Metal-Organic Frameworks as Supports for Functional Materials
Date
2022
Authors
Tsoukatos, Steven
Editors
Advisors
Doonan, Christian
Sumby, Christopher
Sumby, Christopher
Journal Title
Journal ISSN
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Thesis
Citation
Statement of Responsibility
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Abstract
Metal-organic frameworks (MOFs) are intrinsically porous, crystalline materials formed from the assembly of metal nodes and organic linkers. The building-block type synthesis of MOFs has led to the formation of materials with well-defined structures, poised for specific applications. This extends to post-synthetic modification of MOFs, permitting the introduction of added relevance for certain applications. Such materials afforded by this process can be unique and inaccessible via traditional synthetic processes. In this thesis, two avenues for post-synthetic modification of MOFs with metals have been investigated. This includes the post-synthetic metalation of MnMOF-1 with Au(I) and assessment of MOF-derived Ru/TiO2 for CO2 methanation. Both areas highlight the exceptional ability MOFs display as support materials, exploiting their intrinsic properties in diverse ways. The work presented herein has the potential to influence further development of flexible materials and assist in progressing strategies for utilisation of captured anthropogenic CO2 for value-added product formation. The first chapter introduces MOFs and their conception from supramolecular chemistry. It discusses the dynamic properties MOFs can exhibit and the forms which they take, leading to inherently interesting materials with applicability to a wide range of different areas. It also introduces MOFs as versatile materials for heterogenous catalysis, capable as acting as both a catalyst itself, and an exceptional support for a catalytic material in both fundamental and applied research. Work in Chapter 2 details the investigation of ruthenium-loaded titanium MOF-derived catalysts (Ru/TiO2) for CO2 methanation. Two Ti MOFs, MIP-207 (Materials of the Institute of Porous Materials from Paris) and the MUV-10(X) (Materials of Universidad de Valencia) heterometallic Ti MOF family, were synthesised, loaded with Ru, and activated under both reaction conditions (in operando), and via calcination. The pure Ti MOF yielded catalysts prone to degradation with successive cycles, whereas the heterometallic Ti MOFs yielded highly active catalysts comparable to the most successful Ru/TiO2 standard. Chapter 3 explores the metalation of MnMOF-1, a flexible MOF with a free bis-pyrazole coordination site, with Au(I). Single crystal X-ray diffraction (SCXRD) and supporting analyses revealed quantitative metalation of a single pyrazole nitrogen of the bis-pyrazole site in its anti conformation, the first example of this coordination geometry in MnMOF-1. This unique post-synthetically metalated material displays retention of the intrinsic flexibility of the framework, otherwise lost for samples chelated to the bis-pyrazole moiety in the syn conformation. The material played a critical role in understanding the conformation and determining of coordination modulated on-off switching of flexibility of a Cu(I) complex in MnMOF-1, a novel mechanism in which to realise reversible structural flexibility in dynamic frameworks.
School/Discipline
School of Chemistry and Physics : Physics
Dissertation Note
Thesis (MPhil) -- University of Adelaide, School of Physical Sciences, 2022
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