Date of Award

Fall 2018

Project Type

Thesis

Program or Major

Chemistry

Degree Name

Master of Science

First Advisor

Gonghu Li

Second Advisor

Chrostopher F Bauer

Third Advisor

Margaret E Greenslade

Abstract

In recent years, exploration of the functionalization of nanoparticle surfaces has gained more interest. This can overcome the high energy band gap problem of a semiconductor such as TiO2. Furthermore, this kind of modification can widen the range of catalytic or other uses for the material. In this work TiO2 in various crystal forms was modified towards both degradation of water contamination as well as the reduction of CO2. Iron was covalently attached to TiO2 using a bottom up synthetic strategy incorporating a photoactive linker designed for photocatalytic applications. The resulting surface Fe(II)-terpyridine complex was characterized with techniques including microscopy and spectroscopy, and was investigated in the degradation of Orange II in the presence of H2O2. Under visible-light irradiation, activity of the photocatalyst was found to be dependent on the crystallinity of the supporting TiO2. Furthermore, the Fe(II)-terpyridine complex grafted on TiO2 showed significantly greater activity than the same complex grafted on zirconia in the degradation of the azo dye, Orange II.

Other modifications are explored as well that make use of tin or copper on the surface of TiO2. Tin and copper are covalently grafted to the surface of TiO2 to explore as a possible CO2 reduction photocatalysts. In each of these explorations, the morphology of the TiO2 nanoparticle was explored as a main factor in determining the efficacy of its function. Sample characterization was conducted via UV/Vis and infrared spectroscopy as well as nitrogen adsorption surface area analysis, and electron microscopy. Catalyst performance was probed using UV/Vis spectroscopy, in-situ FTIR and gas chromatography.

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