The combined action of methanolysis and heterogeneous photocatalysis in the decomposition of chemical warfare agents

Petrea, Nicoleta; Petre, Răzvan; Epure, Gabriel; Şomoghi, Vasile; Tănase, Liviu Cristian; Teodorescu, Cristian M.; Neaţu, Ştefan

doi:10.1039/c6cc07551g

Cited by 13 publications

(19 citation statements)

References 28 publications

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“…Metal nanoparticles (NPs) supported on metal oxides have been shown to be effective catalysts for CO oxidation, − methanol oxidation, , and the decomposition of organophosphorus chemical warfare simulants/agents. − The most commonly studied metal NPs are precious metals (Au, Pd, Pt, Ir) due to their high catalytic activity and selectivity toward desired products. However, more Earth-abundant metals are desirable.…”

Section: Introductionmentioning

confidence: 99%

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst

et al. 2020

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Carbon monoxide (CO) oxidation is not only an important industrial reaction but also a useful model system for investigations into reaction dynamics involving new catalyst designs. In this work, we use CO oxidation to probe the metal−support interactions between Cu nanoparticles and a TiO2 aerogel support. We utilized a packed-bed reactor to demonstrate the activity of a Cu/TiO2 aerogel catalyst for CO oxidation at temperatures above 463 K. In situ infrared spectroscopic methods revealed that the reaction proceeds primarily by a Cu-assisted Mars-van-Krevelen type mechanism. Results indicate that Ti4+ sites are reduced by CO to generate Ti3+ sites adjacent to oxygen vacancies. Lattice oxygen extraction appears to be accompanied by interfacial charge transfer from lower work function copper nanoparticles to the TiO2 support, as evidenced by variable-temperature infrared spectroscopic studies of adsorbed CO. The charge transfer is evidenced by differences in the nature of CO bound to Ti4+ sites within aerogels in the presence and absence of Cu. The Cu particles on the TiO2 support lower the vibrational frequency for CO bound to Ti4+ sites by 3 cm–1 and increase the binding enthalpy by 7 kJ/mol. Infrared spectroscopic probes of oxidation state cycling during catalysis contribute toward the development of an overall CO oxidation reaction mechanism on the Cu/TiO2 aerogel.

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Section: Introductionmentioning

confidence: 99%

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst

et al. 2020

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“…In the event of deliberate or accidental release of CWAs it is essential to detect and destroy these highly toxic materials. A large number of hydrolytic, enzymatic and thermal destruction/degradation methods have been proposed (6)(7)(8) as have detection systems based on spectroscopic or spectrometric approaches (9,10). However, recent interest in the supramolecular chemistry of CWAs has led to a significant number of reports exploring the molecular recognition properties of these molecules by functional materials.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Sambrook

Gass

Cragg

2017

Supramolecular Chemistry

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A computational protocol to predict the infrared spectra of chemical warfare agents (CWAs) tabun (GA), sarin (GB), soman (GD) and cyclosarin (GF) has been developed. Sarin was used to benchmark the method through gas phase simulations. DFT calculations using the EDF2 functional and diffuse 6-311++G** basis set was found to give the closest match to experimental infrared spectra. Using the same functional the 6-31G (2df, 2p) basis set was found to be superior when hydrated sarin was modelled. GA, GB, GD and GF, together with 11 commonly used simulants, were modelled in the gas and hydrated states. Complexes of GB and a number of CWA mimics with α-cyclodextrin were modelled to give insight into their different modes of inclusion

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“…The resulting radical cation intermediates can eliminate chloroethylene (or its hydration product) to form surface-bound thiyl radicals, which recombine to disulfides (Figure 11). [137] Subsequently,t he photocatalytic decomposition of mustard analogs was tested in the presence of doped TiO 2 (V,F e, Mn, W), [137,138] Au-supported TiO 2 , [139,140] ZnO, [141,142] and MnO 2 nanomaterials, [143] all suitable for visible light harvesting. Doped TiO 2 (V,F e, Mn, W) and Au-supported TiO 2 displayed improved sulfur mustard degradationc ompared with TiO 2 ,e specially under visible irradiation.…”

Section: Semiconductors/metaloxidesasp Hotocatalystsmentioning

confidence: 99%

“…Subsequently, the photocatalytic decomposition of mustard analogs was tested in the presence of doped TiO 2 (V, Fe, Mn, W), [137, 138] Au‐supported TiO 2 , [139, 140] ZnO, [141, 142] and MnO 2 nanomaterials, [143] all suitable for visible light harvesting. Doped TiO 2 (V, Fe, Mn, W) and Au‐supported TiO 2 displayed improved sulfur mustard degradation compared with TiO 2 , especially under visible irradiation.…”

Section: Photocatalytic Neutralizationmentioning

confidence: 99%

Catalytic Processes for the Neutralization of Sulfur Mustard

Oheix

Gravel

Doris

2020

Chemistry A European J

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Research on the decontamination of the chemical warfare agent sulfur mustard pursues severalo bjectives that include the neutralization of spared ammunition,t he cleaning of affected areas, and also the development of protective equipment or tools. Neutralizationo fv esicant sulfur mustard involves different chemical routes such as hydroly-sis, dehydrochlorination, oxidation, or complete mineralization. This review weighs the pros and cons associated with the different systems reported in the literature, with an emphasis on catalytic procedures, to selectively convert sulfur mustard or its simulants into harmless products.

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The combined action of methanolysis and heterogeneous photocatalysis in the decomposition of chemical warfare agents

Cited by 13 publications

References 28 publications

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Catalytic Processes for the Neutralization of Sulfur Mustard

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The combined action of methanolysis and heterogeneous photocatalysis in the decomposition of chemical warfare agents

Cited by 13 publications

References 28 publications

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO2 Aerogel Catalyst

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO2 Aerogel Catalyst

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Catalytic Processes for the Neutralization of Sulfur Mustard

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Product

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Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst

Electronic Metal–Support Interactions in the Activation of CO Oxidation over a Cu/TiO₂ Aerogel Catalyst