Photocatalysis with Covalent Organic Frameworks

Accounts of Chemical Research, Год журнала: 2024, Номер 57(21), С. 3182 - 3193

Опубликована: Окт. 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.

Язык: Английский

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Gold-Modified Covalent Organic Frameworks-Assisted Laser Desorption/Ionization Mass Spectrometry for Analysis of Metabolites Induced by Triclosan Exposure

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Янв. 17, 2025

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) holds great promise for the rapid and sensitive detection of biomolecules, but its precise small molecule metabolites is hindered by severe background interference from organic matrix in low molecular weight range. To address this issue, nanomaterials have commonly been utilized as substrates LDI-MS. Among them, covalent frameworks (COFs), known their unique optical absorption structural properties, garnered significant attention. Despite these advantages, ionization efficiency remains a challenge. Herein, composite material COF-S@Au nanoparticles (NPs), incorporating Au NPs into sulfur-functionalized COF (COF-S) through postsynthetic modification, was designed adopted substrates. This hybrid leverages synergistic effects COF-S to improve minimize interference. The demonstrated 5-16-fold improvement MS signals biomolecules along with clean excellent resistance salt protein Their corresponding limits (LODs) were achieved at ∼pmol. Furthermore, applied analyze triclosan (TCS)-exposed mouse model, successfully identifying 10 differential associated TCS toxicity. work provides foundation developing advanced LDI-MS materials high-performance metabolic analysis offers valuable insights toxicity potential applications environmental toxicology.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

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Covalent organic frameworks as advanced materials for adsorption and analysis of contaminants in environmental, biological and food matrices

Coordination Chemistry Reviews, Год журнала: 2025, Номер 533, С. 216507 - 216507

Опубликована: Фев. 21, 2025

Язык: Английский

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Catalyst-Derived Hierarchy in 2D Imine-Based Covalent Organic Frameworks

Nanoscale, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Dual role of scandium triflate as catalyst and growth modifier enables hierarchical 2D imine-based covalent organic framework sorbents.

Язык: Английский

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Three-Dimensional Covalent Organic Frameworks with lil Topology

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 8, 2025

The diversity of covalent organic frameworks (COFs) is continuously expanding, providing various materials with tailor-made structures and properties. However, the development crystalline three-dimensional (3D) COFs new topologies an essential but arduous challenge. In this study, we first developed one kind 3D lil topological structure, which were assembled by D4h- C2h-symmetric building blocks. determined in a space group Imma, each D4h-symmetric unit connected four units, forming noninterpenetrated network. densely packed copper phthalocyanine stable polyimide linkage render these as polymeric material high dielectric constant low loss at frequencies (>1 kHz). Significantly, was 63, constitutes record value among phthalocyanine-based polymers. Therefore, study not only provides important guidance for design lil-net also supplies promising application high-energy-density pulsed capacitors.

Язык: Английский

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Designed Synthesis of Covalent Organic Multicycles

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

Covalent organic multicycles (COMs) have been designed and synthesized via the covalent assembly of rigid three-arm Y-shaped U-shaped building blocks. These COMs a precise tricyclic structure exhibit remarkable solubility in range common solvents. Featuring well-defined cavities with electron-rich structures, these displayed good adsorption capabilities for iodine both its vapor liquid states. Moreover, solution processability allows facile fabrication as uniform films on different substrates spin coating methods.

Язык: Английский

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

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

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Superacid In Situ Protected Synthesis of Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

Covalent organic frameworks, as a class of fascinating crystalline porous materials, are attracting increasing attention in various fields. Synthesizing these materials to attain crystallinity and porosity is essential; however, it time-consuming, not cost-effective, energy-demanding involves extensive screenings reaction conditions employs undesired aromatic solvents. Despite recent progress the synthesis, finding an efficient, convenient, low-toxicity, widely applicable method remains challenging goal. Here, we report situ-protected strategy for synthesizing imine-linked frameworks by exploring triflic acid catalyst replace traditional acetic deploying alcohols single-component medium instead We found that function threefold: rapidly protonates amino groups amine monomers into ammonium cations, protects formyl units aldehyde converting them acetals, improves solubilities both monomers. The situ-protection scheme greatly changes their concentrations reactivities, making reactions highly controllable reversible. This general monomer combinations develop with different topologies, including tetragonal, rhombic, pentagonal, hexagonal, kagome, dual trigonal, hexagonal shapes, pore sizes from micropores mesopores, presenting facile simple way synthesize 28 yet high-quality n-butanol/water. Remarkably, nine new synthesized first time, which cannot be prepared systems. porphyrin exhibited exceptional photocatalytic activities activation molecular oxygen produce reactive species singlet oxygen.

Язык: Английский

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Reticular Design and Synthesis of Covalent Organic Frameworks with Irregular Hexagonal Tiling

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because strict constraints on tile lengths and angles. Guided by reticular chemistry, we deconstructed type III hexagonal into a combination D2h + monomers achieved first successful synthesis 2D COFs such with hit topology. By tuning crystal growth conditions, obtained set isomers, COF-hit COF-bex, distinct structures. Powder X-ray diffraction high-resolution transmission electron microscopy were employed to precisely characterize their topology demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design using opens new avenue diversify structural types topological varieties promote chemistry.

Язык: Английский

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