EP1224024A2 - Matieres en polyoxometalate, matieres contenant du metal, et procede d'utilisation correspondant - Google Patents

Matieres en polyoxometalate, matieres contenant du metal, et procede d'utilisation correspondant

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Publication number
EP1224024A2
EP1224024A2 EP00970807A EP00970807A EP1224024A2 EP 1224024 A2 EP1224024 A2 EP 1224024A2 EP 00970807 A EP00970807 A EP 00970807A EP 00970807 A EP00970807 A EP 00970807A EP 1224024 A2 EP1224024 A2 EP 1224024A2
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EP
European Patent Office
Prior art keywords
compound
polyoxometalate
composition
modified
contaminant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00970807A
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German (de)
English (en)
Inventor
Craig Hill
Ling Xu
Jeffrey T. Rhule
Eric A. Boring
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Emory University
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Emory University
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Publication date
Application filed by Emory University filed Critical Emory University
Publication of EP1224024A2 publication Critical patent/EP1224024A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D5/00—Composition of materials for coverings or clothing affording protection against harmful chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/24—Organic substances containing heavy metals
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/26—Organic substances containing nitrogen or phosphorus
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

  • the present invention relates to materials containing a polyoxometalate or a metal compound, wherein the metal compound is not a polyoxometalate.
  • the invention further relates to methods for removing a contaminant from an environment by contacting the environment with a polyoxometalate material or a non-polyoxometalate material.
  • Creams also referred to as topical skin protectants (TSPs) have been developed to protect soldiers from the threat 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 normal skin functions.
  • a preferred TSP affords protection against CWAs and other toxic or irritating materials in all of the forms in which they might be encountered (e.g., liquid, aerosolized liquid and vapor).
  • CWAs 2,2'-dichlorodiethylsulfide (also known as "HD” or "sulfur mustard”), which was first used during World War I.
  • U.S. Patent No. 5,607,979 to McCreery discloses topical creams formed from about 35% to about 50% fine particulates of certain poly(tetrafluoroethylene) (PTFE) resins dispersed in pertluorinated polyether oils having viscosities from about 20 cSt to about 350 cSt.
  • PTFE poly(tetrafluoroethylene)
  • the creams afford protection against chemical warfare agents such as sulfur mustard (HD), lewisite (L), sulfur mustard/Lewisite mixtures (HL), pinacolyl methylphospho no fluoridate (so man or GD), thickened so man (TGD), and O-ethyl- S-2-diisopropylaminoethyl methylphosphonothiolate (VX).
  • chemical warfare agents such as sulfur mustard (HD), lewisite (L), sulfur mustard/Lewisite mixtures (HL), pinacolyl methylphospho no fluoridate (so man or GD), thickened so man (TGD), and O-ethyl- S-2-diisopropylaminoethyl methylphosphonothiolate (VX).
  • 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.
  • POM polyoxometalate
  • U.S. Patent No. 5,356,469 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 phospho silicate pigment, and at least one heteropoly anion.
  • the metal pigment particles possess increased stability against attack by water.
  • 4054127 to Terumo Corp. discloses the use of heteropoly acid salts as anti-tumor agents.
  • the heteropoly acid salts can be administered in the form of a powder or suspended in solution.
  • 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 containing a polyoxometalate to remove a contaminant from the environment.
  • 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 environment.
  • POM polyoxometalate
  • 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 environment.
  • 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 time using lAu/2Cu/3NO 3 ; 2Cu/3NO 3 ; and lAu/3NO 3 .
  • 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 5 PV,Mo, professionO 4() ; K,Si(H 2 0)Mn W u 0 39 ; K 4 Si(H 2 O)Mn IV W ⁇ 0 39 ; or K 5 Co m W I2 O 4u
  • the invention further 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 5 PV 2 Mo 10 O 4O ; K 5 Si(H 2 O)Mn m W n O 39 ; K 4 Si(
  • the invention further relates to a method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of the present invention with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.
  • the invention further relates to a method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.
  • the 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 invention further relates to a method for removing a contaminant from an environment, comprising contacting a modified material with the environment containing the contaminant for a sufficient time to remove the contaminant from 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.
  • the invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical earner, 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.
  • 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 5 PV 2 Mo l ⁇ 0 4(1 ; K 5 Si(H 2 0)Mn m W n 0 39 ; K Si(H 2 0)Mn lv W ⁇ O : m
  • the 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 invention further relates to 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.
  • the invention further relates to an article comprising the modified material of the present invention.
  • polyoxometalates known in the art can be used in the present invention to remove a contaminant from an environment.
  • Polyoxometalates are also referred to in the art as heteropoly compounds, heteropoly acids, isopoly compounds, and isopoly acids, which are subsets of polyoxometalates.
