Nanosized inorganic metal oxides as heterogeneous catalysts for the degradation of chemical warfare agents

Bisio, Chiara; Carniato, Fabio; Palumbo, Chiara; Safronyuk, Sergey L.; Starodub, M. F.; Katsev, Andrey M.; Marchese, Leonardo

doi:10.1016/j.cattod.2015.12.023

Cited by 44 publications

(19 citation statements)

References 48 publications

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“…In the presence of TiO 2 , 44% of CEES abatement was recorded after 5 h and attained 58% after 24 h (Bisio et al, 2016). The WO 3 sample, on the other hand, showed a better catalytic performance in terms of conversion.…”

Section: Decontamination From Blistering and Nerve Agent Simulantsmentioning

confidence: 84%

“…Nanometer-sized titanium dioxide, TiO 2 material was prepared as previously detailed (Bisio et al, 2016).…”

Section: Methodsmentioning

confidence: 99%

“…On the other hand, the solid formulation WO 3 plus UHP could not be used in these tests. In fact, although UHP was successfully used in combination with other oxides (Bisio et al, 2016), it was found to be extremely reactive and unstable in the presence of WO 3 , as the self-decomposition of the oxidant and the in situ formation of large amounts water occurred immediately during the mixing of the two solid components.…”

Section: Decontamination From Blistering and Nerve Agent Simulantsmentioning

confidence: 99%

“…The catalytic properties of W-based materials (WO 3 and W-POSS) in the liquid-phase oxidative abatement of the blistering agent simulant (2-chloroethyl)ethylsulfide, CEES (Bartelt-Hunt et al, 2008) were compared with a nanostructured titanium dioxide, TiO 2 , a material which has already shown interesting properties in the degradation of CWAs and can be thus considered as a benchmark powder catalyst for non-photocatalytically driven decontamination reactions too (Bisio et al, 2016;Prasad et al, 2009;Štengl et al, 2005). The experiments have been performed at room temperature, 25 °C, in the presence of 30 wt.% aqueous hydrogen peroxide, in n-heptane used as a region defined by the potential barriers (Chen, Zhou, Liu, Liu, & Zou, 2012) and is a clear clue of the bulk nature of the WO 3 species.…”

Section: Catalytic Degradation Of Blistering Agent Simulants: the Casmentioning

confidence: 99%

“…Most of them showed, as a matter of example, very good conversion and selectivity in the oxidation reaction of organic sulfides into sulfoxides, whose reactivity mimics the oxidative abatement and detoxification of blistering warfare agents. More recently, layered solids and especially clays (Carniato, Bisio, Psaro, Marchese, & Guidotti, 2014;Michalkova et al, 2006;Plachá et al, 2014) or nanostructured inorganic metal oxides, such as aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), magnesium oxide (MgO) and titanium oxide (TiO 2 ), were widely studied and used with good results in CWA oxidation and/or degradation reactions (Beer Singh et al, 2010;Bisio et al, 2016;Neatu et al, 2010;Zafrani et al, 2011). The catalytic performance of inorganic oxides in the decontamination of hazardous chemicals is, to a large extent, related to their form, size and shape.…”

Section: Introductionmentioning

confidence: 99%

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

Costenaro

Bisio

Carniato

et al. 2017

Global Security: Health, Science and Policy

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Tungsten(VI) oxide, WO 3 , 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 WO 3 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, WO 3 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 WO 3 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 TiO 2 catalyst, taken as a reference material. The environmental impact of the WO 3 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), WO 3 did not cause damage to the photosynthetic apparatus of the plant, whereas a clear inhibition of the seed germination was evidenced.

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Section: Decontamination From Blistering and Nerve Agent Simulantsmentioning

confidence: 84%

“…Nanometer-sized titanium dioxide, TiO 2 material was prepared as previously detailed (Bisio et al, 2016).…”

Section: Methodsmentioning

confidence: 99%

Section: Decontamination From Blistering and Nerve Agent Simulantsmentioning

confidence: 99%

Section: Catalytic Degradation Of Blistering Agent Simulants: the Casmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

Costenaro

Bisio

Carniato

et al. 2017

Global Security: Health, Science and Policy

Self Cite

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A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

Dong

Chi

et al. 2017

Angewandte Chemie

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A novel double-anion complex, H 13 [(CH 3 ) 4 N] 12 -[PNb 12 O 40 (V V O) 2 ·(V IV 4 O 12 ) 2 ]·22 H 2 O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H 2 O 2 with a turnover frequency (TOF) of 16 000 h À1 . Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.

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A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

et al. 2017

View full text Add to dashboard Cite

A novel double-anion complex, H [(CH ) N] [PNb O (V O) ⋅(V O ) ]⋅22 H O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H O with a turnover frequency (TOF) of 16 000 h . Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.

show abstract

Nanosized inorganic metal oxides as heterogeneous catalysts for the degradation of chemical warfare agents

Cited by 44 publications

References 48 publications

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

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

A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

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