Polyoxometalate materials, metal-containing materials, and methods of use thereof

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 H 5 PV 2 Mo 10 O 40 ; K 5 Si(H 2 O)Mn III W 11 O 39 ; K 4 Si(H 2 O)Mn IV W 11 O 39 ; or K 5 Co III W 12 O 40 . 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 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.

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 H 5 PV 2 Mo 10 O 40 ; K 5 Si(H 2 O)Mn III W 11 O 39 ; K 4 Si(H 2 O)Mn IV W 11 O 39 ; or K 5 Co III W 12 O 40 .  
     
     
         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+ Z 12−b−c   i+ O x ] u− [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.  
     
     
         28 . The composition of  claim 27 , wherein the polyoxometalate has the formula [X g+ V b   j+ Z 12−b   i+ O 40 ] 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+ Z 12−c   i+ O 40 ] 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 [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-, 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 [X 2   r+ V u   s+ Z 18−u   y+ O 62 ] 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 [X 2   r+ M v   t+ 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.  
     
     
         33 . The composition of  claim 1 , wherein the polyoxometalate has the formula [YV p Z 12−p O 40 ][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 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 K 8 Co 2 W 11 O 39 ; K 8 SiCoVW 10 O 39 ; K 7 SiCoVW 10 O 39 ; Na 8 Co 2 W 11 O 39 ; Ag 5 PV 2 Mo 10 O 40 ; Ag 6 PV 3 Mo 9 O 40 ; Ag 8 CoVW 11 O 40 ; Ag 12 Ce(PW 11 O 39 ) 2 ; Na 12 Ce(PW 11 O 39 ) 2 ; K 12 Ce(PW 11 O 39 ) 2 ; Na 5 PCuW 11 O 39 ; H 6 PV 3 Mo 9 O 40 ; or K 5 Cu II PW 11 O 39 .  
     
     
         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 H 5 PV 2 Mo 10 O 40  and (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 .  
     
     
         38 . The composition of  claim 36 , wherein (1) the pre-modified polyoxometalate is H 5 PV 2 Mo 10 O 40 ; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the gold compound is HAuCl 4 .  
     
     
         39 . The composition of  claim 36 , wherein (1) the pre-modified polyoxometalate is H 5 PV 2 Mo 10 O 40 ; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the platinum compound is H 2 PtCl 6 .  
     
     
         40 . The composition of  claim 36 , wherein (1) the pre-modified polyoxometalate is Na 5 PV 2 Mo 10 O 40  and (2) the silver compound is AgNO 3 , AgClO 4 , or a combination thereof.  
     
     
         41 . The composition of  claim 36 , wherein (1) the pre-modified polyoxometalate comprises Na 4 PVMo 11 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Na 6 PV 3 Mo 9 O 40 ; Na 5 H 2 PV 4 W 8 O 40 ; Na 9 PV 6 Mo 6 O 40 ; Na 5 CuPW 11 O 39 ; Na 5 CuPW 11 O 40 ; Na 5 MnPW 11 O 40 ; K 5 CoPW 11 O 39 ; (ndec 4 ) 6 HMnNb 3 P 2 W 15 O 62 ; or K 12 Cu 3 (W 9 PO 34 ) 2 , and (2) the gold compound is HAuCl 4 .  
     
     
         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 environment 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 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 environment 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 H 5 PV 2 Mo 10 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Li 5 PV 2 Mo 10 O 40 ; K 5 PV 2 Mo 10 O 40 , or a combination thereof, and (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 .  
     
     
         60 . The modified polyoxometalate of  claim 58 , wherein (1) the pre-modified polyoxometalate is H 5 PV 2 Mo 10 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Li 5 PV 2 Mo 10 O 40 ; K 5 PV 2 Mo 10 O 40 , or a combination thereof; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the gold compound is HAuCl 4 .  
     
     
         61 . The modified polyoxometalate of  claim 58 , wherein (1) the pre-modified polyoxometalate is H 5 PV 2 Mo 10 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Li 5 PV 2 Mo 10 O 40 ; K 5 PV 2 Mo 10 O 40 , or a combination thereof; (2) the cerium compound is (NH 4 ) 2 Ce(NO 3 ) 6 ; and (3) the platinum compound is H 2 PtCl 6 .  
     
     
         62 . The modified polyoxometalate of  claim 58 , wherein (1) the pre-modified polyoxometalate is H 5 PV 2 Mo 10 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Li 5 PV 2 Mo 10 O 40 ; K 5 PV 2 Mo 10 O 40 , or a combination thereof, and (2) the silver compound is AgNO 3 .  
     
     
         63 . The modified polyoxometalate of  claim 58 , wherein (1) the pre-modified polyoxometalate independently comprises Na 4 PVMo 11 O 40 ; Na 5 PV 2 Mo 10 O 40 ; Na 6 PV 3 Mo 9 O 40 ; Na 5 H 2 PV 4 W 8 O 40 ; Na 9 PV 6 Mo 6 O 40 ; Na 5 CuPW 11 O 39 ; Na 5 CuPW 11 O 39 ; Na 5 MnPW 11 O 40 ; K 5 CoPW 11 O 39 ; (n-Dec 4 ) 6 HMnNb 3 P 2 W 15 O 62 ; or K 12 Cu 3 (W 9 PO 34 ) 2 , and (2) the gold compound is HAuCl 4 .  
     
     
         64 . A polyoxometalate comprising K 8 Co 2 W 11 O 39 ; K 8 SiCoVW 10 O 39 ; K 7 SiCoVW 10 O 39 ; Ag 5 PV 2 Mo 10 O 40 ; Ag 6 PV 3 Mo 9 O 40 ; Ag 8 CoVW 11 O 40 ; or Ag 12 Ce(PW 11 O 39 ) 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 AgNO 3 , AgClO 4 , or a combination thereof.  
     
     
         77 . The modified material of  claim 65 , wherein 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; (12) gold, chloride, and nitrate; or (13) cerium compound.  
     
     
         78 . The modified material of  claim 65 , wherein the metal compound comprises gold, chloride, and nitrate.  
     
     
         79 . The modified material of  claim 65 , wherein the metal compound comprises mixing (1) (NEt 4 )AuCl 2  and (2) CuSO 4 , MnSO 4 , VOSO 4 , Ti(SO 4 ) 2 , Fe 2 (SO 4 ) 3 , NiSO 4 , ZnSO 4 , Cr 2 (SO 4 ) 3 , MgSO 4 , CoSO 4 , Pd(NO 3 ) 4 , Na 2 SO 3 , or NBu 4 NO 3 , or a combination thereof.  
     
     
         80 . An article comprising the modified material of  claim 65 .  
     
     
         81 . 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.