Novel synthesis of metal-organic materials for human health and energy applications

Abstract

Chapter 2 presents an electrochemical synthesis of the Fe3+ framework MIL-101. Due to the typically harsh synthetic conditions required to synthesize green alternatives were pursued. Utilizing an oxidative room temperature technique I am able to synthesize MIL-101 via facile conditions. Furthermore, this technique allows for controlled growth on the electrode surface. ☐ Chapter 3 addresses a challenge faced during coordination cage synthesis, phase control. When the zirconocene capped cages, which resemble UiO-66, are studied in situ utilizing 1H NMR and mass spectrometry some were found to isomerize to a cigar-like structure type. By utilizing different types of functional groups, it is possible to control the structure type formed, both in the solid state and in situ. ☐ Chapter 4 describes a water-modulated synthesis of UiO-66. Typically to form nanoparticles of UiO-66 to desired sizes the addition of a modulator is required. These modulators lead to defects in the structure altering the porosity and gas storage properties of the material. Use of water as a modulator leads to nanoparticle formation of defect-free material via a non-toxic modulator. These particles were then used in a subsequent study to test the cargo storage and biocompatibility of these nanoparticles. ☐ Lastly, in chapter 5, the discrepancy between bulk and crystallographic density and its impact on CH4 storage is discussed. In all cases the bulk density of the selected MOF was lower than the crystallographic density, reducing the volumetric storage capacity of the material. A potential solution was explored by creating a composite of MOF and porous polyhedra. Through the use of helium pycnometry it is possible to measure the apparent density of potential storage materials. With this technique I measured the apparent density of over 40 materials to study the “upper limit” of density of the desired storage targets, giving a better estimate on what potential maximum volumetric capacities may be.