CA2387092A1 - Metal-containing materials and methods of use thereof - Google Patents

Abstract

The invention relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H5PV2Mo10O40; K5Si(H2O)MnIIIW11O39; K4Si(H2O)MnIVW11O39; or K5CoIIIW12O40. The invention further relates to a method for removing a contaminant from an environment by the composition and contacting a polyoxometalate powder or a polyoxometalate coating with the environment. It further relates to a modified polyoxometalate, comprising the admixture of (1) a polyoxometalate and (2) a cerium, a silver, a gold, a platinum compound, or a combination thereof. The invention further relates to a method for removing a contaminant from an environment by contacting a modified material comprising (1) a material and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate. The invention further relates to an article comprising the modified material.

Description

POLYOXOMETALATE MATERIALS, METAL-CONTAINING MATERIALS, AND METHODS OF USE THEREOF
FIELD OF THE INVENTION
The present invention relates to materials contaitW ~~ a polyoxometalate or a metal compound, wherein the metal compound is not a polyoxometalate. The uivention further relates to methods for removuig a contaW rant from an enviromnent by contacting the envirotnnent with a polyoxometalate material or a non-polyoxometalate material.
BACKGROUND OF THE INVENTION
Decreasing the potential danger of contaminants from the environment has long been a significant issue. For example, the removal of offensive odors originating from cigarette smoke, sweat, exliaust gases, and rotten food in the work place, the home, and elsewhere would be quite beneficial to the public-at-large. Additionally, materials that can remove highly toxic contaW rants, such as chemical warfare agents (CWAs), from the environment can ultimately reduce a soldier's exposure to the agent.
Examples of materials that would be useful include creams, powders, coatings, and fabrics.
Creams, also referred to as topical skin protectants (TSPs), have been developed to protect soldiers from the tlueat of dermal exposure to chemical warfare agents. TSPs require an inert material which can be applied on the skin in a thin layer to form an antipenetrant barrier to CWAs or other contact irritants that will not interfere excessively with nomal skin functions. A preferred TSP affords protection against CWAs and other toxic or irritating materials in all of the forms in which they nught be encountered (e.g., liquid, aerosolized liquid and vapor). Perhaps the best-known vesicant CWA is 2,2'-diclllorodiethylsulfide (also known as "HD" or "sulfur mustard"), 3Q which was first used during World War I. Improved TSPs, however, are needed for protecting n ulitary persomel and civilians ti-om percutaneous exposure to CWAs and protecting the skin from contact dermatitis arising from other sources as well.

U.S. Patent No. x,607,979 to McCreery discloses topical creams formed from about 35~c to about 50% fme particulates of certain poly(tetrafluoroethylene) (PTFE) resins dispersed in pertluorinated polyether oils having viscosities from about 20 cSt to about 350 cSt. The creams afford protection agaiilst chemical warfare ay~ents such as sulfur mustard (HD), lewisite (L), sulfur mustard/Lewisite mixtures (HL), pinacolyl methylphosphonotluoridate (somas or GD), tluckened somas (TGD), and O-ethyl-S-2-diisopropylamiiloethyl methylphosphonotluolate (VX). These cream, however, can ot>ly provide limited exposure to a CWA for a short period of tune.
Furthermore, the creams cannot convert the CWA to an inactive form, which will reduce the overall toxicity of the CWA.
Thus, there is a need for a material, which is also referred to herein as a support, that can remove a contaminant from the environment for an extended period of time.
The incorporation of a polyoxometalate (herein referred to as "POM") into a material such as a cream, coating, powder, or fabric, is one approach to removing a contaminant from an environment. Gall et al. CChem. Mat. 8, pp. 2523-2527, 1996) disclose the immobilization of HSPV~Mo1"O~" on carbon cloth iil order to detennilie the ability of HSPV,Mo,~,O~~ to remove sulfur contaiiW g compounds from toluene. Johnson et al.
(Proc. ERDEC Sci. Conf. Chem. Biol. D~f. Res., 1998, pp. 393-399) disclose suspending H;PV~Mo",O~"; K;Si(H,O)Mn~W"03~; K~Si(H~O)Mn'~'W"O~',; or KSCo~WI~O", in a perflouropolyether baiTier cream to determine the creams ability to detect the presence of mustard gas. Johnson et al., however, is not concerned with the removal of the mustard gas from the gas phase.
The prior art also discloses the incorporation of polyoxometalates into powders and coatings. For example, U.S. Patent No. x,356,469 to Curcio et al. disclose a metal pigment composition suitable for the formation of a coating composition. The coating composition is composed of a solvent, a metal pigment, at least one phosphosilicate pigment, and at least one heteropoly anon. The metal pigment particles possess increased stability against attack by water. Japanese patent application number 4054127 to Terumo Corp. discloses the use of heteropoly acid salts as anti-tumor J
agents. The heteropoly acid salts can be adinii>istered in the form of a powder or suspended in solution. Although the prior art discloses a number of different applications of polyoxometalate powders or coatings, the art does not disclose the use of a powder or coating contaiiW g a polyoxometalate to remove a contaminant from the enviromnent.
In light of the above, it would be very desirable to have au article and a method of using an article for the removal of toxic and/or malodorous compounds without adding stoiclliometric amounts of additives or compounds to the article. The present invention solves such a need iii the art while providing surprising advantages. The present invention herein incorporates a polyoxometalate (POM) into a material such as a topical carrier, powder, or coating, which greatly increases the ability of the to remove a contaminant from the environrrient. The present invention also incorporates a metal compound, wherein the metal compound is not a polyoxometalate, into a in order to remove a contaminant from the enviromnent.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the consumption of oxygen and formation of CEESO as a function of time.
Figure 2 shows CEESO formation as a function of tune using lAu/2Cu/3N03;
2Cu/3N03; and lAu/3N03.
SUMMARY OF THE INVENTION
In accordance with the purposes) of tlus invention, as embodied and broadly described herein; this invention, in one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H;PV,Mo",O",; K;Si(H,O)Mn~W"03~; K~,Si(H~O)Mn'~'W103,; or K;Co~WI~O~~,.

The ilivention further relates to a polyoxometalate topical composition for removing a contanW ant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H;PV~Mo1~04";
KSSi(H,O)Mn~W,~039; K4S1(H~O)Mll"'~W,1O39~ KsCo~Wl~Oao; or H6(PV3Mo9O4o).
The invention further relates to a method for removilig a contamiliant ii~om an enviromnent, comprising contacting the polyoxometalate topical composition of the present iilvention with the enviromnent contailW g the contamiirant for a sufficient tune to remove the contaW rant ti-om the enviromnent.
The invention further relates to a method for removing a contaW rant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the enviromnent containing the contaminant for a sufficient tune to remove the contaminant from the environment.
The invention further relates to a modified polyoxometalate, whereui the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platilium compound, or a combination thereof.
The invention further relates to a method for removing a contamiirant from an enviromnent, comprising contacting a modified material with the enviromnent containing the contaW rant for a sufficient tune to remove the contaW rant fi-om the environment, wherein the modified material comprises (1) a material and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.
3p The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises ( 1) a material J
comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound. an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.
The invention further relates to an article comprising the modified of the present invention.
Additional advantages of the invention will be set forth iii part u1 the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory oily and are not restrictive of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.
Before the present methods and articles are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be lirnitilig.
In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following mear>jngs:
The singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.
"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and uistances where it does not.
In accordance with the purposes) of this invention, as embodied and broadly described herein, this unvention, iin one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H;PV,MoI"04"; K;Si(H~O)Mn~'W"0,~; K~Si(H,O)MnjvW1,03~; or KSComW,~O~~.
Tlne invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.
The itlvention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprisiing a topical carrier, a powder, a coatiing, or a fabric, and (2) a metal compound comprising a transition metal compound, an actiinide compound, a lanthaude compound. or a combiliation thereof, wherein the metal compound is not a polyoxometalate.
Tlne uivention further relates to an article comprising the modified material of the present invention.
Many polyoxometalates known iinthe art can be used i1i the present invention to remove a contaminant from an enviromnent. Polyoxometalates are also referred to hi the art as heteropoly compounds, heteropoly acids, isopoly compounds, and isopoly acids, which are subsets of polyoxometalates. Examples of polyoxometalates useful ili the present invention are disclosed in Pope, M.T. ili Hetet-opoly and Isopoly Oxometalatev, Springer Verlag, 1983, and Chetnicctl Reviems, vol. 98, no. l, pp. 1-389, 1998, which are incorporated by this reference in their entirety.
The selection of the polyoxometalate used in the present invention is dependent upon the contaminant or contaminants to be removed from the enviromnent. In one embodunent, the polyoxometalate has the formula 1 of [V,.Mo",W"NboTaPMqXrO~]Y-[A], wherein M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium, molybdenum, tungsten, nobium, or tantalum; X
is at least one p-, d-, or t-block element, whereiil X is not oxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o is from 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; s is sufficiently large that y is greater than zero;
and y is greater than zero, wherein the sum of k, m, n, o, and p is greater than or equal to four; and the sum of k, tn, and q is greater than zero, and A is one or more different counterions. In one embodhnent, s is from 19 to 460. The charge on the POM, y, is dictated by the values of k, tn; n, o, p, q, r and s. The p-, d-, and f-block elements can exist in any oxidation state.
Generally, M can be any d-block element haviilg at least one d-electron or f block element having at least one f-electron. Typically, M comprises titanium, chromium, manganese, cobalt, iron, t>ickel, copper, rhodium, silver, palladium, platW nn, mercury, rutheuum, cerium, or europium. In a preferred embodiment, M
comprises manganese, cobalt, or ruthet>ium. In another embodiment, X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron. When the polyoxometalate has the Keggiil structure XM,~, then it is possible for X and at least one M
to be the same d- or f-block element. Not wishing to be bound by theory, it is believed that the metal ion M of the polyoxometalate of the present invention is responsible for removilig the contatniilant from tile gas phase, while X, when present, provides structural integrity to the polyoxometalate.
In one embodiment, the sum of k and q is greater than or equal to one, the sum of k, tn, n, o, p, and q is 12, and s is 40. In yet another embodunent, k is not zero. In another embodiment, q is not zero.
In a more specific embodiment. when the polyoxometalate has the formula 1, the polyoxometalate has the formula [Xg+Vn'+M~''+Z1~-n-~'+O~]"-[A], whereiil X
is at least one p-, d-, or f-block element; g is greater than or equal to 2; M is at least one f block element or d-block element having at least one d-electron, wherein M is not vanadium;
h is from 1 to 7; i is from 5 to 6; j is from 4 to 5; x is 39 or 40; Z is tungsten, molybdenum, niobium, or a combiliation thereof; b is from 0 to 6; c is from 0 to 6; a is from 3 to 9; and A is a counterion. The values of u, x, i, b, c, g, h, and j will vary depending upon the selection of X, 1~T. and Z. The variables are related to one another and can be derived by the following formula:
a = 2(x) -i( 12-b-c) - g - c(h) - b(j) The values of h, i, and j are average charges, and depend upon the selection and number of X, M, Z, and V present iii the POM. For example, when Z is Nb+5 and Nb~ (i.
e., two Nb atoms present in the POM), the value of i+ is 5.5.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [Xg+V,,'+Zl,-b'+Oa"]'"[A], wherein X is at least one phosphorus, silicon, almniimm, boron, zinc, cobalt, or iron; b is from 1 to 6, and a is from 3 to 9.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the structure [Xg+M~''+Z,,_~'+O~"]°-[A], whereui X is at least one phosphorus, silicon, aluW num, boron, ziilc, cobalt, or iron; c is from 1 to 6, and a is from 3 to 9.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X,r+V«5+M,.'+Z,~_«_V5,+OZ)'"-[A~, wherein X is at least one p-, d-, or f-block element: r is greater than or equal to 1; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium;
t is from 1 to 7; s is from 4 to ~; Z is tungsten, molybdenum, i>iobiuin, or a combination thereof: a is from 0 to 9; v is from 0 to 9; y is from ~ to 6; z is 61 or 62;
w is greater than or equal to ~; and A is a counterion. Similar to the fornula above, the values of r, s, t, u, v, w, y, and z, will vary depending upon the selection of X, M, and Z. The variables are related to one another and can be derived by the following formula:
w = 2(z) -y(18-u-v) - 2r - v(t) - u(s) The values of r, s, t, and y are also average charges, and depend upon the selection and number of X, M, Z, and V atoms present iii the POM.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the fornula [XZ'+V 5+Z,~_"''+O6~]'"-[A], wherein X is at least one phosphorus, sulfur, silicon, aluiniiiuin, boron; zinc, cobalt, or iron; a is from 1 to 9; and w is greater than or equal to 4.
In a more specific embodiment, when the polyoxometalate has the formula l, the polyoxometalate has the formula [X~'+M~'+Z,~_~Y+O6~]"'[A], wherein X is at least one phosphorus, sulfur, silicon, aluinuium, boron, zinc, cobalt, or iron; v is from 1 to 9; and w is greater than or equal to 4.
hi a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the fornula [YV~,ZIZ_~,Oa"][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment. Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z is molvbdenuin.

