Green and selective oxidation reactions catalyzed by kaolinite covalently grafted with Fe(III) pyridine-carboxylate complexes

被引：49

作者：

de Faria, Emerson H. ^{[1
]}

Ricci, Gustavo P. ^{[1
]}

Marcal, Liziane ^{[1
]}

Nassar, Eduardo J. ^{[1
]}

Vicente, Miguel A. ^{[2
]}

Trujillano, Raquel ^{[2
]}

Gil, Antonio ^{[3
]}

Korili, Sophia A. ^{[3
]}

Ciuffi, Katia J. ^{[1
]}

Calefi, Paulo S. ^{[1
]}

机构：

[1] Univ Franca, BR-14404600 Franca, SP, Brazil

[2] Univ Salamanca, Dept Quim Inorgan, Fac Ciencias Quim, E-37008 Salamanca, Spain

[3] Univ Publ Navarra, Dept Appl Chem, Pamplona, Spain

来源：

CATALYSIS TODAY | 2012年 / 187卷 / 01期

基金：

巴西圣保罗研究基金会;

关键词：

Kaolinite; Heterogeneous catalysis; Fe(III)-picolinates and dipicolinates; Oxidation reactions; Baeyer-Villiger; BAEYER-VILLIGER OXIDATION; HYBRID MATERIALS; IRON; FUNCTIONALIZATION; INTERCALATION; CYCLOHEXANE; IMMOBILIZATION; OXYGENATION; PERFORMANCE; DERIVATIVES;

D O I：

10.1016/j.cattod.2011.11.029

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The immobilization of Fe(III) picolinate and Fe(III) dipicolinate complexes on kaolinite furnished heterogeneous catalysts, whose catalytic activity was evaluated. The precursor materials were kaolinite grafted with picolinic (Ka-pa) and dipicolinic (Ka-dpa) acids obtained by melting of the pyridine carboxylic acids. To obtain the catalysts Fe(Ka-pa)-n and Fe(Ka-dpa)-n (n = 1, 2, or 3 is the ligand/Fe ratio), the precursors were suspended in Fe3+ solutions with cation/ligand ratios of 1:1,1:2, or 1:3. The resulting materials were characterized by thermal analyses (simultaneous TG/DTA), X-ray diffraction, UV/vis and infrared spectroscopies, and transmission electron microscopy. The grafted complexes were employed as heterogeneous catalysts in the epoxidation of cis-cyclooctene to cis-cyclooctenoxide and in the oxidation of cyclohexane to cyclohexanol and cyclohexanone at ambient temperature and pressure. Hydrogen peroxide was used as oxygen donor at a catalyst/oxidant/substrate molar ratio of 1:300:100. Fe(Ka-pa)-n catalysts were very efficient for cis-cyclooctene epoxidation (38% conversion). For cyclohexane oxidation, Fe(Ka-dpa)-n was 100% selective for cyclohexanone formation, with substrate conversion of 14%. This last series of catalysts was also very effective in the Baeyer-Villiger reaction, with 60% substrate conversion and 100% selectivity for xi-caprolactone. After reuse (5 times), the catalysts still led to high substrate conversion. (C) 2011 Elsevier B.V. All rights reserved.

引用

页码：135 / 149

页数：15

共 61 条

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