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用于噻吩选择氧化和模型燃料深度脱硫的吡嗪二羧酸桥联含稀土多钨砷酸盐聚集体的制备、表征和催化性能。

Preparation, characterization, and catalytic performances of a pyrazine dicarboxylate-bridging rare-earth-containing polytungstoarsenate aggregate for selective oxidation of thiophenes and deep desulfurization of model fuels.

机构信息

Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, Henan, China.

出版信息

Dalton Trans. 2018 Jul 24;47(29):9677-9684. doi: 10.1039/c8dt01243a.

Abstract

A new polytungstoarsenate, K6LiH6[Ce4(H2O)14(pzdc)(H2pzdc)As3W29O103]·22H2O (1) (H2pzdc = 2,3-pyrazinedicarboxylic acid), was synthesized via a conventional aqueous solution method. In this synthetic approach, the organic ligand pyrazine dicarboxylate acid was introduced into the arsenotungstate system. The synthesized compound 1 was well characterized using elemental analysis, IR spectroscopy, UV-vis spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. The catalytic activity of compound 1 was tested in acetonitrile to oxidize organosulfur compounds (benzothiophene (BT) and dibenzothiophene (DBT)) with hydrogen peroxide as an oxidant at room temperature. Two substrates were oxidized to their corresponding sulfones with high conversion and selectivity. Taking advantage of this remarkable catalytic move, the 1/H2O2/CH3CN system was further utilized in the oxidation of model fuels (MF) including a mixture of BT and DBT in octane. As a result, the organosulfur compounds in the model fuels were fully converted into their corresponding sulfones. Furthermore, the fluorescence properties of 1 were also investigated.

摘要

一种新的多钨砷酸盐,K6LiH6[Ce4(H2O)14(pzdc)(H2pzdc)As3W29O103]·22H2O(1)(H2pzdc=2,3- 吡嗪二羧酸),通过常规的水溶液法合成。在这种合成方法中,有机配体吡嗪二羧酸被引入到砷钨酸盐体系中。通过元素分析、红外光谱、紫外可见光谱、热重分析(TGA)、粉末 X 射线衍射(PXRD)和单晶 X 射线衍射对合成的化合物 1 进行了很好的表征。在室温下,以过氧化氢为氧化剂,考察了化合物 1 在乙腈中对有机硫化合物(苯并噻吩(BT)和二苯并噻吩(DBT))的催化活性。两种底物被氧化为相应的砜,转化率和选择性高。利用这一显著的催化作用,1/H2O2/CH3CN 体系进一步用于氧化模型燃料(MF),包括在辛烷中的 BT 和 DBT 的混合物。结果,模型燃料中的有机硫化合物完全转化为相应的砜。此外,还研究了 1 的荧光性质。

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