Amit Saxena

Removal of sulphur mustard, sarin and simulants on impregnated silica nanoparticles.

Silica nanoparticles of diameter, 24-75 nm and surface area, 875 m(2)/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 2.8 min 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.

Kinetics of adsorptive removal of DEClP and GB on impregnated Al2O3 nanoparticles

Nanoparticles of AP-Al(2)O(3) (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 2-30 nm with high surface area (375 m(2)/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-Al(2)O(3) nanoparticles based sorbent systems AP-Al(2)O(3) 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 30 min for the removal of DEClP and GB, respectively, whereas unimpregnated AP-Al(2)O(3) 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.

Impregnated silica nanoparticles for the reactive removal of sulphur mustard from solutions

High surface area (887.3m(2)/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N(2)-Brunauer-Emmet-Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24-75 nm 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)=2.8 min) 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.

Kinetics of adsorption of 2-chloroethylethylsulphide on Al2O3 nanoparticles with and without impregnants.

Alumina nanoparticles in the size range of 2-30 nm and surface area 375 m(2)/g were synthesized using aerogel route and then characterized using N(2)-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-Al(2)O(3) with 10% impregnation of MoVPA (V(3)) and NaOH showed the maximum (574 mg/g) and minimum (88 mg/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-Al(2)O(3) 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.

Catalytic removal of carbon monoxide over carbon supported palladium catalyst.

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 CO(2) through the catalyzed reaction, i.e., CO+1/2O(2)→CO(2). 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.

Adsorption of diethylchlorophosphate on metal oxide nanoparticles under static conditions.

Nanoparticles of MgO, Al(2)O(3), CaO and SiO(2) were synthesized using aerogel route, and characterized by N(2)-BET, SEM, TEM, XRD, TGA and FT-IR techniques. Characterization indicated 2-75 nm diameter nanoparticles with 135-887 m(2)/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 (1011 mg/g) and minimum (690 mg/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.

In-situ degradation of sulphur mustard using (1R)-(-)-(camphorylsulphonyl) oxaziridine impregnated adsorbents.

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 120 min. 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.

Development and Evaluation of Impregnated Carbon Systems Against Iodine Vapours

In order to understand the breakthrough behaviour of iodine vapours on impregnated carbon systems, an active carbon, 80 CTC grade, BSS particle size and surface area, was impregnated with metal salts such Cu, Cr, Ag, Mo and Zn, and an organic compound Triethylene diamine (TEDA) to prepare different carbon systems such as whetlerite, whetlerite/TEDA, whetlerite/KI/KOH and ASZMT. The prepared adsorbents along with active carbon were characterized for surface area and pore volume by adsorption at liquid nitrogen temperature. These carbon systems were compared for their CT (concentration X time) values at 12.73 to 53.05 cm/sec space velocities and 2 to 5 cm carbon column bed heights. The carbon column of 5.0 cm bed height and 1.0 cm diameter was found to be providing protection against iodine vapours up to 5.5 h at 3.712 mg/L iodine vapour concentration and 12.73 cm/sec space velocity. The study clearly indicated the adsorption capacities of carbon systems to be directly proportional to their surface area values. Dead layer with all the prepared carbon systems was found to be less than 2.0 cm indicating it to be minimum bed height to have protection against vapours. Effect of carbon bed height and flow rate was also studied. The active carbon showed maximum protection at all bed heights and flow rates in comparison to all other impregnated carbon systems, showing that only physical adsorption is responsible for the removal of iodine vapours.

Zero valent metal loaded silica nanoparticles for the removal of TNT from water

Silica nanoparticles with a surface area of 673.60 m2/g and particle size of 8-12 nm were prepared using aerogel process (AP) followed by super critical drying. Zero valent Fe, Co, Pt, and bimetallic Fe/Pt and Fe/Co were loaded using an incipient wetness impregnation technique and subsequent reduction. Scanning electron microscopy-energy dispersive X-ray (SEM-EDX) and transmission electron microscopy-energy dispersive X-ray (TEM-EDX) characterizations indicated fine dispersion of iron on AP-SiO2 +Fe system. Prepared nanoparticles were evaluated for the adsorptive removal of 2,4,6-trinitrotoluene (TNT) from water. Surface area normalized rate constant values indicated the adsorptive removal potential of prepared nanoparticles to be: AP-SiO2 + Fe/Co > AP-SiO2 + Fe > CM (commercial) SiO2 + Fe > AP-SiO2 + Co > AP-SiO2 + Fe/Pt > AP-SiO2 + Pt. Lower pH helped in accelerating the reactive removal of TNT on zero valent iron loaded silica. AP-SiO2 + Fe/Co system showed the maximum adsorption potential (74 mg/g) after five cycles.

Breakthrough behaviour of NBC canister against carbon tetrachloride: a simulant for chemical warfare agents

A nuclear, biological, chemical (NBC) canister was indigenously developed using active carbon impregnated with ammoniacal salts of copper (II), chromium (VI) and silver (I), and high efficiency particulate aerosol filter media. The NBC canister was evaluated against carbon tetra chloride (CCl4) vapours, which were used as a simulant for persistent chemical warfare agents under dynamic conditions for testing breakthrough times of canisters of gas masks in the National Approval Test of Respirators. The effects of CCl4 concentration, test flow rate, temperature, and relative humidity (RH) on the breakthrough time of the NBC canister against CCl4 vapour were also studied. The impregnated carbon that filled the NBC canister was characterized for surface area and pore volume by N2 adsorption-desorption isotherm at liquid nitrogen temperature. The study clearly indicated that the NBC canister provides adequate protection against CCl4 vapours. The breakthrough time decreased with the increase of the CCl4 concentration and flow rate. The variation in temperature and RH did not significantly affect the breakthrough behaviour of the NBC canister at high vapour concentration of CCl4, whereas the breakthrough time of the NBC canister was reduced by an increase of RH at low CCl4 vapour concentration.