Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis : Synthesis and Characterization

• Main Author: Gustafsson, Mikaela
• Format: Doctoral Thesis
• Language: English
• Published: Stockholms universitet, Institutionen för material- och miljökemi (MMK) 2012
• Subjects: metal-organic frameworks; zeolitic imidazolate frameworks; functionalized linkers; structural transformation; heterogeneous catalysis
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-74431; http://nbn-resolving.de/urn:isbn:978-91-7447-451-0

Metal-organic frameworks (MOFs) are crystalline hybrid materials with interesting chemical and physical properties. This thesis is focused on the synthesis and characterization of different MOFs and their use in heterogeneous catalysis. Zeolitic imidazolate frameworks (ZIFs), including ZIF-4, ZIF -7 and ZIF -62, Ln(btc)(H2O) (Ln: Nd, Sm, Eu, Gd, Tb, Ho, Er and Yb), Ln2(bpydc)3(H2O)3, (Ln: Sm, Gd, Nd, Eu, Tb, Ho and Er), MOF-253-Ru and Zn(Co-salophen) MOFs were synthesized. Various characterization techniques were applied to study the properties of these MOFs. X-ray powder diffraction (XRPD), single crystal X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) were extensively used. The effect of synthesis parameters, such as batch composition and temperature, on the formation and morphology of ZIF-7 and ZIF-62 was studied. Structural transformation and flexibility of two series of lanthanide-based MOFs, Ln(btc)(H2O) (Ln: Nd, Ho and Er) and Ln2(bpydc)3(H2O)3, (Ln: Sm and Gd) upon drying and heating were characterized. Relations between metal coordination, structure flexibility and thermal stability among the Sm2(bpydc)3(H2O)3, Nd(btc)(H2O) and MOF-253 were investigated. Salophen- and phenanthroline-based organic linkers were designed, synthesized and characterized. Metal complexes were coordinated to these linkers to be used as catalytic sites within the MOFs. Catalytic studies using two MOF materials, Ln(btc) and MOF-253-Ru, as heterogeneous catalysts in organic transformation reactions were performed. The heterogeneous nature and recyclability of these MOFs were investigated and described. === <p>At the time of doctoral defence the following papers were unpublished and had a status as follows: Paper nr 4: Submitted; Paper nr 5: Submitted</p>