Sulfone‐Modified Covalent Organic Frameworks Enabling Efficient Photocatalytic Hydrogen Peroxide Generation via One‐Step Two‐Electron O₂ Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 25, 2023

Abstract Photocatalytic oxygen reduction reaction (ORR) offers a promising hydrogen peroxide (H 2 O ) synthetic strategy, especially the one‐step two‐electron (2e − ORR route holds great potential in achieving highly efficient and selectivity. However, 2e is rarely harvested underlying mechanism for regulating pathways remains greatly obscure. Here, by loading sulfone units into covalent organic frameworks (FS‐COFs), we present an photocatalyst H generation via from pure water air. Under visible light irradiation, FS‐COFs exert superb yield of 3904.2 μmol h −1 g , outperforming most reported metal‐free catalysts under similar conditions. Experimental theoretical investigation reveals that accelerate separation photoinduced electron‐hole (e ‐h + pairs, enhance protonation COFs, promote adsorption Yeager‐type, which jointly alters process two‐step to one, thereby with high

Язык: Английский

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Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 5, 2023

Singlet oxygen (1 O2 ) is an excellent reactive species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to huge dilemma synthesizing single-site type catalysts, control and regulation 1 generation AOPs still challenging underlying mechanism remains largely obscure. Here, taking advantage well-defined flexibly tunable sites covalent frameworks (COFs), we report first achievement precisely regulating ROSs peroxymonosulfate (PMS)-based by site engineering COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway 100 % , whereas biphenyl-based (BPD-COFs) almost identical structures activate produce radicals (⋅OH SO4.- ). The BPY-COFs/PMS system delivers boosted performance degradation target pollutants from water, which ca. 9.4 times that its BPD-COFs counterpart, surpassing most reported PMS-based systems. Mechanism analysis indicated highly electronegative pyridine-N atoms on BPY-COFs provide extra adsorb terminal H PMS, resulting simultaneous adsorption O one pyridine ring, facilitates cleavage S-O bond generate .

Язык: Английский

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Effective degradation of phenol by activating PMS with bimetallic Mo and Ni Co-doped g C3N4 composite catalyst: A Fenton-like degradation process promoted by non-free radical 1O2

Environmental Research, Год журнала: 2023, Номер 243, С. 117848 - 117848

Опубликована: Дек. 6, 2023

Язык: Английский

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Singlet oxygen in biochar-based catalysts-activated persulfate process: From generation to detection and selectivity removing emerging contaminants

Chemical Engineering Journal, Год журнала: 2024, Номер 485, С. 149724 - 149724

Опубликована: Фев. 16, 2024

Язык: Английский

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Carbon nitride with grafted molecular as electron acceptor and active site to achieve efficient photo-activated peroxymonosulfate for organic pollutants removal

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 345, С. 123693 - 123693

Опубликована: Янв. 4, 2024

Язык: Английский

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Fe(II) and Pyridinic N complex sites synergy to activate PMS for specific generation of 1O2 to degrade antibiotics with high efficiency

The Science of The Total Environment, Год журнала: 2023, Номер 892, С. 164067 - 164067

Опубликована: Май 30, 2023

Язык: Английский

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Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 16, 2024

Abstract Photocatalytic oxygen reduction to produce hydrogen peroxide (H 2 O ) is a promising route providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts efficient overall H production in pure water has impeded ongoing research and practical thrusts. Here we present cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting hole accumulated BTT electron‐rich TBTN block. Under one sun, 11013 μmol h −1 g yield rate achieved without any sacrificial agent, outperforming most previous reports. Furthermore, DFT calculation situ DRIFTS spectrums suggesting Yeager‐type absorption *O ⋅ − intermediate cyanide active site, which prohibits formation superoxide radical revealing favored pathway.

Язык: Английский

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Ce-doped CuCoO2 delafossite with switchable PMS activation pathway for tetracycline degradation

Chemical Engineering Journal, Год журнала: 2024, Номер 481, С. 148633 - 148633

Опубликована: Янв. 12, 2024

Язык: Английский

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Anthraquinone centers modified covalent organic frameworks for boosted photocatalytic O2-to-H2O2 synthesis: Inhibiting the in-situ decomposition of H2O2

Chemical Engineering Journal, Год журнала: 2024, Номер 481, С. 148494 - 148494

Опубликована: Янв. 4, 2024

Язык: Английский

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Pyridine‐Based Covalent Organic Frameworks with Pyridyl‐Imine Structures for Boosting Photocatalytic H₂O₂ Production via One‐Step 2e⁻ Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 3, 2024

Bipyridine-based covalent organic frameworks (COFs) have emerged as promising contenders for the photocatalytic generation of hydrogen peroxide (H

Язык: Английский

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