Title of Invention

"IMPREGNATED ALUMINA NANOPARTICLES FOR DETOXIFICATION OF CHEMICAL CONTAMINANTS"

Abstract

The present invention relates to impregnated alumina nanoparticies for detoxification of chemical contaminants. It also relates to the development of compositions having alumina nanoparticies and reactive chemicals loaded/impregnated over it to give it a permanent self decontaminating feature. This material can be used with gas phase chemical agents removal/decontamination devices and filtration systems with suitable modifications (converting impregnated nanoparticies to granules by mechanical compression technique) to remove and detoxify chemical agents effectively in less time.

Full Text

Field of invention The invention relates to impregnated alumina nanoparticles for detoxification of chemical contaminants and more particularly, it relates to the development of compositions having alumina nanoparticles and reactive chemicals loaded/impregnated over it to give it a permanent self decontaminating feature. This material can be used with gas phase chemical agents removal/decontamination devices and filtration systems with suitable modifications (converting impregnated nanoparticles to granules by mechanical compression technique) to remove and detoxify chemical agents effectively in less time. Background of art Use of toxic chemicals to produce physical immobilization in war is known from early ages. The chemical agents and the toxicants are of the kind of nerve agents and its stimulants, blister causing agents and its stimulants and chemical contaminants and toxicants. The defense against these toxic chemicals can be done by creating a barrier (metal/concrete shields and adsorbents) between humans and agents. Shields can be used for shorter durations but the best way is to remove these toxicants permanently. This can he achieved by utilizing a suitable material, which can perform the function the function of physiosorption (physical adsorption) followed by chemisotption, i.e, chemical degradation. Reference may be made to the recent technologies in literature for the decontamination (Yang, Y.C.; Baker, J. A.; Ward, J. R.; Chem. Rev. 1992, 92, 1729). These agents involve the use of corrosive chemicals such as DS2 (mixture of diethylenetriamine 70 %, ethylene glycol monomethylether 28% and sodium hydroxide 2%), hypochlorite solutions, etc. These are useful decontaminants but are corrosive to most metals and fabrics, as well as to human skin. Furthermore, it results in large quantities of effluent, which must be disposed off in an environmentally sound manner. In general, solution based contaminants is applicable only for vehicles, equipments, area and skin; however, these cannot be effectively used for decontamination of chemical agents available as gases in the contaminated zone. For that the best way may be the use of reactive particles sprayed through spraying devices. Incineration of these toxicants in incineration plants is another way to dispose them but it requires the mobile incineration plants or the agent has to be carried at the established incineration plant. Technology currently in use to provide protection for respiratory track is the utilization of filtration system, which includes adsorbents, i.e. impregnated carbon. Impregnated carbon suffers from the fact that it does not destroy persistent chemical agents but merely holds them by adsorption forces (physiosorption). Therefore, it creates problem of safe disposal of used filtration systems, if after use these are thrown carelessly or not disposed off properly. This problem of safe disposal can be overcome, if the adsorbent material itself these agents after adsorption, i.e, physiosorption followed by chemisorption. Therefore, there is great need for compounds and adsorbents, which are effective against the whole spectrum of chemical agents and are easily transportable, do not harm skin or equipment, and require the employment in small amounts of liquids with minimal or no effluent. World wide the investigations are under way to find safe and effective material which can be used in filtration (with suitable modifications) and decontamination systems to detoxify these chemicals without endangering human life or the environment. Highly porous multifunctional materials have attracted increasing attention in recent years. These materials are typically obtained via soft chemistry by sol-gel process. Such an approach offers the possibility to synthesize porous nano materials in different forms to suit widespread technological applications. Thus produced inorganic metal oxide nanoparticles are currently under consideration due to its unusual chemical and physical properties and have the potential to be used as reactive adsorbents for the destruction of toxicants. The destructive adsorption of these toxicants take place on the surface of nanocrystals, so that the adsorbate is chemically dismantled and thereby made non-toxic. Reference may be made to adsorbents in the literaure, it has been suggested (Li et al; Environment Science and Technology 1994, 28, 1248) in the past to employ nanoparticles of MgO or CaO for the destructive adsorption of chlorinated benzenes. Klabunde et al (High Temperature Materials Science 1995, 33, 99) has advocated the destructive adsorption of chloro carbons at high temperature through the use of MgO/Fe2O3 composites. WO 98/07493 (Klabunde et al) discloses use of nanometer size metal oxide particles for ambient temperature adsorption of toxic chemicals, which includes 2-chloroethylethyl sulfide (2-CEES), dimethylmehtyl phosphate, paraoxon, sulphur dioxide, carbon dioxide, etc. WO 03/094977 (Okun et al) discussed the compositions of polyoxometalate/cationic silica material, copper salts and combinations thereof to decontaminate 2-CEES. This material is associated with low surface area values and does not belong to the category of nanomaterials. WO 01/78506 and US6653519 discloses the use of nanoparticles as destructive adsorbents for biological and chemical contamination. The document discloses preferred metal oxides such as MgO, CaO, TiO2, ZrO2) FeO, Mn2O3, Fe2O3, NiO, CuO, A12O3, ZnO and their mixtures thereof. The coatings of a second metal oxide are different form the first metal oxide, selected from a group of Sr, Fe, Cu, Ni, Zn, etc. The coating of second metal oxide has also been discussed by Decker et al (Environmental Science and Technology 2002, 36, 762; Journal of American Chemical Society 1996, 118, 12465 and Chemistry of Materials 1998, 10, 674.) Destruction of chemical agents such as blister and nerve agents on metal oxide nanoparticles has been discussed by George W. Wagner (Journal of Physical Chemistry B 1999, 103, 3225; J. Ame. Chem. Soc. 2001, 123, 1636 and J. Phy. Chem. B 2000, 104, 5118). All above discussed systems are effective against chemical agents but their efficiency can further be enhanced by impregnating them with those reactive chemicals, which have already been proved to be reactive against such chemical agents. Carbon 2006, 44, 907; Carbon Science 2005, 6(3), 158; J. Haz. Mater. 2006, 134 (1-3), 104 and J. Haz. Mater. 2006, 133 (1-3), 106, teaches that single metal oxide particles do not show much promising results, hence these nano adsorbents can further be modified for second generation nano adsorbents by loading/impregnation with those reactive compounds, which have already proven to be active against chemical agents, however, the possibility of new compounds for impregnation also exist. Choudhary et al. (Adv. Syn. Catal. 2004, 346, 45) suggest one such material, osmate stabilized on nanocrystalline magnesium oxide and used for chiral dihydroxylation of olefins to diols in the presence of a cooxidant (N-methylmorpholine-N-oxide). WO 03/092656 discloses the embodiments of the decontaminating compositions which comprises an inorganic nanoparticle and an organic reactive molecule (e.g. Molecule with hydantoin rings) grafted via a linker group (polymer) on to the inorganic nanoparticle. This material suffers from the fact that the surface area of the material is low due to which it does not attract the bigger doses of chenf ^al agents to be removed permanently. Attempts have also been made to prepare adducts of nanosize metal oxide particles with halogens to make a selective catalyst for halogenation of organic r olecules (J. Amer. Chem. Soc. 1999, 121, 5587; J. Amer. Chem. Soc. 2003, 125, 12907 and Langmuir 2002, 18, 6679.) Organic reactive chemicals such as polyoxometalates (POMs) and oxaziridines are mostly used for impregnation of nanoparticles. Oxaziridines are heterocyclic compounds containing oxygen, nitrogen and carbon atoms in a three-membered ring. These are highly reactive molecules and display novel and unusual chemistry. These are aprotic oxidizing agents capable of selectively oxidizing sulphides and disulfide to sulphoxides without over oxidation. The use of POMs for impregnation of nanosize metal oxides can be explored as these have already been proven to be useful for the degradation of chemical agents. POMs also known as heteropolyacids are a large class of metal oxide cluster compounds comprised of d° transition metal atoms, typically W(VI), V (V), Mo (VI), Nb(V) and Ta(V) bridged by oxygen atoms. They have proven values in catalysis and other areas, partly because of their extremely versatile redox potential, acidity, polarity, solubility, etc. Heteropolyanion salt (Na5PV2Mo10O40) has been supported on micro porous carbon and tested against 2-chloroethylethyl sulphide and tetrahydrothiophene (M. L. Shih et al, J. Appl. Toxicol. 