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

被引：0
作者：
Zhao, Qixin [1 ]
Zeng, Yang [1 ]
Jiang, Zhiqiang [1 ]
Huang, Zhenxuan [1 ]
Long, De-Liang [2 ]
Cronin, Leroy [2 ]
Xuan, Weimin [1 ]
机构：
[1] Donghua Univ, Coll Chem & Chem Engn, State Key Lab Modificat Chem Fibers & Polymer Mat, Shanghai 201620, Peoples R China
[2] Univ Glasgow, Sch Chem, Glasgow G12 8QQ, Scotland
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2025年 / 64卷 / 10期
基金：
英国工程与自然科学研究理事会; 中国国家自然科学基金; 欧洲研究理事会;
关键词：
polyoxometalates; high-nuclearity cluster; porous framework; catalysis; BUILDING-BLOCKS; CROWN HETEROPOLYANION; CATALYSTS; DRIVEN; PHOSPHOTUNGSTATE; NUCLEATION; REDUCTION;
D O I：
10.1002/anie.202421132
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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 [P8W48O184]40- precursor, which produced two new high-nuclearity polyoxotungstates, a half-closed [H16P8W58O218]32- {W58} and a fully-closed [H16P8W64O236]32- {W64}. By in situ synthesis, unique MOFs of copper triazole-benzoic acid (HL) complexes incorporating the negatively-charged {W58} and {W64} as nodes, {Cu11(HL)9W58} HNPOMOF-1 and {Cu9(HL)9W64} HNPOMOF-2, were constructed by delicately tuning the reaction conditions, mainly solution pH, which controls the formation of {W58} and {W64}, 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-2NS 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.
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页数：9
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