In a more specific embodiment, when the polyoxometalate has the formula l, the polyoxometalate has the formula [X~+VhM''+~Z,,_n-~O~,n]° [A], wherein X is at least one p-, d-, or f-block element; g+ is the charge of X; M is at least one f-block element or d-block element having at least one d-electron, whereii M is not vanadium;
h+ is the 5 charge of M; Z is tungsten, molybdenum, niobimn, or a combination thereof; b is from 0 to 6; c is from 0 to 6, whereii the sum of b and c is greater than or equal to one; a is greater than 3; and A is a counterion.
In a more specific embodinent, when tine polyoxometalate has the formula 1, 10 the polyoxometalate has the formula [Xg+VbZh_bO;"]°~[A], wherein X
is at least one phosphorus, silicon, aluminum, boron, ziic, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; b is from 1 to 6; and a is greater than In a more specific embodinent, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X~+M''+~Z,~_~0;,,]"-[A], whereil X is at least one phosphorus, silicon, aluminum, boron, ziic, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; M''+ is at least one f block element or d-block element having at least one d-electron; c is from 1 to 6; and a is greater than 3.
In a more specific embodinent, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X'+~V"M'+~Zl~_"_"O6~]W [A], wherein X is at least one p-, d-, or f-block element; i+ is the charge of X; M is at least one d- or f-block element, wherein M is not vanadium; j+ is the charge of M; Z is tungsten, molybdenum, niobium, or a combination thereof; a is from 0 to 9; v is from 0 to 9, wherein the sum of a and v is greater than or equal to one; w is greater than or equal to 4; and A is a counterion.
In a more specific embodinent, when the polyoxometalate has the formula 1, the polyoxometalate leas the formula [X'+~V~Z,~_~06~]'"-[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z
comprises tungsten, molybdenum, iuobiuin, or a combination thereof; a is from 1 to 9;
and w is greater than or equal to 4.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X'+_M'+~Z,~_~,06,]~"-[A], wherein X is at least one phosphorus, sulfur, silicon, aluinuiuin, boron, zinc, cobalt, or iron; Z
comprises tungsten, molybdenum, iiiobiuin, or a combination thereof; M'+ is at least one d- or f-block element; v is from 1 to 9; and w is greater than or equal to 4.
In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [YV~Z,~_~O~"][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; x is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten: In one embodiment, Y is aluminum and Z is molybdenum.
Polyoxometalates having an organic group, such as an alkyl group or aryl group, an organosilyl group, or other p- or d-block organometallic groups bonded to the POM
can also be used iii the present invention. The orgaiuc group can be branched or straight chain alkyl, alkenyl, or alkyiiyl group or an aryl group of C, to C3". The alkyl group can also be a polyether or polyol. Not wishing to be bound by theory, the organic group is bonded to the polyoxometalate as depicted iii Scheme l, where R is the organic group and Met is generally vanadium, molybdenum, tungsten, niobium, or tantalum:

Scheme I
R
ROH
O
- H?O Meth \Met O II
Meth \Met I YR
YLR;
/O\
Met Met III
The reaction between an alcohol and the polyoxometalate I results iii the loss of water and the formation of the polyoxometalate II, wherein the orgainic group is bonded to an oxygen atom of the polyoxometalate. Any alcohol known in the art can be used 11 the present invention. Examples of alcohols that can be used include, but are not limited to, methanol, ethanol, or tris(hydroxymethyl)methane. The polyoxometalates haviig organic groups bonded to the POM that are disclosed in Gouzerh et al., Cliem.
Rev., 98, pp. 77-111, 1998, which is incorporated by reference in its enti-ety, are useful ii the present invention.
In another embodinent, the polyoxometalate I can be reacted with a compound having the generic formula YLoR~_o, wherein Y is silicon, tin, or an other p-or d-block element; L is a leaving group; R is an orgainic group, such as an alkyl, alkenyl, or alkyinyl group or an alyl group of C, to C~"; and o is from 1 to 4. Suitable leaviig groups for L include, but are not limited to, halides and all:oxides. In Scheme I, the oxygen of polyoxometalate I displaces L from YLR; to fioi~n a new Y-O bond (compound III). Ainy silyl, tii, or orgainic derivative of a p- or d-block element known ii the art can be used in the present invention, provided that tine compound has at least one leaving group.
The counterion A can be any counterion known ui the art. Examples of counterions include, but are not limited to, duatennary atnmot>ium canon, proton, alkali metal catiun, alkaline earth metal ration, anunonum ration, d-block rations, f-block canons, or a combuiation thereof. In one embodiment, the polyoxometalate is an acid, wherein the counteriun A is hydrogen (H+). In one embodiment, the counterion is a d-or f-block metal complex. In one embodiment, the counterion is trilnethyl-triazacyclononane manganese. In another embodiment, the counterion A is hydrogen, lithium (Li+), sodium (Na+), potassium (K+)> or a combination thereof. In another embodunent, A is not hydrogen or potassium In another embodunent, the polyoxometalate comprises a modified polyoxometalate, whereui the modified polyoxometalate comprises the admixture of (1) a pre-modified polyoxometalate and (2) a cerium compouyd, a silver compound, a gold compound, a platinum compound, a copper compound, a cobalt compound, or a combination thereof. The teen "admixture" can refer to the reaction product between the polyoxometalate and the cerium compound, silver compound, gold compound, platinum compound, or a combuiation thereof. For example, the cerium compound, silver compound, gold compound, or platuium compound can undergo ion exchange with the counterion of the polyoxometalate. The cerium compound, silver compound, gold compound, or platuium compound can also react with the polyoxometalate by a redox reaction. The teen "admixture" can also refer to when the cerium compound, silver compound, gold compound, or platinum compound do not react at all with the polyoxometalate. Fur example, the polyoxometalate may absorb the cerium compound, silver compound, gold compound, or platinum compound.
In one embodiment, when the POM is the sodium, litluun~, or potassium salt or the acid form (A is H+), the POM can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.
For example, Ag;PV~Mo",O~" is produced by the ion exchange of NaPV,Mu",0:~"
with a stoicluometric amount AgNOz. Aiiy of the POMs described above can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound.
Depending upon the type and amounts of POM and cerium compound, silver compound, gold compound, or platinum compound used, the ion exchange reaction may or may not go to completion. When the ion exchange does not go to completion, there may be small population of Na+, Li+, K+, or H+ iii the modified-polyoxometalate.
For example, when HSPV,Mo",O~", is admixed with AgN03, the resultant POM may be expressed by the formula Ag~H~_~PV~MoI"O~", where x is from 1 to 5. Here, varying amounts of H+ may be present in the POM.
An example of a cerium compound useful in the present invention includes, but is not limited to, (NHa)ZCe(N03)6. Examples of silver compounds useful in the present invention include, but are not limited to, AgNO~ and AgClOa. Examples of gold compounds useful in the present invention include, but are not limited to, HAuCI~ and salts thereof. Aii example of a platuium compound useful in the present invention includes, but is not limited to, H~PtCIb.
In one embodiment, the counterion is cerium, silver, gold, platinum, or a comb>Iiation thereof. In another embodiment, A is, independently, cerium, silver, gold, or platinum. In another embodiment, .A is (1) cerium and silver; (2) cerium and platinum; (3) cerium and gold; or (4) silver and gold.
In another embodiment, A comprises (1) hydrogen, lithium, sodium, potassium, or a combination thereof, and (2) cerium, silver, gold, platinum, or a combination thereo f.
In one embodiment, ( 1) the pre-modified polyoxometalate is H~PV~Mo"-,O~";
Na;PV~Mo",O;"; Li;PV~Mo",0,~"; K;PV~Mo",O~", or a combination thereof, and (2) the cerium compound is (NH~)~Ce(NO~)6. In another embodiment, ( 1 ) the pre-modified polyoxometalate is H;PV,Mo",O~",: Na~PV,Mo",O~"; Li;PV,Mo",O~"; K~PV,Mo",O~""
or a combiliation thereof; (2) the cerium compound is (NH~)ZCe(NO~)6; and (3) the gold compound is HAuCI~. In another embodiment, (1) the pre-modified polyoxometalate is HSPV~Mo",O~"; Na:PV,Mo",O~"; Li;PV,Mo,;,O~"; K;PV=Mo",O",> or a combination 5 thereof; (2) the cerium compound is ( NH~)~Ce(NO~)6: and (3) the platuium compound is H,,PtClb. In another embodiment, (1) the pre-modified polyoxometalate comprises NaaPVMo"O~"; Na;PV~Mo".,0~",; NahPV_Mo~O~"; Na;H~PV~,WrO",; Na',PV;,Mo;,Oa";
NaSCuPW"039; Na~CuPW"03~; Na;MnPW"039; K;CoPW"039; (n-Dec~)6HMnNb~P,W,50~~; or K,~Cu3(W~PO~~)~, and (2) the gold compound is HAuCI~.
10 In another embodiment, (1) the pre-modified polyoxometalate is Na;PV~Mo",O~" and (2) the silver compound is AgNO~, AgCIO~, or a combination thereof.
In another embodiment, the polyoxometalate comprises K~CO,W"039 K~S1COVW,U039, K~SiCoVW,i~Osy; Na~;Co.,WllOs~; AgsPV.,Mo,uO:~u; Ag6PVsMo90au;
15 AgBCoVW"0,,;,; Agl.,Ce(PW"03y,; Na,,,Ce(PW"039):,; K,ZCe(PW"Os9)z~
NaSPCuW"03~; H6PV3Mo90;"; or K;Cu~PW"03~. In another embodiment, the polyoxometalate is not H6PV;Mo~O~".
Not wislW g to be bound by theory, it is believed that some counterions of the present iilvention can be reduced to the cowespondiiig metal when the polyoxometalate contacts the contatnillant. For example, when the cation is Ag+' or Au+3, these canons can be reduced to silver metal or Au+', respectively, depend>lig upon the contaminant that is to be removed. Thus, the counterion A can exist in multiple valence states.
The phrase "metal compound" refers to one or more transition metal compounds, actiiude compounds, lanthaude compounds, or a combination thereof.
When the metal compound is ony one compound, then the material is directly treated with the metal compound usuig tecluuques described below. WIIen the metal compound is composed of two or more compounds, the material can be sequentially treated with the compounds, or alternatively, the metal compounds can be admixed prior to treating the material with the metal compounds. Dependuig upon the metal compounds that are selected, the metal compounds may react with one another to fom a new species, or they may not react at all with each other to produce a composition or mixture. Materials that contain a metal compound of the present iilvention are referred to herein as "non-POM materials."
J
In one embodiment, the metal compound comprises a cerium compound, a gold compound, a platinum compound, a silver compound, or a combuiation thereof.
Any of the cerium compounds, gold compounds, platiilum compounds, or silver compounds listed above can be used as the metal compound. In another embodiment, the metal compound is a cerium compound and a platinum compound, preferably (NH~)~Ce(NO~)6 and H~PtCIb, respectively. In another embodunent, the metal compound is a cerium compound and a gold compound, preferably (NH;)~Ce(NO3)6 and HAuCI~, respectively. In another embodiment, the metal compound is a silver compound and a gold compound, preferably AgN03 and/or AgCIO~ and HAuCl4, respectively. In another embodiment, the metal compound is a cerium compounds, preferably (NH~)ZCe(N03)6~
In another embodiment, the metal compound comprises (1) gold, copper, and nitrate; (2) gold, iron, and utrate; (3) gold, manganese, and utrate; (4) gold, titaW nn, and tutrate: (5) gold. cobalt, and ntrate; (6) gold and ntrate; (7) copper and ntrate; (8) iron and nitrate; (9) gold, vanadium and utrate; ( 10) gold, tlickel, and utrate; ( 11) gold, silver, and ntrate; or ( 12) gold, chloride, and ntrate. In a preferred embodiment, the metal compound comprises gold, chloride, and nitrate. In another embodiment, the metal compound comprises mixing (NEt~)AuCh with varying amounts of CuS04, MnSOa, VOSOa, Ti(S04).,, Fe.,(SO~)3, NiSO,~, ZnS04, Cr~(SOa)3, MgSO~, CoSO~, Pd(N03)~, Na,,SO~, and/or NBu~NO~. In another embodiment, the metal compound is produced by mixing (NEta)AuBr~ and NBu~NO~.
When the metal compound comprises two or more compounds, the compounds can be admixed using tecln>iques lmown in the art. In one embodiment, the metal compound can be produced by admixing two or more metal salts. The anon of the salt can be any anon known iii the art. Examples of anions include, but are not limited to, sulfate. carbonate, acetate, nitrate, chloride, and stearate. In one embodiment, when two or more compounds are used to produce the metal compound, the compuunds are mixed in the presence of a solvent, preferably an orgaiuc solvent. In one embodiment, After the compounds have been sufficiently admixed, the solvent is removed, and the metal compound is optionally dried. In one embodiment, the drying step is by vacuum.
Any POM or metal compound of the present invention can be incorporated into a material iii order to remove a contaminant from the enviroinnent. Examples of materials include, but are not liiuted to, a topical carrier, a coating, a powder, or a fabric. As described above, a material as used herein refers to a support that holds the POM or metal compound.
In one embodiment, the polyoxometalate and the metal compound can be incorporated sequentially into the material. In one embodiment, the polyoxometalate is incorporated into the material followed by the incorporation of the metal compound into the material. In another embodiment, the metal compound is incorporated uito the material followed by the iiicoiporation of the polyoxometalate into the material.
A wide variety of topical earners can be used in the present invention.
Suitable topically acceptable pharmaceutical carriers are those which typically are used in the topical application of pharmaceuticals and cosmetics. Examples of such carriers include, but are not limited to, lotions, creams, ointments, and gels. Topical carriers are also referred to iii the art as bar-ier creams and topical sklll protectants.
Any of the topical carriers disclosed iii U.S. Patent No. 5,607,979 to McCreery can be used in the present invention, which is incoiTorated by reference in its entirety. In one embodiment, the topical carrier comprises a perfluorinated polymer. In another embodiment, the topical carrier comprises a pertluoropolyether. An example of a perfluoropolyether (PFPE) useful iii the present invention has the general formula CF30[-CF(CF3)CF~O-]~(-CFO-)yCF3). In one embodiment, the topical carrier comprises a perflourinated polymer and one or more ui~tluorinated polymers. In another embodiment, the topical carrier comprises a perfluoropolyether and one or more uiltluoriiiated polyethers.
In one embodiment, the topical carrier may further contain saturated or unsaturated fatty acids such as stearic acid, palinitic acid, oleic acid, palinito-oleic acid, cetyl or oleyl alcohols, stearic acid, fluorinated acids, fluorinated alcohols (e.g., tetrafluoroethanol), or combinations thereof. The cream may also optionally contain one or more surfactants, such as a non-ioiuc surfactant.
In one embodiment, the polyoxometalate topical composition is composed of a pertluoropolyether and the counterion A of the POM is silver. In another enibodiinent, the polyoxometalate topical composition is composed of a pertluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof. In another embodiment; the non-POM material comprises a topical can-ier composed of a perfluoropolyether and the metal compound comprises a silver compound, preferably AgN03 or AgCIO~.
In another embodiment, the non-POM topical composition is composed a pertluoropolyether and the metal compound comprises a cerium compound, a silver compound, a palladium compound, a platinum compound, or a silver compound.
A wide variety of powders and coatings known iii the art can be used as the material of the present invention. In one embodiment, the powder comprises activated carbon.
Any fabric known in the art can be used to produce a polyoxometalate fabric or non-POM fabric of the present invention. In one embodiment, fabrics used to prepare garments, draperies, carpets, and upholstery can be used and articles made fi-om them are a part of this invention. In another embodiment, the fabric can be a knit or non-woven fabric. Useful fibers include, but are not limited to, polyanude, cotton, polyacrylic, polyacryloiutrile, polyester, polyvinylidine, polyoletiii, polyurethane, polytetrafluoroethylene, or carbon cloth, or a combiliation thereof. In one embodiment, the fabric is prepared from cotton, polyacrylic, or polyacrylontrile. In one embodunent, the fabric is prepared from a catioac fiber. In another embodiment, the fabric comprises ( 1) a 50/50 blend of nylon-6,6 and cotton or (2) stretchable carbon blended with polyurethane.
Airy cellulosic fiber can be uiconporated by a POM or metal compound to produce the polyoxometalate fibers or non-POM fibers of the present uivention.
Examples of usehil cellulosic fibers include, but are not Limited to, wood or paper. In a prefewed embodunent, a polyoxometalate or the metal compound of the present invention can be incorporated i11 paper ui order to remove a contanmlant from the gas or liquid phase. In one embodiment, the paper is wallpaper.
The amount of polyoxometalate or metal compound incorporated into the material varies depending upon the contaminant to be removed and the material that is selected. There is no restriction on the amount of POM or metal compound that can be incorporated into the material. In one embodiment, the amount of polyoxometalate or metal compound incorporated in the material is from 0.1 to 95 % by weight of the polyoxometalate material or non-POM material. In one embodi ent, the lower limit of polyoxometalate or metal compound by weight is 0.1, 0.5, 1.0, 2.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 4~, or ~0 ~~c, and the upper limit is 30, 40, 50, 60, 70, 80, 90, or 95 %. In one embodunent, when the material is a topical carrier, the polyoxometalate or metal compound is from ~ to 30 9c by weight of topical composition.
The present invention is capable of removing a single contaminant or multiple contaminants from an enviromnent. The term "enviromnent" as used herein refers to any media that contains at least one contaminant. In one embodiment, the enviromnent comprises a liquid phase. In another embodi ent, the envii-omnent comprises a gas phase.
The term "remove" refers to, but is not lunited to, the degradation of the contaminant, the conversion of the contaminant into another compound that is either less toxic or nontoxic and/or malodorous, or the adsorption of the contaminant by the polyoxometalate or the metal compound. The POM and metal compound can degrade the contaminant by a number of different mechalislns. For example, the POM can 5 aerobically oxidize the contanillant acetaldehyde (CH3CH0). Not wislml~~ to be hound by theory, it is believed that the aerobic oxidation of CH3CH0 proceeds by a radical chain mechanism (i.e., the ilitiation of the radical chain by CH3CH0 + POMoX
'>
CH3C0' + HPOMred)~
10 Contalniilants that can be removed by using the present lllVelltloll lllChlde, but are not limited to, an aldehyde, an aliphatic 1>itrogen compound, a sulfur compound, an aliphatic oxygenated compound, a halogenated compound, an organophosphate compound, a phosphonothioate compound, a phosphorotluoate compound, an arselic compound, a chloroethyl-amine compound, a phosgene compound, a cyanic;
compound, 15 or a combination thereof. In one embodiment, the contaminant is acetaldehyde, methyl mercaptan, alnmollia, hydrogen sulfide, methyl sulfide, diethyl sulfide, Methyl disulfide, dilnethyl sulfide, dilnethyl disulfide, trilnethylalnine, styrene, propiollic acid, n-butyric acid, n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-cllloroethyl ethyl sulfide, carbon monoxide, or a combination thereof. In another embodiment, the 20 polyoxometalate materials and non-pohyoxometalate materials can remove nucrobial life from the gas or liquid phase. Examples of microbial life include, but are not limited to, bacteria, protozoa, and viruses.
hanother embodiment, the contaminant is a chemical warfare agent (CWA).
The chemical warfare agents disclosed in Marrs, Timothy C.; Maynard, Robel-t.
L;
Sidell, Frederick R.; Chemical Wcttfctre Agent.v Toxicology ctnd Treatment;
John Wiley & Sons: Chichester, England, 1996; Compton, James A. F. Military Chemical and Biological Agents Chemical and Toxicological Properties; The Telford Press:
Caldwell, New Jersey, 1988; Somani, Satu M. Chemical Warfare Agents; Acadenic Press: San Diego, 1992, which are herein incorporated by reference in their entirety, can be removed by the polyoxometalate materials of the present invention.

