Photons, Excitons, and Electrons in Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32161 - 32205

Опубликована: Ноя. 18, 2024

Covalent organic frameworks (COFs) are created by the condensation of molecular building blocks and nodes to form two-dimensional (2D) or three-dimensional (3D) crystalline frameworks. The diversity with different properties functionalities large number possible framework topologies open a vast space well-defined porous architectures. Besides more classical applications materials such as absorption, separation, catalytic conversions, interest in optoelectronic COFs has recently increased considerably. electronic both their linkage chemistry can be controlled tune photon absorption emission, create excitons charge carriers, use these carriers photocatalysis, luminescence, chemical sensing, photovoltaics. In this Perspective, we will discuss relationship between structural features properties, starting connectivity, layer stacking 2D COFs, control over defects morphology including thin film synthesis, exploring theoretical modeling structural, electronic, dynamic discussing recent intriguing focus on photocatalysis photoelectrochemistry. We conclude some remarks about present challenges future prospects powerful architectural paradigm.

Язык: Английский

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Highly Efficient Capture of Volatile Iodine by Conjugated Microporous Polymers Constructed Using Planar 3- and 4-Connected Organic Monomers

Molecules, Год журнала: 2024, Номер 29(10), С. 2242 - 2242

Опубликована: Май 10, 2024

The effective capture and recovery of radioiodine species associated with nuclear fuel reprocessing is significant importance in power plants. Porous materials have been proven to be one the most adsorbents for radioiodine. In this work, we design synthesize a series conjugated microporous polymers (CMPs), namely, TPDA–TFPB CMP, TPDA–TATBA TPDA–TECHO which are constructed based on planar rectangular 4-connected organic monomer three triangular 3-connected monomers, respectively. resultant CMPs characterized using various characterization techniques used as iodine capture. Our experiments indicated that exhibit excellent adsorption capacities high 6.48, 6.25, 6.37 g g−1 at 348 K ambient pressure. mechanism was further investigated strong chemical between imine/tertiary ammonia CMPs, 3D network structure accessible hierarchical pores, uniform micromorphology, wide π-conjugated structure, high-density Lewis-base sites synergistically contribute their performance. Moreover, demonstrated good recyclability. This work provides guidance construction novel adsorbent efficiency field.

Язык: Английский

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Taming Two‐Dimensional Polymerization by a Machine‐Learning Discovered Crystallization Model

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 3, 2024

Rapidly synthesizing high-quality two-dimensional covalent organic frameworks (2D COFs) is crucial for their practical applications. While strategies such as slow monomer addition have been developed based on an empirical understanding of formation process, quantitative guidance remains absent, which prohibits precise optimizations the experimental conditions. Here, we use a machine-learning approach that overcomes challenges associated with bottom-up model derivation non-classical 2D COF crystallization processes. The resulting model, referred to NEgen1, establishes correlations among induction time, nucleation rate, growth bond-forming rate constants, and common solution synthesis conditions COFs grow by nucleation-elongation mechanism. results elucidate detailed competition between dynamics in solution, has inappropriately described previously classical, models assumptions invalid polymerization. By dynamic processes at play, NEgen1 reveals simple strategy gradually increasing speed growing large crystals. This insight enables us rapidly synthesize COF-5 colloids, could only be achieved prolonged reaction times or introducing chemical modulators. These highlight potential systematically improving crystal quality COFs, wide-reaching relevance many applications where are speculated valuable.

Язык: Английский

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Isomeric covalent organic frameworks: opportunities and challenges

Trends in Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 1, 2025

Язык: Английский

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Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics

Chemical Research in Chinese Universities, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Язык: Английский

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Aqueous-Phase Synthesis of Cyclic Trinuclear Cluster-Based Metal–Organic Frameworks

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

Опубликована: Апрель 10, 2025

The synthesis of metal-organic frameworks (MOFs) often involves high-boiling-point organic solvents, which can have extensive environmental impact and limit their large-scale applications. Here, we present a one-pot aqueous-phase approach for the rapid preparation 33 trinuclear-copper-cluster-based MOFs (1 to 33) with different pyrazoles under ultrasonic irradiation. To address water-solubility challenge linkers, employ aromatic amines/aldehydes pyrazole aldehydes/amines in situ generate imine-based pyrazoles. This linker dismantling strategy enables formation low-concentration pyrazoles, are essential assembly aqueous phase. use preassembled trinuclear gold complexes instead amines affords an Au-Cu-based MOF (34) alternating copper clusters, rare example mixed yet precise arrangement metal compositions. Additionally, direct addition pyruvic acid reaction mixture results facile carboxylic-acid-functionalized (35), eliminating need preinstallation or postmodification steps traditional synthesis. Furthermore, demonstrate 11-AA as efficient photocatalyst cross-dehydrogenative coupling (CDC) reactions, exploiting synergetic effect substrate activation on sites subsequent initiated by photosensitive linkers. work offers simple solution making minimal impact; it also opens up possibilities developing multifunctional diverse