  • Examples of polyoxometalates useful in the present invention are disclosed in Pope, M.T. in Heteropoly and Isopoly Oxometalates, Springer Verlag, 1983. and Chemical Reviews, vol. 98, no. 1, pp. 1-389, 1998. which are incorporated by this reference in their entirety.
  • the polyoxometalate used in the present invention is dependent upon the contaminant or contaminants to be removed from the environment.
  • the polyoxometalate has the formula 1 of [V k Mo m W n Nb 0 Ta p M q X r OJ 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: u 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
  • s is from 19 to 460.
  • the charge on the POM, y is dictated by the values of k, m, n, o, p, q, r and s.
  • the p-, d-, and f-block elements can exist in any oxidation state.
  • M can be any d-block element having at least one d-electron or f- block element having at least one f-electron.
  • M comprises titanium, chromium, manganese, cobalt, iron, nickel, copper, rhodium, silver, palladium, platinum, mercury, ruthenium, cerium, or europium.
  • M comprises manganese, cobalt, or ruthenium.
  • X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron.
  • the metal ion M of the polyoxometalate of the present invention is responsible for removing the contaminant from the gas phase, while X, when present, provides structural integrity to the polyoxometalate.
  • 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. In yet another embodiment, k is not zero. In another embodiment, q is not zero.
  • the polyoxometalate when the polyoxometalate has the fo ⁇ nula 1, the polyoxometalate has the foraiula [X g+ V b j+ M c h+ Z 12 . b . c i O x ]" " [A], wherein 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 combination thereof; b is from 0 to 6; c is from 0 to 6; u is from 3 to 9; and A is a counterion.
  • h, i, and j are average charges, and depend upon the selection and number of X, M, Z, and V present in 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.
  • the polyoxometalate has the formula 1, the polyoxometalate has the foraiula [X E+ V b J+ Z 12 _ b ' + O 4(1 ] l,” [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.
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the structure [X E+ M c ll+ Z 12 . C 'O 4 ⁇ 1 ] 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
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the formula [X 2 r+ V u s+ M v t+ Z 18 . u _ v y+ O z ] w" [A], wherein X is at least one p-.
  • 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.
  • r, s, t, and y are also average charges, and depend upon the selection and number of X, M, Z, and V atoms present in the POM.
  • the polyoxometalate when the polyoxometalate has the formula 1, the polyoxometalate has the foraiula [X 2 r+ V u s+ Z 18 . u y O 62 ] " [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.
  • the polyoxometalate when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X 2 r+ M v l+ Z 18 . v y+ O 62 ] 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.
  • the polyoxometalate has the foraiula [YV p Z 12 . p O 4n ][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion.
  • Y is phosphorus and Z is molybdenu
  • Y is phosphorus and Z is tungsten.
  • Y is silicon and Z is molybdenum.
  • Y is silicon and Z is tungsten.
  • Y is aluminum and Z is tungsten.
  • Y is aluminum and Z is tungsten.
  • Y is aluminum and
  • Z is molybdenum.
  • the polyoxometalate has the foraiula 1
  • the polyoxometalate has the foraiula [X E+ V b M h+ c Z 12 . b.c 0 4u ] u" [A]
  • 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, wherein M is not vanadium:
  • h+ is the charge of M
  • Z is tungsten, molybdenum, niobium, or a combination thereof
  • b is from
  • c is from 0 to 6, wherein the sum of b and c is greater than or equal to one; u is greater than 3; and A is a counterion.
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the foraiula [X 8+ V b Z 12.b 0 4 ⁇ ] u" [A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; b is from 1 to 6; and u is greater than 3.
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the foraiula [X + M il+ c Z 12 . c 0 4l ,]" " [A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; M h+ is at least one f-block element or d-block element having at least one d-electron; c is from 1 to 6; and u is greater than 3.
  • the polyoxometalate when the polyoxometalate has the fo ⁇ nula 1, the polyoxometalate has the formula [X 1+ 2 V u M j+ Z 18 . u.v O 62 ] 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; u is from 0 to 9; v is from 0 to 9, wherein the sum of u and v is greater than or equal to one; w is greater than or equal to 4; and A is a counterion.
  • the polyoxometalate when the polyoxometalate has the fo ⁇ nula 1, the polyoxometalate has the foraiula [X 1+ 2 V u Z I8 . u 0 62 ] " [A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; u is from 1 to 9; and w is greater than or equal to 4.
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the foraiula [X 1+ 2 M ,+ .Z 1> . V 0 62 1 " [A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; M J+ is at least one d- or f- block element; v is from 1 to 9; and w is greater than or equal to 4.
  • the polyoxometalate when the polyoxometalate has the foraiula 1, the polyoxometalate has the foraiula [YV x Z 12 . 0 4 ⁇ ][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; x is from 1 to 6, and A is a counterion.