The present invention can remove a contaW rant from the enviromnent ui the gas phase under mild conditions. In one embodiment, the contanniinant can be removed from -~0 °C to 250 °C at a pressure of from 0.1 ppb to 30 atnn, preferably from 25 °C
to 105 °C at 1 atlas. In another embodiment, the lower temperature lillllt is -S0, -40, -30, -20, -10, 0, 10, 20, S0, 75, 100, or 150 ° C, and the upper temperature limit is 50, 75, 100, 12~, 150, 175, 200, 22~, or 250 °C. In a preferred embodiment, the present invention can remove a contalnilrant from the envii~omnent at room temperature (approximately 25 °C) and at 1 atm. In another embodiment, the present invention can remove a contaminant from the gas phase that has a partial pressure of from 0.1 ppb to 2 atm, 10 ppb to 2 atlas, 100 ppb to 2 atlas, 200 ppb to 2 atm, and 0.5 ppm to 2 atlas.
Similarly, the present invention can remove a contaW rant under mild conditions when the enviromnent is a liquid phase. In one embodiment, the contaminant can be removed from a liquid media at from 0 ° C to 200 ° C. The temperature depends upon the liquid media that is beislg contacted and the contaminant to be removed.
The POMs and metal compounds are typically used ill the presence of an oxidizer to remove a contaminant from the environment. In one embodiment, the POMs and/or metal compounds are used un the presence of air, which oxidizes the POM and/or metal compound. In another embodiment, additional oxidizers can be used iln combination with au' to oxidize the POM and/or metal compound. Examples of oxidizers include, but are not limited to, peroxides and peracids. In a prefen-ed embodiment, air is used as the oxidizer.
The environment contailnillg the contaW rant can be contacted by the polyoxometalate materials or non-POM materials using a variety of teclllliques. For example, when the contalnilnant is iin the liquid phase, the polyoxometalate material or.
non-POM material can be dipped or submersed into the liquid phase.
Alternatively, the liquid phase can be filtered or passed through the polyoxometalate material or non-POM material. When the contaminant is iln the gas phase, tine polyoxometalate material or non-PO'_VI material is typically placed iln au open or closed enviromnent that contains the contannilnant(s).

