Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene

Long-range ordered mesoporous silica SBA-15 of high surface area and uniform pore size was obtained by hydrothermal synthesis using tetraethyl orthosilicate (TEOS) as silica source and Pluronic P123 copolymer as surfactant in acidic media. Functionalization of SBA-15 with 3-aminopropyltriethoxysilan...

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Main Author:	Saadon, Nurafiqah
Format:	Thesis
Language:	English
Published:	2015
Subjects:	QD Chemistry
Online Access:	http://eprints.utm.my/id/eprint/81509/1/NurafiqahSaadonMFS2015.pdf
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spelling	my-utm-ep.815092019-08-23T05:19:20Z Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene 2015 Saadon, Nurafiqah QD Chemistry Long-range ordered mesoporous silica SBA-15 of high surface area and uniform pore size was obtained by hydrothermal synthesis using tetraethyl orthosilicate (TEOS) as silica source and Pluronic P123 copolymer as surfactant in acidic media. Functionalization of SBA-15 with 3-aminopropyltriethoxysilane (APTES) via sol-gel reaction gave NH2-SBA-15 which was qualitatively confirmed with FTIR spectroscopy. Meanwhile, tetra-(p-chlorophenyl)porphyrin (TClPP) was synthesized using modified Alder-Longo method. Insertion of zinc(II) into metal-free TClPP was achieved using zinc(II) acetate to obtain ZnTClPP. The successful complexation of zinc(II) in porphyrin molecule was supported by the disappearance of two Q bands and the presence of Soret band in the UV-Vis spectra. ZnTClPP was also characterized using 1H NMR spectroscopy, MALDI-TOF MS and elemental CHN analysis. Heterogeneous catalyst NH2-SBA-15-ZnP was synthesized by incorporating various loadings of the ZnTClPP into NH2-SBA-15 and characterized by DR-UV Vis spectroscopy, N2 adsorption-desorption isotherm, SAXS, FESEM and TEM. The DR-UV Vis spectra of NH2-SBA-15-ZnP exhibit absorption peaks similar to free ZnClTPP indicating that porphyrin molecule is confined in the SBA-15. Furthermore, the intensity of Soret and Q bands increases with increasing of ZnTClPP loading. The hexagonal mesopore structure of SBA-15 was still intact after the modification treatments as shown by the SAXS patterns, FESEM and TEM images. The catalytic activity of homogeneous catalysts ZnClTPP was compared with the heterogeneous NH2-SBA-15-ZnP in the epoxidation of limonene in the presence of H2O2 oxidant. GC-FID and GC-MS detection analysis showed that the activity of heterogeneous catalysts NH2-SBA-15-ZnP were active in the formation of limonene oxide as main product. The limonene conversion (34.72%) when catalyzed by free ZnTClPP is comparable to NH2-SBA-15-ZnP (26.24%) with ~95% selectivity. The catalytic activity of NH2-SBA-15-ZnP increases with the increase of ZnTClPP loading on the SBA-15 support. For the liquid-phase epoxidation of limonene over NH2-SBA-15-ZnP catalyst in acetonitrile, the optimum conditions for the highest percentage of limonene conversion was at reaction temperature of 80°C during 24h and using H2O2 as oxidant. 2015 Thesis http://eprints.utm.my/id/eprint/81509/ http://eprints.utm.my/id/eprint/81509/1/NurafiqahSaadonMFS2015.pdf application/pdf en public http://dms.library.utm.my:8080/vital/access/manager/Repository/vital:120133 masters Universiti Teknologi Malaysia Chemistry
institution	Universiti Teknologi Malaysia
collection	UTM Institutional Repository
language	English
topic	QD Chemistry
spellingShingle	QD Chemistry Saadon, Nurafiqah Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
description	Long-range ordered mesoporous silica SBA-15 of high surface area and uniform pore size was obtained by hydrothermal synthesis using tetraethyl orthosilicate (TEOS) as silica source and Pluronic P123 copolymer as surfactant in acidic media. Functionalization of SBA-15 with 3-aminopropyltriethoxysilane (APTES) via sol-gel reaction gave NH2-SBA-15 which was qualitatively confirmed with FTIR spectroscopy. Meanwhile, tetra-(p-chlorophenyl)porphyrin (TClPP) was synthesized using modified Alder-Longo method. Insertion of zinc(II) into metal-free TClPP was achieved using zinc(II) acetate to obtain ZnTClPP. The successful complexation of zinc(II) in porphyrin molecule was supported by the disappearance of two Q bands and the presence of Soret band in the UV-Vis spectra. ZnTClPP was also characterized using 1H NMR spectroscopy, MALDI-TOF MS and elemental CHN analysis. Heterogeneous catalyst NH2-SBA-15-ZnP was synthesized by incorporating various loadings of the ZnTClPP into NH2-SBA-15 and characterized by DR-UV Vis spectroscopy, N2 adsorption-desorption isotherm, SAXS, FESEM and TEM. The DR-UV Vis spectra of NH2-SBA-15-ZnP exhibit absorption peaks similar to free ZnClTPP indicating that porphyrin molecule is confined in the SBA-15. Furthermore, the intensity of Soret and Q bands increases with increasing of ZnTClPP loading. The hexagonal mesopore structure of SBA-15 was still intact after the modification treatments as shown by the SAXS patterns, FESEM and TEM images. The catalytic activity of homogeneous catalysts ZnClTPP was compared with the heterogeneous NH2-SBA-15-ZnP in the epoxidation of limonene in the presence of H2O2 oxidant. GC-FID and GC-MS detection analysis showed that the activity of heterogeneous catalysts NH2-SBA-15-ZnP were active in the formation of limonene oxide as main product. The limonene conversion (34.72%) when catalyzed by free ZnTClPP is comparable to NH2-SBA-15-ZnP (26.24%) with ~95% selectivity. The catalytic activity of NH2-SBA-15-ZnP increases with the increase of ZnTClPP loading on the SBA-15 support. For the liquid-phase epoxidation of limonene over NH2-SBA-15-ZnP catalyst in acetonitrile, the optimum conditions for the highest percentage of limonene conversion was at reaction temperature of 80°C during 24h and using H2O2 as oxidant.
format	Thesis
qualification_level	Master's degree
author	Saadon, Nurafiqah
author_facet	Saadon, Nurafiqah
author_sort	Saadon, Nurafiqah
title	Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
title_short	Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
title_full	Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
title_fullStr	Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
title_full_unstemmed	Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
title_sort	synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene
granting_institution	Universiti Teknologi Malaysia
granting_department	Chemistry
publishDate	2015
url	http://eprints.utm.my/id/eprint/81509/1/NurafiqahSaadonMFS2015.pdf
_version_	1747818347298291712

Synthesis and characterization of zinc porphyrin complex heterogenized in functionalized sba-15 for liquid phase epoxidation of limonene

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