Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(19)

Опубликована: Фев. 15, 2022

Synthesizing H

Язык: Английский

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Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 28, 2023

Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative reductive reaction centers remain a challenge. In this study, benzotrithiophene-based with spatially separated redox are rationally designed for the photocatalytic production of hydrogen peroxide from water oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity H2O2 photogeneration, yield rate 2111 μM h-1 (21.11 μmol 1407 g-1 h-1) solar-to-chemical conversion efficiency 0.296%. Codirectional charge transfer large energetic differences between linkages linkers verified in double donor-acceptor structures periodic frameworks. sites mainly concentrated on electron-acceptor fragments near imine bond, which regulate electron distribution adjacent carbon atoms to optimally reduce Gibbs free energy O2* OOH* intermediates during formation H2O2.

Язык: Английский

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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Язык: Английский

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A novel organic/inorganic S-scheme heterostructure of TCPP/Bi12O17Cl2 for boosting photodegradation of tetracycline hydrochloride: Kinetic, degradation mechanism, and toxic assessment

Applied Surface Science, Год журнала: 2022, Номер 610, С. 155346 - 155346

Опубликована: Окт. 30, 2022

Язык: Английский

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Developing Ni single-atom sites in carbon nitride for efficient photocatalytic H2O2 production

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 6, 2023

Photocatalytic two-electron oxygen reduction to produce high-value hydrogen peroxide (H2O2) is gaining popularity as a promising avenue of research. However, structural evolution mechanisms catalytically active sites in the entire photosynthetic H2O2 system remains unclear and seriously hinders development highly-active stable photocatalysts. Herein, we report high-loading Ni single-atom photocatalyst for efficient synthesis pure water, achieving an apparent quantum yield 10.9% at 420 nm solar-to-chemical conversion efficiency 0.82%. Importantly, using situ synchrotron X-ray absorption spectroscopy Raman directly observe that initial Ni-N3 dynamically transform into high-valent O1-Ni-N2 after O2 adsorption further evolve form key *OOH intermediate before finally forming HOO-Ni-N2. Theoretical calculations experiments reveal structure reduces formation energy barrier suppresses O=O bond dissociation, leading improved production activity selectivity.

Язык: Английский

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Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H₂O₂ Production

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(5), С. 2975 - 2984

Опубликована: Янв. 25, 2023

Multicomponent reactions (MCRs) can be used to introduce different functionalities into highly stable covalent organic frameworks (COFs). In this work, the irreversible three-component Doebner reaction is utilized synthesize four chemically quinoline-4-carboxylic acid DMCR-COFs (DMCR-1-3 and DMCR-1NH) equipped with an acid-base bifunctionality. These show superior photocatalytic H2O2 evolution (one of most important industrial oxidants) compared imine COF analogue (Imine-1). This achieved sacrificial oxidants but also in pure water under oxygen or air atmosphere. Furthermore, high photostability, durability, recyclability. MCR-COFs thus provide a viable materials' platform for solar chemical energy conversion.

Язык: Английский

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Pyrene‐Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 10, 2023

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2 O2 production. The experimental studies are complemented by density functional theory calculations, proving that the unit is more active production than bipyridine (diarylamino)benzene reported previously. decomposition experiments verified distribution of over a large surface area COFs plays an important role in catalytic performance. Py-Py-COF though contains other which induces high due to dense concentration close proximity limited area. Therefore, two-phase reaction system (water-benzyl alcohol) was employed inhibit decomposition. This first report on applying pyrene-based generation.

Язык: Английский

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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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Solar‐to‐H₂O₂ Catalyzed by Covalent Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Авг. 14, 2023

Abstract Benefiting from the excellent structural tunability, robust framework, ultrahigh porosity, and rich active sites, covalent organic frameworks (COFs) are widely recognized as promising photocatalysts in chemical conversions, emerged hydrogen peroxide (H 2 O ) photosynthesis 2020. H , serving an environmental‐friendly oxidant a liquid fuel, has attracted increasing researchers to explore its potential. Over past few years, numerous COFs‐based developed with encouraging achievements production, whereas no comprehensive review articles exist summarize this specific significant area. Herein we provide systematic overview of advances challenges COFs photocatalytic production. We first introduce priorities photosynthesis. Then, various strategies improve efficiency discussed. The perspective outlook for future emerging field finally offered. This timely will pave way development highly efficient practical production value‐added chemicals not limited .

Язык: Английский

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Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H₂O₂

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(9)

Опубликована: Дек. 30, 2022

The full reaction photosynthesis of H2 O2 that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization overcome complex reaction-process anthraquinone-oxidation. Here, a kind oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through covalent-coupling tetrathiafulvalene (photo-oxidation site) benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency photo-redox sites enables generation . Specifically, record-high yield (TTF-BT-COF, ≈276 000 μM h-1 g-1 ) for achieved among porous crystalline photocatalysts. This first work design COFs , might extend scope in production.

Язык: Английский

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