25027-40-1Relevant articles and documents
Versatile catalysts constructed from hybrid polyoxomolybdates for simultaneously detoxifying sulfur mustard and organophosphate simulants
Hou, Yujiao,An, Haiyan,Chang, Shenzhen,Zhang, Jie
, p. 2445 - 2455 (2019)
Chemical warfare agents (CWAs) containing sulfur mustard and organophosphates are among the most toxic materials known to mankind and have caused lots of casualties during wars and terrorist attacks. Development of catalysts with selective oxidation and hydrolysis abilities for detoxification of these two types of CWAs is highly desired. Here, we report a series of carboxylic acid modified polyoxomolybdate derivatives with high catalytic performance in the degradation two typical chemical warfare agent simulants: 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), at room temperature. Our results demonstrate that CEES can be highly-selectively degraded to the corresponding far less toxic 2-chloroethyl ethyl sulfoxide (CEESO) with the oxidant H2O2 within 12 minutes, and DECP is almost completely hydrolysed to nontoxic products within 10 minutes. The catalytic activities of these compounds were found to be influenced by the metal cations, carboxylic acid ligands and heteroatoms of polyoxoanions. The corresponding order is respectively Co2+ > Ni2+, Zn2+, Mn2+; PABA > Ala, Ac; AsMo > TeMo.
Selective Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic Metal-Organic Framework
Liu, Yangyang,Howarth, Ashlee J.,Hupp, Joseph T.,Farha, Omar K.
, p. 9001 - 9005 (2015)
The photooxidation of a mustard-gas simulant, 2-chloroethyl ethyl sulfide (CEES), is studied using a porphyrin-based metal-organic framework (MOF) catalyst. At room temperature and neutral pH value, singlet oxygen is generated by PCN-222/MOF-545 using an inexpensive and commercially available light-emitting diode. The singlet oxygen produced by PCN-222/MOF-545 selectively oxidizes CEES to the comparatively nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) without formation of the highly toxic sulfone product. In comparison to current methods, which utilize hydrogen peroxide as an oxidizing agent, this is a more realistic, convenient, and effective method for mustard-gas detoxification.
Synthesis of 2-chloroethyl alkyl sulfones by the oxidative chlorination of 2-hydroxyethyl alkyl sulfides
Derzhinskii,Konyushkin,Vershinin,Varshaver,Mokrushin,Prilezhaeva
, (1976)
1. The corresponding 2-chloroethyl alkyl(phenyl) sulfones were obtained in high yield by oxidizing the 2-hydroxyethyl alkyl(phenyl) sulfides with chlorine in water; the dehydrohalogenation of the former in the presence of bases yields the corresponding vi
Oxidation studies on mustard gas, and the first crystal structure of a metal-mustard gas complex
Rajapakse, Nimal,Mehraban, Shahram,Pacheco, Andrew,Patrick, Brian O.,James, Brian R.
, p. 62 - 66 (2018)
Attempts to selectively oxidize mustard gas [(ClCH2CH2)2S, abbreviated as BCES] to the non-toxic sulfoxide using a trans-Ru(TMP)(O)2/O2 catalyst (TMP = porphyrin dianion of 5,10,15,20-tetramesitylporphyrin) have led to isolation and characterization, including an X-ray structure, of trans-Ru(TMP)(BCES)2, the first such report of a metal-mustard gas complex.
Mono-transition-metal-substituted polyoxometalate intercalated layered double hydroxides for the catalytic decontamination of sulfur mustard simulant
Sun, Xiangrong,Dong, Jing,Li, Zhen,Liu, Huifang,Jing, Xiaoting,Chi, Yingnan,Hu, Changwen
, p. 5285 - 5291 (2019)
The Keggin-type mono-transition-metal-substituted [PW11M(H2O)O39]5? (PW11M, M = Ni, Co, Cu) were intercalated into Zn2Cr-based layered double hydroxide (Zn2Cr-LDH) by an exfoliation-reassembly method and the synthesized Zn2Cr-LDH-PW11M composites were thoroughly characterized by Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), solid state 31P nuclear magnetic resonance (31P NMR) spectroscopy, thermogravimetric analysis (TGA), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The three composites can be used as heterogeneous catalysts to promote the oxidative decontamination of the sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES). Interestingly, a cooperative effect between the PW11M cluster and Zn2Cr-LDH is evidenced by the fact that the composites have a higher catalytic performance than either of the individual constituents alone. The catalytic activity of Zn2Cr-LDH-PW11M is significantly influenced by the substituted transition metals, showing the order: Zn2Cr-LDH-PW11Ni > Zn2Cr-LDH-PW11Co > Zn2Cr-LDH-PW11Cu. Under ambient conditions, the Zn2Cr-LDH-PW11Ni composite can convert 98% of CEES in 3 h using nearly stoichiometric 3% aqueous H2O2 with the selectivity of 94% for the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). Moreover, the decontaminating material, Zn2Cr-LDH-PW11Ni, is stable to leaching and can be readily reused for up to ten cycles without obvious loss of its activity.
