Viologen Covalent Organic Framework Mediates Near-Infrared Light-Induced Electron Transfer for Catalytic Oxidative Coupling Reactions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Near-infrared (NIR) light-driven photoreactions are advantageous over visible ones because NIR photons have lower energy and fewer side reactions, deeper penetration in reaction media, high abundance the solar spectrum. However, currently available covalent organic frameworks (COFs) absorb UV-vis region catalyze under blue or white light irradiation. Herein, we report a linker-to-linker charge transfer process viologen-linked porphyrin COF (Vio-COF), leading to novel type of hyperporphyrin effect extending absorption into with an edge at 998 nm. Under irradiation, photoinduced separation Vio-COF generates viologen radical that efficiently reduces oxygen form superoxide radicals for catalytic oxidative coupling reactions. The proximity units within framework significantly enhances performance Vio-COF, outperforming its homogeneous counterparts aerobic amidation amine was readily recycled used six

Language: Английский

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Machine Learning Accelerated Discovery of Covalent Organic Frameworks for Environmental and Energy Applications

Environmental Science & Technology, Journal Year: 2025, Volume and Issue: unknown

Published: March 30, 2025

Covalent organic frameworks (COFs) are porous crystalline materials obtained by linking ligands covalently. Their high surface area and adjustable pore sizes make them ideal for a range of applications, including CO2 capture, CH4 storage, gas separation, catalysis, etc. Traditional methods material research, which mainly rely on manual experimentation, not particularly efficient, while with advancements in computer science, high-throughput computational screening based molecular simulation have become crucial discovery, yet they face limitations terms resources time. Currently, machine learning (ML) has emerged as transformative tool many fields, capable analyzing large data sets, identifying underlying patterns, predicting performance efficiently accurately. This approach, termed "materials genomics", combines ML to predict design high-performance materials, significantly speeding up the discovery process compared traditional methods. review discusses functions screening, design, prediction COFs highlights their applications across various domains like thereby providing new research directions enhancing understanding COF applications.

Language: Английский

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Low-energy photoredox catalysis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Language: Английский

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Insights into Substituent Effects on the Fundamental Photocatalytic Processes of Covalent Organic Frameworks toward H₂ Evolution and H₂O₂ Production Reactions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11262 - 11272

Published: July 13, 2024

Language: Английский

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Electrocatalytic Generation of Singlet Oxygen via ROS-Mediated Redox Chain Reaction for Efficient Disinfection

Nano Letters, Journal Year: 2024, Volume and Issue: 24(23), P. 6939 - 6947

Published: May 30, 2024

The risk of harmful microorganisms to ecosystems and human health has stimulated exploration singlet oxygen (1O2)-based disinfection. It can be potentially generated via an electrocatalytic process, but is limited by the low production yield unclear intermediate-mediated mechanism. Herein, we designed a two-site catalyst (Fe/Mo–N/C) for selective 1O2 generation. Mo sites enhance generation precursors (H2O2), accompanied intermediate •HO2/•O2–. Fe site facilitates activation H2O2 into •OH, which accelerates •HO2/•O2– 1O2. A possible mechanism promoting through ROS-mediated chain reaction reported. as-developed electrochemical disinfection system kill 1 × 107 CFU mL–1 E. coli within 8 min, leading cell membrane damage DNA degradation. effectively applied medical wastewater. This work provides general strategy electrocatalysis efficient

Language: Английский

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Reticular Materials for Photocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Abstract Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional sources and has attracted significant research interest. Reticular materials, including metal‐organic frameworks (MOFs) covalent organic (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination bonds, respectively. function as heterogeneous catalysts, combining well‐defined structures high tailorability akin homogeneous catalysts. In this review, regulation light absorption, charge separation, surface in photocatalytic process through precise molecular‐level design based features reticular is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects performance delved, with emphasis their unique dynamic flexible microenvironments. For COFs, inherent excitonic effects due fully nature discussed highlight strategies regulate charge‐ and/or energy‐transfer‐mediated photocatalysis. Finally, current challenges future directions field, aiming provide comprehensive understanding how be optimized enhanced photocatalysis discussed.

Language: Английский

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A Universal Approach to Anchoring Chromophores onto Magnetic Scaffold for Achieving Easily Recyclable Heterogeneous Photocatalytic Systems

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Photocatalysis based on chromophores such as porphyrin, coumarin, anthraquinone, and pyrene is a promising technology to achieve green synthesis of various high-value chemicals, but the robust non-covalent immobilization onto light-inert scaffolds for industrialization-oriented heterogeneous photocatalysis remains challenging. In this work, simple universal strategy presented preparing highly efficient recyclable photocatalysts from chromophores, which achieved via biotinylation chromophore molecules subsequent supramolecular binding chromophore-biotin dyads streptavidin-decorated magnetic beads. As an example, commercial beads modified by 5,10,15,20-tetrakis(4-aminophenyl) porphyrin not only possessed remarkable photocatalytic activities oxidative coupling benzylamine derivatives oxidation thioanisole with highest product yields beyond 95% turnover numbers approaching 10000, driven photogenerated reactive oxygen species also demonstrated impressive chemical stability recyclability separation during 10 successive test cycles. The findings revealed in work pave way advancing valuable organic compounds pharmaceutical industry, agricultural sector, etc., rationally designed systems.

Language: Английский

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Reactive oxygen species generation for catalysis and biotherapeutic applications based on crystalline porous materials

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 518, P. 216068 - 216068

Published: July 17, 2024

Language: Английский

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Photocatalytic Applications of Covalent Organic Frameworks: Synthesis, Characterization, and Utility

Nanoscale, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This review highlights the recent advances in utilizing covalent organic frameworks (COFs) for photocatalytic applications.

Language: Английский

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Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 436, P. 115627 - 115627

Published: July 1, 2024

Language: Английский

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