1999, 19 S83 and R.D. Gall et al, J. Catal. 1996, 159, 473). Reference may be made to POMs reaction with topical skin protectant cream (R.D.Gail et al, proceedings from the 6th CBW protection symposium, Stockholm, Sweden , May 10, 1998). Hill et al (1998) teaches that POMS are able to decompose VX and HD in solution (C.L.Hill et al, Proc. ERDC Conf. on Chem. Def. Res. 1988, 45). POMs on cationic silica nanoparticles has also been explored as heterogeneous oxidation catalyst (N. M. Okun, Chem. Mater. 2004, 16, 2551). POMs have been widely used for the decontamination of chemical agents, but these have never been loaded on metal oxide nanoparticles especially alumina to degrade chemical agents. This attract the attention to explore the opportunity. WO 2004/032624 (Carnes et al.) discloses the use of nano metal oxides, hydroxides and their mixtures thereof with various biocides and liqui' carriers for the decontamination of chemical agents. It also teaches the presence of reactive nanoparticles enhances the neutralization of undesired chemicals. The decontaminant can be in the form of liquid, fog, aerosol, spray, paste, gel wipe or foams. Nanoscale materials, Inc., 1310 Research Park Drive, Manhattan, KS 66502, has developed an equipment for gas phase decontamination of chemical agents, by the name of FAST-ACT (First Applied Sorbent Treatment - Against Chemical Threats) formulation, which is based on non-toxic nano materials effective for neutralizing a wide range of toxic chemicals with the added capability to destroy chemical agents. Several analytical techniques are available for the characterization of nano adsorbents, i.e. synthesized metal oxide nanoparticles. The particle size determination can be based on (i) direct observation of the particles, in the nano meter range especially by transmission electron microscopy (TEM), (ii) measurement of the coherence length of the particle, e.g. By X Ray Diffraction (XRD), where the particle size is related to the diffrac'" ^n peak broadening. Scanning electron microscopic (SEM) analysis is also used to analyze the morpiiology of the metal oxide nanoparticles. Using XRD data and Scherrer formula the crystalline domain size, i.e. the particle diameter of nano material can be obtained. As discussed in the literature, either high surface area metal oxides/hydroxides with reactive surfaces have also been alone for the degradation of chemical agents or these have been mixed with decontamination solutions, foams, etc. Overall, scanty literature is available for the preparation of adducts of nano adsorbents with those reactive compounds, which have already been known to degrade chemical agents. These adducts have also been not much exploited for the degradation of chemical agents, this provides open field for research, attracts attention for further work and develop impregnated nanoparticles with more reactivity than non impregnated nanoparticles for real time decontamination of chemical agents. In recent years, the scientific community has expressed increasing concern about the possibilities of use of toxic chemicals. Spills of these toxic chemicals can create extreme environmental hazards, which must be effectively cleaned up and controlled. Investigations are underway to find safe, effective measures to detoxify these chemicals without endangering the human life or the environment. Technologies currendy in use include activated carbon adsorbents and highly caustic solutions. Activated carbon suffers from the fact that it does not destroy the toxicant but merely holds it by physiosorption, which does not guarantee the safe removal of the agent. Hypochlorides, caustic wash and DS2 solutions create problems because of their tendency to corrode the materials/equipments. Moreover, these solutions are inherently heavy and dangerous to handle. Further more, it results in large quantities of effluent, which must be disposed off in an environmentally sound manner. In general solution based decontamination is applicable only for vehicles, equipments, area and skin; however, these can not be effectively used for decontamination of chemical agents available as gases in the contaminated zone. For that the best way may be the use of reactive particles sprayed through spraying devices. Incineration plants is another way to dispose them but it requires the mobile incineration plants or the agent has to be carried at the established incineration plant. Therefore, there is great need for compounds and adsorbents, which are effective against the whole spectrum of chemical agents and are easily transportable, do not harm skin or equipment, and require the employment in small amounts of liquids with minimal or no effluent. World wide the investigations are under way to find safe and effective material which can be used in filtration (with suitable modifications) and decontamination systems to detoxify these chemicals without endangering human life or the environment. Highly porous multifunctional materials have attracted increasing attention in recent years. These materials are typically obtained via soft chemistry by sol-gel process. Such an approach offers the possibility to synthesize porous nano materials in different forms to suit widespread technological applications. Thus produced inorganic metal oxide nanoparticles are currently under consideration due to its unusual chemical and physical properties and have the potent to be used as reactive adsorbents for the destruction of toxicants. The destructive adsorption of these toxicants take place on the surface of nanocrystals, so that the adsorbate is chemically dismantled and thereby made non-toxic. Therefore, it is the need of hour to develop the indigenous adsorbent material, which can be used in decontamination devices and filtration systems. The use of impregnated alumina nanoparticles for chemical detoxification of chemical contaminants of present invention is environmentally safe and does not result into any toxic by-products. The destructive adsorption of these toxicants take place on the surface of nanocrystals, so that the adsorbate is chemically dismantled and thereby made non-toxic. The decontaminant composition of present invention is easily transportable and do not harm skin or equipment. Objectives of the invention: The objective of the present invention is to develop impregnated alumina nano particles based system to degrade chemical agents like blister causing agents and nerve agents. Another objective of the present invention is to develop a process for preparation of impregnated alumina particles to degrade chemical agents. Yet, another objective of the present invention is to develop impregnated alumina particles, which can be used in an environmentally safe manner. Yet another objective of the present invention is to develop alumina nanoparticles based adsorbent systems, or as granules in filtration systems. Still one more objective of the present invention is to develop impregnated alumina nanoparticles based adsorbent material, which has lesser t1/2values for adsorptive removal of toxicants and has higher adsorption equilibration capacities under static conditions. Further objective of the present invention is to develop the alumina nanoparticles based adsorbent material, which has the potentiality to be used as granules in filtration systems. STATEMENT OF INVENTION According to the present invention there is provided a Impregnated alumina nanoparticles for detoxification of chemical contaminants, comprising alumina nanoparticles impregnated with 5 to 15 wt% of impregnants selected from a group consisting of ruthenium trichloride, sodium hydroxide, potassium osmate, (lR)-(-)-(camphorylsulphonyl) oxaziridine and polyoxometalates, wherein said polyoxometalates are selected from 11-molybdo-l-vanadophosphoric acid, 10-molybdo-2- vanadophosphoric acid, 9-molybdy-3-vanadophosphoric acid, ll-tungstocupro(II) borate salt, 11- tungstocupro(II) zincate salt, 12-tungstocobaltate(III) salt, 9-tungstosilicate (IV) salt, 10- vanadonickelate (II) salt, 11-tungstovanado (IV) zincate salt, 11-tungstovanado (IV) borate salt, dodeca tungstophosphoric acid, dodeca molybdophosphoric acid, dodeca tungstosilicic acid, dodeca tungstophophoric acid sodium salt, dodeca molybdophosphoric acid sodium salt. Summary of invention: Accordingly, the present invention provides impregnated alumina nanoparticles and a process for preparation thereof. For the development of impregnated alumina nanoparticles, nanoparticles and reactive impregnants have to be produced. The method for preparation of impregnated alumina nanoparticles comprises (i) synthesis of alumina