3D and 4D printing of metal-organic frameworks

Marshall, Ellis Scott

October 2019

Thesis or dissertation

© 2019 Ellis Scott Marshall. All rights reserved. No part of this publication may be reproduced without the written permission of the copyright holder.

This thesis describes the development of new composite materials by the 3D printing of metal- organic frameworks. The application of these composites in various settings is described.

Chapter 1 contains a review of the area of additive manufacturing with a focus on 3D printing and 4D printing. This introduces applications of 3D printing within the chemistry field and wider fields and gives a review of metal-organic frameworks. The application of metal-organic frameworks as catalysts and in 3D printing are described.

Chapter 2 describes the experimental work undertaken and the design of the experimental rig for the printing of UV-curable polymer matrices under an inert atmosphere. This chapter contains detailed synthetic methods and procedures used for characterisation equipment used for this work and any characterisation limitations.

Chapter 3 contains the work related to the use of magnetically aligned MOFs by the addition of iron. A method for the alignment of iron-rich MOF particles and adsorbed iron oxide nanoparticles in solution by the application of a magnetic field is presented. The alignment of MOF particles with up to 10wt.% iron oxide nanoparticles in a photo-curable polymer resin is demonstrated and the anisotropic optical response of the same is described. The 4D printing of magnetically aligned MOFs in a polymer resin is described.

Chapter 4 contains works related to the ability of UiO-66 to catalyse and degrade nerve agent simulant as a novel 4D printed polymer composite. This demonstrates that a macroscopic MOF composite can be used to degrade a nerve agent simulation. A new technique is trialled for the partial calcination of the polymer composite resulting in a micro and meso porous structure with a high specific surface area (633 m²g-¹). This technique and the physical properties investigated of the resulting monolith are described.

Chapter 5 presents results of metal-organic framework gels as potential additives for 3D printing and a novel direct-write ink. Metal-organic framework gels of UiO-66, UiO-66-NH₂ and ZIF-8 are fabricated and their ability to act as a rheology modifiers are investigated. Trials are described for the novel 3D printing of metal-organic framework gels and adsorption properties investigated.

Department of Chemistry, The University of Hull
Sponsor (Organisation)
University of Hull
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