Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 31, 2024

Abstract Perylene diimides (PDIs) have garnered considerable attention due to their immense potential in photocatalysis. However, manipulating the molecular packing within aggregates and enhancing efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate incorporation a PDI unit into covalent organic framework (COF), named PDI‐PDA, by linking an ortho‐substituted with p ‐phenylenediamine (PDA) control its intermolecular aggregation. The enables precise modulation electron‐transfer dynamics, leading ten‐fold increase photocatalytic oxidation thioether sulfoxide PDI‐PDA compared counterpart, yields exceeding 90 %. Electron property studies density functional theory calculations show that well‐defined crystal structure, enhances π–π stacking lowers electron transition barrier. Moreover, strong electron‐withdrawing ability promotes spatial separation valency band maximum conduction minimum suppressing rapid electron‐hole pairs improving charge‐separation give high efficiency. This study provides brief but effective way for commonly used PDI‐based dyes integrating them skeleton.

Language: Английский

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Optimizing selectivity via membrane molecular packing manipulation for simultaneous cation and anion screening

Science Advances, Journal Year: 2024, Volume and Issue: 10(39)

Published: Sept. 25, 2024

Advancing membranes with enhanced solute-solute selectivity is essential for expanding membrane technology applications, yet it presents a notable challenge. Drawing inspiration from the unparalleled of biological systems, which benefit sophisticated spatial organization functionalities, we posit that manipulating arrangement membrane’s building blocks, an aspect previously given limited attention, can address this We demonstrate optimizing face-to-face orientation blocks during assembly covalent-organic-framework (COF) improves ion-π interactions multivalent ions. This optimization leads to extraordinary in differentiating between monovalent cations and anions their counterparts, achieving factors 214 K + /Al 3+ 451 NO 3 − /PO 4 3− . Leveraging attribute, COF facilitates direct extraction NaCl seawater purity 99.57%. These findings offer alternative approach designing highly selective materials, offering promising prospects advancing membrane-based technologies.

Language: Английский

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Electron Push-Pull Effect of Benzotrithiophene-Based Covalent Organic Frameworks on the Photocatalytic Degradation of Pharmaceuticals and Personal Care Products

Molecules, Journal Year: 2025, Volume and Issue: 30(2), P. 336 - 336

Published: Jan. 16, 2025

A covalent organic framework (COF) has emerged as a promising photocatalyst for the removal of pharmaceutical and personal care product (PPCP) contaminants; however, high-performance COF photocatalysts are still scarce. In this study, three were successfully synthesized by condensation benzo[1,2-b:3,4-b':5,6-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) with 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (TAPT), 1,3,5-Tris(4-aminophenyl)benzene (TAPB), 4,4',4''-nitrilotris(benzenamine) (TAPA), namely, BTT-TAPA, BTT-TAPB, BTT-TAPT, respectively. The surface areas BTT-TAPT found to be 800.46, 1203.60, 1413.58 cm2∙g-1, respectively, providing abundant active sites photocatalytic reactions. Under visible-light irradiation, exhibited highest rate tetracycline (TC), reaching 82.7% after 240 min. superior performance was attributed its large specific area strong electron-acceptor properties triazine group. Electron paramagnetic resonance capture experiments liquid chromatograph mass spectrometer analysis confirmed that superoxide radicals played pivotal role in degradation TC ciprofloxacin. Moreover, high stability reproducibility during process. This study confirms BTT-based COFs class PPCPs water, their can further optimized tuning structure composition frameworks.

Language: Английский

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Synthesis, derivation, and applications of imine-linked covalent organic frameworks: A comprehensive review

Microporous and Mesoporous Materials, Journal Year: 2025, Volume and Issue: unknown, P. 113516 - 113516

Published: Jan. 1, 2025

Language: Английский

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sp² Carbon‐Conjugated Covalent Organic Frameworks (sp²c‐COFs): Synthesis and Application in Photocatalytic Water Splitting

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Abstract Preparation of irreversible sp 2 carbon‐conjugated covalent organic frameworks (sp c‐COFs) with specific porosity, easy structural functionalization, high chemical stability, and unique π‐electron conjugation structure (especially the combination π–π stacking interactions system), can remove barrier electron transfer provide a advantage for photocatalytic water splitting. Herein, based on three kinds reactions (Aldol condensation reaction, Knoevenagel Horner‐Wadsworth‐Emmons reaction) guided by precise modulation ligand topology, this review summarizes synthesis c‐COFs their applications in photoelectrocatalytic splitting (hydrogen evolution oxygen reactions). Furthermore, challenges possible research directions are also provided.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Language: Английский

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Recent Advances in Covalent Organic Frameworks as Photocatalysts for Organic Transformations

Journal of environmental chemical engineering, Journal Year: 2025, Volume and Issue: unknown, P. 116253 - 116253

Published: March 1, 2025

Language: Английский

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2D sp2 carbon-linked benzotrithiophene covalent organic frameworks for selective sulfoxidation with oxygen driven by green light

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: unknown, P. 124628 - 124628

Published: Sept. 1, 2024

Language: Английский

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Linkage Conversion in Covalent Organic Frameworks: An Efficient Strategy to Promote Photocatalytic Organic Transformations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(20)

Published: June 19, 2024

Abstract Covalent organic frameworks (COFs) are emerging as promising heterogeneous photocatalysts for transformations, owing to their fascinating optical properties, excellent recyclability, and customizable chemical structures. To maximize the photocatalytic activity of COFs, various strategies have been explored, including metal complexation, construction donor‐acceptor structures, modification functional groups, hybridization with inorganic semiconductors, linkage conversion. Among these, conversion has proved be particularly effective, driving production numerous value‐added chemicals. In this concept article, we present a comprehensive overview latest advancements in highlight most enlightening examples that adopted such strategy boost capabilities COFs transformations. It is anticipated will assist researchers designing novel multifunctional linkages, paving way towards broader application synthesis.

Language: Английский

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Converting the covalent organic framework linkage from hydrazone to thiadiazole toward blue light-powered selective conversion of organic sulfides

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(36), P. 24144 - 24155

Published: Jan. 1, 2024

TDA-COF, a triazine-based COF with an irreversible thiadiazole linkage, swiftly carries out the blue light-powered selective conversion of thioanisoles O 2 .

Language: Английский

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