Covalent Organic Frameworks for Photocatalysis

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

Published: Dec. 9, 2024

Abstract The global energy crisis and environmental concerns are driving research into renewable sustainable conversion storage technologies. Solar energy, as an ideal resource, has significant potential to contribute the goal of net‐zero carbon emissions if effectively harnessed converted a reliable storable form energy. Photocatalysts have convert sunlight chemical carriers. In this respect, covalent organic frameworks (COFs) shown great promise due their tunable structure on different length scales, high surface areas, beneficial optical properties such broad visible light absorption. This review offers comprehensive overview key developments in COF‐based photocatalysts for various applications, including water splitting, hydrogen peroxide generation, transformations, dioxide nitrogen reduction. underlying mechanisms, essential principles material design, structure‐function relationships COFs photocatalytic applications discussed. challenges faced by also summarized strategies enhance performance explained, improving crystallinity, regulating molecular structures, tailoring linkages, incorporating cocatalysts. Finally, critical proposed utilization photocatalytically generated chemicals value‐added products.

Language: Английский

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Linkage Microenvironment Modulation in Triazine‐Based Covalent Organic Frameworks for Enhanced Photocatalytic Hydrogen Peroxide Production

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 26, 2025

Abstract Covalent organic frameworks (COFs), known for the precise tunability of molecular structures, hold significant promise photocatalytic hydrogen peroxide (H 2 O ) production. Herein, by systematically altering quinoline (QN) linkages in triazine (TA)‐based COFs via multi‐component reactions, six R‐QN‐TA‐COFs are synthesized with identical skeletons but different substituents. The fine‐tuning optoelectronic properties and local microenvironment is allowed, thereby optimizing charge separation improving interactions dissolved oxygen. Consequently, MeO‐QN‐TA‐COF customized to achieve an impressive rate H production up 7384 µmol g⁻ 1 h⁻ under air atmosphere water without any sacrificial agents, surpassing most reported COF photocatalysts. Its high stability demonstrated through five consecutive recycling experiments characterization recovered COF. reaction mechanism further investigated using a suite quenching experiments, situ spectroscopic analysis, theoretical calculations. enhanced over 2e⁻ oxygen reduction oxidation pathways. Overall, crucial role linkage modulation design solar‐driven effective

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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Isomeric 2D and 3D covalent organic frameworks induced by inter-modular hydrogen bonds for photocatalytic CO2 reduction

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160788 - 160788

Published: Feb. 1, 2025

Language: Английский

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Covalent Metal–Organic Frameworks: Fusion of Covalent Organic Frameworks and Metal–Organic Frameworks

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

ConspectusMetal-organic frameworks (MOFs) and covalent organic (COFs), as emerging porous crystalline materials, have attracted remarkable attention in chemistry, physics, materials science. MOFs are constructed by metal clusters (or ions) linkers through coordination bonds, while COFs prepared pure building blocks via bonds. Because of the nature linkages, their own shortcomings. Typically, relatively weak bond strengths bonds lead to poor chemical stability MOFs, which limits practical implementations. On other hand, due strong exhibit rather higher under harsh conditions, compared MOFs. However, lack open sites restricts functionalization application. Therefore, it is hypothesized that "cream-skimming" would address these drawbacks produce a new class material, namely, metal-organic (CMOFs), with unprecedented structural complexity advanced functionality. The CMOFs reveal synthetic approach for preparation reticular materials. Specifically, ions reacted chelating ligands assemble complexes or functional reactive (e.g., -CHO, -NH2), can be further connected form networked structures dynamic chemistry (DCC). isolated complex cluster precursors show enhanced prevents decomposition rearrangements during self-assembly process CMOFs. Since topology preassembled nodes well-defined, structure readily predicted upon directed networking Unaccessible from unstable highly ion/clusters traditional conditions DCC approach. Moreover, synergize advantages COFs, containing active ensuring various interesting properties, linkages allow high even conditions. In past few years, our group has specifically focused on development general strategies coinage (Cu, Ag, Au)-based cyclic trinuclear units (CTUs) DCC. CTUs trigonal planar functionalized sites, such -NH2 react afford Notably, also features properties including metallophilic attraction, π-acidity/basicity, luminescence, redox activity catalytic activity, incorporated into we envision promising platforms not only novel but potential applications many research fields gas absorption/separation, sensing, full-color display, catalysis, energy, biological applications. this Account, summarize recent studies CMOFs, starting linkage topological design, transformation, morphological control, fields. We discuss future opportunities challenges rapidly developed field hope Account may promote scientific discoveries CMOF-based technologies future.

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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Single-atom Cu sites on covalent organic frameworks with Kagome lattices for visible-light-driven CO2 reduction to propylene

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 361, P. 124587 - 124587

Published: Sept. 11, 2024

Language: Английский

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Efficient photoresponsive one-dimensional covalent organic framework as oxidase-like enzyme for ultrasensitive detection of antioxidants

Talanta, Journal Year: 2025, Volume and Issue: 286, P. 127519 - 127519

Published: Jan. 4, 2025

Language: Английский

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Regulating Charge Distribution in Porphyrin‐Based Polymer for Achieving Photocatalytic CO₂ Conversion to CH₄ or C₂H₆

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

Abstract The photocatalytic conversion of CO 2 into products such as CH 4 and C H 6 poses a significant challenge due to the lengthy reaction steps high energy barrier involved. In this study, both benzothiadiazole (BTD) hydroxyl groups (‐OH) are introduced cobalt‐based polymerized porphyrinic network (PPN) through C‐C coupling reaction. This modification orbital levels that strengthens ability gain electrons facilitates charge transfer in PPN. Hydroxyl group largely enhances for light response, while thiadiazole unit tunes molecular proper level. By way, BTD‐DBP‐PPN(Co) achieves capability under irradiation light. Co active site is reduce facilitate transfer. pathway production has been studied further mechanism explanation. Overall, series porphyrin centers with donor–acceptor (D‐A) structure designed synthesized enhance reduction performance achieve formation 300‐W Xe lamp irradiation.

Language: Английский

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Interfacial imine-bridging and charge directional migration dual regulation of ZnO/covalent organic frameworks S-scheme heterostructure for boosting photocatalytic CO2 reduction

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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