Heterogeneous selective oxidation catalysts based on coordination polymer MIL-101 and transition metal-substituted polyoxometalates

被引：366

作者：

Maksimchuk, N. V. ^{[1
]}

Timofeeva, M. N. ^{[1
]}

Melgunov, M. S. ^{[1
]}

Shmakov, A. N. ^{[1
]}

Chesalov, Yu. A. ^{[1
]}

Dybtsev, D. N. ^{[2
]}

Fedin, V. P. ^{[2
]}

Kholdeeva, O. A. ^{[1
]}

机构：

[1] Boreskov Inst Catalysis, Novosibirsk 630090, Russia

[2] Nikolaev Inst Inorgan Chem, Novosibirsk 630090, Russia

来源：

JOURNAL OF CATALYSIS | 2008年 / 257卷 / 02期

基金：

俄罗斯基础研究基金会;

关键词：

metal-organic framework; MIL-101; supported polyoxometalate; composite materials; Co(II); Ti(IV); selective oxidation; alkene; molecular oxygen; hydrogen peroxide;

D O I：

10.1016/j.jcat.2008.05.014

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Titanium- and cobalt- monosubstituted Keggin heteropolyanions, [PW11CoO39](5-) and [PW11TiO40](5-), were electrostatically bound to the chromium terephthalate polymer matrix MIL-101. The MIL-supported polyoxometalate (POM) catalysts were characterized by elemental analysis, XRD, N-2 adsorption, and FT-IR-spectroscopy. The catalytic performance of both MIL-101 and the novel composite materials M-POM/MIL-101 was assessed in the oxidation of three representative alkenes-alpha-pinene, caryophyllene, and cyclohexene-using molecular oxygen and aqueous hydrogen peroxide as oxidants. Ti-POM/MIL-101 demonstrated fairly good catalytic activity and selectivity in alpha-pinene allylic oxidation and caryophyllene epoxidation with hydrogen peroxide, whereas Co-POM/MIL-101 catalyzed alpha-pinene allylic oxidation by molecular oxygen. Both composite materials are stable to POM leaching, behave as true heterogeneous catalysts, and can be used repeatedly without sustaining a loss of activity and selectivity in oxidations with O-2 and H2O2, provided that rather mild reaction conditions (T < 50 degrees C, [H2O2] < 0.2 M) are used with the latter oxidant. (c) 2008 Elsevier Inc. Alt rights reserved.

引用

页码：315 / 323

页数：9

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