  • Y is phosphorus and Z is molybdenu
  • Y phosphorus and Z is tungsten.
  • Y silicon and Z is molybdenum
  • Y silicon and Z is tungsten.
  • Y aluminum and Z is tungsten.
  • 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 organometaUic groups bonded to the POM can also be used in the present invention.
  • the organic group can be branched or straight chain alkyl, alkenyl, or alkynyl group or an aryl group of C, to C 3 ⁇ .
  • the alkyl group can also be a polyether or polyol.
  • the organic group is bonded to the polyoxometalate as depicted in Scheme 1 , where R is the organic group and Met is generally vanadium, molybdenum, tungsten, niobium, or tantalum: Scheme I
  • the reaction between an alcohol and the polyoxometalate I results in the loss of water and the formation of the polyoxometalate II, wherein the organic group is bonded to an oxygen atom of the polyoxometalate.
  • Any alcohol known in the art can be used in the present invention. Examples of alcohols that can be used include, but are not limited to, methanol, ethanol, or tris(hydroxymethyl)methane.
  • the polyoxometalates having organic groups bonded to the POM that are disclosed in Gouzerh et al, Chem. Rev., 98, pp. 77-111, 1998, wliich is incoiporated by reference in its entirety, are useful in the present invention.
  • the polyoxometalate I can be reacted with a compound having the generic foraiula YL 0 R 4 . 0 , wherein Y is silicon, tin, or an other p- or d-block element; L is a leaving group; R is an organic group, such as an alkyl, alkenyl, or alkynyl group or an aryl group of C, to C 3II ; and o is from 1 to 4. Suitable leaving groups for L include, but are not limited to, halides and alkoxides.
  • the oxygen of polyoxometalate I displaces L from YLR 3 to forai a new Y-0 bond (compound III). Any silyl, tin, or organic derivative of a p- or d-block element known in the art can be used in the present invention, provided that the compound has at least one leaving group.
  • the counterion A can be any counterion known in the art. Examples of counterions include, but are not limited to. quaternary ammonium cation, proton, alkali metal cation, alkaline earth metal cation, ammonium cation, d-block cations, f-block cations, or a combination thereof.
  • the polyoxometalate is an acid, wherein the counterion A is hydrogen (FT).
  • the counterion is a d- or f-block metal complex.
  • the counterion is trimethyl- triazacyclononane manganese.
  • the counterion A is hydrogen, lithium (Li + ), sodium (Na + ), potassium (K + ), or a combination thereof. In another embodiment, A is not hydrogen or potassium.
  • 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.
  • the tera "admixture" can refer to the reaction product between the polyoxometalate and the cerium compound, silver compound, gold compound, platinum compound, or a combination thereof.
  • the cerium compound, silver compound, gold compound, or platinum compound can undergo ion exchange with the counterion of the polyoxometalate.
  • the cerium compound, silver compound, gold compound, or platinum compound can also react with the polyoxometalate by a redox reaction.
  • the terai "admixture" can also refer to when the cerium compound, silver compound, gold compound, or platinum compound do not react at all with the polyoxometalate.
  • the polyoxometalate may absorb the cerium compound, silver compound, gold compound, or platinum compound.
  • the POM when the POM is the sodium, lithium, or potassium salt or the acid forai (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.
  • Ag 5 PV 2 Moplace,O 4ll is produced by the ion exchange of Na ? PV 2 Mo 1() O 4sky with a stoichiometric amount AgNO,.
  • Any of the POMs described above can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound.
  • the ion exchange reaction may or may not go to completion.
  • the ion exchange does not go to completion, there may be small population of Na + , Li + , K + , or H + in the modified-polyoxometalate.
  • the resultant POM may be expressed by the foraiula Ag H 5 . x PV 2 Mo HI O 41l , where x is from 1 to 5.
  • varying amounts of H + may be present in the POM.
  • cerium compound useful in the present invention includes, but is not limited to, (NH 4 ) 2 Ce(NO 3 ) 6 .
  • silver compounds useful in the present invention include, but are not limited to, AgNO 3 and AgClO .
  • gold compounds useful in the present invention include, but are not limited to, HAuCl 4 and salts thereof.
  • platinum compound useful in the present invention includes, but is not limited to, HJPtC ⁇ .
  • the counterion is cerium, silver, gold, platinum, or a combination thereof.
  • A is, independently, cerium, silver, gold, or platinum.
  • A is (1) cerium and silver; (2) cerium and platinum; (3) cerium and gold; or (4) silver and gold.
  • A comprises (1) hydrogen, lithium, sodium, potassium, or a combination thereof, and (2) cerium, silver, gold, platinum, or a combination thereof.