Decontamination and remediation of the sulfur mustard simulant CEES with “off-the-shelf” reagents in solution and gel states: A proof-of-concept study
Hiscock, Jennifer R.,Bustone, Gianluca P.,Clark, Ewan R.
, p. 497 - 500 (2017)
The decontamination and remediation of sulfur mustard chemical warfare agents remains an ongoing challenge. Herein, we report the use of “off-the-shelf” metal salts alongside commercially available peroxides to catalyze the degradation of the simulant 2-chloroethyl ethyl sulfide (CEES) in solution and encapsulated within a supramolecular gel.
A peroxotungstate-ionic liquid brush assembly: An efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H2O 2 solution in neat water
Shi, Xianying,Ma, Wenjuan,Ou, Hui,Han, Xiaoyan,Lu, Congmin,Chen, Yan,Wei, Junfa
, p. 1536 - 1542 (2012)
An efficient and reusable heterogeneous catalytic assembly of peroxotungstate held in a ionic liquid (IL) brush was synthesized and an environmentally-friendly procedure was developed for selective oxidation of sulfides at room temperature using 30 wt.percent hydrogen peroxide as the terminal oxidant and water as a sole solvent. No organic co-solvent or other additive was needed. A 1.5-2.0 molpercent (based on W atom) loading catalyst was found to be sufficient for a smooth and clean reaction. Both aliphatic and aromatic sulfides were efficiently and selectively transformed into their respective sulfoxides or sulfones by simply controlling of equivalents of hydrogen peroxide. In addition to the high catalytic activity, the catalyst exhibits excellent chemoselectivity. Sensitive functional groups, such as double bond and hydroxyl, remained under the oxidation conditions the reaction even with an excess hydrogen peroxide. The catalyst was easily recovered (via simple filtration) and reused at least eight times without a noticeable loss of activity. ?2012 Sociedade Brasileira de Qui?mica.
Oxidation of a mustard gas analogue using an aldehyde/O2 system catalyzed by V-doped mesoporous silica
Livingston, Stephanie R.,Landry, Christopher C.
, p. 13214 - 13215 (2008)
Vanadium-doped mesoporous silica was shown to be an effective heterogeneous catalyst for the oxidation of a mustard gas analogue, 2-chloroethyl ethyl sulfide (CEES), in the presence of an aldehyde and molecular oxygen. The oxidation was shown to involve a radical mechanism, which was indicated by the appearance of an induction period when the reaction occurred in the presence of a free radical scavenger. The reaction was initially selective for the oxidation of CEES to the sulfoxide, CEESO, although oxidation of the sulfoxide to the sulfone occurred once all the CEES had been oxidized. Chemical analysis indicated that V species did not leach from the silica support when the reaction was performed in the fluorinated solvent HFE-7100. Copyright
Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring
Picard, Baptiste,Gouilleux, Boris,Lebleu, Thomas,Maddaluno, Jacques,Chataigner, Isabelle,Penhoat, Ma?l,Felpin, Fran?ois-Xavier,Giraudeau, Patrick,Legros, Julien
, p. 7568 - 7572 (2017)
The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea–H2O2 adduct/MeSO3H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR=3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.
A New Hexa-TiIV-Substituted Sandwich-Type Polyoxotungstate: Hydrothermal Synthesis, Structure, and Oxidative Decontamination of Chemical Warfare Agent Simulant
Qin, Dan,Sun, Jun-Jun,Wang, Yue-Lin,Yang, Guo-Yu
, p. 475 - 479 (2020/02/04)
A new hexa-TiIV-substituted sandwich-type silicotungstate, Na2(H2enMe)4[Ti6(μ-O)9(A-α-SiW9O34H2)2]·16H2O (1, enMe = 1,2-diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A-α-SiW9O34]10– Keggin moieties sandwiching a trigonal-prismatic [Ti6(μ-O9)]6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), using H2O2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability.
Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant
Atilgan, Ahmet,Beldjoudi, Yassine,Deria, Pravas,Enciso, Alan E.,Hupp, Joseph T.,Roy, Indranil,Stoddart, J. Fraser,Wasielewski, Michael R.,Weber, Jacob A.,Young, Ryan M.,Yu, Jierui
, (2020/07/06)
Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well-defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g?1 in ExBox?PSS. Efficient intersystem crossing is achieved by combining the spin-orbit coupling associated to Br heavy atoms in 1,3,5,8-tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP?ExBox4+ supramolecular dyad. The TBP?ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed-electronic states. The lowest triplet state (T1, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP?ExBox4+, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4, confirming the importance of the newly formed excited-state manifold in TBP?ExBox4+ for the population of the low-lying T1 state. The high stability, facile preparation, and high performance of the TBP?ExBox?PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.