nanoparticles, by adding Al powder to methanol in presence of catalyst. Toluene is added to the solution after stirring. The solution is then hydrolyzed by addition of distilled water, methanol and toluene. Further stirring of the solution turns the solution into a gel, followed by drying to obtain a powder. The powder is then impregnated by the impregnants to obtain impregnated alumina nanoparticles of the present invention. Impregnated alumina nanoparticle based adsorbent system of the present invention can be used with gas phase chemical agents removal/decontamination devices (Handecon, under development) and filtration systems with suitable modifications (converting impregnated nanoparticles to granules by mechanical compression technique) to remove and detoxify chemical warfare agents effectively n less time. Handecon equipment, i.e impregnated alumina particles in pressurized cylinders can be safely applied to any liquid spill or vapor release enabling emergency responders to utilize the technology when faced with chemicals hazards. Since the dry powder absorbs all spills and is effective against both liquid and vapor hazards upon contact, on-site incident management and clean up times is reduced. Description of figures: AP refers to the particles prepared by the process if the present invention. CM refers to commercially available particles. For eg: AP-Al(OH)3 refers to the aluminium hydroxide particles prepared by the method of present invention and AP-A12O3 refers to the alumina particles prepared by the process of present invention. CM-/ 03 refers to commercially available alumina. Figure 1: shows the general schematic for the synthesis of metal oxide nanoparticles. Figure 2: shows (a) AP-Al(OH)3 gel, (b) Fluffy AP-Al(OH)3 after supercritical drying and (c) powder, granules and pellets of prepared alumina nanoparticles based system. Figure 3: shows the adsorption isotherms of AP-Al(OH)3, AP-A12O3 and CM-A12O3. Figure 4: shows the BJH pore size districutions of AP-Al(OH)3, AP-A12O3 and CM-A12O3. Figure 5: shows the N2-adsorption isotherms of AP-A12O3 with and without impregnants. Figure 6: shows the BJH pore size distributions of AP-A12O3 with and without impregnants. Figure 7: shows the SEM of AP-Al(OH)3. Figure 8: shows the SEM of AP-A12O3. Figure 9: shows the TEM of AP-Al(OH)3. Figure 10: shows the TEM of AP-A12O3. Figure 11: shows the XRD pattern of AP-Al(OH)3, AP-A12O3 and CM-A12O3. Figure 12: shows the FTIR of AP-Al(OH)3, AP-A12O3 and CM-A12O3. Figure 13: shows the thermograms of AP-Al(OH)3, AP-A12O3 and CM-A12O3. Figure 14: shows the kinetics of removal of HD on POM impregnated AP-A12O3 nanoparticles. Figure 15: shows the kinetics of removal of 2-HEES on impregnated AP-A12O3 nanoparticles. Figure 16: shows the kinetics of removal of 2-CEES on impregnated AP-A12O3 nanoparticles. Figure 17: shows the kinetics of removal of HD on impregnated AP-A12O3 nanoparticles. Figure 18: shows the kinetics of removal of DECIP on impregnated AP-A12O3 nanoparticles. Figure 19: shows the kinetics of removal of sarin on impregnated AP-A12O3 nanoparticles. Figure 20: shows the kinetics of adsorption of 2-CEES on impregnated AP-A12O3 nanoparticles under static conditions. Figure 21: shows the kinetics of adsorption of HD on impregnated AP-A12O3 nanoparticles under static conditions. Detailed Description of the invention: The present invention provides impregnated alumina nanoparticles for chemical detoxification of chemical contaminants and a process for preparation thereof. The use of impregnated alumina nanoparticles for chemical detoxification of chemical contaminants of present invention is environmentally safe and does not result into any toxic by-products. The destructive adsorption of these toxicants take place on the surface of nanocrystals, so that the adsorbate is chemically dismantled and thereby made non-toxic. The decontaminant composition of present invention is easily transportable and do not harm skin or equipment. Although the invention has been described in detail with reference to preferred embodiments, it is to be understood that the above description is susceptible to considerable modification, variations and adaptations, such modification are intended to be within the scope and spirit of the present invention. Impregnated alumina nanoparticles for detoxification of chemical contaminants, comprises alumina nanoparticles impregnated with 5 to 15 wt% of impregnants capable of detoxifying chemical contaminants. The polyoxometalates can be used as impregnants. The 'mpregnants are selected from a group consisting of ruthenium trichloride, sodium hydx oxide, potassium osmate, (lR)-(-)-(camphorylsulphonyl) oxaziridine and polyoxometalates selected from 11-molybdo-l-vanadophosphoric acid, 10-molybdo-2-vanadophosphoric acid, 9-molybdo-3-vanadophosphoric acid, U-tungstocupro (II) borate salt, 11-tungstocupro (II) zincate salt, 12-tungstocobaltate(HI) salt, 9-tungstosilicate (IV) salt, 10-vanadonickelate (II) salt, 11-tungstovanado (IV) zincate salt, 11-tungstovanado (IV) borate salt, dodeca tungstophosphoric acid, dodeca moiybdophosphoric acid, dodeca tungstosilicic acid, dodeca tu ,tophophoric acid sodium salt, dodeca moiybdophosphoric acid sodium salt. The alumina nanoparticles have a particle size of n -30 nm before impregnation. For the development of impregnated alumina nanoparticles, nanoparticles and reactive impregnants have to be produced. The method of preparation of impregnated alumina nanoparticles comprises the following steps: (i) synthesis of alumina particles: (a) adding aluminium powder to methanol, followed by addition of mercuric chloride catalyst. The mercuric chloride added to the solution may be in the range of 0.05 g to 0.2 g, preferably O.lg. (b) stirring the solution of step (a) for 15 to 35 hrs. (c) adding 350 to 500 ml toluene and further stirring the solution; preferably for 30 minutes; (d) hydrolyzing the solution obtained in step (c) by adding a solution comprising distilled water, methanol and toluene; (e) stirring the hydrolysed solution obtained in step (d) for 18 to 30, preferably 24 hrs to obtain a gel; (f) drying the gel obtained in step (e) to a powder by flushing inert gas at a pressure of 50-200 psi, preferably 100 psi, raising the pressure to 600 to 1000 psi and temperature to 255° C to 275 ° C, preferably 265 ° C, at the rate of 0.5° C to 1.5° C/min, maintaining the temperature of the reactor for 5 to 15 minutes, venting the reactor to atmospheric pressure for over a period of 1 to 3 minutes, preferably 1 minute, to obtain powder; (g) flushing inert gas through the powder obtained in step (d) for 10 to 20 minutes, preferably 15 minutes to remove the remaining solvent vapours; (h) heating the powder of step (g) in an evacuated thermal reactor by raising the temperature to 500° C under dynamic vacuum of 10"2 to 10"3 torr for 8 to 12 hrs, preferably 10 hrs. (ii) impregnating alumina nanoparticles produced in step (h) with impregnants by incipient wetness technique. The addition of aluminium to methanol is stoichiometry based, preferably 10.0 g of aluminium powder is added to 500 ml of methanol. Similarly, hydrolysis of aluminium methoxide with water is stoichiometry based. The solution obtained in step (c) is added to a solution comprising 20 ml distilled water, 200 to 260 ml, preferably 230 ml of methanol and 725 to 825 ml, pi rably 675 ml of toluene. Impregnated alumina nanoparticles as prepared in the present invention has surface area in the range of 250-350 m /g and a bulk density of In an embodiment alumina nanoparticles is impregnated with 10% w/w of 9-molybdo-3-vanadophosphoric acid. In another embodiment the solution in step (a) is stirred for 24 hrs. Yet, in another embodiment impregnated alumina nanoparticles are in form of 80 to 300 mg pellets, having density of 0.1 -0.3 g/cc by applying a pressure of 5.0 to 15 x 105 N/mYet, in another embodiment impregnated alumina nanoparticles are in form of granules of particle size 12x30BSS. The impregnated alumina nanoparticles based adsorbent material, has lesser tlf2 values for adsorptive removal of toxicants and has higher adsorption equilibration capacities under static conditions. The alumina nanoparticles based adsorbent material has the potentiality to be used as granules in filtration systems. The impregnated alumina nanoparticles can be used in decontamination systems and filtration systems for detoxification of nerve agents and its stimulants, blister causing agents and its stimulants and chemical contaminants and toxicants. The kind of blister causing agents could be sulphur mustard and the like. Nerve agents could be diethylchlorophosphate, DECIP and the like. A method of preparation of impregnated alumina nanoparticles, wherein alumina is reacted with methanol wherein, for each 10 g of alumina, 500 ml of methanol is added in presence of mercuric chloride catalyst to prepare aluminium methoxide, followed by addition of 875 to 1250 mL of toluene for 1 M of aluminium methoxide formed, hydrolyzing the aluminium methoxide with a solution consisting of methanol, toluene and water, 3 M distilled water for