The polyoxometalate materials or non-POM materials of the present invention have a number of advantages over the prior art materials that do not use a polyoxometalate to remove a contmnir~ant fi-om the environment. One advantage is that the present invention can remove a contamiirant from the enviromnent startuig within milliseconds of contact and can remove the contaminant for extended periods of time, rangin~~ from several days to ilidefnlitely. The POMs and metal compounds used in the present itlvention are capable of beuig regenerated to an active form that permits the removal of the contaW rant. Another advantage is that some POMs and metal compounds can render the material more water resistant and increase the surface area of the material. Fuially, when the material is a fabric or cellulosic fiber, the POM and metal compound can eWance the dyeability, light fastness, color fastness, and weaving properties of the fabric or cellulosic fiber.
The polyoxometalate and metal compound can be incorporated into the material using tecln>iques known i11 the art. In one embodunent, when the material is a topical carrier, powder, or coating, the polyoxometalate or metal compound is directly added to and admixed with the material. In another embodiment, the material (topical carrier, powder, coatilig, or fabric) is contacted with a mixture comprising the polyoxometalate or metal compound and a solvent. The polyoxometalate or metal compound can be soluble, partially soluble, or insoluble ui the solvent, dependiilg upon the polyoxometalate or metal compound and solvent selected. In one embodiment, the solvent is water. In another embodiment, the solvent can be an organs solvent.
Examples of orgauc solvents useful in the present invention include, but are not limited to, acetoutrile, acetone, toluene, carbon dioxide, xylenes, 1-methyl-2-pyrrolidiiione, ditnethyl sulfoxide, or an alcohol, such as methanol, ethanol, 1-propanol, or 2-propanol.
In one embodiment, when the material is a fabric or cellulosic fiber, the polyoxometalate or metal compound mixture is from 0.1 to 20 ~/c by weight polyoxometalate or metal compound and from 80 to 99.9 % by weight water, preferably from 0.3 to 15 % by weight polyoxometalate or metal compound and 85 to 99.7 ~/c water. Generally, the fabric or cellulosic fiber is dipped or iininersed into the mixture containing the POM or metal compound for several hours to days at a temperature of from 0 °C to 100 °C, preferably for ? hours to 2 days at from 2~
°C to 80 °C. In another embodiment, the POM or metal compound can be admixed with a resin or adhesive, and the resultant adhesive is applied to the surface of or admixed with the fabric or cellulosic fiber.
Typically, once the material has been contacted with the POM or metal compound mixture, the polyoxometalate material or non-POM material is dried iii order to remove residual solvent. In one embodiment, the polyoxometalate materials or non-POM
material is heated from 0 °C to 220 °C at or below atmospheric pressure, preferably from 25 °C to 100 °C. In another embodiment, the polyoxometalate material or non-POM material is dried iv vcecuo (i.o., less than or equal to 10 torr).
In another embodiment, when the material is a fabric or cellulosic fiber, the POM
or metal compound can be il~corporated into the fabric or cellulosic fiber by depositing the POM or metal compound on the surface of an existing fabric or cellulosic fiber, covalently bonding the POM or metal compound to the fibers of the fabric or cellulosic fiber, impregnating or intimately mixing the POM or metal compound with the fabric or cellulosic fiber, electrostatically bondilig the POM or metal compound to the fabric or cellulosic fiber, or datively bonding the POM or metal compound to the fabric or cellulosic fiber via the coordination of a d- or f- block metal ion on the surface of the POM or metal compound with a functional group on the fabric. In the case of electrostatically bonding the POM to the fabric or cellulosic fiber, the positively charged functional groups on the fabric or cellulosic fiber and the negatively charged POM can form an electrostatic bond. In one embodiment, when the counterion of the polyoxometalate is a proton or the metal compound is an acid, the fabric or cellulosic fiber can be protonated by the polyoxometalate or metal compound to produce a positively charged fiber, which then electrostatically bonds to the polyoxometalate or metal compound aiuon. In one embodiment, a cationic polymer can be used as a binding agent to incorporate an ai>ioilic polyoxometalate or metal compound into an EXAMPLES
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions, materials, 5 and methods claimed hereui are made and evaluated, and are intended to be purely exemplary of the ilivention and are not uiCended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Uness indicated otherwise, parts are parts by weight, target 10 odorants/toxics are expressed iii parts per million, temperature is in °C or is at ambient temperature and pressure is at or near atmospheric.
The tei-in "consumption" or "consumed" refers to the removal or adsorption of a contaminant or contaminants from the environment or the conversion of the 15 contaminant or containiliants to another compound that is nontoxic and/or non-malodorous.
General Considerations 20 Materials. PFPE #1511 is composed of 35-50 % polytetrafluoroethylene thickening absent dispersed in a perfluoropolyether oil with water as a co-surfactant.
PFPE #1~ 11 was provided by Dr. E. H. Braue of the Uiuted States Ai-iny Medical Research Institute for Chemical Defense.
25 All reagents used in the examples were obtained from Aldrich Chemical Company, Milwaukee, WI, and were used without further purification. The following reagents were used in the examples (the purity of the reagent is in parenthesis): CEES
(98%), HPLC grade acetoi>itrile, tetratluorethylene (99.5%), 1;3-diclllorobenzene (98 -%), dimethyl sulfoxide (DMSO) (99.8%), AgNO; (99+%), HAuCI, (99+%), CuCI., (99 -+%), FeCl3 (98%), AgCIO~ (99.9%), (NEt~)AuCI." CuSO, (99.99%), MnSO;
(98%), VOSO~ (99.99%), Ti(SO~)., (99%), Fe.,(SO,~)3 (97%), NiSO,~ (99%), ZnSO~ (99%), Cr,(SO~)3 (99.999~7c), MgSO~ (999c), CoSO~ (99.998~~c), Pd(NO;)~ (98c'/c), Na,,S03 (99%), and NBu~NO, (97%). NBu~NO, (98%) was purchased from Fluka.
Synthesis of Aa.Na:_,PV,NIo,oO ~
NaSPV,Mo",O~" was prepared by the literature procedure outlined inn Petterson, L.; Anldersson, L; Selling, A.; Grate, J. H. Inorgl. Chem. 1994, 33, 982.
Ag~Na;_~PV~Mo",O~" was prepared using the following procedure. Ground HSPV,Mo",O.", (30.9 g, 1.78 x10-'- mol) was dissolved inn 200 tnL of distilled water. The orange solution was filtered three tunes to remove any undissolved POM. Ground AgNO: (15.2 g, 8.94 x10-' mol) was added with vigorous stitrinlg. The mixture was stirred overnight at room temperature. The product precipitated as a dark red-orange powder and was removed by suction filtration over a medium fritted glass funnel. The product was dried in vctcuo ovenni~~llt. Tlne IR spectrum of the resultant powder confirmed the formation of Ag~Na;_~PV~Mo",0,,~.
Synthesis of Additional Polvoximetalates The following POMs listed in Table 8 were prepared by literature procedures (the entry number in Table 8 and the bibliographical information are in parenthesis):
NaSCuPW ."03~; Na;MnPW"0~~,; K;MnPW,IO~y; and K;CoPW,lO;,: (Entries 2-4 and, 6, respectively; Maksitnov, G. M.; Kustova, G. N.; Matveev, K. L; Lazarenko, T. P
Koord. Khim. 1989, IS(6), 788-96).
NaSPV~Mo1"O~" and H;PV,Mo",O~": (Entries 7 and 20, respectively; O'Dotlinell, Stephen E.; Pope, Michael T. J. Chem. Soc., Dalton Trctn,s~. 1976, 21, 2290-7).
Na4PVMo"O~": (Entry 11; So, Hyunsoo; Pope, Michael T. Inorg. Chew. 1972, II(6), 1441-3).

Na6PV;Mo~O~" and HhPV~Mo,,O~": (Entries 8 and 21, respectively; Pope, Michael T.;
O'Domell, Stephen E.; Prados, Ronald A. J. Chern. Soc., Chem. Common. 197, 1, 3).
Na;H,PV~Mo~O", and H,PV~Mo~O~": (Entries 9 and 22, respectively; Yurcheuko, E.
N.
J. Mol. Strctct. 1980, 60, 325-31).
NaSFeSiW1103~, and IC~,FeSiW"0;~: (Entries 12 and 36, respectively; Peacock, R. D.;
Weakley, T. J. R. J. Clzem.. Soc. A 1971, 12, 1937-400).
Na~SiVW,IO~",: (Entry 13; Tourne, Claude; Toume, Gilbert. Bttll. Soc. Chim. Fr-. 1969, 4, 1124-36).
K~Co(II)P~W1~061: (Entry 15; Marcu, Gheorghe; Patrut, Adrian; Botar, Alexandra.
Rev. Clzim. (Bucharest) 1989, 40( 11 ), 870-5).
Kl~pd~(PW903,~),: (Entry 16; Kuznetsova, N. L; Kuznetsova, L. L; Detusheva, L.
G.;
Likholobov, V. A.; Fedotov, M. A.; Koscheev, S. V.; Burgina, E. B. Stctd.
Scetf: Sci.
Catal. 1997, I10 (3rd World Congress on Oxidation Catalysis, 1997), 1203-1211).
K~Cu(II)P~W1~06,: (Entry 17; Hamlaoui, Mohamed Larbi; Vlassenlco, Konstautiit;
Messadi, Djelloul. C. R. l'Acctdernie Sci., Ser. 11 Univens 1990, 311 (7), 79~-8).
Na~PVMo,IO~"and Na~PMo,,O~": (Entriesl8 and 19, respectively; So, Hyunsoo;
Pope, Michael T. Inor-g. Chew. 1972, 11 (6), 1441-3).
Nal6P~W3"Cu~011~: (Entry 24; Huang, Ru-Dan; Bei, Bao-Li; Wang, En-Bo; Li, Bai-Tao;
Zhang, Su-Xia. Cccodeng Xceexiao Hetaxue Xitebcto 1998, 19(11), 1721-1723).
K"~Ce(PW"039),: (Entry 26; Peacock, R. D.; Weakley, T. J. R. J. Chem. Soc. A
1971, 12, 1937-40).

K,CuSiW"039 and Na~CuSiW"039: (Entries 27 and 30, respectively; Teze, Andre;
Souchay, Pierre. C. R. Acted. Sci., Ser. C 1973, 276( 19), 1525-8).
Na;NiPWIIO~y: (Entry 31; Maksiinov, G. M.; Kustova, G. N.; Matveev, K. L;
Lazarenko, T. P. Koord. Khi.nu.. 1989, IS(6)> 788-96).
Na3AsW1~0~": (Entry 35; Tsyganok, L. P.; Statsenko, V. P.; Vil'dt, A. L. Zh.
Neorg.
Khim. 1974, 19(11), 3071-7).
K~NiP~W"061: (Entry 37; Han~laoui, Mohamed Larbi; Vlassenko, Konstantiii;
Messadi, Djelloul. C. R. l'Academie Sci., Ser. II Univers 1990, 311 (7), 795-8).
(Me4N)1"(Co~SiW90~",H6): (Entry 38; Nomiya, Kenji; Miwa, Makoto. Polyhedron 198, 4(8), 1407-12).
Na3V,~O,a: (Entry 40; Preuss, F.; RoseWalu~, L. J. Inorg. Nucl. Cl7en1. 1972, 34(5), 1691-703).
K~p2Wl.,(I~~O.,)Ob,: (Entry 42; Gong, Jian; Li, Guopuig; Wang, Fuduan; Qu, Lunyu.
Wuji Hacaxue Xccebcco 1995, 1l (3), 232-7).
(NHa)6P,FeW,~06,: (Entry 43; Peacock, R. D.; Weakley; T. J. R. J. Chem. Sot. A
1971, Issue 12, 1937-40).
K~Mn(II)P,~VI~O6,: (Entry 44; Marcu, Glieorghe; Patrut, Adrian; Botar, Alexandra. (1).
Rev. Chim. (Bucliarest) 1989, 40(11), 870-5).
(~4)6P''~1~~62~ (Entry 30; Varga, Gideon M., Jr.; Papaconstantinou, Elias;
Pope, Michael T. Inorg. Chem. 1970, 9(3), 662-7).
NagPV6MobOa": (Entry 1; Ret'yakov, V. P.; Volkova, L. K.; Ziintseva, G. P.;
Rudakov, E. S. Kinet. Katal. 1993, 34(1), 183).
KI~Cu~(WyP03~),: (Entry 10; Weakley, Timothy J. R.; Finke, Richard G. Inorg.
Chem.
1990, 29(6), 1235-41).
K(NH~)6RuBW,l039: (Entry 34: Liu, Huizhang; Sun, Wenliang; Yue, Bin; Li, MlllEYlll~: Chen, Zhujiang; Jiii, Songlin; Xie, Gaoyan~: Shao, QiaWen; Wu, Tailiu;
Chen, Shiinity; Yan, Xiaoming. Wuji Huaxue Xccebao 1997, 13(3), 2~1-2~7).
K~"Ni~P~W1,06,: (Entry 14; Yon, David K.; Miller, Warren K.; Novet, Thomas;
Domaille, Peter J.; Evitt, Eric; Johnson, David C.; Fii~lce, Richard G. J. Am.
Chem. Soc.
1991, 113(19), 7209-21).
KI~Co~P~W1~06~: (Entry 39; Evans, Howard T.; Tourne, Claude M.; Tourne, Gilbert F.;
Weakley, Timothy J. R. J. Chem. Soc., Dalton Trans. 1986, 12, 2699-705).
K1OMI14(PW9O34)2' (Entry 41; Gomez-Garcia, C. J.; Coronado, E.; Gomez-Romero, P.;
Casan-Pastor, N. Inorg. Chem. 1993, 32(15), 3378-81).
K",Cu~P,WI~;Obx: (Entry 45; Weakley, Timothy J. R.; Fiiike, Richard G. Inorg.
Clzem.
1990, 29(6), 1235-41).
K~zPaW~sNlsOes~ (Entry 47; Gomez-Garcia, Carlos J.; Coronado, Eugeuo; Ouahab, Lahcene. Angevv. Chem. 1992, 104(5), 660-2).
Na6P~W3"Mn(II)4011z~ (Entry 49; Gomez-Garcia, C. J.; Borras-Alinenar, J. J.;
Coronado, E.; Ouahab, L. Inorg. Chem. 1994, 33(18), 4016-22).
K~CO~W1,O39' (Entry 29; Walinsley, F. J. Chem. Ed. 1992, 69(11), 936-38).
JO
(NH~,)"Na(NaSb9W~,)0~~: (Entry ~ 1; Minami, N.; Hii-aoka, M.; Izmni, K.;
Ucluda, Y.

