Date of Award

Summer 8-9-2023

Degree Type

Dissertation

Degree Name

PhD. Chemistry

Department

Chemistry and Biochemistry

Advisor

James E. Hanson, PhD

Committee Member

Sergiu M. Gorun, PhD

Committee Member

Joseph J. Badillo, PhD

Committee Member

Stephen P. Kelty, PhD

Keywords

Fluorinated Phthalocyanines, Photocatalysis, Simulants, Detoxification, Adsorption, Nanoparticles

Abstract

The adsorption and photocatalytic properties of fluorinated phthalocyanines (F64PcZn) on metal oxide solid supports were investigated. The supported F64PcZn complexes were characterized by diffuse reflectance, infra-red and fluorescence spectroscopies and with SEM, TEM, and EDS imaging. Phthalocyanines (Pcs) function as photosensitizers to generate singlet oxygen (1O2) using visible light. 1O2 can react to form other reactive oxygen species (ROS), possibly including hydroxyl (HO·) and superoxide (O2-·) radicals. The metal oxide adsorbed F64PcZn was shown to be capable of generating ROS using only visible light and air: an environmentally friendly, green photo-oxidation catalyst.

The degradation of organic sulfides was investigated under several conditions: homogeneous photocatalysis using F64PcZn and heterogeneous photocatalysis using F64PcZn adsorbed on alumina, titania, and zirconia nanoparticles. Heterogeneous photocatalysis was performed in solvent-rich and solvent-less systems. Different solvents resulted in different product selectivity. Different light wavelengths and intensities were used to investigate the kinetics and stability of the supported catalyst. GC-MS was used to identify degradation products and the reaction kinetics were determined using GC-FID. Photocatalysis in solvent-rich systems (homogeneous or heterogeneous) followed first order kinetics while solvent-free systems followed zero order kinetics. No degradation products were observed in the absence of phthalocyanine. Catalyst stability was confirmed by diffuse reflectance and IR spectroscopy, and catalyst re-usability was demonstrated.

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