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Polyoxometalate‐Based Metal‐Organic Frameworks as Heterogeneous Catalysts for Selective Oxidation of Ethylbenzene

2010; Wiley; Volume: 2010; Issue: 28 Linguagem: Inglês

10.1002/ejic.201000491

1099-0682

Yu Fan, Pei‐Qing Zheng, Yu‐Xiang Long, Yan‐Ping Ren, Xiang‐Jian Kong, La‐Sheng Long, Youzhu Yuan, Rong‐Bin Huang, Lan‐Sun Zheng,

Advanced Nanomaterials in Catalysis

Abstract The catalytic properties of four polyoxometalate (POM)‐based metal‐organic frameworks, {[Cu 2 (4,4′‐bipy) 4 (H 2 O) 4 ](SiW 12 O 40 )(H 2 O) 18 } n ( 1 ), {[Cu 2 (4,4′‐bipy) 4 (H 2 O) 4 ](SiW 12 O 40 )(4,4′‐bipy) 2 (H 2 O) 4 } n ( 2 ), {[Cu 2 (4,4′‐bipy) 4 (H 2 O) 4 ](PW 12 O 40 )(H 2 O) 18 } n ( 3 ), and {[Cu 2 (4,4′‐bipy) 4 (H 2 O) 4 ](PMo 12 O 40 )(H 2 O) 18 } n ( 4 ) (bipy = bipyridine), for the oxidation of ethylbenzene were investigated. Complexes 1 – 4 , which feature 3D frameworks formed through static incorporation between distinct Keggin POMs and the same voids in the 2D network of [Cu 2 (4,4′‐bipy) 4 (H 2 O) 4 ] n 4 n + , show the distinct conversion and selectivity for the oxidation of ethylbenzene. Investigation into the difference in the catalytic activity of 1 – 4 reveals that the oxidation of the substrate was performed in the pore of the framework and that the valence of the metal ion in the polyoxometalates significantly affects the catalytic activity of the 3D framework.