  • the pre-modified polyoxometalate is H PV 2 M ⁇ lll 0 4 ⁇ ; Na 3 PV 2 Mo 10 O 4 ⁇ ,; Li 5 PV 2 Mo, ruleO 4(l ; K 5 PV 2 Mo lu O 4( personally or a combination thereof, and (2) the cerium compound is (NH 4 ) 2 Ce(N0 3 ) 6 .
  • the pre-modified polyoxometalate is H 5 PV 2 Mo.don0 ll ; Na 5 PV,Mo I( ,O 4(l ; Li,PV 2 Mo l ⁇ 0 1 ,; K s PV 2 Mo l ⁇ 0 41 randomly or a combination thereof; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the gold compound is HAuCl 4 .
  • the pre-modified polyoxometalate is H 5 PV 2 Mo 1( ,O 4() ; Na 5 PV 2 Mo l ⁇ 0 40 ; Li 5 PV,Mo 1() O 4l) ; K s PV 2 Mo 1M O 4ll , or a combination thereof; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the platinum compound is H PtCl ⁇ .
  • the pre-modified polyoxometalate comprises Na 4 PVMo H 0 4 ⁇ ; Na,PV 2 Mo, ll O 4() ; Na 6 PV ?
  • the pre-modified polyoxometalate is Na 5 PV 2 Mo l ⁇ 0 l] and
  • the silver compound is AgN0 3 , AgC10 4 , or a combination thereof.
  • the polyoxometalate comprises K 8 Co 2 W u O 39 ; K 8 SiCoVW 1(J O 39 ; K 7 SiCoVW 10 O 39 ; Na 8 Co 2 W n O 39 ; Ag s PV,Mo lu O 4 ⁇ ; Ag 6 PV 3 Mo 9 O 4(J ; Ag 8 CoVW n O 4(l ; Ag 12 Ce(PW u O 39 ) 2 ; Na 12 Ce(PW u O 39 ) 2 ; K 12 Ce(PW u O 39 ) 2 ;
  • the polyoxometalate is not H 6 PV 3 Mo 9 O 4 ⁇ .
  • some counterions of the present invention can be reduced to the co ⁇ esponding metal when the polyoxometalate contacts the contaminant.
  • the cation is Ag +1 or Au +3
  • these cations can be reduced to silver metal or Au +1 , respectively, depending upon the contaminant that is to be removed.
  • the counterion A can exist in multiple valence states.
  • metal compound refers to one or more transition metal compounds, actinide compounds, lanthanide compounds, or a combination thereof.
  • the metal compound is only one compound, then the material is directly treated with the metal compound using tecliniques described below.
  • the metal compound can be sequentially treated with the compounds, or alternatively, the metal compounds can be admixed prior to treating the material with the metal compounds.
  • the metal compounds may react with one another to forai 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 invention are referred to herein as "non-POM materials.”
  • the metal compound comprises a cerium compound, a gold compound, a platinum compound, a silver compound, or a combination thereof. Any of the cerium compounds, gold compounds, platinum compounds, or silver compounds listed above can be used as the metal compound.
  • the metal compound is a cerium compound and a platinum compound, preferably
  • the metal compound is a cerium compound and a gold compound, preferably (NH 4 ),Ce(NO 3 ) 6 and HAuCl 4 , respectively.
  • the metal compound is a silver compound and a gold compound, preferably AgNO 3 and/or AgClO 4 and HAuCl 4 , respectively.
  • the metal compound is a cerium compounds, preferably (NH 4 ) 2 Ce(NO 3 ) 6 .
  • the metal compound comprises (1) gold, copper, and nitrate; (2) gold, iron, and nitrate; (3) gold, manganese, and nitrate; (4) gold, titanium, and nitrate: (5) gold, cobalt, and nitrate: (6) gold and nitrate; (7) copper and nitrate; (8) iron and nitrate; (9) gold, vanadium, and nitrate; (10) gold, nickel, and nitrate; (11) gold, silver, and nitrate; or (12) gold, chloride, and nitrate.
  • the metal compound comprises gold, chloride, and nitrate.
  • the metal compound comprises mixing (NEt 4 )AuCl 2 with varying amounts of CuSO 4 , MnSO 4 , VOSO 4 , Ti(SO 4 ) 2 , Fe 2 (SO 4 ) 3 , NiSO 4 , ZnSO 4 , Cr 2 (SO ) 3 , MgSO 4 , CoSO 4 ,
  • the metal compound is produced by mixing (NEt 4 )AuBr 2 and NBu 4 NO 2 .
  • the compounds can be admixed using techniques known in the art.
  • the metal compound can be produced by admixing two or more metal salts.
  • the anion of the salt can be any anion known in the art. Examples of anions include, but are not limited to, sulfate. carbonate, acetate, nitrate, chloride, and stearate.
