Zero platinum group metal catalysts

Abstract

The present invention pertains to catalyst systems for nitrogen oxide, carbon monoxide, hydrocarbon, and sulfur reactions that are free or substantially free of platinum group metals. The catalyst system of the present invention comprise a substrate and a washcoat, wherein the washcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. The catalyst system may optionally have an overcoat, wherein the overcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. The catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalysts, or mixtures thereof.

1 . A catalyst system, comprising:
 a substrate; and   a washcoat,
 wherein the washcoat comprises at least one oxide solid,
 wherein the oxide solid is selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof, 
 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         2 . The catalyst system of  claim 1 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         3 . The catalyst system of  claim 1 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof. 
     
     
         4 . The catalyst system of  claim 2 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof. 
     
     
         5 . The catalyst system of  claim 2 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttirum, lanthanides, actinides, and mixtures thereof. 
     
     
         6 . The catalyst system of  claim 5 , wherein the oxygen storage material comprises one or more selected from the group consisting of (a) a mixture of ceria and zirconia; (b) a mixture of ceria, zirconia, and lanthanum; and (c) a mixture of ceria, zirconia, neodymium, and praseodymium. 
     
     
         7 . The catalyst system of  claim 1 , further comprising an overcoat comprising at least one oxide solid, wherein the overcoat oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. 
     
     
         8 . The catalyst system of  claim 7 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         9 . The catalyst system of  claim 7 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof. 
     
     
         10 . The catalyst system of  claim 8 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof. 
     
     
         11 . The catalyst system of  claim 8 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         12 . The catalyst system of  claim 1 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         13 . A catalyst system, comprising:
 a substrate;   a washcoat,
 wherein the washcoat comprises one or more selected from the group consisting of a carrier material oxide, ceramic, and mixtures thereof; and 
   an overcoat,
 wherein the overcoat comprises a catalyst,
 wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and a mixture thereof, and 
 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         14 . The catalyst system of  claim 13 , further comprising one or more selected from the group consisting of a perovskite, a spinel, an oxygen storage material, alumina, and mixtures thereof. 
     
     
         15 . The catalyst system of  claim 14 , further comprising one or more selected from the group consisting of a spinel, an oxygen storage material, alumina, and mixtures thereof. 
     
     
         16 . The catalyst system of  claim 15 , further comprising one or more selected from the group consisting of a spinel, an oxygen storage material, alumina, and mixtures thereof. 
     
     
         17 . The catalyst system of  claim 15  or  16 , further comprising one or more selected from the group consisting of (a) a spinel and at least one oxygen storage material; and (b) alumina and at least one oxygen storage material. 
     
     
         18 . The catalyst system of  claim 1  or  13  wherein the catalyst comprises at least one transition metal and at least one carrier material oxide,
 wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, silver, and tungsten.   
     
     
         19 . The catalyst system of  claim 18 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         20 . The catalyst system of  claim 19 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         21 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises copper and at least one carrier material oxide. 
     
     
         22 . The catalyst system of  claim 21 , wherein the catalyst is about 5% to about 50% by weight. 
     
     
         23 . A catalyst system, comprising:
 a substrate,
 wherein the substrate comprises cordierite; 
   a washcoat,
 wherein the washcoat comprises copper, a spinel, and at least one oxygen storage material,
 wherein the spinel comprises magnesium aluminum oxide, 
 wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, and lanthanum; and 
 
   an overcoat,
 wherein the overcoat comprises copper, a spinel, and at least one oxygen storage material,
 wherein the spinel comprises magnesium aluminum oxide, 
 wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, neodymium, and praseodymium, 
 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         24 . The catalyst system of  claim 23 , wherein the aluminum oxide and oxygen storage material of the overcoat is present in a weight ratio of about 75 to about 25. 
     
     
         25 . The catalyst system of  claim 23 , wherein the copper in the overcoat is about 5% to about 50% by weight. 
     
     
         26 . The catalyst system of  claim 25 , wherein the copper in the overcoat is about 10% to about 16% by weight. 
     
     
         27 . The catalyst system of  claim 23 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         28 . A catalyst system, comprising:
 a substrate,
 wherein the substrate comprises cordierite; 
   a washcoat,
 wherein the washcoat comprises lanthanum aluminum oxide and at least one oxygen storage material; and 
   an overcoat,
 wherein the overcoat comprises copper oxide, lanthanum aluminum oxide, and at least one oxygen storage material, 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         29 . The catalyst system of  claim 28 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         30 . The catalyst system of  claim 28 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, neodymium, praseodeymium, and mixtures thereof. 
     
