High-Nuclearity Polyoxometalate-Based Metal-Organic Frameworks for Photocatalytic Oxidative Cleavage of C-C Bond.

Autor: Zhao Q; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China., Zeng Y; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China., Jiang Z; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China., Huang Z; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China., Long DL; School of Chemistry, The University of Glasgow, Glasgow, G12 8QQ, UK., Cronin L; School of Chemistry, The University of Glasgow, Glasgow, G12 8QQ, UK., Xuan W; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, P. R. China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 09, pp. e202421132. Date of Electronic Publication: 2024 Dec 09.
DOI: 10.1002/anie.202421132
Abstrakt: High-nuclearity polyoxometalate (POM) clusters are attractive building blocks (BBs) for the synthesis of metal-organic frameworks (MOFs) due to their high connectivity and inherently multiple metal centers as functional sites. This work demonstrates a strategy of step-wise growth on ring-shaped [P 8 W 48 O 184 ] 40- precursor, which produced two new high-nuclearity polyoxotungstates, a half-closed [H 16 P 8 W 58 O 218 ] 32- {W 58 } and a fully-closed [H 16 P 8 W 64 O 236 ] 32- {W 64 }. By in situ synthesis, unique MOFs of copper triazole-benzoic acid (HL) complexes incorporating the negatively-charged {W 58 } and {W 64 } as nodes, {Cu 11 (HL) 9 W 58 } HNPOMOF-1 and {Cu 9 (HL) 9 W 64 } HNPOMOF-2, were constructed by delicately tuning the reaction conditions, mainly solution pH, which controls the formation of {W 58 } and {W 64 }, and at the same time the protonation of triazole-benzoic acid ligand thus its coordination mode to copper ion that creates the highest nuclearity POM-derived MOFs reported to date. HNPOMOF-1 features 3D framework possessing cage-like cavities filled with exposed carboxyl groups, while the inherent 2D layer-like HNPOMOF-2 allows for facile exfoliation into ultrathin nanosheets, and the resulted HNPOMOF-2 NS exhibits superior activity towards photocatalytic oxidative cleavage of C-C bond for a series of lignin models. This work not only provides a strategy to build high-nuclearity POM cluster-based frameworks, but also demonstrates their great potential as functional materials for green catalysis.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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