Constitutional-isomerized covalent organic frameworks (COFs), constructed by swapping monomers around imine bonds, have attracted attention for their distinct optoelectronic properties, which significantly impact photocatalytic performance. However, limited research has delved into the inherent relationship between isomerization and the enhancement of HO photosynthesis. Herein, a pair of isomeric COFs linked by imine bonds (PB-PT-COF and PT-PB-COF) is synthesized, and it is proved that isomeric COFs exhibit different rate-determining steps in the generation process of HO, resulting in a twofold increase in photocatalytic efficiency. Specifically, PT-PB-COF demonstrates effective adsorption and activation of molecular oxygen (O + e → •O + e → HO), leading to a significant improvement in HO photocatalytic efficiency. In contrast, PB-PT-COF exhibits robust interaction with HO, enabling direct oxidation of HO (HO + h → HO). This study provides a thorough understanding of the intrinsic mechanism underlying the constitutional-isomerized COFs in the photocatalytic HO generation, offering insights for further optimizing building units.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/smll.202406527 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Bioinspired Photo-Thermal Catalytic System using Covalent Organic Framework-based Aerogel for Synchronous Seawater Desalination and H2O2 Production.
Angew Chem Int Ed Engl
January 2025
Nankai University, School of Materials Science and Engineering, National Institute for Advanced Materials, TKL of Metal and Molecule-Based Material Chemistry, CHINA.
Efficient utilization of solar energy is widely regarded as a crucial solution to addressing the energy crisis and reducing reliance on fossil fuels. Coupling photothermal and photochemical conversion can effectively improve solar energy utilization yet remains challenging. Here, inspired by the photosynthesis system in green plants, we report herein an artificial solar energy converter (ASEC) composed of light-harvesting units as solar collector and oriented ionic hydrophilic channels as reactors and transporters.
View Article and Find Full Text PDFInterlocked 2D Covalent Organic Frameworks from Overcrowded Nodes.
J Am Chem Soc
January 2025
POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, Donostia-San Sebastián 20018, Spain.
A challenging aspect in the synthesis of covalent organic frameworks (COFs) that goes beyond the framework's structure and topology is interpenetration, where two or more independent frameworks are mechanically interlocked with each other. Such interpenetrated or interlocked frameworks are commonly found in three-dimensional (3D) COFs with large pores. However, interlocked two-dimensional (2D) COFs are rarely seen in the literature, as 2D COF layers typically crystallize in stacks that maximize stabilization through π-stacking.
View Article and Find Full Text PDFLuminescent cyclometalated gold(iii) complexes covalently linked to metal-organic frameworks for heterogeneous photocatalysis.
Chem Sci
December 2024
Department of Chemistry, State Key Laboratory of Synthetic Chemistry, The University of Hong Kong Pokfulam Road Hong Kong P. R. China
Phosphorescent gold(iii) complexes possess long-lived emissive excited states, making them ideal for use as molecular sensors and photosensitizers for organic transformations. Literature reports indicate that gold(iii) emitters exhibit good catalytic activity in homogeneous photochemical reactions. Heterogeneous metal-organic framework (MOF)-supported gold(iii) photocatalysts are considered to show high recyclability in photochemical reactions and potentially provide new selectivities.
View Article and Find Full Text PDFRapid and Scalable Preparation of High-Crystalline Carboxyl-Functionalized Covalent Triazine Frameworks via Friedel-Crafts Reaction.
Angew Chem Int Ed Engl
January 2025
Westlake University, School of Engineering, 18 Shilongshan Road, 310024, Hangzhou, CHINA.
The Friedel-Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel-Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel-Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time.
View Article and Find Full Text PDFBionic Luminescent Sensors Based on Covalent Organic Frameworks: Auditory, Gustatory, and Olfactory Information Monitoring for Multimode Perception.
ACS Nano
January 2025
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, China.
The synthesis of covalent organic frameworks (COFs) with excellent luminescent properties and their effective application in the field of bionic sensing remain a formidable challenge. Herein, a series of COFs with different numbers of hydroxyl groups are successfully synthesized, and the number of hydroxyl groups on the benzene-1,3,5-tricarbaldehyde (BTA) linker influences the properties of the final COFs. The COF (HHBTA-OH) prepared with hydrazine hydrate (HH) and BTA containing one hydroxyl group as the ligands exhibits the best fluorescent performance.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!