Ru-polyoxometalates immobilized on SBA-15 as heterogeneous catalysts for n-hexadecane oxidation

doi:10.3969/j.issn.0438-1157.2013.02.019

CIESC Journal ›› 2013, Vol. 64 ›› Issue (2): 547-554.DOI: 10.3969/j.issn.0438-1157.2013.02.019

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Ru-polyoxometalates immobilized on SBA-15 as heterogeneous catalysts for n-hexadecane oxidation

CHEN Lifang, CAO Wenrong, MIAO Gai, WANG Cuihua, FANG Yunjin, QI Zhiwen

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2012-07-17 Revised:2012-11-08 Online:2013-02-05 Published:2013-02-05
Supported by:
supported by the National Natural Science Foundation of China (21006029, 21076074) and the Natural Science Foundation of Shanghai(10ZR1407200).

SBA-15锚定的钌杂多酸催化剂的合成及其催化正十六烷氧化

陈立芳, 曹文荣, 苗改, 王翠花, 方云进, 漆志文

华东理工大学化工学院,化学工程联合国家重点实验室,上海 200237

通讯作者: 漆志文。第一作者:陈立芳(1975—),女,博士,副教授。
作者简介:陈立芳(1975—),女,博士,副教授。
基金资助:
国家自然科学基金项目(21006029,21076074);上海市自然科学基金项目(10ZR1407200)。

Abstract

Abstract: The selective oxidation of alkanes as a green process remains a challenging task because of inactive C—H oxidation.Heterogeneous Ru-polyoxometalates catalysts were synthesized by using organo-ruthenium supported heteropolytungstates, [Sb₂W₂₀O₇₀(RuC₆H₆)₂]^10-, [Bi₂W₂₀O₇₀(RuC₆H₆)₂]^10-, [Sb₂W₂₀O₇₀(RuC₁₀H₁₄)₂]^10-, and [Bi₂W₂₀O₇₀(RuC₁₀H₁₄)₂]^10- anchored on 3-aminopropyltriethoxysilane (apts)-modified mesoporous SBA-15.The catalysts were characterized by X-ray diffraction (XRD), N₂-adsorption measurements and Fourier transform infrared reflectance (FT-IR) spectroscopy.The results of these analyses indicated that these catalysts had high surface area, uniform hexagonal channels which were similar to those of SBA-15, and organo-ruthenium supported heteropolytungstates were highly dispersed in the pores of the modified silica.The heterogeneous Ru-polyoxometalates catalysts were used as catalysts for the solvent-free aerobic oxidation of n-hexadecane to alcohols and ketones by using air as the oxidant under ambient conditions.They exhibited exceptionally high catalytic performance through a classical free-radical autoxidation mechanism.Therefore, the catalysts demonstrated the prospect of this type of heterogeneous catalyst for practical applications.

Key words: n-alkane oxidation, immobilization, SBA-15, heterogeneous catalysis, Ru-polyoxometalates

摘要： 利用(3-氨丙基)三乙氧基硅烷(apts)将钌金属杂多酸[X₂W₂₀O₇₀(RuY)₂]^10-(其中,X为锑或铋,Y为苯或对异丙基苯甲烷)固定在介孔的SBA-15上可得到一系列性能优良的SBA-15锚定的钌杂多酸催化剂。采用XRD、N₂吸附-脱附实验和FT-IR红外光谱对此类催化剂进行表征,并检测其对正十六烷氧化的催化性能。结果表明,以空气为氧化剂,在无任何溶剂的条件下,该锚定的钌杂多酸催化剂遵循传统的自由基自氧化机理,将正十六烷烃氧化成各种醇类和酮类,显示出优良的催化性能。因此,这类多相催化剂对环境友好的烷烃氧化反应具有较高的应用价值。

关键词: 烷烃氧化, 锚定, SBA-15, 多相催化剂, 钌杂多酸

CLC Number:

TQ028.8

CHEN Lifang, CAO Wenrong, MIAO Gai, WANG Cuihua, FANG Yunjin, QI Zhiwen. Ru-polyoxometalates immobilized on SBA-15 as heterogeneous catalysts for n-hexadecane oxidation[J]. CIESC Journal, 2013, 64(2): 547-554.

陈立芳, 曹文荣, 苗改, 王翠花, 方云进, 漆志文. SBA-15锚定的钌杂多酸催化剂的合成及其催化正十六烷氧化[J]. 化工学报, 2013, 64(2): 547-554.

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Ru-polyoxometalates immobilized on SBA-15 as heterogeneous catalysts for n-hexadecane oxidation

SBA-15锚定的钌杂多酸催化剂的合成及其催化正十六烷氧化

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