New oxidation catalysts based on iron(III) porphyrins immobilized on Mg-Al layered double hydroxides modified with triethanolamine

被引:45
作者
Dias de Freitas Castro, Kelly Aparecida [1 ]
Bail, Alesandro [1 ]
Groszewicz, Pedro Braga [1 ]
Machado, Guilherme Sippel [1 ]
Schreiner, Wido Herwig [3 ]
Wypych, Fernando [2 ]
Nakagaki, Shirley [1 ]
机构
[1] Univ Fed Parana, Lab Quim Bioinorgan & Catalise, BR-81531990 Curitiba, Parana, Brazil
[2] Univ Fed Parana, Dept Quim, Ctr Pesquisas Quim Aplicada CEPESQ, Lab Quim Estado Solido, BR-81531990 Curitiba, Parana, Brazil
[3] Univ Fed Parana, Dept Fis, BR-81531990 Curitiba, Parana, Brazil
关键词
Ironporphyrin; Oxidation; Catalysis; LDH; Triethanolamine; Immobilization; Heterogeneous catalysis; IRON PORPHYRINS; MANGANESE PORPHYRINS; INTERCALATION; COMPLEXES; SILICA; HYDROXYLATION; EPOXIDATION; METALLOPORPHYRINS; DERIVATIVES; ACTIVATION;
D O I
10.1016/j.apcata.2010.07.031
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
An Mg-Al layered double hydroxide containing intercalated NO3- anions (LDH-N) was synthesized and subsequently submitted to a reaction with triethanolamine as modifying agent (LDH-TEA). A neutral iron(III) porphyrin was immobilized onto both solids LDH-N and LDH-TEA, and the catalytic activity of the resulting FePor-LDH-N and FePor-LDH-TEA was evaluated in the oxidation of (Z)-cyclooctene, cyclohexane, and heptane using iodosylbenzene as oxidant. Characterization of FePor-LDH-N and FePor-LDH-TEA by UV-vis, FTIR, XRD, XPS, EPR, TGA/DTA, and SEM was also accomplished. The products from the catalytic reactions were analyzed by GC, using an FID detector. The catalytic activity of FePor-LDH-TEA in the oxidation of cyclohexane was around 5 times higher than that obtained with FePor-LDH-N. which does not contain the modifying agent. Moreover, the FePor-LDH-TEA solid displayed significant selectivity in the oxidation of heptane, a substrate that is difficult to oxidize; in fact, a total product yield over 30.0% was achieved. Finally, the performance of the FePor-LDH-TEA catalyst can be attributed to the higher FePor load in this solid, which is 3 times larger compared with FePor-LDH-N. A proposal concerning the mode of FePor immobilization onto the modified LDH is suggested. (C) 2010 Elsevier B.V. All rights reserved.
引用
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页码:51 / 59
页数:9
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