Dynamic Systems for Catalytic Decontamination of Chemical Warfare Agents and Photoanode Stability Studies Open Access

Collins-Wildman, Daniel (Fall 2020)

Permanent URL: https://etd.library.emory.edu/concern/etds/dr26xz67s?locale=en


There is increasing awareness, both scientifically and at a societal level, that anthropogenic activities are having a variety of adverse effects on our planet. There is also an understanding that these negative impacts on the environment will directly affect the quality of life for populations around the globe, and in some cases, pose direct threats to human health and safety. The scientific community is therefore invested in developing technologies to address and overcome these challenges. One of the greatest synthetically generated threats toward humans, are the highly toxic compounds known as chemical warfare agents (CWAs). Although significant efforts have been made in the development of protective materials, there remains a need for fast and truly catalytic systems to remove the two primary classes of CWAs: nerve agents and blister agents. 

This dissertation describes two catalytic decontamination systems, one for each class of CWAs. Chapter 2 investigates the use of a Zr-containing polyoxometalate catalyst which effectively hydrolyzes nerve agent simulants to their non-toxic products. The nature of the buffer ions used in the system are shown to dramatically affect the rate of catalysis and speciation of the catalyst. This provides new insights for both enhancing the reactivity and brings increased awareness toward product inhibition. Chapter 3 demonstrates a fast and effective solid catalyst formulation that selectively converts the blister agent, sulfur mustard, to the decontaminated sulfoxide. In addition, this work reveals the dynamic role of copper in this system. Finally, chapter 4 investigates the stability of a photoelectrochemical film, a crucial component in addressing another major global concern, which is the ability to store energy from the sun in the form of chemical fuels. 

Table of Contents

Table of Contents

Chapter 1: Introduction – History and Overview of Chemical Warfare Agent Decontamination

1.1 History of Chemical Warfare

1.2 Nerve Agents

1.3 HD Sulfur Mustard

1.4 Polyoxometalates in Decontamination Catalysis

1.5 Scope of the Current Work

1.6 References

Chapter 2: Buffer-Induced Acceleration and Inhibition in Polyoxometalate-Catalyzed Organophosphorus Ester Hydrolysis

2.1 Introduction

2.2 Experimental

2.2.1 Materials and General Methods

2.2.2 Catalyst Preparation and Characterization

2.2.3 Hydrolysis Studies

2.2.4 Computational Methods

2.3 Results and Discussion

2.4 Conclusions

2.5 References

Chapter 3: A Solvent-Free Solid Catalyst for the Selective and Color-Indicating Ambient-Air Removal of Sulfur Mustard

3.1 Introduction

3.2 Experimental

3.2.1 Materials and General Methods

3.2.2 Synthesis of 2-chloroethyl ethyl sulfoxide (CEESO) standard

3.2.3 Gas Chromatography Measurements

3.2.4 Solution Oxidation Studies

3.2.5 Solution NMR experiments

3.2.6 Stopped-Flow Studies

3.2.7 UV-vis Studies

3.2.8 Solid Formulation Catalyst (SFC) Preparation

3.2.9 Solid Formulation Catalyst (SFC) Studies

3.2.10 CEES Oxidation with SFC Under Relevant Battlefield Conditions

3.2.11 Live Agent Studies

3.2.12 X-ray Absorption Fine Structure (XAFS) experiments

3.3 Results and Discussion

3.3.1 Mechanistic Studies in Acetonitrile.

3.3.2 The solid, color-indicating, aerobic mustard (HD) oxidation catalyst

3.4 Conclusion

3.5 References

Chapter 4: A Dual-Purpose Atomic Layer Deposition Metal Oxide Coating for Photoelectrochemical Water Oxidation

4.1 Introduction

4.2 Experimental

4.2.1 Photoanode Film Preparation

4.2.2 Photoelectrochemical Measurements

4.3 Results and Discussion

4.4 Conclusion

4.5 References

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