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

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(40)

Published: July 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.

Language: 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, Journal Year: 2024, Volume and Issue: 146(42), P. 28932 - 28940

Published: Oct. 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.

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

Published: Jan. 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.

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

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 13, 2024

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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Singlet‐Oxygen‐Driven Cooperative Photocatalytic Coupling of Biomass Valorization and Hydrogen Peroxide Production Using Covalent Organic Frameworks

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Traditional H 2 O photocatalysis primarily depends on photoexcited electrons and holes to drive oxygen reduction water oxidation, respectively. However, singlet ( 1 ), often underappreciated, plays a pivotal role in production. Meanwhile, photocatalytic biomass conversion has attracted attention, yet studies combining synthesis with valorization remain rare typically yield low‐value products. Herein, strategy of furfuryl alcohol (FFA) coupled the efficient co‐production is reported, enabled by covalent organic frameworks (COFs) induced, ‐participated Achmatowicz rearrangement. This study introduces polyimide‐based COF‐N 0‐3 tailored nitrogen content, representing an unprecedently platform for Remarkably, reducing content COF enhances production, significantly boosting generation rate. In FFA, primary pathway production rearrangement, achieving rate ten times higher than that reliant reaction pure water, reaching 4549 µmol g⁻¹ h⁻¹. Mechanism revealed selectively engaged bypassing hole oxidation trigger producing valuable 6‐hydroxy‐(2H)‐pyranone 99% 92% selectivity. work establishes coupling simultaneous biochemicals, offering transformative approach sustainable photocatalysis.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 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.

Language: Английский

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

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 518, P. 216068 - 216068

Published: July 17, 2024

Language: Английский

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Isoreticular Covalent Organic Pillars: Engineered Nanotubular Hosts for Tailored Molecular Recognition

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20963 - 20971

Published: July 20, 2024

In the realm of nanoscale materials design, achieving precise control over dimensions nanotubular architectures poses a substantial challenge. our ongoing pursuit, we have successfully engineered novel class single-molecule nanotubes─isoreticular covalent organic pillars (iCOPs)─by stacking formylated macrocycles through multiple dynamic imine bonds, guided by principles reticular chemistry. Our strategic selection rigid diamine linkers has facilitated synthesis diverse array iCOPs, each retaining homologous structure yet offering distinct cavity shapes influenced linker choice. Notably, three these iCOP variants feature continuous one-dimensional channels, exhibiting length-dependent host-guest interactions with α,ω-dibromoalkanes, and presenting critical guest alkyl chain length threshold for efficient encapsulation. This newfound capability not only provides platform tailoring structures precision, but also opens new avenues innovative applications in molecular recognition purification complex mixtures.

Language: Английский

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