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Abstract: Carbon supported palladium (Pd/C) catalyst was prepared by impregnation of palladium chloride using incipient wetness technique, which was followed by liquid phase reduction with formaldehyde. Thereafter, Pd/C catalyst was characterized using X-ray diffractometery, scanning electron microscopy, atomic absorption spectroscopy, thermo gravimetry, differential scanning calorimetry and surface characterization techniques. Catalytic removal of carbon monoxide (CO) over Pd/C catalyst was studied under dynamic conditions. Pd/C catalyst was found to be continuously converting CO to CO2 through the catalyzed reaction, i.e., CO+1/2O2 →CO2. Pd/C catalyst provided excellent protection against CO. Effects of palladium wt%, CO concentration, humidity, space velocity and reaction environment were also studied on the breakthrough behavior of CO. [Copyright &y& Elsevier]

Abstract: Silica nanoparticles of diameter, 24–75nm and surface area, 875m2/g were synthesized using aero-gel route. Thereafter, nanoparticles were impregnated with reactive chemicals, and used as reactive adsorbent to study the removal of toxic nerve and blister chemical warfare agents and their simulants from solutions. Trichloroisocyanuric acid impregnated silica nanoparticles showed the best performance and indicated physisorption followed by chemisorption/degradation of toxicants. This indicated their suitability as universal decontaminant for nerve and blister agents. This system showed a decrease in t 1/2 from 1210 to 2.8min for the removal of king of chemical warfare agents, i.e., sulphur mustard. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of toxicants over impregnated silica nanoparticles. [Copyright &y& Elsevier]

Abstract: Nanoparticles of MgO, Al2O3, CaO and SiO2 were synthesized using aerogel route, and characterized by N2-BET, SEM, TEM, XRD, TGA and FT-IR techniques. Characterization indicated 2–75nm diameter nanoparticles with 135–887m2/g surface area and microporous–mesoporous characteristics. Prepared nanoparticles were tested for their adsorptive potential by conducting studies on kinetics of adsorption of diethylchlorophosphate under static conditions. The kinetic parameters such as equilibration constant, equilibration capacity, diffusional exponent and adsorbate–adsorbent interaction constant have been determined using linear driving force model and Fickian diffusion model. AP-MgO and AP-CaO showed the maximum (1011mg/g) and minimum (690mg/g) uptake of DEClP, respectively. All nanoparticles showed the values of diffusional exponent to be >0.5, indicating the diffusion mechanism to be anomalous. Hydrolysis reaction (identified using GC/MS technique) was found to be the route of degradation of DEClP. [Copyright &y& Elsevier]

Abstract: Nanoparticles of AP-Al2O3 (aero-gel produced alumina) have been produced by an alkoxide based synthesis involving aluminum powder, methanol, toluene and water. Thus produced alumina nanoparticles were characterized and the data indicated the formation of nanoparticles of alumina in the size range of 2–30nm with high surface area (375m2/g). Thereafter, these nanoparticles were impregnated with reactive chemicals. Adsorptive removal kinetics for DEClP (diethylchlorophosphate) and GB (isopropylmethylphosphonofluoridate, sarin) was monitored by GC–FID (gas chromatograph coupled with flame ionization detector) technique and found to be following pseudo first order reaction kinetics. Among impregnated AP-Al2O3 nanoparticles based sorbent systems AP-Al2O3 impregnated with 9-molybdo-3-vanadophosphoric acid (10%, w/w) was found to be the most reactive with least half-life values of 7 and 30min for the removal of DEClP and GB, respectively, whereas unimpregnated AP-Al2O3 nanoparticles showed the best adsorption potential among all studied systems. In addition to this, hydrolysis reaction {identified using GC/MS (gas chromatograph coupled with mass spectrometer) technique} was found to be the route of degradation of DEClP and GB on impregnated alumina nanoparticles. [Copyright &y& Elsevier]

Abstract: Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in-situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different adsorbents systems loaded with (1R)-(-)-(camphorylsulphonyl) oxaziridine were prepared. Solution of sulphur mustard and its simulants was prepared in carbon tetrachloride and taken for uniform adsorption on the impregnated systems using incipient volume. Degradation kinetics monitored by GC/FID were found to be first-order. The half-life of degradation reactions for simulants was obtained in less than 30 and for HD in 120min. From the studied kinetics it was observed that reaction was very rapid with simulants and decreased rate was found for HD. The order of reactivity of MgO/Oxa system for HD and simulants was found to be DBS>HEES>HD. Reaction products of the oxidation reaction of simulants and HD on adsorbents were extracted in dichloromethane and analysed by GC–MS. The products were found to be non-toxic sulphoxide. The objective of the study is to develop a reactive adsorbent for in-situ degradation of sulphur mustard which could be used in nuclear biological and chemical (NBC) filtration systems. [Copyright &y& Elsevier]

