Photocatalysis with Covalent Organic Frameworks

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(21), P. 3182 - 3193

Published: Oct. 7, 2024

ConspectusUtilizing light to enable chemical conversions presents a green and sustainable approach produce fuels chemicals, photocatalysis is one of the key technologies that needs be well developed in this century. Despite continuous progress advancement various photocatalysts based on small inorganic organic compounds, polymers, networks, designing constructing combine activity, selectivity, reusability remains challenging goal. For catalytic difficulty originates from complexity photochemical reactions, where light-harvesting system, multielectron multihole-involving processes, pinpoint mass delivery simultaneously need established system. stems elaborate design sites space, especially their orbital energy levels, spatial arrangement, environment; developing molecular strategy enables an overall control these factors different aspects necessary yet arduous. reusability, arises stability recyclability upon operation under photoredox reaction conditions. How recover energy-saving way cyclic use while retaining activity selectivity at core problem. These bottleneck issues reflect photocatalyst not simple summation above requirements, but systematic scheme can organically interlock needed.To such precise control, basic requirement scaffold for promising its primary high-order structures should molecularly predesignable synthetically controllable. Such regime has successfully evolved natural photosynthesis, chlorophyll antennae photocatalytic centers are spatially well-organized energetically well-defined build ways exciton migration, photoinduced electron transfer charge separation, hole flows, oxidation water reduction carbon dioxide, thereby converting into oxygen release ATP NADPH via dioxide glucose with through dark reaction. Similarly, polymeric would integrating complex processes construct photocatalysts.Covalent frameworks (COFs) class extended materials organization units or metallo-organic moieties architectures. In principle, COFs designable topology diagrams controllable polymerization offering irreplaceable platform synthesizing photocatalysts. This feature enticed researchers develop drove rapid field over past decade. Account, we summarize recent advances synthetic COF photocatalysts, by highlighting achievements harvesting, trigger allow carrier transport delivery, level, environmental engineering, aim reveal full picture field. By scrutinizing typical show problems addressed predict future directions.

Language: Английский

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Accelerating Anhydrous Proton Transport in Covalent Organic Frameworks: Pore Chemistry and Its Impacts

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: June 6, 2024

Abstract Proton conduction is important in both fundamental research and technological development. Here we report designed synthesis of crystalline porous covalent organic frameworks as a new platform for high‐rate anhydrous proton conduction. By developing nanochannels with different topologies pathways loading neat phosphoric acid to construct robust carrier networks the pores, found that pore topology crucial Its effect on increasing conductivity an exponential mode other than linear fashion, endowing materials exceptional conductivities exceeding 10 −2 S cm −1 over broad range temperature low activation energy barrier down 0.24 eV. Remarkably, size controls mechanism, where mesopores promote via fast‐hopping while micropores follow sluggish vehicle process. Notably, decreasing content drastically reduces greatly increases barrier, emphasizing pivotal role well‐developed network transport. These findings insights unveil general transformative guidance designing framework systems ion conduction, storage, conversion.

Language: Английский

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Remarkable increase in electrochemiluminescence of isomeric bipyridine-based covalent organic frameworks via regulating the direction of imine linkage for sensing application

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 684, P. 262 - 271

Published: Jan. 7, 2025

Language: Английский

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Emerging Trends in Conductive Two-Dimensional Covalent Organic Frameworks for Large-Area Electronic Applications

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Two-dimensional covalent organic frameworks (2D COFs) are emerging as promising materials for advanced electronic applications due to their tunable porosity, crystalline order, and π-conjugated structures. These properties enable efficient charge transport bandgap modulation, making 2D COFs strong candidates devices such transistors memristors. However, the practical application of remains limited by challenges in achieving high-quality thin films with large-area uniformity improved crystallinity. This review explores recent advancements fabrication conductive electronics. Various synthesis strategies, including direct growth, vapor-assisted conversion, interfacial methods, discussed context enhancing film quality scalability. The integration into is classified based on operation mechanism─planar vertical field-effect (FETs), electrochemical (ECTs), memristors─to highlight device performance. Looking forward, large-scale production, material compatibility, outlined, alongside potential solutions through innovative techniques collaborative research efforts. By addressing these challenges, poised drive breakthroughs adoption next-generation semiconducting technologies.

