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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Functional crystalline porous framework materials based on supramolecular macrocycles

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Here we summarize the progress of developing crystalline porous framework materials with supramolecular macrocycles for their applications in solid state, guiding readers through future chemistry, and commercialization.

Language: Английский

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Bifunctional catalysts based on 2-amino-1,10-phenanthroline-containing podands for cyclic carbonates synthesis from CO2 and epoxides under mild conditions

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 579, P. 115019 - 115019

Published: March 22, 2025

Language: Английский

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Cyano‐Cyclotrimerization Strategy for Constructing Bi‐Functional Acid‐Base Sites in Covalent Organic Frameworks for Achieving Synergistic‐Optimization of Catalytic Activity and Rapid‐Recyclability in CO₂ Cycloaddition

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

Published: Jan. 24, 2025

Abstract For the cycloaddition of CO 2 to epoxides be a viable non‐redox fixation pathway, it is crucial develop active, stable, selective, metal‐free, rapidly separable, and cost‐effective catalysts. To this end, three novel catalysts are synthesized via cyano‐trimerization reactions on cyano‐groups sp ‐c linked COF─CN, using two cyano‐monomers polymers intrinsic microporosity (PIM‐1). Among these, powder (COF─CN─COOH, COF─CN─NH ), featuring acidic hydrogen‐bond donors (─COOH, ─NH ) basic sites (triazine ring), exhibited excellent catalytic performance in reaction due their customizable sites, high affinity, stability. Notably, COF─CN─COOH achieved yield 99.9% with selectivity exceeding 99%. The 20%COF─CN@sPIM‐1 membrane catalyst, formed by covalent‐connection between COF─CN PIM‐1, demonstrates good interfacial compatibility, facilitating easy recycling while maintaining activity. Furthermore, density functional theory (DFT) studies promoted mechanism reveal that hydrogen bond (HBDs) can significantly reduce activation energy. Therefore, work introduces trimerization strategy utilizing COF as establishing unique acid‐base synergistic‐catalytic system laying foundation for development separated exhibiting activity

Language: Английский

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Transforming Boron Monoxide Monolayer with Light Metal Atoms: Stability and Electronic Properties

ACS Applied Electronic Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Language: Английский

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Synthesis of a Nitrile- and Ether-Rich Covalent Organic Framework as a Filler and Its Application for Proton Exchange Membranes

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

In the fabrication of proton exchange membranes (PEMs), incorporating nanomaterials into polymer matrix is a promising strategy for enhancing membrane stability. However, this approach often results in trade-off with conductivity. To address limitation and develop efficient additives, we synthesized novel covalent organic framework high density ether nitrile groups (COF-EN) via nucleophilic substitution as nanofiller. This nanofiller was specifically designed to enhance both conductivity stability membranes. The chemical structure COF-EN confirmed through various analytical techniques, it subsequently integrated sulfonated poly(ether ketone) (SPEEK) fabricate advanced composite resulting demonstrated enhanced dimensional, thermal, oxidative due strong intermolecular interactions between SPEEK chains COF-EN. Additionally, polar facilitated water absorption membranes, contributing improved As result, SPEEK/COF-EN_3 exhibited 2.3-fold increase power compared pristine membrane, establishing an effective PEM fabrication.

Language: Английский

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Remarkably high tensile strength and lattice thermal conductivity in wide band gap oxidized holey graphene C2O nanosheet

Discover Nano, Journal Year: 2024, Volume and Issue: 19(1)

Published: June 11, 2024

Abstract Recently, the synthesis of oxidized holey graphene with chemical formula C 2 O has been reported (J. Am. Chem. Soc. 2024, 146, 4532). We herein employed a combination density functional theory (DFT) and machine learning interatomic potential (MLIP) calculations to investigate electronic, optical, mechanical thermal properties monolayer, compared our findings those its N counterpart. Our analysis shows that while monolayer exhibits delocalized π-conjugation 2.47 eV direct-gap semiconducting behavior, counterpart an indirect gap 3.47 eV. found strong absorption in visible spectrum, initial peaks lattice occur at around 5 eV, falling within UV spectrum. Notably, we nanosheet presents significantly higher tensile strength MLIP-based show room temperature, can exhibit remarkably high conductivity 42 GPa 129 W/mK, respectively. The combined insights from DFT results provide comprehensive understanding electronic optical nanosheets, suggesting them as mechanically robust highly thermally conductive wide bandgap semiconductors.

Language: Английский

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Solvent-free synthesis of covalent-framework 2D crown ether and its application for polylactic acid nanocomposites having antibacterial property

Materials Today Chemistry, Journal Year: 2024, Volume and Issue: 42, P. 102444 - 102444

Published: Dec. 1, 2024

Language: Английский

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Hydrocarbon-based Composite Membranes Containing Sulfonated Poly(arylene thioether sulfone)-grafted 2D Crown Ether Framework Coordinated with Cerium Ions for PEMFC Applications

Journal of Membrane Science, Journal Year: 2024, Volume and Issue: 715, P. 123483 - 123483

Published: Nov. 5, 2024

Language: Английский

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Ordered crown-ether 2D framework based loose nanofiltration membranes for improved separation and stability

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A loose nanofiltration membrane with a 2D crown-ether framework (C 2 O) shows high water permeability (39 L m −2 h −1 bar ), excellent dye/salt selectivity (EBT/NaCl of 295), and remarkable stability under varying pH conditions.

Language: Английский

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