each 1 M of aluminiu; methoxide formed, ratio of methanol to the ratio of distilled water is 10:1 to 13:1 and ratio of toluene to distilled water is 31:1 to 36:1. A method of preparation of impregnated alumina nanoparticles, wherein 0.125 to 0.5 g, preferably 0.25 g of mercuric chloride catalyst is used for preparing 1 M of aluminium methoxide. Examples: The following examples are for the purpo of illustration only and therefore should not be construed to limit the scope of present invention: Example 1: Synthesis of AP-Al?Qv The most common and widely used "bottom up" wet chemical method for the synthesis of metal oxide nanoparticles has been the aero-gel process (AP). The process involves the conversion of metal to metal alkoxide followed by the hydrolysis of the latter in organic media to metal hydroxide. Then a modified aerogel hypercritical drying procedure has been employed to yield high quality gels under rapid gelation conditions. This gives high surface area metal hydroxide nanoparticles, which are converted to metal oxide nanoparticles by thermal dehydration. The Figure 1 provides a schematic with brief detail of the synthetic procedure in general. Synthesis of 0.4 M AP-A12O3 In order to synthesize AP-A12O3 nanoparticles 10.0 g of aluminium powder cleaned with acetone immediately before the reaction was taken with 500 ml of methanol in 1000 ml round bottom flask and connected to water condenser. The reactants were stirred in presence of 0.1 g mercuric chloride at room temperature for 24 hrs under inert atmosphere of nitrogen gas. To this 425 ml of toluene was added and the solution was stirred for 30 minutes. Hvdrolvis of aluminium methoxide: A solution of stoichiometric amount, i.e. 20 mL (1.2 M) of triple distilled and deionized water in 230 mL of methanol and 675 mL of toluene was prepared. This solution was slowly add d to the solution made earlier using step-I with vigorous stirring in a 3.0 L round bottom flask. The solution was covered with aluminium foil and stirred for 24 hrs. this resulted in to slightly grey liquid like gel (Figure 2a). Autoclave treatment (supercritical drying) of aluminium hydroxide gel: 600 mL of thus produced aluminium hydroxide gel was transferred to lOOOmL capacity parr autoclave. The gel . as first f 'led with nitrogen and the reactor was slowly heated from room temperature to 265 C for 10 minutes and the system was quickly vented to the atmosphere for over a minute period, the furnace switched off and the aluminium hydroxide flushed with nitrogen for 15minutes to remove the remaining solvent vapurs. This produced fluffy light grey powder of AP-A12O3(figure 2 b). Thermal treatment of AP-A12O3 25 g of thus produced nano aluminium hydroxide powder was placed in 500 mL capacif 'hernial reactor. This was evacuated for 30 minutes at room temperature. Later, it was slowly heated tor 6 hrs from room temperature to 500 ° C under dynamic vacuum of 10 "2 torr and kept under this condition for 10 hrs. this resulted in to the fine light grey powder AP-A12O3, which was due to the conversion of residual organic groups (-OCH3)on AP-A12O3 to carbon during heat treatment of AP-A12O3 at 500 ° C. finally, the material was cooled to room temperature under vacuum, flushed with nitrogen and stored in air tight bottles till further use. Example 2: Synthesis of POMs and screening for the best POMs against HD: In general most common preparative method for the synthesis of POMs is the addition of metal oxoanion to acidic solution in stoichiometric preparations. Metal oxoanions self assembles at appropriate pH (the polymerization of addenda polyhedra around a hetero atom as the solution is acidifed). 12MoO4 + HPO4" + 23H+ = (PMo12O4o)- + 12H2O These heteropoly anions can be precipitated out off the solution by the addition of counter ions such as alkali metal, ammonium, etc. Some POMs can be extracted using diethyl ether and crystallized by the evaporation of extract. The chemical name and molecular formula of the POMs synthesized using standard preparation methods are given as follows:- 1. 11-molybdo-1 -vanadophosphoric acid [MoVPA(V1)]:H4[PMouV04o].32.5H2O 2. 10-molybdo-2-vanadophosphoric acid [MoVPA(V2)]: H5[PMo10V204o].34.5H2O 3. 9-molybdo-3-vanadophosphoric acid [MoVPA(V3)]: H6[PMo9V304o].34H2O 4. 11 -tungstocupro(H) borate salt (TCBS, C^BCuW! Ao-17H20 5. 1 l-tungstocupro(n) zincate salt (TCZS): K7Na4ZnCuWu04oH2.14H2O 6. 12-tungstocobaltate(in) salt (TCS): K5CoW12O40.20H2O 7. 9-tungstosilicate (IV) salt (TSS): N^SiW9O34H.O 8. 10-vanadonickelate (II) salt (VNS): K2Ni2V10O28.16H2O 9. 11-tungstovanado (IV) zincate salt (TVZS): K8ZnVWnO40.5H2O 10. 11-tungstovanado (IV) borate salt (TVBS): K7BVW11O40Fe 1. Synthesis of [MoVPA(V1)]: In one of the embodiment 7.1 g disodium hydrogen phosphate was dissolved in 100 mL distilled water and mixed with the solution of 6.1 g sodium metavanadate in 100mL boiled distilled water. The mixture was cooled and 5mL cone. Sulphuric acid was added to it. Solution turns red in color. To this mixture a solution of 133 g sodium molybate in 200 mL distilled water was added. Finally in the resulting solution, 85mL cone. Sulphuric acid was added slowly with vigorous stirring. With this addition dark red color changed to light red. The heteropoly acid was extracted with 400mL diethyl ether. The heteropoly etherate was present in the middle layer. Air was passed through the heteropoly etherate to free it of ether. The orange solid that remained was dissolved in 50mL water, concentrated in a vacuum dessicator over concentrated sulphuric acid, and then allowed to crystallize. The orange crystals of [MoVPA(Vt)] were filtered, washed with water and air dried. 2. Synthesis of [MoVPA(V2)]: [MoVPA(V2)] wa synthesized using the same synthetic procedure as mentioned for [MoVPA(V,)] except the anounts of chemicals, which were taken stoichiometrically. 3. Synthesis of [MoVPA(V3)]: [MoVPA(V3)] was synthesized using the same synthetic procedure as mentioned for [MoVPA(V1)] except the anounts of chemicals, which were taken stoichiometrically. 4. Synthesis of TCBS: 36.3 g sodium tungstate was dissolved in 150mL water and the pH was adjusted to 6.3 with acetic acid. 2.5 g boric acid was added to it and mixture was heated to 80-90 C. In the resulting mixture aqueous solution of 0.01 mole Cu (II) was added drop wise, followed by 15-20 g potassium chloride. On cooling pale green cubic crystals of TCBS were obtained. 5. Synthesis of TCBS: TCZS was synthesized using the same synthetic procedure as mentioned for TCBS except the anounts of chemicals, which were taken stoichiometrically. 6. Synthesis of TCS: A solution of 19.8 g sodium tungstate in 40 mL water was brought to pH 6.5-7.5 with glacial acetic acid. The solution was heated near to boiling and added to the solution of cobalt acetate (2.5 g cobalt acetate in 12 ML water and 2 drops of glacial acetic acid). The reaction mixture was boiled for 15 min and 13.0 g potassium chloride was added to it. Then the solution was allowed to cool at room temperature and the precipitate was separated by filtration. The precipitate was dried, weighed 25 g and 40 mL of 2 M sulphuric acid was added to it. Mixture was heated and solid K2S2Og was added until the solution turn to gold color. The mixture was cooled in an ice bath and yellow crystals of TCS were obtained. 7. Synthesis of TSS: Sodium silicate (12 g) was dissolved in 250 mL of cold water and 150 g of sodium tungstate was added to it. HC1 (6 M, 95 mL) was slowly poured into the vigorously stirred solution. The silica was filtered off and the solution was left to stand at room temperature for crystallization. 8. Synthesis of VNS: Solution of potassium metavanadate was prepared in acetic acid-potassium acetate in the ratio of 3:5:5 and treated with nickel sulphate and finally greenish-tinged yellow crystals of VNS were obtained. 9. Synthesis of TVZS: 0.11 mole sodium tungstate solution was prepared in 150 mL distilled water. pH was adjusted to f 3 with acetic acid. 0.01 mole zinc chloride solution was added to it. After this, the solution was heated to 80 to 90 ° C, the 0.01 mol vanadyl (IV) sulfate solution was added. Color changed to dark red-brown. Solid potassium chloride was added to the hot solution and on cooling crystals of TVZS were obtained. 