Japanese Patent JP 08113731 A2 1996, Chem. Ahstr. 1996, 12~, 117542).
Na~HzPMo~O~~: (Entry 48; Wouye, Y.; Tokutake, Y.; Kunihara, J.; Yoshida, T.;
Yamase, Y.; Nakata, A.; Nakamura, S. Chem. Pharm. Bull. 1992, 40, 80~-807).
K~CoVW,IO~": (Entry 28: Bas-Serra, J.; Todorut, et al. Synth. React. Inorg.
Met.-Org.
Chem. 1995, 25(6), 869-82).
H~NaI~[Fe(lll),(NaH~O)~(P~W150;6)~]: (Entry 25; Slugeta, S.; Mori, S.;
Watanbe, J.;

10 Baba, M.; Khenkiil, A. M.; Hill, C. L.; Sclmiazi, R. F. Antiviral Chem.
Chemother.
1996, 346-352).
IC6SiTiW~IO~": (Entry 33; Blasecki, J. W. Top. Mol. Org. Eng. 1994, 10, 373-38S).
15 K~Cu(ll)P~W1~06,: (Entry 17; Marcu, Gheorghe; Patrut, Adrian; Botar, Alexandru. Rev.
Chirp. (Bucharest) 1989, 40(11), 870-5).
(n-Dec~)6HMnNb3P2W,5062: (Entry 5; Gong, J., Chen, et al. Polyhedron, 1996, I5, 2273-7).
The following POMs were prepared by the following experimental procedures.
K~Si(NbO,)W,10~" (Entry 46): 1.0g of K,HNb60,6 was dissolved ui 75-mL of deionized H~O. To this solution, 2-mL of 30 ~Ic HzO~ was added. A few drops of HCl were added to briilg the pH to approximately 6. KrSiW,lO3y (15.8 g) was added, wluch resulted in gas evolution. To the swirling mixture, 25-mL of HBO
followed by 12-mL of 3M HCl were added. The color of the solution was yellow and the pH
was approximately 1. The mixture was stirred for an additional 30 minutes, then 14 g of solid KCl was added, which resulted u1 the formation of a pale yellow solid.
Tlle solid -was collected by filtration and dried resultitlg 114.7 g of KSSi(NbO.,)W"O~".

Na6SIVNbW,lO3~ (Entry 32): 6.64 g of K~Hb6019 was dissolved in 800-mL of H,O. To this solution, 80-mL, of 30 % H~O~ solution was added and the pH was adjusted to 6.0 with KOH. Solid K,,SiVW,~,039 was added slowly to produce a final pH
of 8.5. To this mixture, 40-mL of 3M HCl was added dropwise. The addition was stopped occasionally to agitate the solid. The solution was then stirred for 1~ mitmtes.
Additional 3M HCl (40-tnL) was added to give a pH of 1.5. The solution was stirred for 1 hour, and 160 g of solid KCl was added. The orange precipitate was filtered off and dried, yielding 40.85 g of K~SIVNbW1,O39. K~SIVNbW"O39 and water were passed through an Atnberlite IR-120 ion exchange column which was charged with NaCI. The volatiles were removed from the collected solution by vacuum to produce Na6SiVNbW,l039 as a yellow, crystalline solid. The Amberlite is a product of Rohm and Haas and was purchased from Aldrich.
Instrumentation. Gas chromatography analysis was conducted using a Hewlett-Packard Series 5890 Gas Chromatograph equipped with a flame ionization detector and fitted with a non-polar 5% PHME siloxane, 30 meter column.
Alternatively, the gas chromatograph was equipped with ati FID detector and a 5%
phenyl methyl silicone capillary column. Mass abundance determinations were performed using a HP 5890 GC with a 5% phenyl methyl silicone capillary column and a ~971A Mass Selective Detector. Gas chromatography/mass spectroscopy was performed using a Hewlett-Packard Series II 5890 Gas Chromatograph equipped with a 5971A mass selective detector and fitted with a non-polar 5% PHME siloxane, 25 meter column. For both GC and GC-MS, ntrogen was used as the carrier gas. In Examples 5 and 6, all reactions were montored using a Hewlett-Packard 6890 gas chromatograph with flame ionization detector and HP-5 (5% phenylmethylsilicone capillary column. UV-visible spectra were run on a HP 8452A Diode Array Spectrophotometer. The percentages of O2 of the reaction atmosphere were varied using a Series 810 Mass Trak flowmeter with dried argon as the other gas.

Example 1: Oxidation of CEES to CEESO by a POM/TSP Mixture under Ambient Conditions after 40 Days.
PFPE .#1511 (0.525 g) was combined with Ag~Na;_~PV~MoI~O~,~ (0.066 g, 3.81 x 10-5 mol) to give a 11 % weight/weight POM/cream mixture. The POM/cream mixture was placed in a 18 mL glass vial fitted with a poly(tetrafluoroethylene) (PTFE) stopper.
A sufficient amount of 2-chloroethyl ethyl sulfide (CEES) was added to the mixture to completely submerge the POM/cream mixture. After 40 days, 10 ~L of the CEES
solution surrounduig the POM/cream mixture was removed and diluted uito 100 ~L
of 2,2,2-trif7uoroethanol (TFE). GC-MS of this solution showed the presence of 2-chloroethyl ethyl sulfoxide (CEESO).

"., JJ
Example 2: Oxidation of CEES to CEESO by POM/TSP Mixtures under Ambient Conditions.
The CEES composition used in all trials was composed of 9.0 mL of CEES
combuied with 100 ~uL of 1,3-dichlorobenzene, where the 1,3-dichlorobenzene was added as an internal reference. Each POM/PFPE #1511 cream mixture (approximately 0.3 g) was smeared at the bottom of an 18 inL glass vial and fitted with a PTFE cap.
The CEES composition ( 1.0 mL) was then added and each vial was left undisturbed for several days under ambient conditions, with periodic GC analysis of the CEES/reference solution to check for CEESO formation. For GC analysis, 10 ~tL
of the CEES/reference solution surrounding the POM/cream mixture was diluted in ~L of TFE and analyzed. The results are shown iii Table 1.
Table 1 Entry Catalyst Weight Turnovers Percents after 9 Daysn 1 cream only N/A 0 2 AgNO~ 20.3 % 0 3 HSPV.,Mo ",0.," 5.8 % 0 4 HSPV.,Mo",0:,~, 20.8 % 0 5 AgvNa;_~PV~Mo",O~"5.6 % 0 6 Ag~Na~_~PV~Mo,~,O~,~,20.6 % 0 7 HAuCI~ 7.1 % 0 $ HAuCI~, AgN03, 7.6% 5 ° Weight Percent = (mass of POM (g)) / (mass of cream (g) + mass of POM
(g)) x 100 b Turnovers = (mol of CEESO/ mol of catalyst) x 100 ' Tlus mixture was composed of 1 equiv. of HAuCI~, 1.25 equiv. of AgCIO.~, and 0.75 equiv. of AgNO~. The weight percent is reported as the (weight of all components, g)/(weight of cream, g + weight of components, g) x 100 Examule 3: Catalytic Oxidation of CEES by POMs in 2,2,2-Trifluoroethanol after 14 Days under Ambient Conditions.
A CEES solution was prepared by mixing 85.8 mM of CEES; 1.51 x 10-5 to 1.82 x 10~' mol of catalyst; 100 E.tL 1,3-dichlorobenzene (uiternal standard);
and 85 mL
of 2,2,2-tritluoroethanol, at 25 °C under ambient air. In a typical run, 5.0 mL of the CEES solution was combiiled with enough catalyst to yield a CEES:POM ratio of 20:1, and the mixture was stiwed for 14 days. The results are shown ill Table 2.
Table 2 Entry Catalyst CEESO Turnovers 1 AgNO~ 0.42 2 AgYHS_APV~Mo,~,Oa"8.13 3 AgwH~_~PVMo"Oa" 1.18 4 NatPV~Mo".,0:~" 0.00 5 KSCo V W"O~" 0.00 6 KSCullPW"0,9 15.33 7 AgvK,~.,Ce(PW"0~9)~4.47 8 (NH~)~Ce(NOz),~ 18.53 9 A~,.K;.,.CunPW 15.21 Oz ° Turnovers = (mol of CEESO/ mol of catalyst) x 100 Example 4: Aerobic Oxidation of Acetaldehyde Catalyzed by Polyoxometalates.
In a 20 inL vial, 0.961 ininol acetaldehyde, 2 ing of POM, and pentane (intenial standard) (34.7 uL) were stirred iii 2 1L, of chlorobenzene under 20 inL (0.82 inmol) of O, at 298 K for 24 hours. Under these conditions, the POM was totally insoluble at all times during the reaction. For the cloth samples, the polyoxometalate was deposited as a 59c by weight solution of HBO and subsequently dried. BHT (2,6-di-tert-butyl-p-cresol) was used as a radical inhibitor in a 1.2 mol ratio versus POM. The aerobic oxidation of acetaldehyde by the POMs is shown in Table 3.

J

~ ~ 00 T ~" .-J

~

J
Q O N N oo O M ~ ~' N O ~
~ p~ ~ ., ~ N ~ ~J ~ N

J

Q

~

, 00 I~ M ~ M ~ M N d' 00 ,~ ap ~ N N M O N M oo O l~
a\ Q\ a1 00 ~ I~ Gv G~

_ ~

y U
U

M ~
Q

00 ~ M ~ ~ Vr 00 00 U ' ~ ~ ~ ' o 0 y "~~'~ .-~r...~ M M N ~-' !"' uj U

W t ~ v '~ 'n 'n 'n ~, ~ ~
N N N N N N ~ N N N N

a a > v a ~ ~~ a ~I C) O O 0 O
U U

3 > > 3 > >

o O ~'~ O o .. ~ U
U U ~ ~j U U o 0 a m z z ~ ~ oa z ~ x v v .-.- N M ~ v~ V t~ I~ o0 G~ O

O
~

Eduivalents of Acetaldehyde = moles of acetaldehyde (material)/moles of POM.
For the last three reactions (Entries S-8) after 24 h another 0.961 inmol acetaldehyde was added, and the suspension was allowed to stir for an additional 8 h. All values are averages of two experiments.
S 6 % Conversion = (moles of acetaldehyde consumed/moles of initial acetaldehyde) x 100.
' % Yield = (moles of acetic acid/moles of initial acetaldehyde) x 100.
'' Turnovers = [moles of acetic acid (iii the run with catalyst) - moles of acetic acid (iu the blank run without catalyst)]/moles of catalyst.
Example ~: Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase by Modified Polyoxometalates and Metal Compounds.
Tetrahydrotluophene (THT) (0.445 mmol, 0.64 M) and 1,3-dichlorobenzene 1S (internal standard) iii the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 mL of acetoiutrile in 20 mL vials under 1 atm O~ at room temperature. The aerobic oxidation of THT by modified polyoxometalates and metal compounds is shown in Table 4. In Entries 3-7 and 12, 2 x 10-6 mol of polyoxometalate or metal compound was placed in the vial before adding the reagent and internal standard. In Entries 8-14, the polyoxometalate and metal compound (Entries 11 and 14)or the metal compounds were placed iii the vial before the addition of the reagent and the internal standard. In Entries 8-14, 2 x 10-6 mol of each POM or metal compound was used in a 1/1 ratio.