     
         31 . The catalyst system of  claim 28 , wherein the lanthanum aluminum oxide and oxygen storage material of the overcoat is present in a weight ratio of about 75 to about 25. 
     
     
         32 . The catalyst system of  claim 28 , wherein the copper is present in about 5% to about 50% by weight. 
     
     
         33 . The catalyst system of  claim 28 , wherein the aluminum oxide and the oxygen storage material of the overcoat is present in the overcoat in a weight ratio of about 75 to about 25. 
     
     
         34 . The catalyst system of  claim 28 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         35 . A catalyst system, comprising:
 a substrate;   a washcoat,
 wherein the washcoat comprises tin aluminum oxide, copper, cerium, zirconium, lanthanum, and at least one oxygen storage material,
 wherein the oxygen storage material comprises a mixture of cerium, zirconium, neodymium, and praseodymium; and 
 
   an overcoat,
 wherein the overcoat comprises aluminum, copper, and at least one oxygen storage material, 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         36 . The catalyst system of  claim 35 , wherein the oxygen storage material of the overcoat comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         37 . The catalyst system of  claim 35 , wherein the aluminum oxide and oxygen storage material are present in the washcoat in a weight ratio of 25:75 to about 75:25. 
     
     
         38 . The catalyst system of  claim 35 , wherein the aluminum oxide and oxygen storage material are present in the washcoat in a weight ratio of about 60 to about 40. 
     
     
         39 . The catalyst system of  claim 35 , wherein the aluminum and at least one oxygen storage material are present in the overcoat in a weight ratio of about 60 to about 40. 
     
     
         40 . The catalyst system of  claim 35 , wherein the copper present in the overcoat is about 5% to about 20% by weight. 
     
     
         41 . The catalyst system of  claim 35 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         42 . A catalyst system, comprising:
 a substrate; and   a washcoat,
 wherein the washcoat comprises copper, tin aluminum oxide, and at least one oxygen storage material, 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         43 . The catalyst system of  claim 42 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, and praseodymium, and mixtures thereof. 
     
     
         44 . The catalyst system of  claim 43 , wherein the oxygen storage material comprises a mixture of cerium, zirconium, and lanthanum. 
     
     
         45 . The catalyst system of  claim 44 , wherein the cerium, zirconium, and lanthanum is present in the washcoat in a weight ratio of about 60 to about 30 to about 10. 
     
     
         46 . The catalyst system of  claim 42 , wherein the washcoat further comprises at least one transition metal. 
     
     
         47 . The catalyst system of  claim 42 , wherein the copper present in the washcoat is about 5% to about 30% by weight. 
     
     
         48 . The catalyst system of  claim 42 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         49 . A catalyst system, comprising:
 a substrate; and   a washcoat,
 wherein the washcoat comprises aluminum oxide, copper, and at least one oxygen storage material,
 wherein the oxygen storage material comprises a mixture of cerium, zirconium, and lanthanum, 
 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         50 . The catalyst system of  claim 49 , wherein the aluminum oxide and the oxygen storage material are present in the washcoat in a weight ratio of about 60 to about 40. 
     
     
         51 . The catalyst system of  claim 49 , wherein the copper present in the washcoat is about 5% to about 20% by weight. 
     
     
         52 . The catalyst system of  claim 49 , wherein the washcoat further comprises one or more selected from the group consisting of a transition metal, ceria, and a mixture thereof. 
     
     
         53 . The catalyst system of  claim 49 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         54 . A catalyst system, comprising:
 a substrate; and   a washcoat,
 wherein the washcoat comprises at least one carrier material oxide and a perovskite,
 wherein the perovskite comprises Ce 0.6 La 0.4 Mn 0.6 Cu 0.4 O 3 , 
 
   wherein the catalyst system is substantially free of platinum group metals.   
     
     
         55 . The catalyst system of  claim 54 , wherein the carrier material oxide comprises one or more oxygen storage material. 
     
     
         56 . The catalyst system of  claim 55 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, praseodymium, and mixtures thereof. 
     
     
         57 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises at least one transition metal, at least one alkaline earth metal, cerium, and a carrier material oxide,
 wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof, and   wherein the alkaline earth metal comprises one or more selected from the group consisting of magnesium, calcium, barium, strontium, and mixtures thereof.   
     
     
         58 . The catalyst system of  claim 57 , wherein the alkaline earth metal and cerium are present in about 5% to about 50% by weight. 
     
     
         59 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises at least one transition metal, at least one alkaline earth metal, and a carrier material oxide,
 wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof, and   wherein the alkaline earth metal comprises one or more selected from the group consisting of magnesium, calcium, barium, strontium, and mixtures thereof.   
     
