Novel nanoscopic FeF 3 –based materials
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Mathematisch-Naturwissenschaftliche Fakultät I
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Abstract
Das Hauptaugenmerk dieser Arbeit liegt auf einer Pilotstudie zur Darstellung von Eisen(III)fluorid (FeF3) unter Verwendung von Sol-Gel-Syntheserouten. Eine modifizierte fluorolytische Sol-Gel-Synthese wurde entwickelt um bi-acide auf FeF3 basierende Materialien zu erhalten. Die Synthese erzeugt Hydroxygruppen, die potentiellen Brønsted-sauren Zentren, auf der Oberfläche der klassischen Lewissäure FeF3. Im Anschluss wurde Magnesiumfluorid (MgF2) als Matrix eingesetzt. Verglichen mit FeF3 zeigen ternäre FeF3-MgF2 bemerkenswert hohe Oberflächen und verbesserte Porosität. Das Wichtigste jedoch ist, das hauptsächlich starke Lewis- und mittelstarke Brønsted-saure Zentren auf der FeF3-MgF2 vorhanden sind. Des Weiteren wurden, unter Verwendung anderer Erdalkalimetallfluoride (CaF2 oder SrF2) und Zinkfluorid (ZnF2) als Matrix, Serien ternärer Fluoridmaterialien synthetisiert und systematisch untersucht. Durch Charakterisierung der FeF3-MF2-Oberflächen konnten systematische Veränderungen hinsichtlich Größe der Oberfläche, Porosität und Azidität festgestellt werden. Mit abnehmender Atomnummer (von Sr zu Mg) erhöht sich die Stärke der sauren Zentren, während die mittlere Porengröße dramatisch abnimmt. Darüber hinaus führt ein größeres M-zu-Fe-Verhältnis generell zu kleineren Porengrößen und höheren Oberflächen. Diese Ergebnisse implizieren, dass die Eigenschaften ternärer FeF3-MF2 durch Veränderung der MF2-Matrix oder des M-zu-Fe-Verhältnisses einstellbar sind. Schlussendlich konnte anhand einer Modellreaktion, der Isomerisierung von Citronellal zu Isopulegolen, die katalytische Aktivität der bi-aziden Zentren der auf FeF3 basierenden Materialien nachgewiesen werden. Zusätzlich wurde in dieser Arbeit diskutiert wie Oberfläche, Porosität und Azidität gemeinsam die katalytische Aktivität von FeF3-MgF2 bestimmen. Diese Arbeit beweist damit die Realisierbarkeit der Synthese neuer nanoskopischer Metallfluoride mit gewünschten Oberflächeneigenschaften.
This work serves as a pilot study on the development of iron(III) fluoride (FeF3) based materials with surface bi-acidity. A modified fluorolytic sol-gel route was established to prepare the bi-acidic FeF3-based materials. The synthesis procedure introduced hydroxyls, the potential Brønsted acid sites, on the surface of a classic Lewis acid, FeF3. Subsequently, magnesium fluoride (MgF2) was used as matrix. Comparing with FeF3, the ternary FeF3-MgF2 showed remarkable high surface area and enhanced porosity. Most importantly, strong Lewis and medium strong Brønsted acid sites were found predominant on the FeF3-MgF2 surface. Next a series of ternary fluoride materials were synthesised and studied systematically, using other alkaline earth metal fluorides (CaF2 or SrF2) as well as zinc fluoride (ZnF2) as matrices. Surface characterisation of FeF3-MF2 revealed systematic changes in their surface area, porosity, and surface acidity. With decreasing atom numbers (from Sr to Mg), strengths of surface acidic sites and surface area increased, while the average pore size decreased drastically. Moreover, higher M-to-Fe ratio generally resulted in smaller pore size and larger surface area. These findings imply that the properties of ternary FeF3-MF2 are tunable by changing the MF2 matrix or the M-to-Fe ratio or both. Last but not least, in the model reaction, isomerisation of citronellal to isopulegols, FeF3-based materials were highly active due to their bi-acidity. Finally this work discussed how surface area, porosity, and surface acidity jointly determined the catalytic activity of FeF3-MF2. In conclusion, this work demonstrates the feasibility to synthesise novel nanoscopic metal fluorides with desirable surface properties.
This work serves as a pilot study on the development of iron(III) fluoride (FeF3) based materials with surface bi-acidity. A modified fluorolytic sol-gel route was established to prepare the bi-acidic FeF3-based materials. The synthesis procedure introduced hydroxyls, the potential Brønsted acid sites, on the surface of a classic Lewis acid, FeF3. Subsequently, magnesium fluoride (MgF2) was used as matrix. Comparing with FeF3, the ternary FeF3-MgF2 showed remarkable high surface area and enhanced porosity. Most importantly, strong Lewis and medium strong Brønsted acid sites were found predominant on the FeF3-MgF2 surface. Next a series of ternary fluoride materials were synthesised and studied systematically, using other alkaline earth metal fluorides (CaF2 or SrF2) as well as zinc fluoride (ZnF2) as matrices. Surface characterisation of FeF3-MF2 revealed systematic changes in their surface area, porosity, and surface acidity. With decreasing atom numbers (from Sr to Mg), strengths of surface acidic sites and surface area increased, while the average pore size decreased drastically. Moreover, higher M-to-Fe ratio generally resulted in smaller pore size and larger surface area. These findings imply that the properties of ternary FeF3-MF2 are tunable by changing the MF2 matrix or the M-to-Fe ratio or both. Last but not least, in the model reaction, isomerisation of citronellal to isopulegols, FeF3-based materials were highly active due to their bi-acidity. Finally this work discussed how surface area, porosity, and surface acidity jointly determined the catalytic activity of FeF3-MF2. In conclusion, this work demonstrates the feasibility to synthesise novel nanoscopic metal fluorides with desirable surface properties.
Description
Keywords
heterogene Katalyse, Bi-Azidität, Eisenfluorid, Nanomaterial, Sol-Gel-Synthese, heterogeneous catalysis, bi-acidity, iron fluoride, nanomaterial, sol-gel process
Dewey Decimal Classification
540 Chemie und zugeordnete Wissenschaften
Citation
Guo, Ying.(2013). Novel nanoscopic FeF 3 –based materials. 10.18452/16787