Metalloporphyrin-functionalized hexagonal mesoporous silica: Synthesis, structural properties and catalytic activity as cytochrome P450 model
Metalloporphyrin-functionalized hexagonal mesoporous silica: Synthesis, structural properties and catalytic activity as cytochrome P450 model
复制标题
DOI：
10.1016/j.micromeso.2012.09.039
复制
发表时间：
2013-03-01
影响因子：
5.2
通讯作者：
Iamamoto, Yassuko
中科院分区：
文献类型：
--
作者：
Bolzon, Lucas B.;Airoldi, Heide R.;Iamamoto, Yassuko
成功地将锰（III）和铁(III)-5,10,15,20-四（五氟苯）卟啉氯化物固定在HMS介孔内，并通过各种物理技术对其进行了表征。采用正十二烷基胺和正十六烷基胺两种不同的表面活性剂，组装了FeP-HMS C-12、FeP-HMS C-16、MnP-HMS C-12和MnP-HMS C-16催化剂，比较了不同固体的骨架结构和催化性能。通过XRD和N-2吸附-脱附等温线对HMS材料的介孔结构进行了表征。MnP-HMS体系的孔径（5.05 ~ 5.72 nm）大于FeP-HMS体系（2.38 ~ 4.09 nm）。SEM图像显示了所有催化剂的组织结构。MeP/PhIO体系在(Z)-环烯氧化过程中获得了高的催化收率和短的反应时间，这表明反应物很容易接近催化剂的反应位点。测试了MnP-HMS C-12、MnP-HMS C-16、FeP-HMS C-12和FeP-HMS C-16材料的稳定性，MnP-HMS C-16在10个反应循环中保持了催化活性。在环己烷氧化过程中，研究了载体对FeP-HMS C-12、FeP-HMS C-16、MnP-HMS C-12和MnP-HMS C-16催化性能的影响。对环己醇具有较高的选择性，说明中孔内有利于氧回弹机制，从而防止溶剂笼逃逸和自由基过程。催化结果表明，MePs包封在介孔中，使反应部位的微环境具有一定的疏水性，从而增强了这些材料的仿生性能。(C) 2012爱思唯尔公司版权所有。
The manganese(III) and iron(III)-5,10,15,20-tetrakis(pentafluoropheny)porphyrin chlorides were successfully immobilized inside the mesopores of HMS and characterized by a variety of physical techniques. The assembly of the catalysts FeP-HMS C-12, FeP-HMS C-16, MnP-HMS C-12, and MnP-HMS C-16 was achieved by using two different surfactants, n-dodecylamine and n-hexadecylamine, so as to compare the framework structure and the catalytic behavior of the different solids. The mesoporous structure of the HMS materials was confirmed by XRD and N-2 adsorption-desorption isotherm. The MnP-HMS systems have larger pore sizes (5.05-5.72 nm) compared with the FeP-HMS systems (2.38-4.09 nm). The SEM images revealed an organized structure for all the catalysts. The high catalytic yields and the short reaction time obtained for the MeP/PhIO systems during the oxidation of (Z)-cyclooctene indicated the easy access of the reactants to the reactive sites of the catalysts. The stabilities of the materials MnP-HMS C-12, MnP-HMS C-16, FeP-HMS C-12 and FeP-HMS C-16 were tested, and MnP-HMS C-16 maintained its catalytic activity during 10 reaction cycles. The effect of the support on the catalytic performance of FeP-HMS C-12, FeP-HMS C-16, MnP-HMS C-12, and MnP-HMS C-16 was studied during the oxidation of cyclohexane. The higher selectivity toward cyclohexanol suggested that the oxygen rebound mechanism was favored inside the mesopores, thus preventing solvent cage escape and radical processes. The catalytic results indicated that the encapsulation of MePs into mesopores confered some hydrophobicity to the reaction site microenvironment, thereby enhancing the biomimetic behavior of these materials. (C) 2012 Elsevier Inc. All rights reserved.