Date of Completion

4-30-2020

Embargo Period

4-29-2023

Keywords

Reactive Oxygen Species, Heterogeneous, Catalysis, Materials, Synthesis

Major Advisor

Steven L. Suib

Associate Advisor

Christian Bruckner

Associate Advisor

Alfredo Angeles-Boza

Field of Study

Chemistry

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

There are 4 chapters in this thesis. Chapter 1 presents photo-assisted PMS activation using cobalt doped mesoporous iron oxide with exceptional activity and stability up to 6 cycles and very low cobalt leaching. The effects of cobalt doping are shown using different characterization techniques. The high surface area and monomodal pore sizes are maintained with minimal cobalt incorporation. This study correlates the activity to increased labile oxygen induced by cobalt doping. Chapter 2 details the synthesis of mesoporous first–row transition metal ferrites. M2+ (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) ferrite synthesis was systematically studied using a Biotage Initiator microwave apparatus and the effects of reaction time and initial M2+ concentration on the structure, morphology, composition, and catalytic activity were evaluated. These materials were then applied to electrochemical oxygen evolution reaction where NiFe2O4 showed high activity vs. the other ferrites with a low overpotential of 278 mV at 10 mA/cm2. Chapter 3 presents a photo-assisted selective catalytic oxidation of acetonitrile to acetamide on octahedral molecular sieves.

(K-OMS-2) catalysts with oxygen as the sole oxidant. Under this protocol, the catalysts exhibit 100% selectivity towards the formation of acetamide and 15% conversion. The role of light and oxygen is discussed along with a kinetic study of the reaction. Kinetic isotope effect (KIE) studies were conducted to identify the rate-determining step (RDS) and an inverse KIE is observed. Chapter 4 is a review that surveys the chemistry of molecular oxygen, the generation mechanisms and detection methods of reactive oxygen species in heterogeneous selective catalytic oxidations.

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