     
         60 . The catalyst system of  claim 59 , wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, and mixtures thereof. 
     
     
         61 . The catalyst system of  claim 59 , wherein the alkaline earth metal comprises one or more selected from the group consisting of barium, strontium, and mixtures thereof. 
     
     
         62 . The catalyst system of  claim 59 , wherein the alkaline earth metal and the transition metal are present in a molar ratio of about 1:10 to 1:1. 
     
     
         63 . The catalyst system of  claim 59 , wherein the alkaline earth metal and the transition metal is about 2% to about 50% weight. 
     
     
         64 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises at least one transition metal and a perovskite having the formula ABO 3 ,
 wherein A comprises one or more selected from the group consisting of lanthanum, cerium, magnesium, calcium, barium, strontium, lanthanides, actinides, and mixtures thereof,   wherein B comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof.   
     
     
         65 . The catalyst system of  claim 64 , wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, manganese, iron, chromium, niobium, molybdenum, tungsten, silver, and mixtures thereof. 
     
     
         66 . The catalyst system of  claim 65 , wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, cobalt, and mixtures thereof. 
     
     
         67 . The catalyst system of  claim 64 , wherein the transition metal is present in about 2% to about 30% by weight. 
     
     
         68 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a perovskite, at least one transition metal, and at least one carrier material oxide. 
     
     
         69 . The catalyst system of  claim 68 , wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, and mixtures thereof. 
     
     
         70 . The catalyst system of  claim 68 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         71 . The catalyst system of  claim 70 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         72 . The catalyst system of  claim 68 , wherein the perovskite and transition metal are present in about 5% to about 50% by weight. 
     
     
         73 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises at least one transition metal and a spinel having the formula AB 2 O 4 ,
 wherein A comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, niobium, titanium, tin, and mixtures thereof; and   wherein B comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, niobium, titanium, tin, and mixtures thereof,
 wherein A and B are different. 
   
     
     
         74 . The catalyst system of  claim 73 , wherein the transition metal comprises one or more selected from the group consisting of manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof. 
     
     
         75 . The catalyst system of  claim 73 , wherein the spinel has the formula MgAl 2 O 4 . 
     
     
         76 . The catalyst system of  claim 73 , wherein the transition metal is present in about 2% to about 30% by weight. 
     
     
         77 . The catalyst system of  claim 73 , further comprising a carrier material oxide. 
     
     
         78 . The catalyst system of  claim 77 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         79 . The catalyst system of  claim 78 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         80 . The catalyst system of  claim 73 , wherein the spinel and transition metal are present in about 5% to about 50% by weight. 
     
     
         81 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a mixed metal oxide and at least one transition metal,
 wherein the mixed metal oxide comprises one or more selected from the group consisting of alkali metals, alkaline earth metals, lanthanides, actinides, and mixtures thereof.   
     
     
         82 . The catalyst system of  claim 81 , wherein the mixed metal oxide comprises one or more selected from the group consisting of a spinel, a perovskite, a delafossite, a lyonsite, a garnet, and a pyrochlore. 
     
     
         83 . The catalyst system of  claims 1  or  13 , wherein the catalyst comprises a perovskite having the formula ABO 3 ,
 wherein A comprises one or more selected from the group consisting lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, and mixtures thereof, and   wherein B comprises at least one transition metal.   
     
     
         84 . The catalyst system of  claim 83 , wherein the transition metal comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof. 
     
     
         85 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a perovskite having the formula A a-x B x MO b ,
 wherein A comprises one or more selected from the group consisting lanthanum, lanthanides, actinides, cerium, magnesium, calcium, barium, strontium, and mixtures thereof,   wherein B comprises one or more transition metal,   wherein a is selected from the group consisting of 1 and 2,   wherein b is selected from the group consist of 3, when a is 1, and 4 when a is 2, and   wherein z is a number defined by 0.1≦x<0.7.   
     
     
         86 . The catalyst system of  claim 85 , wherein the transition metal comprises one or more selected from the group consisting of iron, manganese, copper, nickel, cobalt, cerium, and mixtures thereof. 
     
     
         87 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a perovskite having the formula AMn 1-x Cu x O 3 ,
 wherein A comprises one or more selected from the group consisting of lanthanum, cerium, barium, strontium, lanthanides, actinides, and mixtures thereof, and   wherein x is 0 to 1.   
     
     
         88 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a perovskite having the formula ACe 1-x Cu x O 3 ,
 wherein A comprises one or more selected from the group consisting of barium, strontium, calcium, and mixtures thereof, and   wherein x is 0 to 1.   
     