Abstract: Alumina nanoparticles in the size range of 2–30nm and surface area 375m2/g were synthesized using aerogel route and then characterized using N2–BET, SEM, TEM, XRD, FTIR and TGA techniques. Thereafter, these were impregnated with reactive chemicals and tested for their potential by conducting studies on kinetics of adsorption of 2-chloroethylethylsulphide (2-CEES) under static conditions. Kinetics was studied using linear driving force and Fickian diffusion model. The kinetics parameters such as equilibration constant, equilibration capacity, diffusional exponent and adsorbate–adsorbent interaction constant were also determined. AP-Al2O3 with 10% impregnation of MoVPA (V3) and NaOH showed the maximum (574mg/g) and minimum (88mg/g) uptake of 2-CEES among impregnated systems respectively. All impregnated systems except NaOH impregnation showed the values of diffusional exponent to be <0.5, indicated the diffusion mechanism to be Fickian, whereas AP-Al2O3 with and without NaOH impregnation showed the diffusional mechanism to be anomalous. Hydrolysis and dehydrohalogenation reactions (identified using GC/MS technique) were found to be the route of degradation of 2-CEES. [Copyright &y& Elsevier]

Abstract: High surface area (887.3m2/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N2-Brunauer–Emmet–Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24–75nm with mesoporous characteristics. Later, these were impregnated with reactive chemicals such as N-chloro compounds, oxaziridines, polyoxometalates, etc., which have already been proven to be effective against sulphur mustard (HD). Thus, developed novel mesoporous reactive sorbents were tested for their self-decontaminating feature by conducting studies on kinetics of adsorptive removal of HD from solution. Trichloroisocyanuric acid impregnated silica nanoparticles (10%, w/w)-based system was found to be the best with least half-life value (t 1/2 =2.8min) among prepared systems to remove and detoxify HD into nontoxic degradation products. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of HD over prepared sorbents. The study also inferred that 10% loading of impregnants over high surface area and low density silica nanoparticles enhances the rate of reaction kinetics and seems to be useful in the field of heterogeneous reaction kinetics. [Copyright &y& Elsevier]

Abstract: Active carbon, grade 80 CTC, of surface area 1199m2/g, 12×30 BSS particle size and coconut shell origin was impregnated (5%, W/W) with various impregnants such as Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate, Cu(II) 1,1,1-trifluoroacetylacetonate, 1-phenylbute-1,3-dione-2-oxime plus Cu(II) using incipient wetness technique. These impregnated carbons along with active carbon (Grade 80 CTC) and whetlerite were studied for the adsorption of dimethyl methylphosphonate (DMMP) at 33±1°C under static conditions. Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon system showed highest uptake (68.5%, W/W) of DMMP amongst all the carbon systems, however, active carbon with higher surface area could adsorb 61.5% (W/W) of DMMP under same conditions. It indicated that the adsorption by Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon was not only due to physisorption but chemisorption as well. Kinetics of adsorption was also studied and various parameters such as equilibration time, equilibration capacity, rate constant (k), diffusional exponent (n) and constant (K) were determined. Carbons with and without DMMP exposure were also studied using IR and TGA techniques. Reaction products were analyzed using gas chromatography coupled with mass spectrometry (GC/MS) and found to be methyl methylphosphonic acid (MMPA) and methylphosphonic acid (MPA) for Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon. [Copyright &y& Elsevier]

Abstract: Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different carbon systems such as 11-molybdo-1-vanadophosphoric acid impregnated carbon (V1/C), ruthenium chloride impregnated carbon (Ru/C) and combination of these two (V1/Ru/C) were prepared. These carbons were characterized for cumulative micropore volume and surface area by N2 BET. The kinetics of the in situ degradation of HD and its simulants were studied and found to be following the first order kinetics. Kinetic rate constants and t 1/2 values were determined. Products were characterized using NMR, IR and GC–MS. Reaction products were found to be sulphoxide and sulphone. The combined system, i.e., 11-molybdo-1-vanadophosphoric acid plus ruthenium chloride (V1/Ru/C) was found to be best for in-situ degradation of HD and its simulants. In-situ degradation by polyoxometalate based system was found to be stoichiometry based while Ru/C oxidized HD in presence of chemisorbed oxygen. In combined system of V1/Ru/C ruthenium worked as a catalyst and polyoxometalate acted as a source of oxygen. Effect of moisture was also studied in combined system. Rate of degradation of HD was found to be increasing with increased percentage of moisture content. [Copyright &y& Elsevier]