Decontamination of Chemical Warfare Agents with Resin-based Catalysts and POMs Public
Yang, Juncheng (2015)
Published
Abstract
Chemical warfare agents pose a great danger to the whole world, therefore in this thesis, I worked on two aspects of chemical warfare agent (CWA) decontamination. The first focus was to develop a heterogeneous catalyst for the oxidation of sulfur mustard. Compared to homogeneous catalysts, heterogeneous catalysts are more amenable to real-life applications such as self-decontaminating fabrics. In this part, I focused on the development of a new series of heterogeneous catalysts (AM series) derived from NO3- and Br- with an ion-exchange resin (AG-MP1), which then was used for the selective oxidation of sulfur mustard. Subsequently I found this heterogeneous catalyst is destroyed when used in solution by chloride exchange (displacement) of NO3- and Br- from the original polymeric catalyst during turnover. Following this, I focused on the decontamination of sulfur mustard vapor using the same polymeric-NO3-+Br- catalysts. It was determined that this AM series catalysts did not work in gas phase either. The second focus of the thesis was to develop a bi-functional catalyst, one capable of simultaneously decontaminating sulfur mustard by selective oxidation and hydrolysis of nerve agents using a combination of NO3-/Br- and two POMs, a polyniobate (henceforth "Nb-POM") and a mixed cesium-proton salt (henceforth "Cs2.5-POM"). The Nb-POM was not compatible with NO3-/Br-, while the Cs2.5-POM was partly compatible, but we needed to find a suitable solvent for the system. In conclusion, this thesis concentrates on the development of new systems for decontaminating two kinds of chemical warfare agents using only air and water.
Table of Contents
Abstract
Acknowledgments
List of Figures
List of Tables
List of Schemes
Part I: Introduction. 1
Part II: Decontamination of Sulfur Mustard in Solution. 5
Part III: Decontamination of Sulfur Mustard Vapor. 24
Part IV: Simultaneous Decontamination of Sulfur Mustard and Nerve Agents. 30
List of Figures
Part I
Figure 1. Structure of Mustard (HD)
Figure 2. Structure of CEES
Figure 3. Mechanism of sulfur mustard's toxicity
Figure 4. The structure of VX
Figure 5. The structure of DMMP
Part II:
Figure 6. Structure of the ion exchange resin, AG-MP1 (AM)
Figure 7. FTIR spectra of AM (black), AM-Br (red), AM-NO3 (blue)
Figure 8. Local FTIR spectra (2400cm-1-400cm-1) of AM (black), AM-Br (red) and AM-NO3 (blue)
Figure 9. Elemental analysis of nitrogen and bromine content in the AM series of catalysts
Figure 10. Oxidation of CEES catalyzed by AM, AM-NO3, AM-Br, AM11
Figure 11. Activity of AM11, AM12, AM21 in selective oxidation of CEES
Figure 12. CEES oxidation activity using different amounts of catalyst
Figure 13. Oxidation activity of AM11, AM13 and AM31 (25 mg)
Figure 14. Activities of air-based CEES oxidation by AM11, AM1+1, AM1+1, AM2+1 (AM1+1, AM1+1, AM2+1 indicate 1:1, 1:2, 2:1 mixture of AM-NO3 and AM-Br respectively)
Figure 15. Control experiments with different amounts of CEES
Figure S1. Local FTIR spectra of AM-Br, AM11, AM21, AM31, AM51, and AM-NO3 (bottom to top)
Figure S2. Local FTIR spectra of AM-NO3, AM11, AM12, AM13, AM15, and AM-Br (bottom to top)
Figure S3. Control catalytic reaction without water
Figure S4. Mixing the supernatant of the reaction system and 1 mol/L AgNO3
Figure S5. Activity of AM11, AM12, AM13, AM15
Figure S6. Activity of AM11, AM21, AM31, AM51
Part III:
Figure 16. Device for assessing the catalytic activity for air-based decontamination of CEES
Figure 17. Close-up of vapor generator
Figure 18. Close-up of the reactor
Figure 19. FTIR spectra of AM, Cu-POM and AM-POM
Figure 20. Activity of 2-component catalyst (AM1+1) and 3-component catalyst (AM1+1+1)
Part IV:
Figure 21. 31P NMR spectrum of the mixture after reaction catalyzed by Cs2.5-POM
List of Tables
Chapter II:
Table 1. Sample names and their preparation conditions
List of Schemes
Chapter II:
Scheme 1. Mechanism of O2-based sulfide oxidation catalyzed by NO3- + Br
Scheme 2. Mechanism of AM series of catalysts in solution
About this Master's Thesis
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