  • the compounds when two or more compounds are used to produce the metal compound, the compounds are mixed in the presence of a solvent, preferably an organic solvent.
  • 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 in order to remove a contaminant from the environment.
  • materials include, but are not limited to, a topical carrier, a coating, a powder, or a fabric.
  • a material as used herein refers to a support that holds the POM or metal compound.
  • 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 into the material followed by the incorporation of the polyoxometalate into the material.
  • Topical carriers can be used in the present invention.
  • Suitable topically acceptable pha ⁇ naceutical carriers are those which typically are used in the topical application of pha ⁇ naceuticals and cosmetics. Examples of such earners include, but are not limited to, lotions, creams, ointments, and gels. Topical earners are also referred to in the art as ba ⁇ ier creams and topical skin protectants. Any of the topical carriers disclosed in U.S. Patent No. 5,607,979 to McCreery can be used in the present invention, wliich is incorporated by reference in its entirety.
  • the topical carrier comprises a perfluorinated polymer. In another embodiment, the topical carrier comprises a perfluoropolyether.
  • PFPE perfluoropolyether
  • the topical carrier comprises a perflo urinated polymer and one or more unfluorinated polymers.
  • the topical canier comprises a perfluoropolyether and one or more unfluorinated polyethers.
  • the topical carrier may further contain saturated or unsaturated fatty acids such as stearic acid, palmitic acid, oleic acid, palmito-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-ionic surfactant.
  • the polyoxometalate topical composition is composed of a perfluoropolyether and the counterion A of the POM is silver.
  • the polyoxometalate topical composition is composed of a perfluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof.
  • the non-POM material comprises a topical canier composed of a perfluoropolyether and the metal compound comprises a silver compound, preferably
  • the non-POM topical composition is composed a perfluoropolyether and the metal compound comprises a cerium compound, a silver compound, a palladium compound, a platinum compound, or a silver compound.
  • 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.
  • fabrics used to prepare garments, draperies, carpets, and upholstery can be used and articles made from them are a part of this invention.
  • the fabric can be a knit or non- woven fabric.
  • Useful fibers include, but are not limited to, polyamide, cotton, polyacrylic, polyacrylonitrile. polyester, polyvinylidine, polyolefm, polyurethane, polytetrafluoroethylene, or carbon cloth, or a combination thereof.
  • the fabric is prepared from cotton, polyacrylic, or polyacrylonitrile.
  • the fabric is prepared from a cationic fiber.
  • the fabric comprises ( 1) a 50/50 blend of nylon-6,6 and cotton or (2) stretchable carbon blended with polyurethane.
  • Any cellulosic fiber can be incoiporated by a POM or metal compound to produce the polyoxometalate fibers or non-POM fibers of the present invention.
  • useful cellulosic fibers include, but are not limited to, wood or paper.
  • a polyoxometalate or the metal compound of the present invention can be incoiporated in paper in order to remove a contaminant from the gas or liquid phase.
  • the paper is wallpaper.
  • the amount of polyoxometalate or metal compound incoiporated 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 embodiment, 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,
  • the polyoxometalate or metal compound is from 5 to 30 % by weight of topical composition.
  • the present invention is capable of removing a single contaminant or multiple contaminants from an environment.
  • the terai "environment" as used herein refers to any media that contains at least one contaminant.
  • the environment comprises a liquid phase.
  • the environment comprises a gas phase.
  • the terai "remove” refers to. but is not limited 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 mechanisms.
  • the POM can aerobically oxidize the contaminant acetaldehyde (CH 3 CHO).
  • CH3CHO acetaldehyde
  • Contaminants that can be removed by using the present invention include, but are not limited to, 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.
  • the contaminant is acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine, styrene, propionic acid, n-butyric acid, 11- valeric acid, iso-valeric acid, pyridine, foraialdehyde, 2-chloroethyl ethyl sulfide, carbon monoxide, or a combination thereof.
  • the polyoxometalate materials and non-polyoxometalate materials can remove microbial life from the gas or liquid phase. Examples of microbial life include, but are not limited to, bacteria, protozoa, and viruses.
  • the contaminant is a chemical warfare agent (CWA).
  • CWA chemical warfare agent
  • the contaminant can be removed from -50 °C to 250 T at a pressure of from 0.1 ppb to 30 atm, preferably from 25 C C to 105 °C at 1 atm.
  • the lower temperature limit is -50, -40, -30, -20, - 10, 0, 10, 20, 50, 75. 100, or 150 °C
  • the upper temperature limit is 50,
  • the present invention can remove a contaminant from the environment 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 atm, 100 ppb to 2 atm, 200 ppb to 2 atm, and 0.5 ppm to 2 atm.
  • the present invention can remove a contaminant under mild conditions when the environment is a liquid phase.