Язык: Английский

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The Rise and Development of COF‐Based Materials for Alkali Metal Chalcogen Batteries: Current Status, Challenges, and Prospects

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 28, 2025

Abstract Alkali metal chalcogen batteries (such as lithium–sulfur/selenium, sodium–sulfur systems, abbreviated Li‐S/Se and Na‐S) have become an important direction for the next generation of high‐energy due to their ultra‐high theoretical energy density cost advantages, but problem rapid capacity decay needs be solved urgently. Covalent organic frameworks (COFs) provide a new idea improving battery performance high specific surface area tunable structure: porous structure can sufficient electrochemical reaction sites optimize ion transport paths, thereby charge‐discharge efficiency rate performance. In this paper, research progress COFs in alkali is systematically reviewed.

Язык: Английский

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Constructing benzothiadiazole‐based donor‒acceptor covalent organic frameworks for efficient photocatalytic H₂ evolution

Aggregate, Год журнала: 2024, Номер unknown

Опубликована: Окт. 3, 2024

Abstract Donor‒acceptor covalent organic frameworks (D‒A COFs) have been regarded as promising materials for photocatalytic water splitting because of their tunable band gaps. However, efficiency is hindered by fast charge recombination and low photostability. Herein, we proposed a donor structural engineering strategy improving the activity D‒A COFs to tackle these problems. Two benzothiadiazole‐based (DHU‐COF‐BB DHU‐COF‐BP) with distinct donors were prepared H 2 evolution reaction (HER). As comparison, DHU‐COF‐TB without benzothiadiazole moieties was also designed synthesized. Impressively, production rate DHU‐COF‐BB reaches 12.80 mmol g −1 h under visible light irradiation (≥420 nm), which nearly 2.0 3.1 times higher than that DHU‐COF‐BP (6.47 ) (4.06 ), respectively. In addition, apparent quantum (AQE) up 5.04% at 420 nm. Photocatalytic electrochemical measurements indicate enhanced hydrogen can be ascribed introduction appropriate benzene moiety into donors, increases separation thereby suppresses electron‒hole recombination. Density functional theory (DFT) calculations revealed both triphenylamine units are main active sites HER over DHU‐COF‐BB. This work provides new insight strategy.

Язык: Английский

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Coupling interface, electronic and conjugation effects in C-COFs/TiO2 composite structure toward boosting photocatalytic hydrogen evolution

International Journal of Hydrogen Energy, Год журнала: 2024, Номер 81, С. 1135 - 1144

Опубликована: Июль 27, 2024

Язык: Английский

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Machine-Learning Discovered Crystallization Model for Two Dimensional Covalent Organic Frameworks: Towards Precise Control of the Crystal Quality

Опубликована: Апрель 12, 2024

The rational molecular design and experimental condition optimizations for two-dimensional co-valent organic frameworks (2D COFs) call a crystallization model capable of capturing exper-imental time size scales. However, accurately describing their process remains significant challenge due to the presence non-classical pathways. Here, we demonstrate implementation machine-learning approach, overcoming difficulties associated with bot-tom-up derivation. resulting model, referred as NEgen1, establishes correlations among induction time, nucleation rate, growth material parameters, common solu-tion synthesis conditions 2D COFs that belong nucleation-elongation category. NEg-en1 represents emergence practical models COFs, enabling direct calculation processes in both times sizes. results elu-cidate detailed competition between dynamics solution, which has been inappropriately apprehended via classical, empirical assumptions invalid COFs. Importantly, potential application NEgen1 opti-mizing conditions, predominantly relied on knowledge date. identification superior those routinely used experimentally reveals promis-ing strategy gradually increasing monomer addition speed growing large COF crystals while maintaining reasonable time. These highlight systemati-cally improving crystal quality wider applications.

Язык: Английский

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