Turning on Singlet Oxygen Generation by Outer‐Sphere Microenvironment Modulation in Porphyrinic Covalent Organic Frameworks for Photocatalytic Oxidation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 29, 2023

Singlet oxygen (

Language: Английский

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Covalent organic frameworks for CO₂ capture: from laboratory curiosity to industry implementation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6294 - 6329

Published: Jan. 1, 2023

Synergistic developments of covalent organic frameworks and engineering processes can expedite the qualitative leap for net-zero carbon emissions.

Language: Английский

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Macrocycle‐Based Covalent Organic Frameworks

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(16)

Published: Jan. 6, 2023

Macrocycles with well-defined cavities and the ability to undergo supramolecular interactions are classical materials that have played an essential role in science. However, one of most substantial barriers limiting utilization macrocycles is their aggregation, which blocks active regions. Among many attempted strategies prevent such installing into covalent organic frameworks (COFs), porous stable reticular networks, has emerged as ideal solution. The resulting macrocycle-based COFs (M-COFs) preserve macrocycles' unique activities, enabling applications various fields single-atom catalysis, adsorption/separation, optoelectronics, phototherapy, structural design forming single-layered or mechanically interlocked COFs. properties unmatchable by any combination other substrates, opening a new chapter advanced materials. This review focuses on latest progress concepts, synthesis, properties, M-COFs, presents in-depth outlook challenges opportunities this emerging field.

Language: Английский

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Blue light photocatalytic oxidation of sulfides to sulfoxides with oxygen over a thiazole-linked 2D covalent organic framework

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 338, P. 123070 - 123070

Published: July 5, 2023

Language: Английский

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Rigid covalent organic frameworks with thiazole linkage to boost oxygen activation for photocatalytic water purification

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 27, 2024

Owing to their capability produce reactive oxygen species (ROS) under solar irradiation, covalent organic frameworks (COFs) with pre-designable structure and unique architectures show great potentials for water purification. However, the sluggish charge separation, inefficient activation poor stability in COFs restrict practical applications decontaminate water. Herein, via a facile one-pot synthetic strategy, we direct conversion of reversible imine linkage into rigid thiazole can adjust π-conjugation local polarization skeleton boost exciton dissociation on COFs. The also improve robustness during consecutive utilization process. More importantly, optimal C 2p states (COF-S) effectively increases activities neighboring benzene unit directly modulate O2-adsorption energy barrier ROS production efficiency, resulting excellent photocatalytic degradation efficiency seven toxic emerging contaminants (e.g. degrading ~99% 5 mg L−1 paracetamol only 7 min) effective bacterial/algal inactivation performance. Besides, COF-S be immobilized continuous-flow reactor enlarged efficiently eliminate pollutants natural sunlight demonstrating feasibility application. Linking by linkages simultaneously enhance stability, separation COFs, performance towards micropollutants

Language: Английский

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Red-Light-Based Effective Photocatalysis of a Photosensitive Covalent Organic Framework Triggered Singlet Oxygen

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2631 - 2641

Published: Feb. 6, 2024

The direct application of low-energy red light for photochemical transformations is synthetically appealing but practically challenging. Covalent organic frameworks (COFs) exhibit significant potential within this domain, owing to their broad spectrum absorption and prevalence in reactions, despite the fact that these photocatalysts are now mainly focused on using ultraviolet (UV) blue light. In study, an imidazole-linked porphyrin-based COF, PyPor-COF, which exhibits a wide band ranging from 200 700 nm, especially strong 630 expected be applied photocatalytic reactions. PyPor-COF possesses capacity selectively generate singlet oxygen (1O2) with high efficiency, renders it efficient photosensitizer reactions olefin cleavages thioanisole photooxidation under present study demonstrates intriguing prospect photoactive COFs as type II utilization photocatalyses.

Language: Английский

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Designing Local Electron Delocalization in 2D Covalent Organic Frameworks for Enhanced Sunlight-Driven Photocatalytic Activity

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3556 - 3564

Published: Feb. 20, 2024

Electron delocalization is a versatile method to tune the electronic structure of materials for maximizing their performances. Herein, TPBD covalent organic frameworks (COFs) with controlled electron-delocalization characteristics (denoted as TPBD-R-COF, R = H, F, CN, and NO2) were synthesized by molecular engineering systematically investigate effect electron on photocatalytic performance. We found that performance can be enhanced modulating local in COFs. The activity TPBD-CN-COF more than 12 times greater TPBD-H-COF oxidative coupling amines imines, where yield product was increased from 8 99%. experimental results theoretical calculations revealed optimal electron-attracting group −CN shows highest charge separation efficiency transport rate, while excessive not better such properties. Our findings provide strategy design optimize COF-based catalysts.

Language: Английский

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Highly Effective Generation of Singlet Oxygen by an Imidazole-Linked Robust Photosensitizing Covalent Organic Framework

ACS Nano, Journal Year: 2022, Volume and Issue: 16(12), P. 21565 - 21575

Published: Dec. 6, 2022

Developing effective photosensitizers to initiate the generation of singlet oxygen (1O2) is great significance in both chemistry and physiology. Herein, linking photoactive porphyrin moieties by situ-formed robust imidazole groups, a covalent organic framework (COF), PyPor-COF, was successfully designed synthesized. Detailed characterizations reveal that it not only possesses high crystallinity, permanent porosity, stability but also shows semiconductive photoresponse activity. As demonstrated electron paramagnetic resonance experiments, COF can 1O2 efficiently under visible-light irradiation, efficiency which higher than pristine porphyrin-based reactant even some commonly used commercially available photosensitizing agents. Anticancer experiments prove trigger production physiological environment. This work demonstrates imidazole-linked porphyrin-incorporated highly promising photosensitizer be applied photodynamic therapy.

Language: Английский

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Cooperative Catalysis between Dual Copper Centers in a Metal–Organic Framework for Efficient Detoxification of Chemical Warfare Agent Simulants

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21046 - 21055

Published: Oct. 31, 2022

Chemical warfare agents (CWAs) are among the most lethal chemicals known to humans. Thus, developing multifunctional catalysts for highly efficient detoxification of various CWAs is great importance. In this work, we developed a robust copper tetrazolate metal–organic framework (MOF) catalyst containing dicopper unit similar coordination geometry active sites natural phosphatase and tyrosinase enzymes. This aided in phosphate ester bond hydrolysis hydrogen peroxide decomposition, ultimately achieving high efficiency against both nerve agent simulant (diethoxy-phosphoryl cyanide (DECP)) with half-life 3.5 min sulfur mustard (2-chloroethyl ethyl sulfide (CEES)) 4.5 min, making it competitive other reported materials. The ZZU-282 provide versatile binding modes substrates, thereby promoting activation substrates enhancing catalytic efficiency. A combination postmodified metal exchange control experiments, density functional theory calculations, evaluations confirmed that dual Cu centers reaction. study offers new design perspective achieve advanced CWA detoxification.

Language: Английский

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Recent advances in metal-free covalent organic frameworks for photocatalytic applications in energy and environmental fields

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(7), P. 3245 - 3261

Published: Jan. 1, 2023

A review on metal-free COF photocatalysts from an environmental perspective is presented.

Language: Английский

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