  • 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 being contacted and the contaminant to be removed.
  • the POMs and metal compounds are typically used in the presence of an oxidizer to remove a contaminant from the environment.
  • the POMs and/or metal compounds are used in the presence of air, which oxidizes the POM and/or metal compound.
  • additional oxidizers can be used in combination with air to oxidize the POM and/or metal compound.
  • oxidizers include, but are not limited to, peroxides and peracids. In a prefe ⁇ "ed embodiment, air is used as the oxidizer.
  • the environment containing the contaminant can be contacted by the polyoxometalate materials or non-POM materials using a variety of techniques.
  • the polyoxometalate material or non-POM material can be dipped or submersed into the liquid phase.
  • the liquid phase can be filtered or passed through the polyoxometalate material or non- POM material.
  • the polyoxometalate material or non-POM material is typically placed in an open or closed environment that contains the contaminant(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 contaminant from the environment.
  • One advantage is that the present invention can remove a contaminant from the environment starting within milliseconds of contact and can remove the contaminant for extended periods of time, ranging from several days to indefinitely.
  • the POMs and metal compounds used in the present invention are capable of being regenerated to an active form that permits the removal of the contaminant.
  • Another advantage is that some POMs and metal compounds can render the material more water resistant and increase the surface area of the material.
  • the POM and metal compound can enhance the dyeability, light fastness, color fastness, and weaving properties of the fabric or cellulosic fiber.
  • the polyoxometalate and metal compound can be incoiporated into the material using techniques known in the art.
  • the material when the material is a topical carrier, powder, or coating, the polyoxometalate or metal compound is directly added to and admixed with the material.
  • the material topical carrier, powder, coating, or fabric
  • the material 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 in the solvent, depending upon the polyoxometalate or metal compound and solvent selected.
  • the solvent is water.
  • the solvent can be an organic solvent.
  • organic solvents useful in the present invention include, but are not limited to, acetonitrile, acetone, toluene, carbon dioxide, xylenes, l-methyl-2- pyrrolidinone, dimethyl sulfoxide, or an alcohol, such as methanol, ethanol, 1- ⁇ ropanol, or 2-propanol.
  • the polyoxometalate or metal compound mixture is from 0.1 to 20 % by weight polyoxometalate or metal compound and from 80 to 99.9 % by weight water, preferably from 0.3 to 15 7c by weight polyoxometalate or metal compound and 85 to 99.7 % water.
  • the fabric or cellulosic fiber is dipped or immersed 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 2 hours to 2 days at from 25 °C to 80 °C.
  • 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.
  • the polyoxometalate material or non-POM material is dried in order to remove residual solvent.
  • 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.
  • the polyoxometalate material or non- POM material is dried in vacuo (i.e., less than or equal to 10 torr).
  • the POM or metal compound when the material is a fabric or cellulosic fiber, can be incorporated 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 bonding 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.
  • 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.
  • the fabric or cellulosic fiber can be protonated by the polyoxometalate or metal compound to produce a positively charged fiber, wliich then electrostatically bonds to the polyoxometalate or metal compound anion.
  • a cationic polymer can be used as a binding agent to incorporate an anionic polyoxometalate or metal compound into an anionic fiber.
  • the te ⁇ n "consumption” or “consumed” refers to the removal or adsorption of a contaminant or contaminants from the environment or the conversion of the contaminant or contaminants to another compound that is nontoxic and/or non- malodorous.
  • PFPE #1511 is composed of 35-50 % polytetrafluoroethylene thickening agent dispersed in a perfluoropolyether oil with water as a co-surfactant.
  • PFPE #151 1 was provided by Dr. E. H. Braue of the United States A ⁇ ny Medical Research Institute for Chemical Defense.
  • NBu 4 N0 3 97%.
  • NBu 4 N0 2 (98%) was purchased from Fluka.
  • Na 4 PVMo u 0 (1 : (Entry 11; So, Hyunsoo; Pope, Michael T. Inorg. Chem. 1972, 77(6), 1441-3).
  • Na 6 PV 3 Mo 9 0 4l , and H 6 PV 3 Mo g O 4 (Entries 8 and 21, respectively; Pope, Michael T.; O'Donnell, Stephen E.; Prados, Ronald A. J. Chem. Soc, Chem. Commun. 1975, 7, 22-
  • Na 5 FeSiW u 0 39 and K 6 FeSiW u 0 39 (Entries 12 and 36, respectively; Peacock, R. D.; Weakley, T. J. R. /. Chem. Soc. A 1971, 72, 1937-400).
  • K 12 Pd 3 (PW 9 O 34 ) 2 (Entry 16; Kuznetsova, N. I.; Kuznetsova, L. I.; Detusheva, L. G.; Likholobov, V. A.; Fedotov, M. A.; Koscheev, S. V.; Burgina, E. B. Stud. Surf. Sci. Catal. 1997, 770 (3rd World Congress on Oxidation Catalysis, 1997), 1203-1211).
