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负载于二氧化硅包覆铜铁氧体上的铜(II)和镍(II)的合成与表征:作为用硼氢化钠还原硝基芳烃的新型可磁重复使用纳米催化剂

Synthesis and Characterization of Copper (II) and Nickel (II) Immobilized on Silica- Coated Copper Ferrite: As Novel Magnetically Reusable Nano Catalysts Towards Reduction of Nitroarenes with NaBH4.

作者信息

Zeynizadeh Behzad, Sadeghbari Maryam, Pesyan Nader N

机构信息

Faculty of Chemistry, Urmia University, Urmia 5756151818, Iran.

出版信息

Curr Org Synth. 2019;16(7):1010-1023. doi: 10.2174/1570179416666190725094949.

Abstract

AIM AND OBJECTIVE

Nowadays, the design, synthesis and application of magnetically nanocomposite systems have attracted the attention of numerous scientists. The huge surface area and magnetic characteristic of nanoparticles as well as the inherent potentiality of the used metal species, makes them susceptible to have different reactivity in chemical reactions. In this context, we therefore encouraged to prepare a new design of magnetic nanocatalysts as CuFe2O4@SiO2@AAPTMS@Ni(II) and CuFe2O4@SiO2@AAPTMS@Cu(II) followed by monitoring of their catalytic activities towards reduction of nitroarenes with NaBH4.

MATERIALS AND METHODS

Magnetically nanoparticles of CuFe2 O4@SiO2@AAPTMS@Ni(II) and CuFe2O4@SiO2@AAPTMS@Cu(II) were prepared through a four-step procedure: i) preparation of CuFe2O4 MNPs, ii) coating of CuFe2O4 nucleus by silica-layer using tetraethyl orthosilicate (TEOS), iii) layering of CuFe2O4@SiO2 MNPs with [3-(2-aminoethylamino)propyl] trimethoxysilane (AAPTMS), and iv) the complexation of CuFe2O4@SiO2@AAPTMS MNPs with an aqueous solution of Ni(OAc)2·4H2O or Cu(OAc)2·H2O.

RESULTS

The catalytic activity of CuFe2O4@SiO2@AAPTMS@Ni(II) and the Cu(II)-analogue towards reduction of nitroarenes with NaBH4 was studied. The examinations resulted that using a molar ratio of 1:2 for ArNO2 and NaBH4 in the presence of 20 mg of nanocomposites in H2O under reflux conditions reduces various aromatic nitro compounds to arylamines in high yields.

CONCLUSION

The immobilization of Ni(II) and Cu(II) species on silica-layered CuFe2O4 was investigated. Magnetically nanoparticles of CuFe2O4@SiO2@AAPTMS@Ni(II) and the Cu(II)-analogue showed the perfect catalytic activity towards reduction of nitroarenes with NaBH4 in H2O. All reactions were carried out within 2- 15 min to afford aniline products in high yields.

摘要

目的

如今,磁性纳米复合体系的设计、合成及应用已引起众多科学家的关注。纳米颗粒巨大的表面积和磁性以及所用金属物种的内在潜力,使其在化学反应中易于呈现不同的反应活性。在此背景下,我们因此受到鼓舞,制备新型磁性纳米催化剂CuFe2O4@SiO2@AAPTMS@Ni(II)和CuFe2O4@SiO2@AAPTMS@Cu(II),随后监测它们对用硼氢化钠还原硝基芳烃的催化活性。

材料与方法

通过四步程序制备CuFe2O4@SiO2@AAPTMS@Ni(II)和CuFe2O4@SiO2@AAPTMS@Cu(II)磁性纳米颗粒:i) 制备CuFe2O4磁性纳米颗粒,ii) 使用正硅酸四乙酯(TEOS)用二氧化硅层包覆CuFe2O4核,iii) 用[3-(2-氨基乙基氨基)丙基]三甲氧基硅烷(AAPTMS)对CuFe2O4@SiO2磁性纳米颗粒进行分层,iv) 使CuFe2O4@SiO2@AAPTMS磁性纳米颗粒与Ni(OAc)2·4H2O或Cu(OAc)2·H2O的水溶液络合。

结果

研究了CuFe2O4@SiO2@AAPTMS@Ni(II)及其铜类似物对用硼氢化钠还原硝基芳烃的催化活性。研究结果表明,在回流条件下,于水中20 mg纳米复合材料存在时,使用1:2的ArNO2与硼氢化钠摩尔比,可将各种芳香硝基化合物高产率地还原为芳胺。

结论

研究了镍(II)和铜(II)物种在二氧化硅包覆的CuFe2O4上的固定化。CuFe2O4@SiO2@AAPTMS@Ni(II)及其铜类似物磁性纳米颗粒在水中对用硼氢化钠还原硝基芳烃显示出优异的催化活性。所有反应在2 - 15分钟内完成,高产率地得到苯胺产物。

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