Detoxification of Chemical Warfare Agents : From WWI to Multifunctional Nanocomposite Approaches

This book presents a detailed history of chemical warfare development during the First World War and discusses design approaches to gas masks and the performance of new filter materials that decontaminate chemical warfare agents (CWA) when applied in the vapor phase. It describes multifunctional nanocomposites containing zinc and zirconium (hydr)oxides, graphite oxide and silver or gold nanoparticles as reactive adsorbents for the degradation of the CWAs vapors. In addition it examines in detail the surface properties that are most important in the mineralization performance. Acknowledgements 7 Contents 8 1 Chemical Warfare Agents (CWAs) 10 1.1 The History of Chemical Warfare Agents 10 1.2 International Agreements Against CWAs 11 1.3 Classification of Chemical Warfare Agents 12 References 12 2 World War I: Militarization of Chemistry 13 2.1 The Chronicle of the Vast Scale Usage of CWAs: The Road to Mustard Gas 13 2.2 Casualties and Fatalities of WWI 17 2.3 First Protection Attempts: Pads, Helmets, and Gas Masks 22 2.3.1 The Germans 22 2.3.2 The British 24 2.3.3 The French 26 2.3.4 The Italians 28 2.3.5 The Russians 29 2.3.6 The Americans 29 References 33 3 Mustard Gas: The King of CWAs 35 3.1 Mustard Gas 35 3.2 Mustard Gas Deployment Post the WWI 36 3.3 Proposed Decomposition Pathways of HD 37 3.4 The Surrogate of Mustard Gas 38 3.4.1 Detoxification Pathways of the Mustard Gas Surrogate, CEES 38 References 39 4 Current Protection Against CWAs 40 4.1 Whetlerites: The Improved Military Activated Carbon 40 4.2 Research on New Adsorption/Detoxification Materials 41 References 43 5 New Approaches in the Detoxification of CWAs 44 5.1 Zinc (Hydr)Oxide-Based Multifunctional Nanocomposites 44 5.1.1 One-Pot Wet Precipitation of Zinc (Hydr)Oxide 44 5.1.1.1 The Role of the Base Addition Rate 44 5.1.1.2 Structural and Morphological Characterization 45 5.1.1.3 The Influence of the PH 48 5.1.1.4 Conclusion 49 5.1.2 Zn(OH)2 Versus ZnO: The Key Role of the Hydroxyl Groups 50 5.1.2.1 Introduction and Materials 50 5.1.2.2 Structural, Chemical, and Optical Characterizations 50 5.1.2.3 Adsorption Performance: The Role of the Visible Light Irradiation 55 5.1.2.4 Role of the Textural Parameters 56 5.1.2.5 Role of the Surface Chemistry 57 5.1.2.6 Characterization of the Exhausted Samples 58 5.1.2.7 Analysis of the Extracts 61 5.1.2.8 Adsorption Mechanism 61 5.1.2.9 Conclusions 63 5.1.3 Effect of GO Phase in Zn(OH)2/GO Composites on the Extent of Photocatalytic Reactive Adsorption 64 5.1.3.1 Introduction and Materials 64 5.1.3.2 Structural and Morphological Characterizations 64 5.1.3.3 Surface Chemistry Analysis 66 5.1.3.4 Adsorption Performance and the Optimum Amount of GO 67 5.1.3.5 Role of the Textural Parameters 68 5.1.3.6 Role of the Surface Chemistry 69 5.1.3.7 Study of the Kinetics and the Maximum Detoxification Performance 69 5.1.3.8 Surface Chemistry Analysis of the Exhausted Samples 72 5.1.3.9 Identification of the Retained on the Surface Reaction Products 74 5.1.3.10 Identification of the Volatile Products in the Headspace 76 5.1.3.11 Detoxification and Adsorption Mechanisms 79 5.1.3.12 Conclusions 82 5.1.4 AuNPs and AgNPs Embedded in Nanostructured Composites of Zinc (Hydr)Oxide/GO 83 5.1.4.1 Materials and Objectives 83 5.1.4.2 Structural and Morphological Characterizations 83 5.1.4.3 Surface Chemistry Analysis 88 5.1.4.4 Estimation of Reactive Oxygen Species 89 5.1.4.5 Study of the Kinetics and the Maximum Detoxification Performance 90 5.1.4.6 Monitoring the Evolution of the Volatile Products in the Headspace 91 5.1.4.7 Detoxification and Adsorption Mechanisms 95 5.1.4.8 Conclusions 96 5.2 Zirconium (Hydr)Oxide-Based Multifunctional Nanocomposites 97 5.2.1 Effect of GO Phase in ZR(OH)4/GO Composites on the Extent of Catalytic Reactive Adsorption 97 5.2.1.1 Materials and Objectives 97 5.2.1.2 Structural and Morphological Characterizations 98 5.2.1.3 Surface Chemistry Analysis 100 5.2.1.4 Adsorption Performance and the Optimum Amount of GO 103 5.2.1.5 Role of the Textural Parameters and Surface Chemistry 104 5.2.1.6 Characterizations of the Exhausted Samples 104 5.2.1.7 Evaluation of the Detoxification Performance 108 5.2.1.8 Identification of the Volatile Products in the Headspace 109 5.2.1.9 Identification of the Surface Reaction Products Retained on the Surface 112 5.2.1.10 Detoxification Mechanism 113 5.2.1.11 Conclusions 113 5.2.2 AgNPs Embedded in Zirconium Hydroxide/GO Composites 114 5.2.2.1 Materials and Objectives 114 5.2.2.2 Structural and Morphological Characterization 114 5.2.2.3 Surface Chemistry Analysis 117 5.2.2.4 Optical Features—Plasmon Effect 119 5.2.2.5 Role of the Textural Parameters and Surface Chemistry on the Adsorption 120 5.2.2.6 Analysis of the Weight Uptake 122 5.2.2.7 Identification of the Volatile Products in the Headspace 122 5.2.2.8 Identification of the Reaction Products Retained on the Surface 123 5.2.2.9 Conclusions 125 References 125 6 Path Towards Future Research 131 6.1 Oxidized Graphitic Carbon Nitride Nanospheres as a New Composite Component 131 6.1.1 Graphitic Carbon Nitride 131 6.1.2 Oxidized Graphitic Carbon Nitride Nanospheres 132 6.1.3 Graphitic Carbon Nitride Nanospheres as CEES Detoxification Media 134 6.1.4 MOFGCNox Composites as Detoxification Media 135 6.2 Mixed (Hydr)Oxides 137 6.3 Reactive and Smart Textiles 140 6.3.1 Porous Carbon Fabrics 140 6.3.2 Cotton Fabrics with Deposited Ferrihydrite 143 6.3.3 Smart Textiles 144 References 147 Front Matter ....Pages i-xii Chemical Warfare Agents (CWAs) (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 1-3 World War I: Militarization of Chemistry (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 5-26 Mustard Gas: The King of CWAs (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 27-31 Current Protection Against CWAs (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 33-36 New Approaches in the Detoxification of CWAs (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 37-123 Path Towards Future Research (Dimitrios A. Giannakoudakis, Teresa J. Bandosz)....Pages 125-144