  • Na 4 PVMo n O 4n and Na 3 PMo 12 O 1l (Entriesl8 and 19, respectively; So, Hyunsoo; Pope, Michael T. Inorg. Chem. 1972, 77(6), 1441-3).
  • K 7 CuSiW n 0 39 and Na 7 CuSiW n 0 39 (Entries 27 and 30, respectively; Teze, Andre; Souchay, Pierre. C. R. Acad. Scl, Ser. C 1973, 276( 19), 1525-8).
  • Na 5 NiPW u 0 9 (Entry 31; Maksimov, G. M.; Kustova, G. N.; Matveev, K. I.; Lazarenko, T. P. Koord. Khim. 1989, 75(6), 788-96).
  • K 8 P 2 W 17 (NbO 2 )O 61 (Entry 42; Gong, Jian; Li, Guoping; Wang, Fuquan; Qu, Lunyu. Wuji Huaxue Xuebao 1995, 77(3), 232-7).
  • K(NH 4 ) 6 RuBW u 0 39 (Entry 34; Liu, Huizhang; Sun, Wenliang; Yue, Bin; Li, Mingxing: Chen, Zhijiang; Jin, Songlin; Xie, Gaoyang; Shao, Qianfen; Wu, Tailiu; Chen, Shiming; Yan, Xiaoming. Wuji Huaxue Xuebao 1997, 73(3), 251-257).
  • K10Mn4(PW 9 O 34 ) 2 (Entry 41; Gomez-Garcia, C. J.; Coronado, E.; Gomez-Romero, P.; Casan-Pastor, N. Inorg. Chem. 1993, 32(15), 3378-81).
  • Na 3 H 3 PMo 9 0 34 (Entry 48; Inouye, Y.; Tokutake, Y.; Kunihara, J.; Yoshida, T.; Yamase, Y.; Nakata, A.; Nakamura, S. Chem. Pharm. Bull 1992, 40, 805-807).
  • K 5 Si(Nb0 2 )W u O 4 ⁇ (Entry 46): l.Og of K 7 HNb 6 0 16 was dissolved in 75-mL of deionized H 2 O. To this solution, 2-mL of 30 % H 2 O 2 was added. A few drops of 3M HCl were added to bring the pH to approximately 6. K 8 SiW ⁇ 0 39 (15.8 g) was added, wliich resulted in gas evolution. To the swirling mixture, 25-mL of H 2 O followed by 12-mL of 3M HCl were added. The color of the solution was yellow and the pH was approximately 1.
  • Na 6 SiVNbW u O 39 as a yellow, crystalline solid.
  • the Amberlite is a product of Rohm and Haas and was purchased from Aldrich.
  • 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 x Na 5 .
  • PV 2 Mo 10 O u (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.
  • PTFE poly(tetrafluoroethylene)
  • CEES 2-chloroethyl ethyl sulfide
  • TFE 2,2,2-trifluoroethanol
  • 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 combined with 100 ⁇ L of 1,3-dichloro benzene, where the 1 ,3-dichloro benzene was added as an internal reference.
  • Each POM/PFPE #1511 cream mixture (approximately 0.3 g) was smeared at the bottom of an 18 mL 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.
  • 10 ⁇ L of the CEES/reference solution surrounding the POM/cream mixture was diluted in 100 ⁇ L of TFE and analyzed. The results are shown in Table 1.
  • 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 ⁇ L 1 ,3-dichloro benzene (internal standard); and 85 mL of 2,2,2-triiluoroethanol, at 25 °C under ambient air.
  • 5.0 mL of the CEES solution was combined with enough catalyst to yield a CEES:POM ratio of 20:1, and the mixture was st ⁇ red for 14 days. The results are shown in Table 2.
  • Example 4 Aerobic Oxidation of Acetaldehyde Catalyzed by Polyoxometalates.
  • c % Yield (moles of acetic acid/moles of initial acetaldehyde) x 100.
  • d Turnovers [moles of acetic acid (in the run with catalyst) - moles of acetic acid (in the blank run without catalyst)]/moles of catalyst.
  • Example 5 Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase by Modified Polyoxometalates and Metal Compounds.
  • Tetrahydrothiophene (THT) (0.445 mmol, 0.64 M) and 1 ,3-dichloro benzene (internal standard) in the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 mL of acetonitrile in 20 mL vials under latm O 2 at room temperature.
  • the aerobic oxidation of THT by modified polyoxometalates and metal compounds is shown in Table 4.
  • 2 x 10 "6 mol of polyoxometalate or metal compound was placed in the vial before adding the reagent and internal standard.