     
         89 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises a spinel having the formula AB 2 O 4 ,
 wherein A comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, titanium, tin, and mixtures thereof; and   wherein B comprises one or more selected from the group consisting of aluminum, magnesium, manganese, gallium, nickel, copper, cobalt, iron, chromium, titanium, tin, and mixtures thereof,
 wherein A and B are different. 
   
     
     
         90 . The catalyst system of  claim 89 , further comprising a carrier material oxide. 
     
     
         91 . The catalyst system of  claim 90 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         92 . The catalyst system of  claim 91 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         93 . The catalyst system of  claim 89 , wherein the spinel is present in the catalyst in about 5% to about 50% by weight. 
     
     
         94 . The catalyst system of  claim 1  or  13 , wherein the catalyst comprises at least one zeolite and at least one transition metal. 
     
     
         95 . The catalyst system of  claim 94 , wherein the zeolite comprises one or more selected from the group consisting of ZSM5, heulandite, chabazite, and mixtures thereof. 
     
     
         96 . The catalyst system of  claim 94 , wherein the transition metal comprises one or more selected from the group consisting of chromium, gallium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof. 
     
     
         97 . The catalyst system of  claim 96 , wherein the transition metal comprises one or more selected from the group consisting of copper, nickel, gallium, cobalt, and mixtures thereof. 
     
     
         98 . The catalyst system of  claim 94 , wherein the transition metal is present in about 3% to about 25% by weight. 
     
     
         99 . A method of making a catalyst system by impregnation, comprising:
 depositing a washcoat on a substrate,
 wherein the washcoat comprises at least one oxide solid,
 wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof; 
 
   treating the washcoat and the substrate to convert metal salts into metal oxides;
 wherein the catalyst system is substantially free of platinum group metals. 
   
     
     
         100 . The method of  claim 99 , wherein the treating is at a temperature of about 550° C. for about 4 hours. 
     
     
         101 . The method of  claim 99 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         102 . The method of  claim 101 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         103 . The method of  claim 99 , wherein the washcoat comprises copper and at least one oxygen storage material. 
     
     
         104 . The method of  claim 103 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         105 . The method of  claim 99 , further comprising after treating:
 depositing an overcoat on the washcoat,
 wherein the overcoat comprises at least one oxide solid,
 wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof, 
 
   treating the overcoat and the washcoat at a temperature of about 550° C. for about 4 hours.   
     
     
         106 . The method of  claim 105 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         107 . The method of  claim 106 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         108 . The method of  claim 104 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof. 
     
     
         109 . The method of  claim 104 , wherein the washcoat further comprises tin. 
     
     
         110 . The method of  claim 99 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         111 . A method of making a catalyst system by precipitation, comprising:
 precipitating a transition metal salt on a washcoat,
 wherein, the transition metal salt comprises at least one transition metal and at least one carrier material oxide, 
 wherein the washcoat comprises at least one carrier material oxide; 
   treating the precipitated transition metal salt and the washcoat;   depositing the precipitated transition metal salt and the washcoat on a substrate; and   treating the precipitated transition metal salt and the washcoat on the substrate;
 wherein the catalyst system is substantially free of platinum group metals. 
   
     
     
         112 . The method of  claim 111 , wherein the treating is at a temperature of about 550° C. for about 4 hours. 
     
     
         113 . The method of  claim 111 , further comprising after treating the precipitated transition metal salt and the washcoat on the substrate:
 depositing an overcoat on the treated precipitated transition metal salt and the washcoat; and   treating the overcoat, the treated precipitated transition metal salt, and the washcoat.   
     
     
         114 . The method of  claim 111 , wherein the treating is at a temperature of about 550° C. for about 4 hours. 
     
     
         115 . The method of  claim 111 , wherein the overcoat comprises aluminum, copper, and at least one carrier material oxide. 
     
     
         116 . The method of  claim 111  or  113 , wherein the carrier material oxide comprises one or more selected from the group consisting of an oxygen storage material, aluminum oxide, doped aluminum oxide, spinel, delafossite, lyonsite, garnet, perovskite, pyrochlore, doped ceria, fluorite, zirconium oxide, doped zirconia, titanium, tin oxide, silicon dioxide, and mixtures thereof. 
     
     
         117 . The method of  claim 116 , wherein the oxygen storage material comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, yttrium, lanthanides, actinides, and mixtures thereof. 
     
     
         118 . The method of  claim 111 , wherein the transition metal comprises one or more selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, tungsten, silver, and mixtures thereof. 
     
     
         119 . The method of  claim 118 , wherein the transition metal comprises copper. 
     
     
         120 . The method of  claim 111 , wherein the washcoat further comprises tin. 
     