10. Synthesis of TVBS: TVBS was synthesized using the synthetic procedure as mentioned for TVZS except the use of 0.01 mol boric acid solution in place of 0.01 mole zinc chloride solution. Apart from above synthesized POMs commercially available POMs were also taken for the study under consideration and the chemical name and molecular formula of commercially available are as follows: 1. dodeca tungst losphoric acid (TPA): H3PW12O40xH2O 2. dodeca molybdophosphoric acid (MPA): H3PMo12O40.xH2O 3. dodeca tungstosilicic acid (TSA): H4S1W12O40.XH2O 4. dodeca molybdophosphoric acid sodium salt (MPAS): Na3PMo12O40.xH2O In order to screen out the best POM for the degradation of chemical agents 25 mg of each of the POM was taken in test tubes containing 1.0 uL HD and 9.0 jiL carbon tetrachloride. The reactions were monitored at different time interval residual HD was extracted with 1.0 mL carbon tetrachloride and subjected to GC/FED (gas chromatograph equipped with flame ionization detector) analysis using split injection mode. The oven, injection and detector temperature were 120, 220 and 250 ° C respectively. Table 2 describe the degradation results for HD against synthesized POMs. MoVPA (V3) showed maximum (28.2 %) sulphur mustard degradation amongst synthesized POMs in 2 hrs, whereas, TCZS and TCS showed nil degradation capability of MoVPA (V3) was further confirmed by monitoring the degradation percentage for 21 and 46 hrs. All MoVPA (V1, V2 and V3) ployoxometalates showed -50 and -99% degradation in 21 and 46 hrs respectively (Table 2), however, MoVPA (V3) showed maximum degradation among studied POMs. The highest reactivity of MoVPA (V3) than their counter parts MoVPA (Vi) and MoVPA (V2) was due to higher number of nanoparticles powder as such while filtration systems shall require granulled nanoparticles based material. In one of the embodiment 80-300 mg pellets with the density of 0.1-0.3 g/cc were also prepared using manual pelletting machine by applying a pressure of 5.0-15 X 105 N/m2. These pellets of different sizes (3-8 mm diameter and 5-15 mm height) were made and also broken down to granules of different sizes (Figure 2 c). surface area and cumulative desorption pore volume of pellets/granules of AP-A12O3 were found to be within the range of 328-368 m2/g and 0.602-0.644 cc/g respectively. These values are lesser than the values of corresponding metal oxide nanoparticles. This decrease is because of the compression, which collapses the pores within/between nano aggregates of nanoparticles. Thus produced metal oxide granules and pellets represent a new family of porous inorganic materials where pore structure can also be roughly controlled by compression technique. Example 4: Characterization of metal oxide nanoparticles: Prior to use, metal oxide nanoparticles with and without impregnants were characterized for porosity and surface characteristics using various techniques such as surface area analysis, SEM, powder XRD, etc. The material was also characterized for acid/base neutralization capacity, bulk density and moisture content. Characterization for surface area and porosity: In one of the embodiment surface area and pore size distribution of AP (nano, aerogel produced) and CM (commercial) alumina were determined using Autosorb-1-C from Quantachrome, U.S.A. The samples were first outgassed under dynamic vacuum (102 torr) for 8 hrs at 200 °C and then allowed to cool to room temperature. After that, the N2 adsorption-desorption isotherms were obtained at liquid nitrogen temperature, i.e., 77 K. Surface area and micro pore ( Figures 3 and 4 represent the nitrogen adsorption-desorption isotherms and BJH pore size distributions of AP-Al(OH)3, AP-A12O3 and CM-A12O3. AP-Al(OH)3 showed highest uptake of nitrogen and exhibited broad hysteresis loop, which are characteristic of adsorption possessing a portion of mesopores, however, such type of broad hysteresis was not observed with AP & CM-A12O3. Figure 3 clearly indicated that AP-Al(OH)3, AP-A12O3 and CM-A12O3 have the same type of pore size distributions with mesopore maxima at 34.5, 27.5 and 31. 5 A (Table 1) respectively. Apart from mesoporous characteristic AP-Al(OH)3, AP-A12O3 were also found to be having micropores with DR micropore volume of 0.207 and 0.161 cm3/g respectively. The surface area of AP-Al(L.i>/3, was found be 563.2 m2/g. Micropore and cumulative desorption pore volume were also found to be decreased. Moreover, this decrease was due to the dehydration process, which causes severe sintering and damage to the pore structure. Surface area of was found to be 3.6 times of that of the material commercially available CM-A12O3. Figures 5 and 6 represent the nitrogen adsorption-desorption isotherms and BJH pore size distributions of impregnated AP-A12O3, nanoparticles. AP-A12O3 when impregnated with Mo VPA (V3) [10% (w/w)], surface area decreased from 375.7 to 318.1 m2/g. This decrease was due to impregnants, which during impregnation travel through the macro pores and get deposited in the mesopores or the pore opening of micropores to cause the blocking of the meso/micro pores. Decrease in surface area after impregnation was found with all samples, whether synthesized or commercial materials (Table 1). AP-A12O3 with NaOH impregnations (10% w/w) showed maximum reduction in surface area, i.e. from 375.7 to 141.0 m2/g (-1/3 of unimpregnated nanoparticles). This was probably due to the reaction of AP-A12O3 with NaOH. Pore maxima for micro pores of AP-A12O3 withand without impregnation were found to be to -14 A. The mesopore maxima for NaOH and K2OsO4 impreganted AP-A12O3 was found to be to -60 A which was higher than other systems. It was due to the reaction of impregnants with adsorbent, this destroys the small pores. Example 5: Characterization for particle size: In order to determine the particle size of nanoparticles SEM/TEM images and XRD data were used. For SEM characterization, the powder samples were first mounted on brass stubs using double sided adhesive tape and then gold coated for 8 minutes using ion sputter JEOL, JFC 1100 coating unit. Figures 7 and 8 represent the SEM image of AP-Al(OH)3 and AP-A12O3 respectively. These images clearly indicated the material to be having a multitude of thin strands to give fluffy and porous web like structure with wide particle size distributions and a quantum of huge porosity, which is confirmed by high surface area values (AP-Al(OH)3 = 563.2 and AP-A12O3 =375.7 m2/g). In one of the embodiment TEM studies were performed to find out the particle size of the synthesized metal hydroxide and oxide nanoparticles. For that 10 mg of powder sample was mixed in 10 mL of pentane and sonicated for 2 hrs. to achieve a better separation of the particles. A drop of supernatant of the solution was placed on the copper grid of 200 me size followed by carbon coating. TEM images were recorded using JEOL, JEM-1200 Ex. TEM images of AP-Al(OH)3 (Figure 9) and AP-A12O3 (Figure 10) indicated these materials consisting of weblike structure with the particle in the range of 4-30 (maximum particles of 20 nm diameter) and 3-14 (maximum particles of lOnm diameter) nm respectively. Imaging at different scales was performed to estimate correctly the proportion of small particles (2-10 nm) and embedded in agglomerates (10-100nm). Further more, the particles overlapping in agglomerates lead to quite noisy images making the determination of proportion and size of the smallest particle population a very difficult task. Synthesized nanoparticles showed the decrease in particle diameter on conversion from hydroxides to oxides. Smallest particles were of 3nm diameter, however, three to four crystallites aggregate into -10 nm particles, and these particles weakly agglomerate in to a mass with large pores, where the pores are actually the space between the particles (as opposed to holes and channels in the particles themselves). Using XRD spectra the crystalline sizes of the synthesized nanoparticles were also calculated from the line broadening of the peak and using the Scherrer equation. For XRD studies the powder ...nples were heat treated under vacuum before placing onto the sample holder. The instrument used was Philips XRD PW 3020. Cu Ka radiation (k = 0.154 nm) was the light source used with applied voltage of 40 KV and current of 40 mA. The 2 9 angles ranged from 20 ° to 80 ° with a speed of 0.05 °/sec. The crystalline size was then calculated from the XRD spectra using Scherrer equation. XRD spectra of AP-Al(OH)3 and AP-A12O3 indicated and amorphous pattern due to peak broadening with the particle diameter in the range of 2-15 and 2-17 nm (Figure 11) respectively. Moreover, the study of synthesized nanoparticles using SEM/TEM and XRD has clearly indicated them to be nanoparticles of diameter in the range of 2-30 nm. Example 6: Fourier transform infra-red spectroscopy and thermogravimetric analysis: Fourier transform infra-red study of was performed to find out the complete solvent removal after heat treatment. For that a few of the particles of powder nanosize alumina was mixed with 200 mg of potassium bromide, ground to make pellets, dried and finally recorded the IR spectra (Figure 12). Figure 12 represents the IR spectra of prepared and commercially available samples. IR spectrum of AP-A12O3 indicated two absorption peaks at 3600 cm"1 corresponding to isolated surface OH groups. Less intensity of peaks at 1080 and 2800-2950 cm"1 with AP-Al(OH)3 and AP-A12O3 clearly indicated the removal of methoxide groups by heat treatment at 500 °C for the conversion of AP-Al(OH)3 to AP-A12O3. In one of the embodiment TGA was used to study the conversion of nano metal hydroxides to nano metal oxides and make a comparison with commercial metal oxides. Thermograms for materials were recorded from 30 to 800 °C in air using thermogravimetric analyzer, TGA-2950 from TA instruments, USA. The initial sample weight was always 10 mg and the weight loss of 8.2% between 30 and 170 °C (due to the desoiption of physiosorbed water and organic moieties). Destruction of chemisorbed water and organic groups occurred between 170 and 310 °C and it produced a weight loss of only 1.2%. The pronounced weight loss of 10.2% observed between 310 and 600 °C was produced by dehydroxylation of AP-Al(OH)3 to AP-A12O3. The total loss was 20.5%, whereas the conversion of AP-Al(OH)3 to AP-A12O3 should yield a weight loss, i.e. 20.5% indicated AP-Al(OH)3 also contain some part of AP-A12O3, which remains as such on heat treatment and does not result decrease in weight. AP-A12O3, indicated the weight loss of -6.0% up to 110 °C due to absorbed water. Example 7: Acid/base neutralization capacity, bulk density and moisture content: In one of the embodiment to find out acid/base neutralization capacity of the synthesized and commercial material at controlled pH (6.5) 20 mg of samples was taken in 20 mL of triple distilled and deionized water and stirred for 10 minutes. The pH of the solution was continuously noted. Then it was titrated with 0.01 N HCl/NaOH till the pH of the solution reached to its 6.5 (initial value of pH of distilled water). AP-Al(OH)3 showed the decrease in pH (5.68) and to bring it back to 6.5 it required 5.6 mmol of sodium hydroxide per mole of material under investigation. AP-A12O3 indicated basicity requiring 2.92 mmol of HC1 per mole of AP-A12O3 and commercial sample showed an increase in pH of water from 6.5 to 7.6, which was equivalent to 8.85 mmol of HC1. Subsequently, the material was also characterized for bulk density, which was measured by weighing a known volume (20mL) of material and expressed in g/mL. Bulk density AP-A12O3 was found to be much less than the material available commercially. This was because of their fluffy and powdery nature. All prepared alumina nanoparticles based systems indicated bulk densities within 0.043-0.059 g/mL (Table 1). Bulk density of AP-A12O3 was found to be much less than the material available commercially. This was because of their fluffy and powdery nature. All prepared alumina nanoparticles based systems indicated bulk densities within 0.043-0.059 g/mL (Table 1). Bulk density of AP-A12O3 was found to be 0.043 g/mL, which is 1/20 of that of commercially available CM-A12O3 (0.897 g/mL). In addition to this the moisture content of the material was determined by heating a known amount (lg) of sample in oven at 120 °C for 6 hrs., cooling in desiccator for 1 hr. and finally weighing. The weight loss in sample per 100 g was taken as moisture content of the material. Moisture content of synthesized and commercial particles was found to be Example 8 Kinetics of degradation of CW agents on prepared alumina systems: In one of the embodiment to study the kinetics of degradation of HD, 5 uL pentane and spiked over 100 mg of nanoparticles in a stoppered glass tube. Multiple glass tubes were put to use for analysis at room temperature (25 ± 1 °C). After definite time intervals exposed nanoparticles were extracted with 2.0 mL carbon tetrachloride and then extracts were analyzed for residual amount of toxicants using GC/FID (gas chromatograph equipped with flame ionization detector) with split injection mode technique. Chemito 8610 GC equipped with BP10 capillary column and FID was used for analysis. The oven, injection and detector temperature were 150, 220 and 250 °C respectively. In order to find out the potential of unimpregnated AP-A12O3 and CM-A12O3 direct reactions of HD with the systems were performed. The degradation of HD in 3 and 24 hrs was found to be 58 and 100 % with AP-A12O3. Reaction of AP-A12O3 and CM-A12O3 with sulphur mustard indicated the t Vz values to be 2.0 and 14.7 hrs respectively. Half life values with (2.0 hrs) was lesser than reported by Wagner et al (6.3 hrs). These variations were probably due to the use of different analytical techniques (Wagner used MAS-NMR, whereas GC/FID was used in the present invention) considered for studying the kinetics of degradation. The study, however, indicated the suitability of AP over Cm- metal oxides for the destruction of HD. Example 9 Kinetics of removal of CW agents on prepared alumina systems: In one of the embodiment to study the kinetics of removal of HD at room temperature (25±1°C) 2.5 yiL of toxicant was mixed with 4mL of hydrocarbon (pentane/octane) in glass vials (8mL capacity with Teflon septum caps). After that 50 mg of prepared nanoparticles (with and without impregnation) were suspended to the solution and the vials were capped. These were continuously rotated at the speed of 50 rotations per minute using Tarsons Rotospin. After definite time intervals 1 jiL of the solution was taken out from glass vials and analyzed for residual amount of toxicant using GC/FID. Figures 14 to 19 represent the kinetics of removal of toxicants and Tables 3 to 6 show the half life, rate constant and surface area values. When adsorptive removal experiments were repeated using pentane as solvent, Ua values were not in close agreement. It was inferred that this was due to pentane because it is highly volatile and some of its quantity evaporates off from the tall holes generated due to continuous peering of septum to take the sample from the glass vials. This increases the concentration of the toxicant in the vials and shows shower kinetics. When the same experiments were performed with n-octane (less volatile and belongs to same family as pentane) the results were reproducible (7 5%). Experiments for HD removal on AP-AI2O3 nanoparticles using octane as solvent indicated the tm values with reproducibility. Therefore, octane was taken as solvent for further study. In order to study the kinetics of degradation or adsorptive removal of toxicants on metal oxide nanoparticles with and without impregnants, Ln of residual amount of toxicant, i.e., Ln[a/(a-x)] on Y-axis was plotted against reaction time, t on X-axis. Rate constant (K) was calculated using the slope of the straight line and half life (t1/2) by 0.693/K. Kinetics of removal of HD on polyoxometalate, oxaziridine and other reactive chemicals impregnated alumina nanoparticles: Figure 14 and Table 3 represent the kinetics of removal of HD on POM impregnated AP-A12O3. The adsorptive removal was found to be following pseudo first order reaction kinetics. Figure 14 indicated that initially the removal was fast, which gradually slowed down to a steady state. All POMs impregnated system showed more adsorption potential than AP-A12O3 alone. Among synthetic POMs impregnated aluminium oxide nanoparticles AP-A12O3+MoVPA(V3) system showed the fastest adsorption kinetics with rate constant, K=3.24 X10-3 min'1, whereas PTA impregnated AP-A12O3 indicated rate constant, K= 3.08 X10-3 min"1, which was highest among commercially available POMs impregnated AP-A12O3. MoPVA(V3) impregnated system showed better results than PTA based systems. MoVPA(V3) was found to be better than MoVPA(Vl), this was because of increase in number of vanadium atoms and decrease in molybdenum atoms with MoVPA(V3) polyoxometalate. This was in accordance with Johnson et al fin polyoxometalates the order of oxidizing ability of addenda atoms; V(V)>Mo(VI)>W(VI)]. Similar surface area values (~315m2/g) with POMs impregnated AP-A12O3 indicated that surface area values are not the governing proces., it is the degradation, i.e. chemical reaction. Moreover, when nano adsorbents are added to the toxicant solution, toxicant is initially physisorbed and then chemisorbed. i.e., gets reacted with impregnants or the reactive sites of adsorbent to non toxic products. Table 4 represents the effect of percentage of impregnation of oxaziridine on adsorptive removal kinetics. Study has also indicated that 5 and 10% oxaziridine impregnation on AP-A12O3 could not brought down the tl/2 values for the adsorptive removal of HD, whereas 15% impregnation on AP-A12O3 reduced it to 80 from 380 minutes. This highlighted that AP-A12O3 reacts with oxaziridine (an oxidizing agent) and results in the decrease in the activity of both. Impregnation of 15% oxaziridine over powers the activity of AP-A12O3 and remaining oxaziridine (left after reacting with AP-A12O3) reacts with HD and brings down the tm value from 380 to 80 minutes. Impregnation of nanoparticles with oxaziridine resulted in the decrease in surface area values (8-12%), whereas the kinetics of removal was found to be reversed. This clearly indicated that the kinetics of removal of HD was independent of surface area values of oxaziriding impregnated AP-A12O3 system. RuCl3 or NaOH impregnated AP-A12O3 system showed less activity than AP-A12O3 alone (Table 4). Decrease in reactivity of systems due to impregnation of RuCl3 or NaOH has clearly indicated that impregnants have got reacted with nanoparticles and thereby decreased the efficiency of the system. K2Os04 impregnation on AP-A12O3 indicated a little decrease in li/2 value from 380 (with AP-A12O3 alone, Table 3) to 360 minutes (Table 4). Example 10 Kinetics of removal of simulants (2-HEES adn 2-CEES) of blister agent and actual agent (HD) on finally selected systems: On the basis of above discussed results