JS

Table Entry Catalyst Tune (h) Yield % Tumoverb 1 Blank' 3.5 0 _ 2 Blank' 72'' 0 -3 HSPV~Mo",Oa" 3.5 0 0 4 HAuC 1:~ 3.5 0 0 5 HAuC I ~ 72d 0 0 6 (NH~)~Ce(N03)6 3.5 14 12 7 (NH~)~Ce(NO~)6 72d 26 100 8 (NH~,).,Ce(NO,)6 3.5 14 12 +
HSPV,MoI,,O4u 9 (NH;j~Ce(N03)6 + 3.5 67 57 HAuC I

10 (NH~)~Ce(N03)6 + 72d 76 293 HAuC l,~

11 (NH~),Ce(N03)6 + 3.5 65 56 HAuC 1; + HSPV.,Mo ",O,", 12 H~PtC I h 3 0 0 13 (NH~)~Ce(N03)6 + 3 25 21 H~PtC 16 14 (NH~)~Ce(N03)6 + 3 26 23 H.,PtClc + HSPV.,Moi~,Oa"

°Moles of THTO / moles of initial THT.
b Moles of THTO / moles of catalyst.
' No catalysts.
d More THT and O; added to the reaction system after 24 1w of uutial reaction.

Exarnule 6: Aerobic Oxidation of CEES in Liquid Phase by Modified Polyoxometalates and Metal Compounds.
CEES (0.337 ininol, 0.64 M) and 1,3-dichlorobeiizene (internal standard) iii the presence or absence of the polyoxometalate and/or metal compound were stirred iii 4 mL of acetonitrile in 20 inL vials under l atm of O~ at room temperature. The aerobic oxidation of CEES by modified polyoxometalates and metal compounds is shown in Table 5. In Entries 2, 3, 5, and 6, 2 x 10-6 mol of polyoxometalate or metal compound was placed iii the vial before adding the reagent. In Entries 4 and 7-12, the polyoxometalate and/or the metal compounds) (2 x 10-6 mol) were placed iii the vial before adding the reagent solution.

Table Entry Catalyst Tune ConversionYield Turnover' (day) % lcb 1 Blanks 3 0 0 -5 2 HAuC 14 3 0 0 0 3 HSPV.,Mo,~04~, 3 1 0 0 4 HAuCl~ + HSPV~MoI"O.",3 12 3 2 5 (NH4)ZCe(NO3)6 1 16 8 5 6 (NH~)~Ce(N03)6 3 26 18 12 10 7 (NH~)~Ce(N03)6 + HAuCl~1 28 9 6 g (N~I~)ZCe(N03)6 + 3 ~7 36 24 HAuCI~

9 (NH,~)ZCe(N03)6 + 1 47 24 15 H;PV,Mo,"Oa"

10 (NHa)ZCe(N03)6 + 3 64 41 27 HSPV~Mo,~,O~~

11 (NH4)ZCe(NO3)6 + HAuCl41 53 43 28 + HSPV,Mo",0~~, 15 12 (NH4)ZCe(N03)6 + HAuCl43 82 70 46 + HSPV~Mo,~,Oa~, Moles of CEES consumed / moles of initial CEES.
b Moles of CEESO (the GC response factor of CEESO is assumed the same as that of CEES) / moles of initial CEES.
20 'Moles of CEESO (the GC response factor of CEESO is assumed the same as that of CEES) / moles of catalyst.
d No catalyst.

Example 7: Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalate and HAuCI,.
Each POM (9.61 x 10-6 mol); HAuCI~ (4.8 x 10-5 mol); 1,3-dichlorobenzene (9.61 x 10-'' mol), and CEES (9.61 x 10-~' mol) were stirred i114 mL of acetoutrile under 20 mL (0.82 munol) of O, at 298 K. The aerobic oxidation is shown i11 Table 6.
Table Entry Catalyst Time Turnovers Time Turnoversb (Ii of CEES (h) of CEES O
) O

1 Na~PVMo"O~o 4 0 11 1.1 2 NaSPV,Mo,oO~o 4 5.0 11 10.6 3 Na6PV3Mo90~o 4 7.0 11 18.3 4 NaSH,PV~WsO~o 4 4.4 11 14.2 5 Na9PV6MobO~o 4 5.6 11 20.7 6 NaSCuPW1,039 4 59.2 11 83.6 7 HAuCl~ 4 0 11 0 Turnovers = moles of CEESO (catalyst runt - moles of CEESO (blank run))/moles of catalyst.

Examyle 8: Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgN03/HAuCI, System (non-POM system).
A metal compound solution was prepared by combining AgN03 ( 1.0 x 10-5 mol) and HAuCI~ (5.0 x 10-6 mol) in 1 inL of acetoiutrile. To this solution was added CEES
(3.0 x 10-3 mol). Upon addition of CEES to the solution, a white precipitate immediately formed. The precipitate is believed to be a silver containing salt, possibly coordinated to CEES. The solution was allowed to stir for 100 hours, at which time there was loss of CEES iii the solution based on gas chromatography. The filtrate was taken to dryness, and a solution contaiiW g excess CEES in acetoilitrile was added to the yellow oily residue. Gas chromato'>raphy of the solution confirmed the formation of CEESO. The results are shown in Table 7 (entries 1-7).
Examine 9: Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNO~/AgCIO,/HAuCI; System (non-POM system).
A 20 inL vial fitted with a PTFE septum was purged with 1 atm of O~. To this vial were added by syringe, 0.035 inL of AgN03 (0.1013 M in acetonitrile);
0.060 inL
of AgCIO~ (0.1138 M in acetonitrile); and 0.100 mL HAuCl4 (0.0477 M in acetonitrile), and the total volume was adjusted to 1 mL with the addition of HPLC grade acetonitrile.
To this solution, 0.36 inL (2.86 x 10-3 mol) of CEES were added to the solution, and the formation of CEESO was moiutored over time by gas chromatography using 1,3-dichlorobenzene as the internal reference. The results are suininarized in Table 7 (Entries 8-11).

Table 7 Entrv Catalyst Tune Turnover"
(hrs) 1 2 A~NO, 100 0 2 2 AgCIO~ 100 0 3 1 HAuCI~ 100 0.9 4 ~ AgNO; + 1 HAuCI~ 1 13.0 2 A~NO~ + 1 HAuCI~ 2 21.3 6 2 A~N02 + 1 HAuCI 24 83.5 7 2 AgNO~ + 1 HAuCI~ 100 146.3 8 0.75AgN0; + 1.25A_~Cl~ 1 38.3 + IHAuCI, 9 0.75AgN0, + 1.25AgC1~ + 2 50.2 IHAuCI~

10 0.75AgN0, + 1.25AgCl~ + 24 141.9 IHAuCI~

11 0.75A~N0~ + 1.25A~C1 + 100 208.7 IHAuCI

a Moles of CEESO/ moles of catalyst (catalyst is based on moles of HAuCl4 used).

Example 10: Aerobic Oxidation of CEES by POM/HAuCI, and Metal Compound/HAuCI, SystenLS.
One equivalent of the POM or metal compound was combined with five equivalents of HAuCI~ in acetonitrile, wherein the total volume was 1 mL. To this solution, 100 equivalents of CEES was added. The reaction was conducted under one atm of O~ at 298 K. The number of turnovers were calculated at 4 and 11 hours, and the results are summarized iii Table 8a.
Table 8a Entrv POM or Metal Com pound Turnovensa Turnoversb 1 Na"PV Mo O 5.6 20.7 2 Na~CuPW Oz 59.2 83.6 3 Na~MuPW Oz 6.5 29.0 4 KSCoPW O, 38.9 71.9 5 (n-Dec ) HMnNb,P~W SO ~ 5.1 27.9 6 KSPMnW O~ 51.8 76.5 7 NaaPV~Mo O 5.0 10.6 8 Na PVzMo O 7.0 18.3 9 NaSH~PV Mo O 4.4 14.2 10 K ~Cuz(W PO~ )., 5.1 12.2 11 Na PVW O~ 1.6 8.7 12 NaSFeSiW O 0.9 4.6 13 Na~SiVW O 0.0 2.3 14 K Ni. P~W O 3.5 7.5 15 K,Co(II)P~W O 1.0 2.5 16 K ,Pd,(PW O, )~ 4.2 6.4 17 K Cu II)P.,W O 2.0 4.7 18 Na PVMo O 0.0 1.2 19 NazPMo ~O 0.0 0.1 20 HSPV~W O. 0.0 1.4 21 H PV,W O. 0.0 1.2 22 H PV4W,0 0.0 0.9 23 HAuCI 0.0 0.0 24 Na P W Cu O , 1.5 1.5 25 H~Na . Fe(III)~(NaH~O)~(P~W1.0 1.6 ;OS )~

26 K Ce(PW O, )~ 0.6 0.7 27 K CuSiW O~ 1.0 1.1 28 K,CoVW O 1.3 1.1 29 K~Co,W O, 1.5 1.0 30 Na CuSiW Oz 1.1 1.1 31 NasNiPW O~ 0.6 0.9 32 Na SiVNbW Oz 0.7 0.6 33 K~SiTiW" O ", ~ 0.6 I 0.4 I

34 K(NH l RuBW Oz 0.7 0.9 35 Na,AsW ~O 0.7 0.2 36 FeSiW Oz 0.9 0.7 37 K,NiP~W O 0.9 0.9 38 (Me N) (CozSiW~O ) 1.8 1.9 39 K -Co P,W ,O , 1.3 1.6 40 Na,V O~ 1.8 1.7 41 K a (PW Oz. )~ 1.3 1.4 42 KuP~W (NbO~) 1.1 0.9 10 43 (NH ),P~FeW O 0.6 0.5 44 K Mn(II)P~W O 1.0 0.8 45 K ~W ,Cu O , 1.2 1.9 46 KSSi NbO~)W O 0.9 0.7 47 K ,P~W ,NizO 1.0 1.8 15 48 Na,H~Mo O 0.8 0.9 49 Na P Wz n(II) O ~ 1.1 1.4 (NH ) P~W O ~ 0.0 0.3 ~ 1 (NH ) Na(NaSb~,W~ )O~, 0.5 1.8 52 CuCh 0.U 0.4 20 53 FeCI 0.3 0.5 Turnovers after 4 hours b Turnovers after 11 hours 25 Additional POM and/or metal compounds that were tested can be found in Table 8b.
Table 8b Entry Com ound A Com ound B

30 1 5 HAuCl~, 2 Na PVMo O ~, 3 Na. PVMo O " 5 HAuCI~

4 NaSPV~Mo .,O "

NasPV~Mo "O~" 5 HAuCl4 35 6 Na~PV~Mo90 "

7 Na~PV~Mo~04" 5 HAuCI~

$ NaSH~PV~,Mo~O~~

9 NaSH~PV~Mo~O~" 5 HAuCI~

10 Na<,PVfiMofiO~"

40 11 Na<,PVfiMohO ~, 5 HAuCI

12 Na PVW O~n 13 Na PVW O " 5 HAuCI

14 NazPMo ~O

1~ Na,PMo,~O.,~, 5 HAuCl 16 Na~CuPW O,~ 5 HAuCl.

17 (TBAyCuPW O,~ 5 HAuCI

18 Na:MnPW O

19 NaaMmPW O~ 5 HAuCI

20 Na~FeSiW O

21 Na~FeSiW 0~~, 22 NaSSiVW O "

23 Na;SiVW O " 5 HAuCI

24 Na~PV~W "O

?j Na~PV~W "O " 5 HAuCI, 26 Na PVzWQO."

