framework wrapped on multiwalled carbon nanotubes (Co-pCOF@MWCNTs), synthesized via template-directed in situ polymerization. This composite combines high porosity tunable catalytic properties COFs with excellent electrical conductivity MWCNTs. Co-pCOF@MWCNT demonstrates superior ORR activity, exhibiting an onset potential (Eonset) 0.86 V vs RHE 0.1 M KOH, surpassing performance its individual components (Co-pCOF MWCNT) other related materials. enhanced efficiency attributed to synergistic interactions between conductive MWCNT scaffold active COF nanolayers, which facilitate charge transfer increase site exposure. Furthermore, nanocomposite exhibits stability methanol tolerance, establishing as cathodic material cells. work highlights promise integrating materials opens new avenues design advanced energy conversion applications.

Язык: Английский

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Covalent organic framework-based cathodes for beyond lithium-ion batteries

Communications Materials, Год журнала: 2025, Номер 6(1)

Опубликована: Апрель 21, 2025

Язык: Английский

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Highly Crystalline and Robust Donor‐Acceptor Type Covalent Organic Frameworks for Long‐life Sodium‐Ion Battery Cathodes

Small, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

Abstract Covalent organic frameworks (COFs) hold great potential in sodium‐ion battery cathodes. However, most reported COF‐based electrodes show unsatisfying capacity and rate performance due to their limited redox site density, low crystallinity, poor conductivity. Herein, a highly crystalline robust donor‐acceptor type COF with abundant active sites is developed by the polymerization of donor unit benzo[1,2‐b:3,4‐b″:5,6‐b″']trithiophene‐2,5,8‐tricarbaldehyde) (BTT) acceptor s‐indacene‐1,3,5,7(2H,6H)‐tetrone (ICTO) (denoted as BTT‐ICTO) for cathodic Na + storage. The BTT‐ICTO‐graphene composites (BTT‐ICTO@G) synthesized situ growth have loose sheet structure rough surfaces, contributing improved conductivity utilization BTT‐ICTO. Benefiting from robustness BTT‐ICTO linked ethylene bonds, BTT‐ICTO@G cathodes exhibit high 325 mAh g −1 at 0.1 A 80%, excellent 190 5.0 , exceptional cycle performances 196 over 10 000 cycles 2.0 only 0.0015% decay per cycle. These properties make among best‐reported In addition, Raman, ex Fourier transform infrared, theoretical calculations disclose reaction pathway

Язык: Английский

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Boosting porphyrin photocatalysis in thiophenol cross-coupling via supramolecular host-guest engineering

Dyes and Pigments, Год журнала: 2025, Номер 240, С. 112860 - 112860

Опубликована: Апрель 28, 2025

Язык: Английский

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Semiconducting Covalent Organic Frameworks

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Май 14, 2025

Semiconductors form the foundational bedrock of modern electronics and numerous cutting-edge technologies. Particularly, semiconductors crafted from organic building blocks hold immense promise as next-generation pioneers, thanks to their vast array chemical structures, customizable frontier orbital energy levels bandgap easily adjustable π electronic properties. Over past 50 years, advancements in chemistry materials science have facilitated extensive investigations into small compounds, oligomers, polymers, resulting a rich library semiconductors. However, longstanding challenge persists: how organize units or chains well-defined which are crucial for performance Consequently, pursuit methodologies capable synthesizing and/or fabricating with ordered structures has emerged polymeric semiconductor research. In this context, covalent frameworks (COFs) stand out unique platforms allowing integration periodically thus facilitating development extended yet precisely defined architectures. Since initial report 2008, significant strides been made exploring various chemistries develop semiconducting COFs, properties, functions, applications. This review provides comprehensive focused exploration general structural features outlining basic principles design, illustrating linkage synthetic strategies based on typical one-pot polymerization reactions demonstrate growth bulk materials, nanosheets, films, membranes. By elucidating interactions between COFs entities such photons, phonons, electrons, holes, ions, molecules, spins, categorizes nine distinct sections: semiconductors, photoconductors, light emitters, sensors, photocatalysts, photothermal conversion electrocatalysts, storage electrodes, radical spin focusing disclosing structure-originated properties functions. Furthermore, scrutinizes structure-function correlations highlights features, breakthroughs, challenges associated COFs. Furnished knowledges state-of-the-art insights, predicts fundamental issues be addressed outlines future directions offering overview rapidly evolving remarkable field.

Язык: Английский

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Evidence of Heteroepitaxy and Solid Solutions in Lattice Matched Ternary Covalent Organic Framework Systems

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 2, 2025

Covalent organic frameworks (COFs) are crystalline, porous materials with the possibility for broad applications, but their structural diversity remains constrained by simple net topologies, limiting functional versatility. To address this challenge, we developed a strategy incorporating linkers normally mismatched geometries, exemplified [4-c + 2-c 3-c] system pentagonal motifs 2D tiling. Central to approach is derivation of length ratio parameter, α, which provides quantitative guide evaluating compatibility in ternary systems. Investigating model close ideal demonstrate that precise size matching enables formation localized solid solutions and heteroepitaxial interfaces, as seen transmission electron microscopy. These findings showcase pathway expanding complexity COFs, opening new avenues tailored material design.

Язык: Английский

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Mixed dimensional assembly of biodegradable and antifouling wood-based covalent organic framework composite membranes for rapid and efficient dye/salt separation

Journal of Hazardous Materials, Год журнала: 2024, Номер 480, С. 136012 - 136012

Опубликована: Сен. 30, 2024

Язык: Английский

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