离子修饰六方介孔二氧化硅包封的四苯基卟啉锰具有意想不到的增强环氧化选择性

Weijie Zhang, P. Jiang, Ying Wang, Jian Zhang, Pingbo Zhang
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引用次数: 1

摘要

将四苯基卟啉锰(III)氯(Mn-TPP)包裹在六方介孔二氧化硅(HMS)中,通过不同的Lewis酸离子Al、Ti、Zr和W修饰,在温和条件下对不饱和烯烃和更具挑战性的脂肪酸酯进行了选择性氧化试验。在此条件下,纯W-HMS载体无环氧化活性;然而,相对于其他样品,Mn-TPP/W- hms的选择性出乎意料地提高(90%),特别是对均质Mn-TPP,表明W离子的促进作用超过了载体。此外,通过TG分析和润湿接触角测量,揭示了非均相材料的疏水性质,初步探讨了疏水性质是影响催化选择性的因素。即Mn-TPP/W-HMS由于具有较好的疏水性,表现出90%左右的选择性。
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Manganese(III) Tetraphenylporphyrin Encapsulated by Ion-Modified Hexagonal Mesoporous Silica With Unexpected Enhanced Epoxidation Selectivity
Tetraphenylporphyrin manganese (III) chloride (Mn-TPP) was encapsulated into hexagonal mesoporous silica (HMS) modified by different Lewis acid ions Al, Ti, Zr, and W, which have been tested for selective oxidation of unsaturated olefins and more challenged fatty acid esters under mild condition. Pure W-HMS support displayed no epoxidation activity under the present condition; nonetheless, an unexpected enhanced selectivity for Mn-TPP/W-HMS (90%) with respect to the other samples, especially to homogenous Mn-TPP, indicated the promoted role of W ions over the support. In addition, TG analysis and wetting contact angle measurement were determined in order to reveal the hydrophobic nature of heterogeneous materials, which has been preliminarily scrutinized as the factor influencing catalytic selectivity. That is, Mn-TPP/W-HMS exhibited around 90% selectivity because of a better hydrophobic nature.
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