  • the polyoxometalate and metal compound (Entries 11 and
  • Example 6 Aerobic Oxidation of CEES in Liquid Phase by Modified Polyoxometalates and Metal Compounds.
  • CEES 0.337 mmol, 0.64 M
  • 1,3-dichlorobenzene internal standard
  • CEES 0.337 mmol, 0.64 M
  • 1,3-dichlorobenzene internal standard
  • Tlie aerobic oxidation of CEES by modified polyoxometalates and metal compounds is shown in Table 5.
  • 2 x 10 "6 mol of polyoxometalate or metal compound was placed in the vial before adding the reagent.
  • the polyoxometalate and/or the metal compound(s) (2 x 10 "6 mol) were placed in the vial before adding the reagent solution.
  • Example 7 Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalate and HAuCl 4 .
  • Example 8 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgN0 3 / ⁇ AuCl System (non-POM system).
  • a metal compound solution was prepared by combining AgN0 3 (1.0 x 10 '5 mol) and HAuCl 4 (5.0 x 10 "6 mol) in 1 mL of acetonitrile. To this solution was added CEES
  • Example 9 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNOa/AgClOJ ⁇ AuCl, System (non-POM system).
  • a 20 mL vial fitted with a PTFE septum was purged with 1 atm of O 2 .
  • To this vial were added by syringe, 0.035 mL of AgNO 3 (0.1013 M in acetonitrile); 0.060 mL of AgClO 4 (0.1138 M in acetonitrile); and 0.100 mL HAuCl 4 (0.0477 M in acetonitrile), and the total volume was adjusted to 1 mL with the addition of HPLC grade acetonitrile.
  • Example 10 Aerobic Oxidation of CEES by POM/HAuCI 4 and Metal Compound/HAuCl, Systems.
  • Example 11 Oxidation of CEES to CEESO by Metal Compounds (non-POM).
  • Fomblin As the "solvent.”
  • 1.0 mL of Fomblin 0.005g of (NEt )AuCl 2 (1.25 x 10 "5 mol) was admixed in with varying amounts of CuSO 4 , MnSO 4 , VOSO , Ti(SO 4 ) 2 , Fe 2 (SO 4 ) 3 , NiSO 4 , ZnSO 4 ,
  • Figure 2 shows CEESO formation as a function of time for lAu/2Cu(II)/3NO 3 ,
  • 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).
  • Table 11 lists the oxidation of tetrahydrothiophene (THT) by t- butylhydroperoxide (TBHP) catalyzed by the transition metal salts of Me-capped V 6 O 13 .
  • Tl e oxidations were performed by dissolving the particular salt in acetonitrile to give lightly colored orange-yellow solutions.
  • the solutions were placed i 24-mL vials 33 fitted with PTFE septa.
  • THT and TBHP were then syringed in and the reactions were monitored by quantitative GC. Reactions were sti ⁇ ed at room temperature.

Abstract

L'invention concerne une composition topique de polyoxométalate destinée à éliminer un contaminant d'un environnement, renfermant un porteur topique et au moins un polyoxométalate, à condition que le polyoxométalate n'est pas H5PV2Mo10O40; K5Si(H2O)MnIIIW11O39; K4Si(H2O)MnIVW11O39; ou K5CoIIIW12O40. Cette invention concerne, en outre, un procédé permettant d'éliminer un contaminant d'un environnement par le biais de ladite composition et de mettre en contant une poudre de polyoxométalate ou un revêtement de polyoxométalate avec l'environnement. Ladite invention a également trait à un polyoxométalate modifié, renfermant le mélange (1) d'un polyoxométalate et (2) d'un composé de cérium, d'argent, d'or, de platine ou une combinaison correspondante. Par ailleurs, cette invention concerne un procédé permettant d'éliminer un contaminant d'un environnement par mise en contact d'une matière modifiée qui renferme (1) une matière et (2) un composé métallique contenant un composé métallique de transition, un composé d'actinides, un composé de lanthanides ou une combinaison correspondante, le composé métallique n'étant pas un polyoxométalate. La matière modifiée comprend (1) une matière renfermant un porteur topique, une poudre, un revêtement ou un tissu et (2) un composé métallique contenant un composé métallique de transition, un composé d'actinides, un composé de lanthanides ou une combinaison correspondante, le composé métallique n'étant pas un polyoxométalate. Ladite invention a aussi trait à un article contenant la matière modifiée.
EP00970807A 1999-10-12 2000-10-11 Matieres en polyoxometalate, matieres contenant du metal, et procede d'utilisation correspondant Withdrawn EP1224024A2 (fr)

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AU778768B2 (en) 2004-12-23
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WO2001034279A3 (fr) 2002-01-24
AU8013200A (en) 2001-06-06

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