and literature five system ( AP-A12O3 , AP-A12O3+NaOH, AP-A12O3+MoVPA(V3), AP-AI2O3+PTA and AP-A12O3+K2O5O4( (10% w/w) were screened to perform the kinetics of adsorptive removal of simulants blister agent and actual agent (HD). Figures 15, 16 and 17 represent the kinetics of removal of 2-HEES, 2- CEES and HD on AP-A12O3 nanoparticles based system respec ely. Kinetics was found to be fast initially, which gradually slowed down to steady state. For 2-HEES removal AP-A12O3 without impregnation showed the fastest kinetics (Table 5) followed by AP-A12O3+MoVPA (V3). Half life values were found to be in accordance with the surface area of prepared systems for the adsorptive removal of 2-HEES. In order to check, whether 2-HEES is physisorbed or chemisorbed/degraded on nanoparticles based system 2mL of acetone was added to the reaction mixture after kinetics study. The reaction mixture was stirred for 5 minutes and then subjected to GC/FID. This indicated >80% physisorption with all systems for 2-HEES removal. Therefore, the study has clearly indicated that when nano adsorbents are added to the toxicant solution, toxicant is initially physisorbed and then chemisorbed, i.e., gets reacted with impregnants or the reactive sites of absorbent. Physisorbed toxicant comes out when polar solvent is added to the reaction mixture, whereas chemisorbed/degraded toxicant comes out as products of reaction. 2-CEES removal studies indicated the order of reactivity as AP-A12O3+MoVPA (V3)> AP-A12O3 > AP-A12O3 +PTA> AP-A12O3 +K2Os04> AP-A12O3 +NaOH. Lower t1/2 values with AP-A12O3 than AP-A12O3+PTA system also indicated the surface area dependency of adsorption kinetics for the adsorptive removal of 2-HEES & 2-CEES. Extraction with acetone indicated >90% degradation of 2-CEES with POMs impregnated systems in 28 hrs. 2-CEES indicated higher chemisorption/ degradation than 2-HEES on unimpregnated AP-A12O3. POMs impregnated alumina nanoparticles indicted the fastest removal of HD. AP-A12O3+MoVPA (V3) showed the least value of tm (214 ..inutes). Extraction with acetone indicated that adsorption kinetics for HD was much closer to degradation kinetics. The overall ti/2 values were found to be in the order of; HD>2-CEES>2-HEES, whereas extraction of toxicant with acetone indicated that 2-HEES is mostly physisorbed and less degraded than 2-CEES and HD on nanoparticles based systems. Example 11 Kinetics of removal of simulants of nerve agent (diethylchlorophosphate, DECIP) and actual agent (sarin): Alumina nanoparticles based systems also showed surface area dependency for the removal of DECIP and sarin (Figures 18 and 19, and Table 6). POMs impregnated systems showed good results among alumina based impregnated systems. The order of adsorptive removal potential was found to be; AP-A12O3> AP-A12O3 + MoVPA(V3)> AP-A12O3 +PTA > AP-A12O3 + K2OsO4> AP-A12O3 +NaOH. AP-A12O3 +NaOH system showed the slowest kinetics of removal from solutions but extraction with acetone results indicated maximum degradation of DECIP and sarin with these systems. Kinetics of adsorptive removal of diethylcyanophosphate (DECnP) on alumina nanoparticles based systems was also performed. Adsorptive removal kinetics for DECnP was found to be faster than DECIP, whereas the order of reactivity was similar to DECIP. Example 12 Static adsorption studies: In one of the embodiment to carry out the adsorption of 2-CEES or HD under static conditions, 50 mg each of alumina nanoparticles based adsorbents were taken separately in gooch crucibles and placed in desiccators in which 5.0 ml of 2-CEES or HD was placed in the bottom of desiccators. To maintain constant temperature, the desiccators were housed in an environmental chamber kept at 33 ± 1°C. This chamber was used not only to control the temperature but also to house the weighing balance. Vapour pressure of 2-CEES and HD in the desiccators was measured and found to be 3.35 and 0.1 mm Hg at 33°C respectively. Moisture free air was not used for the experiments. The concentration of gas was considered to be constant at atmospheric pressure in the desiccators. As the adsorption of toxicant by the nanoparticles based adsorbents starts it causes the depletion in vapour phase concentration of toxicant in the desiccators. The depletion in concentration is compensated by liquid phase toxicant, which was placed in the bottom of the desiccators. Therefore, the concentration of toxicant vapour in the desiccators remains constant and it ensures a continuous supply of toxicant to the adsorbent. The kinetics of adsorption of 2-CEES and HD was studied by monitoring the percentage of weight gain every hour. Figures 20 and 21 represent the kinetics of adsorption of 2-CEES and HD on alumina nanoparticles based adsorbents. Table 7 shows the kinetics parameters. Adsorption of 2-CEES To illustrate the kinetics of adsorption of 2-CEES, percentage weight gain of adsorbate was plotted versus time (t) and represented graphically in Figure 20. Since moisture free air was not used to monitor the kinetics of adsorption of 2-CEES the possibility of co-adsorption of atmospheric moisture can not be ruled out. However, the co-adsorption of water will be insignificant and will not affect the adsorption of 2-CEES due to very little influence of humidity on adsorption of CW agent simulants. Figure 20 was used to compute the equilibration time (the time at which the adsorption ceases, i.e., no change in weight gain wim respect to time) and equilibration capacity ( amount of adsorbate in mg/g of adsorbent at equilibration time) the values have been tabulated in Table 7. Figure 20 shows the similar shapes of 2-CEES adsorption uptake curves and different adsorption rates for studied nano alumina based adsorbent systems. At initial stages the rate of adsorption was fast, which gradually slowed down to a steady state at later intervals of time. Expect AP-A12O3+NaOH system the rate of adsorption of 2-CEES by the adsorbents was found to be same at initial stages ( up to 10 hrs) after that the rate of adsorption varied. Highest value of equilibration time (170 hrs, Table 7) was found with unimpregnated AP-AI2O3 system, whereas with other systems the equilibrium reached within 50 hrs. AP-A12O3 system also showed the highest equilibration capacity (1694mg/g) among studied systems. This was slightly in agreement with the values of surface area as higher the surface area higher will be the adsorption capacity. Moreover, highest equilibration time and equilibration capacity with AP-A12O3 system indicate the capillary condensation phenomenon, i.e., multilayer condensation of 2-CEES within the pores of the sorbent. In addition to this, AP-A12O3 with surface area 375 m2/g showed the decrease of maximum 60% in surface area value due to impregnation with sodium hydroxide, whereas the adsorption capacity of it for 2-CEES adsorption decreased to 95% of that of AP-A12O3 . It was because of impregnants, which worked as a barrier and resisted the movement of 2-CEES molecules within the pores of AP-A12O3+NaOH. Overall, the adsorption capacities were in agreement to the surface area values of the systems. Example 13 Adsorption of HD Figure 21 represents the adsorption kinetics of HD on nanoparticles of aluminium oxide with and without impregnants. Among studied system AP-A12O3 + MoVPA(V3) showed maximum adsorption potential, i.e., 640/mg/g ( Table 7). This potential was even higher than its corresponding unimpregnated AP-A12O3 system (548 mf/g); however, AP-A12O3+MoVPA (V3) system has lesser surface area than AP-A12O3 system. This clearly indicated that chemisorption is also involved in adsoprtion kinetics. Initially, as the adsorbate (HD) reaches to the adsorbent ( AP-A12O3 +M0VPA (V3) system) it is physisorbed and then it migrates to impregnants and chemisorbed, i.e., gets degraded. The fonnation of reaction products with studies system also indicated the phenomenon of chemisorption. In addition to this, AP-A12O3 +M0VPA (V3) systems(320 hrs.) AP-A12O3+PTA also showed good results, whereas AP-A12O3+NaOH showed very less potential (130mg/g) than nanoparticles of alumina (548mg/g). CM- A12O3 system with lesser surface area showed higher adsorption capacity than AP-A12O3+NaOH. Example 14 Identification of reaction products: In one of the embodiment to investigate the reaction products 10 mg of toxicant exposed nanoparticle based adsorbents were extracted with 2.0mL of acetonitrile for 2 hrs. in a well stoppered test tube. The extracts were centrifuged and transferred to another tube. Acetone extracted solution obtained through kinetics of adsorpth ; removal from solutions studies were also taken for product identifications. The extracts were then purged with nitrogen gas to concentrate the extracted reaction products and subjected to product identification using GC/MS (gas chromatograph coupled with mass spectrometer) instrumental techniques. GC/MS (6890N GC coupled with 5973 inert MS Detector) of Agilent Technologies, USA was used for characterization of reaction products. It was equipped with HP-5MS column of 30m X 0.25 mm X 0.25 Ji dimensions. Temperature programming [50(2 minute