Language: Английский

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Photons, Excitons, and Electrons in Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32161 - 32205

Published: Nov. 18, 2024

Covalent organic frameworks (COFs) are created by the condensation of molecular building blocks and nodes to form two-dimensional (2D) or three-dimensional (3D) crystalline frameworks. The diversity with different properties functionalities large number possible framework topologies open a vast space well-defined porous architectures. Besides more classical applications materials such as absorption, separation, catalytic conversions, interest in optoelectronic COFs has recently increased considerably. electronic both their linkage chemistry can be controlled tune photon absorption emission, create excitons charge carriers, use these carriers photocatalysis, luminescence, chemical sensing, photovoltaics. In this Perspective, we will discuss relationship between structural features properties, starting connectivity, layer stacking 2D COFs, control over defects morphology including thin film synthesis, exploring theoretical modeling structural, electronic, dynamic discussing recent intriguing focus on photocatalysis photoelectrochemistry. We conclude some remarks about present challenges future prospects powerful architectural paradigm.

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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Construction of Highly Porous and Robust Hydrogen‐Bonded Organic Framework for High‐Capacity Clean Energy Gas Storage

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 13, 2024

Abstract Development of highly porous and robust hydrogen‐bonded organic frameworks (HOFs) for high‐pressure methane hydrogen storage remains a grand challenge due to the fragile nature bonds. Herein, we report strategy constructing double‐walled framework target HOF (ZJU‐HOF‐5a) extraordinary CH 4 H 2 storage. ZJU‐HOF‐5a features minimized twofold interpenetration with structure, in which multiple supramolecular interactions are existed between interpenetrated walls. This structural configuration can notably enhance robustness while maintaining its high porosity, affording one highest gravimetric volumetric surface areas 3102 m g −1 1976 cm −3 among reported HOFs so far. thus exhibits an extremely uptake 43.6 L at 77 K/100 bar working capacity 41.3 under combined swing conditions (77 bar→160 K/5 bar), also impressive performance 5–100 187 (or 159) 3 (STP) 270 K 296 K), outperforming most materials. Single‐crystal X‐ray diffraction studies on ‐loaded reveal that abundant binding sites ultrahigh porosities account capacities. Combined stability, super‐hydrophobicity, easy recovery, is placed promising materials applications.

Language: Английский

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Helicene Covalent Organic Frameworks for Robust Light Harvesting and Efficient Energy Transfers

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 18, 2024

Abstract Helicenes represent a class of fascinating π compounds with fused yet folded backbones. Despite their broad structural diversity, harnessing helicenes to develop well‐defined materials is still formidable challenge. Here we report the synthesis crystalline porous helicene by exploring synthesize covalent 2D lattices and layered frameworks. Topology‐directed polymerization [6]helicenes porphyrin creates networks alternate helicene‐porphyrin alignment along x y directions at 1.5‐nm interval develops [6]helicene frameworks through reversed anti‐AA stack z direction form segregated columnar arrays. Notably, this configuration enables be highly red luminescent benchmark quantum yields. The trigger effieicnt intra‐framework singlet‐to‐singlet state energy transfer from facilitate intermolecular triplet‐to‐triplet molecular oxygen produce reactive species, harvesting wide range photons ultraviolet near‐infrared regions for light emitting photo‐to‐chemical conversion. This study introduces new family extended frameworks, laying groundwork unprecedented structures functions.

Language: Английский

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Synergistic linkage engineering in covalent organic frameworks for boosting photocatalytic hydrogen evolution

Journal of Materials Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Enhancing π-conjugation and bond stability, along with the introduction of hydrophilic carboxyl groups into COF channels, significantly boosts photocatalytic performance, reusability, durability COF.

Language: Английский

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Modulating Linker Conjugation and Flexibility of Aggregation‐Induced Emission Covalent Organic Framework for Enhanced Luminescence

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

Published: Feb. 6, 2025

Abstract In order to inhibit non‐radiative decay pathways of covalent‐organic frameworks (COFs), a strategy is proposed block intralayer conjugation and interlayer π–π stacking by using flexible aggregation‐induced emission (AIE) building blocks (4′,4′′′,4′′′′′,4′′′′′′′‐(1,2‐ethenediylidene) tetrakis[1,1′‐biphenyl]‐4‐carbaldehyde (TFBE)) connected weakly conjugated linker. By the TFBE as changing flexibility linker, TFBE‐COFs with different luminescence properties are obtained. Experimental theoretical results show that these have high crystallinity large layer spacing, among which photoluminescence quantum yield hydrazone (Hz)‐COF TFBE‐ODH (oxalyl dihydrazide (ODH)) in solid state reaches 26.28%, superior most COFs reported so far. The excellent attributed non‐planar geometry TFBE, inhibits quenching. Moreover, π‐electron delocalization‐induced leaps suppressed further enhances TFBE‐COFs. Hz‐COF exhibits sensing performance for trace tetracycline, detection limit 0.15 µ m . addition, white light‐emitting diodes coated manufactured achieve high‐quality light emission. This study provides new design application high‐emission COFs.

Language: Английский

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