Dual–Acceptor Engineering in Pyrene‐Based Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Advanced Energy Materials, Год журнала: 2024, Номер 14(40)

Опубликована: Июль 18, 2024

Abstract The integration of electron donor (D) and acceptor (A) units into covalent organic frameworks (COFs) has received increasing interest due to its potential for efficient photocatalytic hydrogen (H 2 ) evolution from water. Nevertheless, the advancement D–A COFs is still constrained by limited investigations on engineering, which enables highly effective charge transfer pathways in deliver photoexcited electrons a preferential orientation enhance performance. Herein, two systems with D–A–A configurations based molecular engineering strategy are proposed construct three distinct COFs. Specifically, TAPPy‐DBTDP‐COF merging one pyrene‐based benzothiadiazole acceptors realized an average H rate 12.7 mmol h −1 g under visible light, among highest ever reported typical D–A‐type COF systems. combination experimental theoretical analysis signifies crucial role dual‐acceptor arrangement promoting exciton dissociation carrier migration. These findings underscore significant structural design, conducive separation holes resulting superior activities.

Язык: Английский

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Single-Crystalline 3D Covalent Organic Frameworks with Exceptionally High Specific Surface Areas and Gas Storage Capacities

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 28932 - 28940

Опубликована: Окт. 11, 2024

Single-crystalline covalent organic frameworks (COFs) are highly desirable toward understanding their pore chemistry and functions. Herein, two 50–100 μm single-crystalline three-dimensional (3D) COFs, TAM-TFPB-COF TAPB-TFS-COF, were prepared from the condensation of 4,4′,4″,4‴-methanetetrayltetraaniline (TAM) with 3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl (TFPB) 3,3′,5,5′-tetrakis(4-aminophenyl)bimesityl (TAPB) 4,4′,4″,4‴-silanetetrayltetrabenzaldehyde (TFS), respectively, in 1,4-dioxane under catalysis acetic acid. Single-crystal 3D electron diffraction reveals triply interpenetrated dia-b networks atom resolution, while isostructure TAPB-TFS-COF was disclosed by synchrotron single-crystal X-ray powder Le Bail refinements. The nitrogen sorption measurements at 77 K disclose microporosity nature both activated COFs exceptionally high Brunauer–Emmett–Teller surface areas 3533 4107 m2 g–1, representing thus far record specific area among imine-bonded COFs. This enables to exhibit also methane uptake capacities up 28.9 wt % (570 cm3 g–1) 25 °C 200 bar all reported far. work not only presents structures exceptional but provides an example engineering adjust permanent microporous for storage.

Язык: Английский

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Supramolecularly Built Local Electric Field Microenvironment around Cobalt Phthalocyanine in Covalent Organic Frameworks for Enhanced Photocatalysis

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

Опубликована: Янв. 16, 2025

The local electric field (LEF) plays an important role in the catalytic process; however, precise construction and manipulation of microenvironment around active site remains a significant challenge. Here, we have developed supramolecular strategy for implementation LEF by introducing host macrocycle 18-crown-6 (18C6) into cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing interaction between 18C6 potassium ion (K+), locally enhanced K+ concentration CoPc can be built to generate catalytically Co site. COF with this supramolecularly realizes activity up 7.79 mmol mmolCo–1 h–1 photocatalytic CO2 reduction reaction (CO2RR), which is 180% improvement compared its counterpart without units. effect subtly controlled fully harnessing K+@18C6 changing salts different counterions. In situ spectroscopy density functional theory calculations show that complexation creates positive stabilizes critical intermediate *COOH involved CO2RR, tuned halide ion-mediated hydrogen-bonding interaction, consequently leading improved performance varying degrees.

Язык: Английский

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

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

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Perfluoroalkyl-modified covalent organic frameworks for continuous photocatalytic hydrogen peroxide synthesis and extraction in a biphasic fluid system

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 13, 2024

Язык: Английский

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Reticular Materials for Photocatalysis

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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.

Язык: Английский

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Multivariate covalent organic frameworks with tailored electrostatic potential promote nitrate electroreduction to ammonia in acid

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 19, 2025

The direct synthesis of ammonia from nitrate (NO3-) reduction in acid is a promising approach for industrialization. However, the difficulty arises intense competition with inevitable hydrogen evolution reaction, which favoured due to overwhelming protons (H+). Here, we systematically explore and rationally optimize microenvironment using multivariate covalent organic frameworks (COFs) as catalyst adlayers promote nitrate-to-ammonia conversion acid. With application tailored positive electrostatic potential generated over COFs, both mass transfer NO3- H+ are regulated via appropriate interactions, thus realizing priority NO3RR respect HER or NO3--to-NO2-. As result, an NH3 yield rate 11.01 mmol h-1 mg-1 corresponding Faradaic efficiency 91.0% attained, solid NH4Cl high purity 96.2% directly collected acid; therefore, this method provides practical economically valorising wastewater into valuable ammonia.

Язык: Английский

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Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Авг. 15, 2024

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist in channels, few studies dedicated improving at the local environments of active sites Herein, we report on new Co‐corrole‐based organic polymers (POPs) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). By tuning pore sizes installing relays Co corrole sites, designed synthesized POP‐2‐OH both channels sites. This POP shows remarkable activity ORR E 1/2 =0.91 V vs RHE OER η 10 =255 mV. Therefore, this work significant present a strategy improve site materials highlight key role such structural functionalization boosting electrocatalysis.

Язык: Английский

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Reactive oxygen species generation for catalysis and biotherapeutic applications based on crystalline porous materials

Coordination Chemistry Reviews, Год журнала: 2024, Номер 518, С. 216068 - 216068

Опубликована: Июль 17, 2024

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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