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Subject: search.filters.subject.Heterogeneous catalysis

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    Multicomponent metal-organic frameworks : tailoring platforms for transition metal- and bioelectrocatalysis : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand
    (Massey University, 2025) Auer, Bernhard Stephan
    MUF-77 (MUF = Massey University Framework) is a quaternary, multicomponent metal-organic framework (MOF), constructed from three topologically distinct carboxylate linkers and Zn4O secondary building units. Multicomponent MOFs such as MUF-77, constructed from a set of ligands with different geometries, provide a valuable platform for obtaining ordered and programmable pore environments. In this context, they show great potential as recyclable and stable, heterogeneous catalysts. In this work, we looked at the typical MUF 77 synthesis conditions and investigated the formation of additional crystalline phases. Several new MOFs were discovered, including new multicomponent MOFs. We then investigated MUF-77 for the incorporation of transition metal catalysts. The work included ligand and MOF syntheses and synthetic modifications of the frameworks upon MOF formation. We also embedded a Au(III) catalyst within the MUF 77 framework and evaluated its catalytic properties upon installation into the framework. Finally, we shifted our focus to systems comprising MOF and enzyme components for their electrochemical application in layer-by-layer-grafted electrodes. The work extended our library of potential heterogeneous catalysts, showcasing the great potential of multicomponent systems.
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    Catalysts derived from metal-organic frameworks : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatu, New Zealand
    (Massey University, 2021) Bandara, W. R. L. Nisansala
    The synthesis of atomic-scale catalysts is a blooming field, and these replace the conventional nanocatalysts due to their high atom utilization, selectivity, and unique catalytic activity. Metal-organic frameworks (MOFs) serve as promising precursors for the synthesis of single-atom catalysts (SACs). This study focused on the synthesis of SACs on nitrogen-doped hollow carbon by using MOFs and MOF composites followed by pyrolysis. The synthesis of two SACs namely rhodium SACs (Rh SACs) and cobalt SACs (Co SACs) by different methods, their characterization, and catalysis was explored. Rh SAC synthesized in this work hydrogenates nitroarenes with high consumption and high selectivity. Moreover, Co SAC did little or no hydrogenation of the nitroarenes. Further applications of these SACs were explored by employing them in oxygen reduction reaction (ORR), NO abatement, and Fenton-like catalysis. Moreover, the synthesis of two types of hollow nanoboxes (HNB) namely HNB-1 and HNB-2; using MOFs and MOF composites, their characterization and applications were also investigated. HNB-1 was used to make electrode supercapacitors and it showed comparable activity to activated carbon. Further attempts were made to use HNB-2 as a fluorescence sensor. Finally, several ideas on synthesising SACs and HNBs were proposed as a part of future work.