     
         121 . The method of  claim 111 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         122 . A method of making a catalyst system by co-milling, comprising:
 milling together a catalyst and at least one carrier material oxide,
 wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and mixtures thereof; 
   depositing the milled catalyst in the form of a washcoat on to a substrate; and   treating the substrate and the washcoat;
 wherein the catalyst system is substantially free of platinum group metals. 
   
     
     
         123 . The method of  claim 122 , wherein the treating is at a temperature of about 550° C. for about 4 hours. 
     
     
         124 . The method of  claim 122 , further comprising:
 depositing an overcoat on the washcoat; and   treating the overcoat and the washcoat.   
     
     
         125 . The method of  claim 124 , wherein the treating is at a temperature of about 550° C. for about 4 hours. 
     
     
         126 . The method of  claim 124 , wherein the overcoat comprises at least one oxide solid, wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and mixtures thereof. 
     
     
         127 . The method of  claim 126 , wherein the overcoat comprises aluminum, copper, and at least one carrier material oxide. 
     
     
         128 . The method of  claim 122 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         129 . A method of reducing pollutants emitted in exhaust, comprising:
 flowing exhaust substantially through a catalyst system,
 wherein the catalyst system comprises,
 a substrate; and 
 a washcoat,
 wherein the washcoat comprises at least one oxide solid, 
  wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof; 
 
 
 wherein the catalyst system is substantially free of platinum group metals; 
 wherein the exhaust comprises pollutants; and 
   reducing the pollutants in the exhaust.   
     
     
         130 . The method of  claim 129 , wherein the washcoat comprises copper. 
     
     
         131 . The method of  claim 130 , wherein the washcoat comprises about 8% copper by weight. 
     
     
         132 . The method of  claim 129 , wherein the catalyst further comprises an overcoat, wherein the overcoat comprises copper and at least one carrier material oxide. 
     
     
         133 . The method of  claim 129 , wherein the aluminum oxide and the carrier material oxide are present in a weight ratio of about 60:40. 
     
     
         134 . The method of  claim 129 , wherein the washcoat further comprises tin. 
     
     
         135 . The method of  claim 129 , wherein the pollutants comprise nitrogen oxide, hydrocarbon, carbon monoxide, and sulfur. 
     
     
         136 . The method of  claim 129 , wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and a mixture thereof. 
     
     
         137 . The method of  claim 129 , wherein the catalyst system further comprises:
 an overcoat,
 wherein the overcoat comprises an catalyst,
 wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and a mixture thereof. 
 
   
     
     
         138 . The method of  claim 129 , wherein the catalyst system is completely free of platinum group metals. 
     
     
         139 . A catalyst system, comprising:
 a first catalyst system, comprising
 a substrate; and 
 a washcoat,
 wherein the washcoat comprises at least one oxide solid,
 wherein the oxide solid comprises one or more selected from the group consisting of a carrier material oxide, a catalyst, and a mixture thereof; 
 
 wherein the first catalyst system is substantially free of platinum group metals; and 
 
   a second catalyst system,
 wherein the second catalyst system comprises at least one platinum group metal; 
   wherein the first catalyst and the second catalyst are in series in any order, and   wherein a gas stream is capable of passing through the first catalyst system and the second catalyst system sequentially.   
     
     
         140 . The catalyst system of  claim 139 , wherein the platinum group metal comprises one or more selected from the group consisting of palladium, platinum, ruthenium, iridium, osmium, and rhodium. 
     
     
         141 . The catalyst system of  claim 139 , wherein the gas stream is capable of passing through the first catalyst system and the second catalyst system in any sequence. 
     
     
         142 . The catalyst system of  claim 139 , wherein the second catalyst system comprises one or more platinum group metal and one or more carrier material oxide. 
     
     
         143 . The catalyst system of  claim 139 , wherein the second catalyst system comprises one or more platinum group metal and one or more carrier material oxide. 
     
     
         144 . The catalyst system of  claim 139 , wherein the oxygen storage material of the first catalyst comprises one or more selected from the group consisting of cerium, zirconium, lanthanum, neodymium, praseodymium, and mixtures thereof. 
     
     
         145 . The catalyst system of  claim 139 , wherein the first catalyst system and the second catalyst system are in series such the gas stream is capable of passing through the second catalyst followed by the first catalyst. 
     
     
         146 . The catalyst system of  claim 139 , wherein the first catalyst system further comprises:
 an overcoat,
 wherein the overcoat comprises a catalyst,
 wherein the catalyst comprises one or more selected from the group consisting of a ZPGM transition metal catalyst, a mixed metal oxide catalyst, a zeolite catalyst, and a mixture thereof.