3D and 4D printing of metal-organic frameworks

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