Date of Award

Spring 2013

Project Type

Thesis

Program or Major

Chemistry

Degree Name

Master of Science

First Advisor

Gonghu Li

Abstract

Immobilization of photoactive molecules on porous and nano-sized solid supports provides unique interactions which affect photophysical properties. In situ diffuse reflectance FTIR and UV-vis spectroscopies were primarily used to investigate the properties of surface functionalized materials. Spectroscopic characterization of photochromic spiropyran molecules physically adsorbed on Y zeolite revealed the importance of surface water in controlling kinetics and reversibility of photoswitching by stabilizing the merocyanine isomer. Re(bpy)(CO)3C1 was both physically adsorbed on a mesoporous ZSM-5 zeolite and covalently bound via the bipyridyl ligand on fumed silica to generate photocatalytic CO2 reduction materials. Upon light irradiation of the solids in the presence of CO2, in situ FTIR spectroscopy shows the formation of Re(bpy)(C0)3(COOH) and Re(bpy)(C0)3(CH0), respectively. FTIR photoexperiments using isotopic 13CO2 and EPR characterization of one electron reduced Re(bpy)(CO)3C1•- after photoirradiation support findings that successful CO2 photoreduction was achieved at the gas-surface interface.

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