2'7 Na PV~WqO ~, 5 HAuCI

2g Na PV W O "

29 Na PV W,;O " 5 HAuCI

30 Na P W~~Cu O

31 Na P Wz"Cu O ., 5 HAuCI

32 H~Na . [Fe(III),(NaH~O)~(P~W
505 )~

33 H~Na . (Fe(III)~(NaH~O)~(P~W 5 HAuCI
5056) 34 K "Ce(PW O~ )., 35 K ~,Ce(PW OzQ)~ 5 HAuCl 36 K CuSiW O~Q

3'7 K CuSiW O~ 5 HAuCl 3g K~CoVW O~Q

39 K~CoVW O~ 5 HAuCl 40 K:CoPW O

41 K:CoPW O~~ 5 HAuCI

42 K,Co~W 0~9 43 K,;Co~W 0~9 5 HAuCI

44 (NDec jfiHMnNbzP~W 50 45 (NDec,)fiHMnNb,P,,W ;O ., 5 HAuCI

46 Na CuSiW 0~~, 4'7 Na CuSiW O~ S HAuCI

4g NaSNiPW O

49 Na~NiPW Oz 5 HAuCI

50 NafiSiVNbW O

51 NafiSiVNbW110~ 5 HAuCI

52 K~PMnW O

j3 K:PMnW O~ 5 HAuCI

54 K~SiTiW O ~, 55 K~,SiTiW O." 5 HAuCI

56 K(NH ) RuBW O

K(NH )fiRuBW O~ S HAuCI

Sg NazAsW ~O

j9 Na,AsW ,O " ~ HAuCI

60 KfiFeSiW O

61 FeSiW O~ 5 HAuCI

62 K~NiP,W O

$ 63 KuNiP,W O 5 HAuCI

64 (Me N) "(Co~SiW~O. ,-~I ) 65 (Me N) "(Co,SiW~O. "H ) 5 HAuCI

66 K ~,Co P,W O a 67 K "Co P,W O 5 HAuCI

68 Na~V ~0., 69 Na~V ~O~ 5 HAuCl 70 K "(Mn )(PW~Oz )~

71 K "(Mn )(PW~O~ )~ 5 HAuCl 72 K .,Cu,(W~,PO~ )., 1 ~ 7 3 K ~Cuz(W9POz )., 5 HAuCI

74 K "Ni P,W O

75 K "Ni P,W O 5 HAuCI

76 K~P~W (NbO~) 77 K~P,W (NbO~) 5 HAuCI

78 (NH ) P~FeW O

79 (NH. ) P~FeW O 5 HAuCI

g0 K~Co(II)P~W O

g 1 K Co(II)P~W O 5 HAuCI

82 K ~Pdz(PWqO~ )~

83 K ~Pd~(PW~O~ )~ 5 HAuCI

g4 K Mn(II)P,W O S HAuCI

g5 K ~,P.,W ,Cu O 5 HAuCI.

g6 K~Cu(II)P~W O 5 HAuCI.

g7 KSSi(NbO.,)W O. ~, 5 HAuCI

88 K ~P,W uNi,O S HAuCI

g9 NazHfiMo O~ 5 HAuCI.

90 Na P. W;"Mn(II) O ~ 5 HAuCI

91 (NH ) P~W ,O .,+SHAuCI 5 HAuCI

92 (NH ) Na(NaSb9W, )O~ 5 HAuCI

93 5 Cu(acetate)~

94 NaSPV,Mo "O " 5 Cu(acetate), 95 5 Co(II)Acac 96 NasPV,Mo ~,O " 5 Co(II)Acac 5 Fe(III)Acac 9g Na~PV,Mo "O " 5 Fe(III)Acac 99 5 MnO

100 Na~PV,Mo ~,0 ,-, 5 MnO

101 5 CuCh 102 Na:PV,Mo O 5 CuCh 103 5 FeClz 104 Na;PV~Mo "O " 5 FeCI, 105 5 CrCI, 106 Na;PV,Mo "O " ~ CrCI, 107 5 CeClz 108 Na;PV,Mo ~0 ,., 5 CeCI, 109 Na~,PV MofiO " 5 FeClz 110 Na~,PV MofiO " 5 CuCh 111 N PV MofiO ~

112 K .,Pd,(PW~O., )., 5 FeCI:

113 K .,Pd.~(PW~,O~ )., 5 CuCI., 114 K ~Pd,(PWQO~ )~

115 Na;CuPW O.

116 Na;CuPW O~ 5 Cr(NO,), 1 S 117 5 CrNO.;

118 Na;CuPW O~~ 5 Co(NOz)~

119 5 Co(NO,) 120 5 Zn(NO,) 121 Na;CuPW O~ 5 Zn(NO,) 122 NaSCuPW O-~Q 5 Cu(NO,) 123 5 Cu(NO,) 124 NaSCuPW O~ 5 Zn(N03)3 125 NaSCuW O~Q 5 Cu(acetate)~

126 Na;CuW O~Q 5 Fe(acetate)~

127 NaSCuW 11 O~ 5 MnO

128 5 NaNO, 129 Li;PVW O " 5 HAuCI

130 A NO~

131 A NO~ 5 HAuCI.

132 NaNp~ 5 HAuCI

133 NaClO 5 HAuCI

134 A Cl0 5 HAuCI

135 LiClO 5 HAuCI.

136 5 (NH. )~Ce(NO~) 137 Na;PVMo O ~ 5 (NH )~Ce(NO~) 138 Na~CuPW O~Q 5 (NH. )~Ce(NO~) 139 Na;PVMo O " 5 CoSO

140 Na;CuPW O~~ S CoSO

141 Na;PVMo 0 ,., 5 Ce(SO )~

142 NaSCuPW O,~ 5 Ce(SO )~

143 Na;PVMo O " 5 H~PtCh 144 Na;CuPW110,~ 5 H,,PtC

145 Na;PVMo O " 5 Pd(NOz)~

146 Na;CuPW O 5 Pd(NO,h 147 NasPVMo O ~, 5 RhCl, 148 Na~CuPW O,~ 5 RhCI, 149 Na~PVMo O " 5 ReO

150 Na~CuPW O~Q 5 ReO

Examine 11: Oxidation of CEES to CEESO by Metal Compounds (non-POM).
(a) Deternuning the Stoichiometry of O~ in the Catalytic Oxidation of CEES. A Schlenk flask fitted with septum was attached to a manometer and purged S with O~. To the flask containing 1.36 mL of acetonitrile, solutions (all in acetonitrile) of 0.200 mL of (NEt4)AuCl2 (5.0 x 10-6 mol), 0.188 mL of AgC104 solution (1.0 x 10-5 mol), 0.094 mL NBu4N03 solution (5.0 x 10-6 mol), 0.166 mL 1,3-dichlorobenzene (7.5 x 10-4 mol) (internal standard for GC), and 0.084 mL CEES (3.8 x 10-4 mol) were added.
The consumption of OZ was recorded, and aliquots were periodically taken a~ld injected 10 into the GC. The stoichiometry of OZ consumption was established using a manometer to determine the amount of O~ consumed while simultaneously monitoring CEESO
formation with a gas chromatograph. Figure 1 reveals that one equivalent of the CEESO formed corresponds to 0.5 equivalents of O2.
15 (b) Cream Formulation Reactions. Experiments were performed usilig the perfluorinated oil, Galden D02, and Fomblin perfluorinated polyether oil as "solvent,"
both of which are components of the cream. Samples were prepared by adding components together, dissolving in a minimal amount of acetonitrile, stirring for 10 minutes, and then removing the solvent by vacuum.
In all the cases where (NEt4)AuCI,, was used as the gold compound, 1.25 x 10' mol of the gold compound was used. The other components which were varied in quantities were NBu4N0~ ( 1.25 x 10-5 - 1.25 x 10-4 mol), and a CuS 04 ( 1.25 x 10-5 -1.25 x 10-4 mol) (Table 9). The gold, copper, and/or nitrate salts were admixed in acetonitrile, then the solvent was removed by vacuum. After the mixture was dried by vacuum in a Schlenk flask, the flask is attached to the manometer and the apparatus is purged with OZ. After purging, 7.0 mL of the perfluorinated fluid was added to the flask. The system was equilibrated to atmospheric pressure then sealed from any external atmosphere. Through the septum 0.05 mL (4.2 x 10-4 mol) of CEES was added and the system was monitored for Oz consumption. Table 9 shows CEESO formation after 1 hour using various cream formulations (7.0 mL Galden D02).

[Au] [NOD] [Cu+'] (CEESO formed]

0 1.25 1.25 3.62 1.25 1.25 1.25 5.80 p 2.50 2.50 x.00 1.25 2.50 2.50 8.06 0 5.00 7.25 8.06 1.25 5.00 7.25 16.20 0 10.00 12.50 10.60 1.25 10.00 12.50 18.70 'All concentrations expressed in lUJ mol.
Another experiment was performed using Fomblin as the "solvent." In this case, 1.0 mL of Fomblin, O.OOSg of (NEt,)AuCh (1.25 x 10-5 mol), was admixed in with varying amounts of CuSO:~, MnSOa, VOSO~, Ti(S04)2, Fe~(SOa)3, NiSO;~, ZnSO,~, Cr~(SO~)3, MgSO.,, CoS04, Pd(N03)~, Na,S03, and/or NBu4N03. The catalyst was prepared and the experiment was performed using the same method as earlier reported.
Table 10 reveals CEESO formation i1i PFPE Surfactant ( 1.0 mL Fomblin) using various metal compounds. The metal compounds are abbreviated for simplicity sake. For example, metal compound lAu/1Cu(II)/1N0~ was prepared by mixing one equivalent each of (NEt~)AuCI." CuSO~, and NBu~NO~.

Metal Compound Turnovers of CEESO after 10 nun (based on Au) lAu/1Cu(II)/1N03 17 lAu/2Cu(II)/1N03 28 lAu/1Cu(II)/2N0~ 115 lAu/2Cu(II)/2N03 155 lAu/1Cu(II)/3N0~ 155 lAu/1Fe(III)/3N0~ 142 lAu/2Mn(II)/3N03 164 lAu/2Ti(IV)/3N03 142 lAu/2Co(II)/3N0~ 177 lAu/4N03 185 lAu/2Cu(II)/3N03 181 lAu/2Cu(II)/4N03 195 lAu/3Cu(II)/3N0~ 165 2Cu(II)/3N03 28 lAul3N03 150 1Fe(III)/3N03 19 lAu/2V(IV)/3N03 160 lAu/2Ni(II)/3N03 140 lAu/2Ag(II)/3N0, 184 Figure 2 shows CEESO formation as a function of time for lAu/2Cu(II)/3N03, 2Cu(II)/3N03, and lAu/3N0~. From the data in Table 10 and Figure 2, it is clear that there was a synergistic effect when certain redox active metals were added to the Au/NO; system For example, one of the most active systems, lAu/2Cu(II)/3N03 was 3.8 and 6.5 tunes more effective after 10 minutes of reaction time than when oilly 2 of SJ
the components were used, lAu/3N03 and 2Cu(II)/3N03 respectively. Also, Figure shows that inubition was less pronounced 11 the three component system.
Another important aspect of this system is that the oxidation teminates to the sultoxide without continued oxidation to yield the su)fone. Tlus is important as it relates to toxicity issues as it is believed that the sultoxide of mustard has is sigWicantly less toxic than the corresponding sulfone.

Examule 12: Synthesis, Characterization, and Reactivity of Organo-Modified POMs (a) Synthesis of A~,_fVf0,3~(OCH,I CCHz~I (A~ Me can) Na,,[V601~((OCH~)3CCH3)2] (Na Me cap, 0.480 g) was dissolved in - 4 mL of distilled water. Tllis was filtered over a medium fritted fumel to remove any undissolved POM. To the dark red-orange solution was added AgNO~ (0.215 g) with stirring. An orange-red precipitate formed immediately. The crude product was separated by suction tiltratioii over a medium frit, washed with room temperature water and ether. The product was dried over night in vctcuo. Crystals were grown by diffusing ether into an acetonitrile solution of the crude product at room temperature.
s'V NMR (0.04 g dissolved in 2.0 mL of MeCN) -499.232 ppm (singlet). Solid-state IR
(KBr pellet, 1400 - 400 cm 1) 1452.11 (m), 1390.47 (w), 1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs), 820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).
(b) Synthesis of Cof V~0,3~OCH,~CCH~~,1 (Co Me can) The same procedure for the synthesis of Ag2[V6013((OCH~)3CCH3)~] was followed, except CoCh was added to foam the Co salt of the POM. Crystals were grown from diffusing isopropyl alcohol into a MeCN solution of crude product.
"V
NMR (0.04 g dissolved in 2.0 W L of MeCN) -500.3 ppm (singlet). Solid-state IR
(KBr pellet, 1400 - 400 cW ') 1452.11 (m), 1390.47 (w), 1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs), 820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).
(c) Reactivity of Or~ano-Modified POMs Table 11 lists the oxidation of tetrahydrothiophene (THT) by t-butylhydroperoxide (TBHP) catalyzed by the transition metal salts of Me-capped V6013~
The oxidations were performed by dissolving the particular salt in acetonitrile to give lightly colored orange-yellow solutions. The solutions were placed in 24-mL
vials JJ
fitted with PTFE septa. THT and TBHP were then syringed iii and dle reactions were monitored by quantitative GC. Reactions were stirred at room temperature.
Table 11. ROOIll Temperature Oxidation of THT to THTO by TBHP Catalyzed by Transition Metal Salts of Me Capped V6013 after 48 Hours.
Catalyst Mols of Mols of Turnover catalyst, THTO, x number x 10-h 10~' Na Me ca 1.76 6.03 34.3 A~ Me ca 1.87 5.59 30.0 Co Me ca 1.61 6.33 39.3 A~NO.: 14.1 1.06 0.754 CoCI, 39.5 2.25 0.570 blanks NA 0 0 '~blanlc reaction:of MeCN, inL of THT,10 inL ernal reference.
3.0 inL 0.018 0.0 of int bTurnover number = (cools of THTO)/(mols of catalyst) x 100 Throughout this application, various publications are referenced. The disclosures of these publications ui their entireties are hereby incorporated by reference into this application iii order to more fully describe the state of the art to which this invention pertains.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present ilivention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary oily.

