Tungsten oxide: a catalyst worth studying for the abatement and decontamination of chemical warfare agents

Abstract Tungsten(VI) oxide, WO3, was studied and used as a heterogeneous catalyst for the liquid-phase oxidative abatement and solid-phase decontamination of simulants of chemical warfare agents, CWAs. The catalytic performance of WO3 was compared to the one of a soluble W-containing model catalyst, W(IV)-heptaisobutyl polyhedral oligomeric silsesquioxane, W-POSS. In liquid-phase abatement tests, WO3 promoted a complete degradation of the toxic agent simulant within 24 h, in the presence of aqueous hydrogen peroxide, at room temperature. In solid-phase decontamination tests, when WO3 was mixed with sodium perborate as a solid oxidant, it was also tested in the decontamination of a cotton textile support from organosulfide and organophosphonate agents (simulants of blistering and nerve CWAs, respectively), showing promising performances comparable to, or sometimes better than, a nanostructured TiO2 catalyst, taken as a reference material. The environmental impact of the WO3 catalyst was assessed on bioluminescent Photobacterium leiognathi Sh1 bacteria, over which no acute nor chronic detrimental effects were recorded. Then, when in contact with a vegetable species such as Phaseolus vulgaris L. (common bean), WO3 did not cause damage to the photosynthetic apparatus of the plant, whereas a clear inhibition of the seed germination was evidenced.

[1]  B. Escher,et al.  Applying mixture toxicity modelling to predict bacterial bioluminescence inhibition by non-specifically acting pharmaceuticals and specifically acting antibiotics. , 2017, Chemosphere.

[2]  J. Forman,et al.  Sampling and analysis of organophosphorus nerve agents: analytical chemistry in international chemical disarmament , 2017 .

[3]  Sergey L. Safronyuk,et al.  Nanosized inorganic metal oxides as heterogeneous catalysts for the degradation of chemical warfare agents , 2016 .

[4]  F. Trifiró,et al.  Chemical risk and chemical warfare agents: science and technology against humankind , 2016 .

[5]  E. Snyder,et al.  Decontamination of personal protective equipment and related materials contaminated with toxic industrial chemicals and chemical warfare agent surrogates , 2016 .

[6]  B. Singh,et al.  Mesoporous binary metal oxide nanocomposites: Synthesis, characterization and decontamination of sulfur mustard , 2016 .

[7]  I. Sazykin,et al.  Synthesis of New ‘Hybrid’ Compounds Based on Benzofuroxans and Aminoalkylnaphthalimides , 2016, Chemical biology & drug design.

[8]  Kibong Kim,et al.  Update 1 of: Destruction and Detection of Chemical Warfare Agents. , 2015, Chemical reviews.

[9]  Guang-jun Liu,et al.  The Facile Hydrothermal Preparation of Orthorhombic WO3 With (001) Facet and Its Photocatalytic Performance. , 2015, Journal of nanoscience and nanotechnology.

[10]  W. R. Creasy,et al.  Nucleophilic Polymers and Gels in Hydrolytic Degradation of Chemical Warfare Agents. , 2015, ACS applied materials & interfaces.

[11]  Frederic D L Leusch,et al.  A sensitive and high throughput bacterial luminescence assay for assessing aquatic toxicity--the BLT-Screen. , 2015, Environmental science. Processes & impacts.

[12]  A. Mazzanti,et al.  Synthesis and antimicrobial activity of novel structural hybrids of benzofuroxan and benzothiazole derivatives. , 2015, European journal of medicinal chemistry.

[13]  G. Wagner Studies on residue-free decontaminants for chemical warfare agents. , 2015, Environmental science & technology.

[14]  Nickolaj F. Starodub,et al.  Nanomaterials: biological effects and some aspects of applications in ecology and agriculture , 2014, Other Conferences.

[15]  F. Carniato,et al.  Niobium(V) saponite clay for the catalytic oxidative abatement of chemical warfare agents. , 2014, Angewandte Chemie.

[16]  O. A. Kholdeeva,et al.  Recent developments in liquid-phase selective oxidation using environmentally benign oxidants and mesoporous metal silicates , 2014 .

[17]  W. R. Creasy,et al.  Nerve Agent Degradation with Polyoxoniobates , 2014 .

[18]  D. Plachá,et al.  Modified clay minerals efficiency against chemical and biological warfare agents for civil human protection. , 2014, Journal of hazardous materials.

[19]  C. Evangelisti,et al.  Nano-structured Solids and Heterogeneous Catalysts for the Selective Decontamination of Chemical Warfare Agents , 2014 .

[20]  T. Chupakhina,et al.  Glycosylated derivatives of substituted hydroxylamine. II. The phase transfer synthesis and the study of the glycosyl transfer reaction of glucosaminides of substituted hydroxylamine , 2013, Russian Journal of Bioorganic Chemistry.

[21]  Jianguo Liu,et al.  Ultrathin, single-crystal WO(3) nanosheets by two-dimensional oriented attachment toward enhanced photocatalystic reduction of CO(2) into hydrocarbon fuels under visible light. , 2012, ACS applied materials & interfaces.

[22]  K. Ganesan,et al.  Comparative evaluation of various sorbent decontaminants against sulphur mustard , 2012 .

[23]  D. Marciano,et al.  The reactivity of quaternary ammonium- versus potassium-fluorides supported on metal oxides: paving the way to an instantaneous detoxification of chemical warfare agents. , 2011, Organic & biomolecular chemistry.

