Relative Local Electron Density Tuning in Metal‐Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 15, 2023

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, systematic studies on structure-functional relationship regarding above based precisely structure model rarely reported. Herein, as a proof-of-concept, we developed new strategy evaluation of by controlling relative electron-deficient (ED) electron-rich (ER) intensity monomer at molecular level three rational-designed vinylene-linked sp2 carbon-covalent organic frameworks (COFs). As expected, as-prepared carbon-conjugated metal-covalent framework (MCOFs) (VL-MCOF-1) with junction exhibited excellent activities -to-HCOOH conversion (283.41 μmol g-1 h-1 ) selectivity 97.1 %, much higher than VL-MCOF-2 g-C34 N6 -COF, which is due synergistic effect multi-electronic metal clusters (Cu3 (PyCA)3 (PyCA=pyrazolate-4-carboxaldehyde) strong ER roles cyanopyridine units ED active sites, well boosted photo-induced efficiency vinyl connection increased light utilization ability. These results not only provide regulating electron-density distribution photocatalysts but also offers profound insights clusters-based COFs effective conversion.

Language: Английский

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Developing new-generation covalent organic frameworks as sustainable catalysts: Synthesis, properties, types and solar energy production

Materials Science and Engineering R Reports, Journal Year: 2024, Volume and Issue: 157, P. 100771 - 100771

Published: Jan. 30, 2024

Language: Английский

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Efficient Photocatalytic CO₂ Reduction in Ellagic Acid–Based Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16229 - 16236

Published: May 30, 2024

Employing covalent organic frameworks (COFs) for the photocatalytic CO2 reduction reaction (CDRR) to generate high-value chemical fuels and mitigate greenhouse gas emissions represents a sustainable catalytic conversion approach. However, achieving superior CDRR performance is hindered by challenges of low charge separation efficiency, poor stability, high preparation costs associated with COFs. Herein, in this work, we utilized perfluorinated metallophthalocyanine (MPcF16) biomolecule compound ellagic acid (EA) as building blocks actualize functional named EPM-COF (M = Co, Ni, Cu). The designed EPCo-COF, featuring cobalt metal active sites, demonstrated an impressive CO production rate selectivity (CDRR). Moreover, following alkaline treatment (EPCo-COF-AT), COF exposed carboxylic anion (COO–) hydroxyl group (OH), thereby enhancing electron-donating capability EA. This modification achieved heightened 17.7 mmol g–1 h–1 outstanding 97.8% efficient CDRR. Theoretical calculations further illustrated that EPCo-COF-AT functionalized COO– OH can effectively alleviate energy barriers involved process, which facilitates proton-coupled electron transfer processes enhances on sites within EPCo-COF-AT.

Language: Английский

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Photothermal Conversion Porous Organic Polymers: Design, Synthesis, and Applications

Small Methods, Journal Year: 2024, Volume and Issue: unknown

Published: March 14, 2024

Abstract Solar energy is a primary form of renewable energy, and photothermal conversion direct process with tunable efficiency. Among various kinds materials, porous organic polymers (POP) are widely investigated owing to their controllable molecular design, tailored structures, good absorption solar light, low thermal conductivity. A variety POP, such as conjugated microporous (CMP), covalent frameworks (COF), hyper‐crosslinked (HCP), intrinsic microporosity (PIM), ionic (PIP), developed applied in applications seawater desalination, latent storage, biomedical fields. In this review, comprehensive overview the recent advances POP for provided. The micro structure characteristics macro morphology designed heat phototherapy photodynamic therapy, drug delivery. Besides, probe into underlying mechanism structural design constructing excellent performance methodicalized. Finally, remaining challenges prospective opportunities future development energy‐driven elucidated.

Language: Английский

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Interfacial coordination bonds accelerate charge separation for unprecedented hydrogen evolution over S-scheme heterojunction

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2024, Volume and Issue: 65, P. 174 - 184

Published: Oct. 1, 2024

Language: Английский

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