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Strategic Immobilisation of Catalytic Metal Nanoparticles in Metal-Organic Frameworks

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Strategic Immobilisation of Catalytic Metal Nanoparticles in Metal-Organic Frameworks STRATEGIC IMMOBILISATION OF CATALYTIC METAL NANOPARTICLES IN METAL-ORGANIC FRAMEWORKS Amanda Anderson A Thesis Submitted for the Degree of PhD at the University of St Andrews 2017 Full metadata for this item is available in St Andrews Research Repository at: http://research-repository.st-andrews.ac.uk/ Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/10816 This item is protected by original copyright Strategic Immobilisation of Catalytic Metal Nanoparticles in Metal-Organic Frameworks Amanda Anderson This thesis is submitted in partial fulfilment for the degree of PhD at the University of St Andrews April 2017 Declarations Declarations 1. Candidate’s declarations: I, Amanda Anderson, hereby certify that this thesis, which is approximately 53,000 words in length, has been written by me, and that it is the record of work carried out by me, or principally by myself in collaboration with others as acknowledged, and that it has not been submitted in any previous application for a higher degree. I was admitted as a research student in August, 2013 and as a candidate for the degree of PhD in July, 2014; the higher study for which this is a record was carried out in the University of St Andrews between 2013 and 2017. Date signature of candidate 2. Supervisor’s declarations: I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of PhD in the University of St Andrews and that the candidate is qualified to submit this thesis in application for that degree. Date signature of supervisor Date signature of supervisor i Declarations 3. Permission for publication: In submitting this thesis to the University of St Andrews I understand that I am giving permission for it to be made available for use in accordance with the regulations of the University Library for the time being in force, subject to any copyright vested in the work not being affected thereby. I also understand that the title and the abstract will be published, and that a copy of the work may be made and supplied to any bona fide library or research worker, that my thesis will be electronically accessible for personal or research use unless exempt by award of an embargo as requested below, and that the library has the right to migrate my thesis into new electronic forms as required to ensure continued access to the thesis. I have obtained any third-party copyright permissions that may be required in order to allow such access and migration, or have requested the appropriate embargo below. The following is an agreed request by candidate and supervisor regarding the publication of this thesis: PRINTED COPY Embargo on all or part of print copy for a period of 1 year on the following ground(s): • Publication would preclude future publication ELECTRONIC COPY Embargo on all or part of electronic copy for a period of 1 year on the following ground(s): • Publication would preclude future publication ABSTRACT AND TITLE EMBARGOES a) I agree to the title and abstract being published YES b) I require an embargo on abstract NO c) I require an embargo on title NO Date signature of candidate signature of supervisor signature of supervisor ii Acknowledgements Acknowledgements To begin, I would like to thank my supervisors Professor Paul Wright and Professor Chris Baddeley for their guidance and support over my PhD. I’m grateful for their encouragement, feedback, and advice throughout my time in St Andrews. I would like to also thank Professor Robert Tooze and Sasol for their discussions and funding. Additionally, I’d like to also thank the EPSRC and the University of St Andrews for funding. I would like to thank Dr. Steve Francis and Dr. Federico Grillo for their help in surface science. Their time and effort towards training, teaching and discussing results with me on the STM, HREELS, XPS and everything else is greatly appreciated. A big thank you also goes out to Dr. Riho Seljamäe-Green for teaching me STM, and Christian Larrea for assistance in fixing and optimizing the HREELS and vacuum. I am thankful for the computational work completed by Dr. Herbert Früctl, and to Professor Neville Richardson for the use of his UHV equipment. I thank Mrs. Sylvia Williamson for training and collection of N2 adsorption data. Thanks to Mrs. Melanja Smith and Dr. Thomas Lebl for the wonderful NMR facilities. Thanks to Dr. Yuri Andreev for the training and technical support for the powder XRD. I’d like to thank Ross Blackley, who provided training and support on the electron microscopes. Also, thank you to Bobby, who has helped massively in fixing things when I break them. I am grateful for the huge amount of support and scientific discussion from both the Wright and Baddeley group. A special thanks to Dr. Alex Greenaway for support, training and a great office atmosphere and Dr. Laura Mitchell for getting me up to speed on MOF catalysis. And a huge thanks to all the Wright group for the fun times in the lab and office and for all the delicious baked goods along the way. Also, an immeasurably large thanks to the Kamer group who let me borrow things constantly, maintained the dry solvent stills and provided access to the high-pressure system. I’d like to give a huge thanks to the friends I have made during my time in St Andrews. These people have helped to get my mind off of the chemistry woes and also as people I could vent to. Thank you to Lorenz, Megan, Esther, Sherry, Paola, Luke, Franziska, iii Acknowledgements Robert, Ciaran, Stefan, Amanda, Rana and everyone else for the lovely meals, games, and pub times. These are memories I will cherish forever. I would also like to my family and friends who were supporting and encouraging me along the way – all the Skype times have made it feel like we aren’t 4,700 miles apart. And finally, Frank, I am so thankful we could have St. Andrews as an adventure together. I appreciate everything you do, from catalysis discussions to cooking dinners (lots of times simultaneously). Thank you for always giving scientific support and personal support. I can’t wait to see what Eindhoven has in store for us next. iv Abstract Abstract This thesis describes the synthesis, characterisation and catalytic testing of multifunctional immobilised metal nanoparticle in metal-organic framework (MOF) materials. Combining the activity of metal nanoparticles with the porosity and Lewis acidity of metal-organic frameworks provides a single catalytic material which can perform multi-step reactions. Strategies to immobilise the metal nanoparticles within the metal-organic frameworks have been investigated. Immobilisation has been achieved by applying three different methodologies. First, deposition of metal nanoparticle precursors within mesoporous MOFs is discussed. Chapter 3 shows the effectivity of the double solvents deposition technique to achieve dispersed and small nanoparticles of around 2.7 nm. The best system combined Pd nanoparticles with MIL-101(Cr). This system was further investigated in tandem reductive amination catalysis, discussed in Chapter 4, to investigate the activity and selectivity provided by these multifunctional catalysts. Another immobilisation technique was performed by coating Pd decorated SiO2 spheres with a MOF layer. Using this technique, MOF was grown cyclically in solution, providing tuneable shell thicknesses of MOF on the metal nanoparticle decorated oxide spheres. While the homogeneity of the MOF shell needs more optimisation, it was determined that the surface charge on the spheres played an important role in the growth of MOF in the desired location. Finally, the third immobilisation technique is the core-shell growth of MOF on colloidal metal nanoparticles. Polymer-capped metal nanoparticles with well-defined shapes were synthesised and characterised. From here, the optimisation of conditions for core-shell growth of UiO-66 and MIL-100(Sc) were investigated. Conditions which provided the desired core-shell morphology were found for both MOF types. These materials were then subsequently used in tandem reductive amination catalysis and a more straightforward styrene hydrogenation. It was shown that the metal nanoparticles remain active catalysts within either MOF shell and the MOF shell stabilises the metal nanoparticle and acts as a Lewis acid catalyst. v vi Table of Contents Table of Contents Declarations ........................................................................................................................i Acknowledgements .......................................................................................................... iii Abstract ............................................................................................................................. v Table of Contents ............................................................................................................ vii Introduction ..................................................................................................... 1 1.1 Background ............................................................................................................. 2 1.2 MOFs as Lewis Acidic Catalysts .............................................................................. 3 1.2.1 HKUST-1 ........................................................................................................... 4 1.2.2 UiO-66 .............................................................................................................. 5 1.2.3 MIL-100 and MIL-101 .....................................................................................
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