Ethynyl‐Linked Donor–Acceptor Covalent Organic Framework for Highly Efficient Photocatalytic H₂O₂ Production

Advanced Energy Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 19, 2025

Abstract Photocatalytic H 2 O synthesis from and is considered to be one of the most promising alternative approaches for manufacturing . Developing highly active selective photocatalysts significant in achieving efficient photosynthesis. Herein, an ethynyl‐linked donor–acceptor covalent organic framework (COF), named EBBT‐COF, prepared condensation reaction between electron‐deficient unit 4,4′,4″‐(1,3,5‐benzenetriyltri‐2,1‐ethynediyl)tris‐benzenamine electron‐rich benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene‐2,5,8‐tricarboxaldehyde. Powder X‐ray diffraction N adsorption isotherm unveil crystalline porous hcb network EBBT‐COF with pores size centered at ca 2.3 nm. Spectroscopic characterizations demonstrate excellent visible‐light absorption capacity enhanced photo‐induced charge separation transport efficiency owing its architecture. Density functional theory calculations electrochemical tests indicate high activity selectivity toward 2e − reduction water oxidation triethynylbenzene trithiophene moieties accelerate ‐to‐H O‐to‐H conversion, respectively. These merits enable a photocatalyst generation yield rate 5 686 µmol g −1 h , optimal apparent quantum 15.14%, solar‐to‐chemical conversion 1.17% (λ > 400 nm), representing best performance among COF‐based reported thus far.

Language: Английский

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Exploring high-connectivity three-dimensional covalent organic frameworks: topologies, structures, and emerging applications

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

The design principles, development process, structural analysis, applications, challenges, and future directions of high-connectivity 3D COFs.

Language: Английский

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The Importance and Discovery of Highly Connected Covalent Organic Framework Net Topologies

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

Published: Jan. 2, 2025

Furthering the field of synthetic organic chemistry from discrete molecules regime to extended structure regime, covalent frameworks (COFs) represent a new genre crystalline porous materials featuring designability with molecular-level precision, well-defined porosity, and exceptional stability imparted by robust linkages reticulating molecules. The topology COFs is principal feature that regulates their functionality usability for emerging technologies. Profound comprehension network topologies maneuvering them toward targeted applications are crucial advancing realm COF research developing novel functional exciting breakthroughs. In this Perspective, we discuss recent pursuits contributing discovery highly connected nets having topologies, assess key challenges achieving such offer insights into current scenario future directions.

Language: Английский

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Porphyrin‐Based Covalent Organic Frameworks for CO₂ Photo/Electro‐Reduction

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Photo/electro-catalytic CO2 reduction into high-value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post-modification capability, excellent stability, porphyrin-based covalent organic frameworks (COFs) have emerged as attractive photo/electro-catalysts towards reduction. In this review, the research progress of COFs photo/electro-catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Language: Английский

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S‐Scheme Heterojunction Fabricated from Covalent Organic Framework and Quantum Dot for Enhanced Photosynthesis of Hydrogen Peroxide from Water and Air

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

Published: Sept. 16, 2024

Abstract Covalent organic frameworks (COFs) with stable crystalline porous structures and flexible assembly properties contribute to the direct photocatalytic synthesis of H 2 O meet growing global demand. To address challenges insufficient redox capacity photogenerated carrier recombination COFs, S‐scheme heterojunction is constructed from COFs quantum dots (QDs) improve production . Herein, 0D ZnCdS QDs (ZCS) uniformly anchor on surface a 2D conjugated tetrathiafulvalene‐based COF (TT‐COF), affording TT‐COF/ZCS. Formation effectively prevents agglomeration ZCS, modulates energy band structure TT‐COF, enhances migration carriers ability. As total consequence, optimized (TZ‐40) able afford in yield up 5171 µmol g −1 h under visible light irradiation , much higher than those for 2520 2647 The present result demonstrates great potential COFs/QDs‐based heterojunctions applications including production.

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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Engineering Polyheptazine and Polytriazine Imides for Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Aug. 27, 2024

Abstract As organic semiconductor materials gain increasing prominence in the realm of photocatalysis, two carbon‐nitrogen materials, poly (heptazine imide) (PHI) and (triazine (PTI), have garnered extensive attention applications owing to their unique structure properties. This review elaborates on distinctive physical chemical features PHI PTI, emphasizing formation mechanisms ensuing Furthermore, it elucidates intricate correlation between energy band structures various photocatalytic reactions. Additionally, outlines primary synthetic strategies for constructing along with characterization techniques identification. It also summarizes enhancing performance whose advantages are discussed. Finally, highlights promising prospects challenges PTI as photocatalysts.

Language: Английский

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Encapsulating perovskite quantum dots into 3D COF for visible light-driven CO2 reduction

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

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3D N-heterocyclic covalent organic frameworks for urea photosynthesis from NH3 and CO2

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 28, 2025

Abstract Artificial photosynthesis of urea from NH 3 and CO 2 seems to remain still essentially unexplored. Herein, three isomorphic three-dimensional covalent organic frameworks with twofold interpenetrated ffc topology are functionalized by benzene, pyrazine, tetrazine active moieties, respectively. A series experiment results disclose the gradually enhanced conductivity, light-harvesting capacity, photogenerated carrier separation efficiency, co-adsorption capacity towards in order benzene-, pyrazine-, tetrazine-containing framework. This turn endows framework superior photocatalytic activity production yield 523 μmol g −1 h , 40 4 times higher than that for benzene- pyrazine-containing framework, respectively, indicating heterocyclic N microenvironment-dependent catalytic performance these photocatalysts. is further confirmed in-situ spectroscopic characterization density functional theory calculations. work lays a way sustainable urea.

Language: Английский

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Porphyrin‐Based Covalent Organic Frameworks for CO₂ Photo/Electro‐Reduction

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Abstract Photo/electro‐catalytic CO 2 reduction into high‐value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post‐modification capability, excellent stability, porphyrin‐based covalent organic frameworks (COFs) have emerged as attractive photo/electro‐catalysts towards reduction. In this review, the research progress of COFs photo/electro‐catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Language: Английский

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