hold) to 280°C (10 minute hold) @ 10°C/minute] with split injection technique (10:1) was used to perform the study. Injection port & GC/MS interface, MS source and quadrupole analyzer were kept at 280, 230 and 150°C respectively. Study on kinetics of degradation/removal indicated that the CW agent molecules interact instantaneously with the active sites of the reactive metal oxide nanoparticles or impregnap^ and thereby made nontoxic due to the conversion of toxicants to non-toxic reaction products. It is difficult to extract the reaction products from metal oxide nanoparticles because as the reaction product is generated, it bounds to the active site of metal oxide nanoparticles, thereby results to surface-bounded reaction products. In the present study reaction products have been identified using GC/MS analysis of extracts. The mass spectra of reaction products were compared with the standard mass spectra from existing libraries (Wiley and NIST) of GC/MS instrument. Results indicated that on the surface of AP-A12O3 nanoparticles HD undergoes the hydrolysis reaction with the formation of intermediate sulphonium ion. Sulphonium ion is formed due to the attack of sulfide on the ß carbon atom of HD and is considered to be SN1 reaction with anchimeric assistance. Sulphonium ion is highly unstable, because of which it could not be extracted and detected. Subsequently, the sulphonium ion undergoes hydrolysis with the water available with nanoparticles under study (no more water is added prior to the reaction). Data illustrates the m/z values at 140, 109, 91 and 63 thus indicating the formation of hemimustard as reaction products and further hydrolysis produces thiodiglycol, which was identified as such and after silylation with BSTFA [bis(trimethylsilyl) trifloro acetamide]. This indicated the role of hydrolysis reaction in the decontamination of HD to hemimustard and thiodiglycol thereby rendering it non toxic. In addition to hydrolysis reaction dehydrohalogenation reaction was also found to be occurring to decontaminate HD. Dehydrohalogenation reaction of HD and hemimustard indicated the formation of its corresponding vinyl products. AP-A12O3+MoVPA (V3) system degraded sulphur mustard via hydrolysis and elimination reactions to 2-chloroethylvinyl sulfide, 2-hydroxyethylvinyl sulfide, 1, 4-oxathiane, hemimustard and thiodiglycol (Scheme 1). In addition to the above products, AP-A12O3+MoVPA (V3) and AP-A12O3+PTA systems also indicated the formation of HD-sulfoxide as one of the reaction product. This was due to the presence of polyoxometalates as impregnants. Oxaziridine and RuCl3 impregnated alumina nanoparticles also indicated the formation of HD- .lfoxide (Scheme 2), as an oxidation product of HD. All alumina nanoparticles based systems degraded 2-CEES to its corresponding hydrolysis product, i.e., 2-HEES. The formation of ethylvinyl sulfide (Scheme 3) was also observed as a reaction product of 2-CEES. Nerve agent and its simulants indicated the formation of corresponding acids as hydrolysis products on prepared alumina nanoparticles based system with and without impregnants. This was due to the fact that nerve agents are highly prone to hydrolysis. DECIP and DECnP were found to be converted to diethyl phosphate (Scheme 4). Sarin was found to be detoxified to its corresponding acid, i.e., isopropylmethylphosphonic acid (IMPA) (Scheme 5), which was identified as isopropyltrimethylisilylmethylphosphonic acid after silylation with BSTFA and using GC-MS technique. We Claims :- 1. Impregnated alumina nanqparticles for detoxification of chemical contaminants, comprising alumina nanoparticks impregnated with 5 to 15 wt% of impregnants selected from a group consisting of ruthenium trichloride, sodium hydroxide, potassium osmate, (lR)-(-}-(camphorylsuipbonyl) oxaziridine and polyoxometalates, wherein said polyoxometalates are selected frorrs 11-molybdo-1-vanadophosphonc acid, 10-moIybdo-2-vanadophosphcric acid, 9-moiybdo-3-nanadophosphoric acid 11-tungstocuproiTI borate salt, 11-tungstocupro(II) zincate salt. 12-tungstocobaltate(IIl) salt. 9-tungstosiiicate (IV) salt. 10-vanadonickelate (H) salt, 11-tungsiovanado (IV) zincate salt. 11-tungsiovanado (IV) borate salt, dodeca tungstophosphoric acid, dodeca moiybdophosphoric acid, dodeca tungstosilicic acid, dodeca tungstophophoric acid sodium salt, dodeca moiybdophosphoric acid sodium salt. 2. Impregnated alumina nanoparticles as claimed in claim 1, wherein the alumina nanoparticles have a particle size of 2-30 nm before impregnation. 3. Impregnated alumina nanoparticles as claimed in claim 1, wherein the surface area of said impregnated alumina nanoparticles is in die range of 250-350 m2/g. 4. Impregnated alumina naiiqparticles as claimed in claim 1. wherein the impregnated alumina nanoparticles has a bulk density 5. Impregnated alumina nanoparticles as claimed in claim 1, wherein alumina nanoparticles are impregnated with 10% w/w of 9-moiybdo-3-vanadophosphonc acid is the best composition among synthesized polyoxometaiate based impregnated systems 6. A method of preparation of impregnated alumina nanoparticles comprising the following steps; (i) synthesis of alumina nanoparticies: (a) adding aluminum powder to methanol, followed by addition of mercuric chloride catalyst; (b) stirring the solution of step (a) for 24 lirs; (c) adding toluene to the solution obtained in step (b) followed by stirring the solution; (d) hydroiyzing the solution obtained in step (c) by adding a solution comprising distilled water, methanol and toluene; (e) stirring the hydrolysed solution obtained in step id) to obtain a gel; (f) drying the gel obtained in step (e) to a powder by flushing inert gas; (g) flushing inert gas through the powder obtained in step (f), (h) heating the powder of step (g) in an evacuated thermal reactor by raising the temperature to 500°C under dyaamic vacuum of 10-2 to 10-3 torr tor 8 to 12 hrs, preferably 10 hrs. impregnating alumina nanoparticles produced in step (h) with impregnants by incipient wetness technique. optionally, preparing 80 to 300 mg pellets of impregnated alumina nanoparticies obtained in step (ii), having density of 0.1 -0.3 g/ by applying a pressure of 5.0 to 15 x 105 N/m2. 7. A method of preparation of impregnated alumina nanoparticles as claimed in claim 6, wherein the solution in step (b) is stirred for 24 hrs 8. A method of preparation of impregnated alumina nanoparticles as claimed in claim 6, wherein the solution in step (c) followed by stirring the solution for 15 to 45 minutes. 9. A method of preparation of impregnated alumina nanoparticles as claimed in claim 6, wherein the solution in step (e) is stirred for 24 hrs. 10. A method of preparation of impregnated alumina nanoparticles as claimed in claim 6, wherein alumina is reacted with methanol wherein, for each 10 g of alumina, 500 ml of methanol is added in presence of mercuric chloride catalyst to prepare aluminum methoxide, followed by addition of 875 to 1250 mL of toluene for 1 M of aluminum metlioxide formed, hydrolyzing the aluminum methoxide with a solution consisting of methanol, toluene and water, 3 M distilled water for each 1 M of aluminum methoxide formed, ratio of methanol to the ratio of distilled water is 10:1 to 13:1 and ratio of toluene to distilled water is 31; 1 to 36:1 11. A method of preparation of impregnated alumina nanoparticles as claimed in claim 10, wherein 0.125 to 0.5 g, preferably 0.25 g of mercuric chloride catalyst is used for preparing 1 M of aluminium methoxide. 12. A method of preparation of impregnated alumina nanoparticles as claimed in claim 7, wherein in step (f) inert gas is flushed at a pressure of 50-200 psi, preferably lOO psi, and the gel is heated in a reactor by raising the pressure to 600 to 1000 psi and temperature to 255 to 275" C, at the rate of 0.5° C to 1.5° C/min, maintaining the temperature of the reactor for 5 to 15 minutes, venting the reactor to atmospheric pressure for over a period of 1 to 3 minutes. preferably I minute, to obtain powder; and flushing the inert gas in step (g) for 10 to 20 minutes, preferably 15 rninutrs; 13. Impregnated alumina nanoparticles as claimed in any of the preceding claims, as and when used in decontamination systems and filtration systems for detoxification of nerve agents and its stimulants, blister causing agents and its stiniulants and chemical conlaminants and toxicants. 14. Impregnated alumina nanoparticles as hereinbefore described with reference to the foregoing examples and accompanying drawings.

Documents:

2820-del-2008-Abstract-(17-02-2014).pdf

2820-del-2008-abstract.pdf

2820-del-2008-Claims-(17-02-2014).pdf

2820-del-2008-claims.pdf

2820-del-2008-Correspondence Others-(17-02-2014).pdf

2820-del-2008-Correspondence Others-(19-02-2014).pdf

2820-DEL-2008-Correspondence-Others-(25-08-2009).pdf

2820-del-2008-correspondence-others.pdf

2820-DEL-2008-Description (Complete).pdf

2820-del-2008-Drawings-(17-02-2014).pdf

2820-DEL-2008-Drawings.pdf

2820-DEL-2008-Form-1.pdf

2820-DEL-2008-Form-2.pdf

2820-DEL-2008-Form-26-(25-08-2009).pdf

2820-DEL-2008-Form-3.pdf

2820-del-2008-form-5.pdf