Claims (80)

What is claimed:

1. A polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H5PV2Mo10O40;
K5Si(H2O)Mn III W11O39; K4Si(H2O)Mn IV W11O39; K5Co III W12O40; or H6(PV3Mo9O40).

2. The composition of claim 1, wherein the polyoxometalate has the formula 1 of [V k Mo m W n Nb o Ta p M q X r O s]y-[A], wherein M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, or tantalum; X is at least one p-, d-, or f-block element, wherein X is not oxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o is from 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; s is sufficiently large that y is greater than zero; and y is greater than zero, wherein the sum of k, m, n, o, and p is greater than or equal to four; and the sum of k, m, and q is greater than zero, and A is one or more different counterions.

3. The composition of claim 2, wherein M comprises a d-block element having at least one d-electron or a f-block element having at least one f-electron.

4. The composition of claim 2, wherein M comprises titanium, chromium, manganese, cobalt, iron, nickel, copper, rhodium, silver, palladium, platinum, mercury, or ruthenium.

5. The composition of claim 2, wherein M comprises manganese.

6. The composition of claim 2, wherein M comprises cobalt.

7. The composition of claim 2, wherein M comprises ruthenium.

8. The composition of claim 2, wherein M comprises copper.

9. The composition of claim 2, wherein X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron.

10. The composition of claim 2, wherein A comprises a quaternary ammonium cation; proton; alkali metal cation; alkaline earth metal cation; ammonium cation; d- or f-block metal complex, or a combination thereof.

11. The composition of claim 2, wherein A comprises cerium, silver, gold, platinum, or a combination thereof.

12. The composition of claim 2, wherein A comprises hydrogen, lithium, sodium, potassium, or a combination thereof.

13. The composition of claim 2, wherein A comprises (1) hydrogen, lithium, sodium, potassium, or a combination thereof, and (2) cerium, silver, gold, platinum, or a combination thereof.

14. The composition of claim 2, wherein A is silver.

15. The composition of claim 2, wherein A is gold.

16. The composition of claim 2, wherein A is platinum.

17. The composition of claim 2, wherein A is cerium.

18. The composition of claim 2, wherein A is cerium and silver.

19. The composition of claim 2, wherein A is cerium and platinum.

20. The composition of claim 2, wherein A is cerium and gold.

21. The composition of claim 2, wherein A is silver and gold.

22. The composition of claim 2, wherein A is not hydrogen or potassium

23. The composition of claim 2, wherein s is from 19 to 460.

24. The composition of claim 2, wherein the sum of k and q is greater than or equal to one, the sum of k, m, n, o, p, and q is 12, and s is 40.

25. The composition of claim 2, wherein k is not zero.

26. The composition of claim 2, wherein q is not zero.

27. The composition of claim 1, wherein the polyoxometalate has the formula [X g+V b j+M c h+Z12-b-c i+O x]u-[A], whereui X is at least one p-, d-, or f-block element;
g is greater than or equal to 2; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; h is from 1 to 7; i is from 5 to 6; j is from 4 to 5; x is 39 or 40; Z is tungsten, molybdenum, nobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6; a is from 3 to 9; and A is a counterion.

28. The composition of claim 27, wherein the polyoxometalate has the formula [X g+V b j+Z12-b i+O40]u-[A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and u is from 3 to 9.

29. The composition of claim 27, wherein the polyoxometalate has the structure [X g+M c h+Z12-c i+O40]u-[A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; c is from 1 to 6, and u is from 3 to 9.

30. The composition of claim 1, wherein the polyoxometalate has the formula [X2 r+V u s+M v t+Z18-u-v y+O z]w-[A], wherein X is at least one p-, d-, or f-block element;
r is greater than or equal to 1; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; t is from 1 to 7; s is from 4 to 5; Z is tungsten, molybdenum, niobium, or a combination thereof; u is from 0 to 9; v is from 0 to 9; y is from 5 to 6; z is 61 or 62;
w is greater than or equal to 4; and A is a counterion.

31. The composition of claim 30, wherein the polyoxometalate has the formula [X2 r+V u s+Z18-u y+O62]w-[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to 9; and w is greater than or equal to 4.

32. The composition of claim 30, wherein the polyoxometalate has the formula [X2 r+M v t+Z18-v y+O62]w-[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and w is greater than or equal to 4.

33. The composition of claim 1, wherein the polyoxometalate has the formula [YV p Z12-p O40][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion.

34. The composition of claim 1, wherein the polyoxometalate further comprises an organic group, an organosilyl group, an other p-block organometallic group, or a d-block organometallic group, wherein the organic group, the organosilyl group, the other p-block organometallic group, or the d-block organometallic group is bonded to the polyoxometalate.

35. The composition of claim 1, wherein the polyoxometalate comprises K8Co2W11O39; K8SiCoVW10O39; K7SiCoVW10O39; Na8Co2W11O39;
Ag5PV2Mo10O40; Ag6PV3Mo9O40; Ag8CoVW11O40; Ag12Ce(PW11O39)2;

Na12Ce(PW11O39)2; K12Ce(PW11O39)2; Na5PCuW11O39; H6PV3Mo40; or K5Cu II PW11O39.

36. The composition of claim 1, wherein the polyoxometalate comprises a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a pre-modified polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, a copper compound, a cobalt compound, or a combination thereof.

37. The composition of claim 36, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40 and (2) the cerium compound is (NH4)2Ce(NO3)6.

38. The composition of claim 36, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; (2) the cerium compound is (NH4)2Ce(NO3)6; and (3) the gold compound is HAuCl4.

39. The composition of claim 36, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; (2) the cerium compound is (NH4)2Ce(NO3)6; and (3) the platinum compound is H2PtCl6.

40. The composition of claim 36, wherein (1) the pre-modified polyoxometalate is Na5PV2Mo10O40 and (2) the silver compound is AgNO3, AgClO4, or a combination thereof.

41. The composition of claim 36, wherein (1) the pre-modified polyoxometalate comprises Na4PVMo11O40; Na5PV2Mo10O40; Na6PV3Mo9O40; Na5H2PV4W8O40;
Na9PV6Mo6O40; Na5CuPW11O39; Na5CuPW11O40; Na5MnPW11O40;
K5CoPW11O39; (ndec4)6 HMnNb3P2W15O62; or K12Cu3(W9PO34)2, and (2) the gold compound is HAuCl4.

42. The composition of claim 1, wherein the topical carrier comprises a perfluorinated polymer.

43. The composition of claim 1, wherein the topical carrier comprises a perfluorinated polymer and at least one unfluorinated polymer.

44. The composition of claim 1, wherein the topical carrier comprises a perfluoropolyether.

45. The composition of claim 1, wherein the topical carrier comprises a perfluoropolyether and at least one unfluorinated polyether.

46. The composition of claim 1, wherein the polyoxometalate is from 0.01 to 95 %
by weight of the polyoxometalate topical composition.

47. The composition of claim 2, wherein the topical carrier is a perfluoropolyether and A is silver.

48. A method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of claim 1 with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

49. A method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of claim 36 with the enviromnent containing the contaminant for a sufficient time to remove the contaminant from the environment.

50. The method of claim 48, wherein the environment comprises the gas phase.

51. The method of claim 48, wherein the environment comprises the liquid phase.

52. The method of claim 48, wherein the contaminant comprises a chemical warfare agent.

53. The method of claim 48, wherein the contaminant comprises an aldehyde, an aliphatic nitrogen compound, a sulfur compound, an aliphatic oxygenated compound, a halogenated compound, an organophosphate compound, a phosphonothioate compound, a phosphorothioate compound, an arsenic compound, a chloroethyl-amine compound, a phosgene compound, a cyanic compound, or a combination thereof.

54. The method of claim 48, wherein the contaminant comprises acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine, styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide, carbon monoxide, or a combination thereof.

55. The method of claim 48, wherein when the environment is the gas phase, the contaminant is removed from the gas phase at from -50 °C to 250 °C and at a pressure of from 0.1 ppb to 30 atm.

56. The method of claim 48, wherein when the environment is the gas phase, the contaminant is removed from the gas phase at from 0 °C to 105 °C
and at 1 atm.

57. A method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the enviromnent containing the contaminant for a sufficient time to remove the contaminant from the environment.

58. A modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

59. The modified polyoxometalate of claim 58, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; Na5PV2Mo10O40; Li5PV2Mo10O40;
K5PV2Mo10O40, or a combination thereof, and (2) the cerium compound is (NH4)2Ce(NO3)6.

60. The modified polyoxometalate of claim 58, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; Na5PV2Mo10O40; Li5PV2Mo10O40;
K5PV2Mo10O40, or a combination thereof; (2) the cerium compound is (NH4)2Ce(NO3)6; and (3) the gold compound is HAuCl4.

61. The modified polyoxometalate of claim 58, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; Na5PV2Mo10O40; Li5PV2Mo10O40;
K5PV2Mo10O40, or a combination thereof; (2) the cerium compound is (NH4)2Ce(NO3)6; and (3) the platinum compound is H2PtCl6.

62. The modified polyoxometalate of claim 58, wherein (1) the pre-modified polyoxometalate is H5PV2Mo10O40; Na5PV2Mo10O40; Li5PV2Mo10O40;
K5PV2Mo10O40, or a combination thereof, and (2) the silver compound is AgNO3.

63. The modified polyoxometalate of claim 58, wherein (1) the pre-modified polyoxometalate independently comprises Na4PVMo11O40; Na5PV2Mo10O40;
Na6PV3Mo9O40; Na5H2PV4W8O40; Na9PV6Mo6O40; Na5CuPW11O39;
Na5CuPW11O39; Na5MnPW11O40; K5CoPW11O39; (n-DeC4)6HMnNb3P2W15O62; or K12Cu3(W9PO34)2, and (2) the gold compound is HAuCl4.

64. A polyoxometalate comprising K8Co2W11O39; K8SiCoVW10O39;
K7SiCoVW10O39; Ag5PV2Mo10O40; Ag6PV3Mo9O40; Ag8CoVW11O40; or Ag12Ce(PW11O39)2.

65. A modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

66. The modified material of claim 65, wherein the metal compound comprises a cerium compound, a platinum compound, a silver compound, a gold compound, or a combination thereof.

67. The modified material of claim 65, wherein the metal compound is a gold compound.

68. The modified material of claim 65, wherein the metal compound is a platinum compound.

69. The modified material of claim 65, wherein the metal compound is a cerium compound.

70. The modified material of claim 65, wherein the metal compound is a silver compound.

71. The modified material of claim 65, wherein the metal compound is a cerium compound and a platinum compound.

72. The modified material of claim 65, wherein the metal compound is a cerium compound and a gold compound.

73. The modified material of claim 65, wherein the metal compound is a silver compound and a gold compound.

74. The modified material of claim 65, wherein the material is a topical carrier and the metal compound is a silver compound.

75. The modified material of claim 65, wherein the topical carrier is a perfluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof.

76. The modified material of claim 65, wherein the topical carrier is a perfluoropolyether and the silver compound is AgNO3, AgClO4, or a combination thereof.

77. The modified material of claim 65, wherein the metal compound comprises gold, chloride, and nitrate.

78. The modified material of claim 65, wherein the metal compound comprises mixing (1)(NEt4)AuCl2 and (2) CuSO4, MnSO4, VOSO4, Ti(SO4)2, Fe2(SO4)3, NiSO4, ZnSO4, Cr2(SO4)3, MgSO4, CoSO4, Pd(NO3)4, Na3SO3, or NBu4NO3, or a combination thereof.

79. An article comprising the modified material of claim 65.

80. A method for removing a contaminant from an environment, comprising contacting a modified material of claim 65 with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.