[24]  R. Vijayaraghavan,et al.  Sun light assisted photocatalytic decontamination of sulfur mustard using ZnO nanoparticles , 2011 .

[25]  Kibong Kim,et al.  Destruction and detection of chemical warfare agents. , 2011, Chemical reviews.

[26]  T. Chupakhina,et al.  Glycosides of hydroxylamine derivatives: I. Phase transfer synthesis and the study of the influence of glucosaminides of isatine 3-oximes on bacterial luminescence , 2011, Russian Journal of Bioorganic Chemistry.

[27]  Nicolas Keller,et al.  Self-decontaminating layer-by-layer functionalized textiles based on WO3-modified titanate nanotubes. Application to the solar photocatalytic removal of chemical warfare agents , 2011 .

[28]  P. Larkin,et al.  Introduction: Infrared and Raman Spectroscopy , 2011 .

[29]  Sigal Saphier,et al.  Efficient heterogeneous and environmentally friendly degradation of nerve agents on a tungsten-based POM. , 2010, Journal of hazardous materials.

[30]  H. García,et al.  Visible-light C–heteroatom bond cleavage and detoxification of chemical warfare agents using titania -supported gold nanoparticles as photocatalyst , 2010 .

[31]  R. Vijayaraghavan,et al.  Modified titania nanotubes for decontamination of sulphur mustard. , 2009, Journal of hazardous materials.

[32]  K. Klabunde,et al.  Defining Reactivity of Solid Sorbents: What Is the Most Appropriate Metric? , 2009 .

[33]  Ramesh C. Gupta,et al.  Handbook of toxicology of chemical warfare agents , 2009 .

[34]  N. Keller,et al.  Layer-by-layer deposited titanate-based nanotubes for solar photocatalytic removal of chemical warfare agents from textiles. , 2009, Angewandte Chemie.

[35]  C. C. Landry,et al.  Oxidation of a mustard gas analogue using an aldehyde/O2 system catalyzed by V-doped mesoporous silica. , 2008, Journal of the American Chemical Society.

[36]  K. Hashimoto,et al.  Efficient visible light-sensitive photocatalysts: Grafting Cu(II) ions onto TiO2 and WO3 photocatalysts , 2008 .

[37]  Guomin Zuo,et al.  Effect of acid and base sites on the degradation of sulfur mustard over several typical oxides , 2008 .

[38]  Bryan M Smith,et al.  Catalytic methods for the destruction of chemical warfare agents under ambient conditions. , 2008, Chemical Society reviews.

[39]  Morton A. Barlaz,et al.  A Review of Chemical Warfare Agent Simulants for the Study of Environmental Behavior , 2008 .

[40]  V. Kotova,et al.  Action of 1,1-dimethylhydrazine on bacterial cells is determined by hydrogen peroxide. , 2007, Mutation research.

[41]  C M Boone,et al.  Present State of CBRN Decontamination Methodologies (Stand van Zaken CBRN- Ontsmettingsmethodieken) , 2007 .

[42]  G. Camino,et al.  Synthesis and Characterisation of Metal Isobutylsilsesquioxanes and Their Role as Inorganic–Organic Nanoadditives for Enhancing Polymer Thermal Stability , 2007 .

[43]  D Leszczynska,et al.  Theoretical study of adsorption of sarin and soman on tetrahedral edge clay mineral fragments. , 2006, The journal of physical chemistry. B.

[44]  D. A. Trubitsyn,et al.  Experimental study of dimethyl methylphosphonate decomposition over anatase TiO2. , 2005, The journal of physical chemistry. B.

[45]  L Szinicz,et al.  History of chemical and biological warfare agents. , 2005, Toxicology.

[46]  A. Kleinhammes,et al.  Decontamination of 2-chloroethyl ethylsulfide using titanate nanoscrolls , 2005 .

[47]  S. Bakardjieva,et al.  Reaction of sulfur mustard gas, soman and agent VX with nanosized anatase TiO2 and ferrihydrite , 2005 .

[48]  C. Hill,et al.  Polyoxometalates on cationic silica: Highly selective and efficient O2/air-based oxidation of 2-chloroethyl ethyl sulfide at ambient temperature , 2003 .

[49]  P. Pescarmona,et al.  Oligomeric silsesquioxanes: Synthesis, characterization and selected applications , 2002 .

[50]  G. Socrates,et al.  Infrared and Raman characteristic group frequencies : tables and charts , 2001 .

[51]  K Maxwell,et al.  Chlorophyll fluorescence--a practical guide. , 2000, Journal of experimental botany.

[52]  J. Yates,et al.  Adsorption and Reaction of 2-Chloroethylethyl Sulfide with Al2O3 Surfaces , 1999 .

[53]  J. V. Van Beeumen,et al.  Preparation and Characterization of a Bis(silsesquioxane)tungsten Complex. , 1998, Inorganic chemistry.

[54]  C. Hill,et al.  Selective Oxidation of Thioether Mustard (HD) Analogs bytert-Butylhydroperoxide Catalyzed by H5PV2Mo10O40Supported on Porous Carbon Materials , 1996 .

[55]  U. Jayasooriya Introduction to infrared and Raman spectroscopy : 3rd Edition. Coltup, Daley & Wiberley. 547 pp. Price $69.50. , 1991 .

[56]  S. Wiberley,et al.  THE VIBRATIONAL ORIGIN OF GROUP FREQUENCIES , 1990 .

[57]  R. Vijayaraghavan,et al.  Decontamination of Chemical Warfare Agents , 2022 .