Donor–Acceptor Fully Sp²‐Carbon Conjugated Covalent Organic Frameworks for Photocatalytic H₂O₂ Production

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 4, 2025

Abstract Covalent organic frameworks (COFs) are promising for photocatalytic H₂O₂ generation. However, imine‐linked COFs often suffer from poor charge separation and low performance. Therefore, constructing sp 2 carbon‐linked with extended π‐conjugation is very significant in boosting the properties, but their synthesis challenging due to reversibility of C═C bond. Here, two vinylene‐linked COFs: BBT‐ACN COF‐1 COF‐2 designed. To investigate effects different structures on exciton binding energy ( E b ), designed possesses a Donor–Acceptor (D–A) structure electron‐deficient benzobisthiazole (BBT) as acceptor benzotrithiophene donor, while latter holds π‐A pyrene π‐unit BBT acceptor. Both show production activity two‐step 2e − oxygen reduction reaction (ORR). As anticipated, D–A structured exhibits lower value, its H O rate pure water air reaches up 2.50 mmol g⁻¹ h⁻¹, ≈3 times higher than that (0.91 h⁻¹). This study reveals fully ‐carbon‐linked beneficial production, which provides an effective approach designing high‐performance photocatalysts.

Язык: Английский

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Editing Benzotrithiophene-Based Covalent Organic Frameworks for Developing New Sonosensitizers

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

Опубликована: Март 2, 2025

Recent insights into covalent organic frameworks (COFs) provide an opportunity for developing new sonosensitizers with the advantages of both small molecules and inorganic nanoagents. Herein, we synthesize two benzotrithiophene-based imine-linked COFs (BTT-DPh-COF BTT-DPy-COF) through density-functional-theory-guided structure editing. The tailored donor-acceptor (D-A) structures optimize band position endow them good intrinsic sonodynamic activity, which can efficiently kill cancer cells, showing excellent therapeutic effect. Particularly, because enhanced D-A effect that promotes charge separation transfer behavior, BTT-DPy-COF exhibits superior ultrasound-triggered reactive oxygen species (ROS) generation capability than BTT-DPh-COF. Therefore, these studies highlight great potential elaborate editing configurations as suitable candidates advanced sonosensitizers.

Язык: Английский

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Design, Synthesis, and Application of Immobilized Enzymes on Artificial Porous Materials

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Апрель 30, 2025

Enzymes have been recognized as highly efficient biocatalysts, whereas characteristics such poor stability and single reaction type greatly significantly limit their wide application. Hence, the exploitation of suitable carriers for immobilized enzymes enables provision a protective layer enzyme, with capability chemical biological cascade catalysis. Among various immobilization carriers, metal-organic frameworks (MOFs), covalent organic (COFs) hydrogen-bonded (HOFs) emerging promising strategy to surpass inherent instability other limitations free enzymes. Specifically, integration artificial porous materials improves reusability enzymes, while simultaneously affording platform multifunctional applications. Herein, this review systematically discusses preparation strategies advantages materials, elucidating effects different methods on enzyme activity. Furthermore, innovative applications in field fields photocatalysts, catalysts sensing are also comprehensively summarized here, thus demonstrating addressing complex biotransformation challenges.

Язык: Английский

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

Journal of Materials Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Amidoxime‐Functionalized sp²‐Carbon‐Conjugated Covalent Organic Frameworks for Overall Photocatalytic Hydrogen Peroxide Production

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 18, 2025

Abstract Cyano‐functionalized sp 2 ‐carbon‐conjugated covalent organic frameworks (CN‐COFs) have been considered as promising candidates for artificial photosynthesis of hydrogen peroxide (H O ). Nevertheless, the performance CN‐COFs is inherently limited by constrained oxygen capture capacity, insufficient charge separation, and rapid carrier recombination. Herein, study rationally reports a strategy integrating amidoxime groups (AO) into COF through one‐step cyano hydrolysis process to increase photocatalytic H production. Combined simulations characterizations reveal that introducing AO enhances hydrophilicity, stabilizes adsorbed Oxygen (O ) via bonding, accelerates separation transfer, well lowers energy barrier reduction reaction pathway, thus achieving an unmatched production rate 6024 µmol h −1 g . Importantly, solar‐to‐chemical conversion (SCC) efficiency PTTN‐AO reaches 0.61%, significantly surpassing natural plants (≈0.1%) most COF‐based photocatalysts. The current findings are encouraging molecular design polymers green efficient

Язык: Английский

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Intralayer Anisotropy in Two-Dimensional Conjugated Covalent Organic Frameworks

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Two-dimensional (2D) covalent organic frameworks (COFs), as stacked 2D polymers, have emerged promising semiconductors with tunable structures and functionalities, offering significant potential in optoelectronics. Achieving in-plane anisotropy their electronic optical properties is particularly desirable for applications electronics, thermoelectrics, photonics but remains a considerable challenge existing design synthesis approaches. Here, we present novel strategy to introduce intralayer conjugated COFs (2D aniso-c-COFs) using nodes large quadrupole moment imbalances identical linkers. By rationally designing twelve aniso-c-COFs based on benzodithiophene (BDT) nodes, impose highly anisotropic structure that results unprecedented bidirectional charge transport, where electrons holes preferentially migrate along divergent directions. These exhibit remarkable mobilities, reaching up 1200 cm²V^{− 1}s^{− 1} 200 holes, predicted by Boltzmann transport theory. Parallel anisotropy, these materials show pronounced including giant birefringence (|Δn| > 1.0) linear dichroism (|Δk| 1.3), which are COFs, enabling selective polarization control responses. Guided insights, synthesized representative aniso-c-COF, TBDT-P-CN, experimentally demonstrated its high intrinsic mobility. establish unique platform polarization-sensitive optoelectronic applications, paving the way future advancements crystalline materials.

Язык: Английский

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Advances in Covalent Organic Frameworks as Fluorescent Sensors for pH

Luminescence, Год журнала: 2025, Номер 40(3)

Опубликована: Март 1, 2025

ABSTRACT pH value is essential for maintaining ecological balance, and it plays a significant role in atmospheric monitoring, water quality assessment, biological health. Therefore, very important developing rapid sensitive detection methods. Covalent organic frameworks (COFs) have emerged as promising fluorescent sensing materials due to their tunable structures, high thermal stability, large specific surface area, making them ideal both environmental samples. This review examines various types of COF fluorescence sensors discusses mechanisms provides the theoretical foundation development more excellent sensors.

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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Rational design of two-dimensional nanosheets membranes for lithium extraction from brine: Recent progress and future opportunities

Desalination, Год журнала: 2025, Номер unknown, С. 118895 - 118895

Опубликована: Апрель 1, 2025

Язык: Английский

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Flexible Units in Covalent Organic Frameworks Promote Photocatalytic Uranium Extraction from Wastewater

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Covalent organic frameworks (COFs) are increasingly being utilized in photocatalysis due to their programmable band gaps and pore geometries. Flexible COFs currently of interest for selective sorption, though use has received little attention date. Herein, we propose a strategy modulating the flexible units facilitate efficient charge carrier separation transfer during photocatalysis. Rotational freedom linkers our led controllable local curvature, thereby optimizing optoelectronic properties boosting photocatalytic activity. One developed (COF-3) showed excellent performance uranium removal from contaminated groundwater tap water. Mechanistic studies revealed that COF-3 photocatalytically generated H₂O₂ under visible light irradiation water, which transformed UO₂²⁺ solid (UO₂)O₂·2H₂O through redox pathway. The results demonstrate an effective design towards COF photocatalysts water potentially many other applications.

Язык: Английский

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