Cleaning ambient air by the movement of a vehicle having a pollutant treating surface

<u style="single">Related application</u>This application is a partial continuation application of US serial number 08 / 376,332 filed on January 20, 1995, and a partial continuation application of US serial number 08 / 410,445 filed on March 24, 1995. There is a partial continuation application of US serial number 08 / 537,206 filed on September 29, 1995, and a partial continuation application of US serial number 08 / 589,182 filed on January 19, 1996. All such applications are incorporated herein by reference.<u style="single">Background of the invention</u><u style="single">Field of invention</u>The present invention relates to an apparatus for cleaning the atmosphere, and more particularly to a vehicle comprising at least one atmospheric contact surface having a contaminant treatment composition on it, and related methods and compositions.<u style="single">Discussion of related technologies</u>A review of the literature on pollutant control reveals that a common approach is to reactively clean up wastewater entering the environment. When too much one or another pollutant was detected or discharged, there was a tendency to focus on the source of the pollutant, the cause of the pollutant or the waste stream containing the pollutant. In most cases, a gaseous stream is treated to reduce contaminants prior to entering the atmosphere. It has been disclosed to treat atmospheric air directed into a closed space to remove unwanted components in the air. However, little effort has been made to treat pollutants already in the environment. The environment has been left in its own self-cleaning system. References are known that disclose the procedural cleaning of the environment. U.S. Pat. No. 3,738,088 discloses an air filtration assembly for cleaning contaminants from the surrounding air by using the vehicle as a movable cleaning device. Various elements are disclosed that are used in combination with a vehicle that cleans the surrounding air as the vehicle is driven through the environment. In particular, conduit structures have been disclosed that control the airflow velocity and direct air to various filtering means. The filter means can include a filter and an electronic precipitant. After contacting filters are disclosed to be useful for treating non-granular or aerosol contaminants such as carbon monoxide, unburned hydrocarbons, nitrous oxide and / or sulfur oxides, and the like. .. German patent DE 43 18 738 C1 also discloses methods for physical and chemical cleaning of the outside of the air. Automobiles are used as carriers for conventional filters and / or catalysts, and these filters and / or catalysts do not constitute a driving component of the vehicle but are used to directly clean the atmospheric air. Another approach is U.S. Pat. No. 5,147, It is disclosed in No. 429. A movable airlift air cleaning station is disclosed. In particular, this patent features an airship for collecting air. The airship has several different types of air cleaning devices contained therein. The disclosed air cleaning devices include wet scrubbers, filtration machines, and cyclone spray scrubbers. The difficulty with the above-mentioned devices disclosed to clean the atmospheric air forward is that they require new and additional equipment. U.S. Pat. No. 3,738, Even the modified vehicles disclosed in 088 require a conduit structure and filter that can include a catalytic filter. DE 40 07 965 C2 to Klaus Hager discloses copper oxide for converting ozone, as well as a mixture of copper oxide and manganese oxide for converting carbon monoxide. This catalyst can be applied as a coating to a self-heating radiator, oil cooler or intake air cooler. The catalytic coating comprises a heat resistant binder, which is also gas permeable. Copper oxide and manganese oxide are widely used in gas mask filters and have the disadvantage of being poisoned by water vapor. However, heating the surface of the car during driving evaporates the water. Since no desiccant is required in this method, continuous use of the catalyst is possible. Manganese oxide is known to contact the oxidation of ozone to produce oxygen. Many commercially available types of manganese compounds and compositions, such as α-manganese oxide, are disclosed to contact the reaction of ozone to produce oxygen. In particular, it is known to use the cryptomelene form of α-manganese oxide to contact the reaction of ozone to generate oxygen. α-manganese oxide was presented in references such as August 25-30, 1991, at the New York City Conference of the American Chemistry Association, a symposium on progress in zeolites and columnar clay structures before the division of the Petrochemical Company, O'. It is disclosed in the references beginning on page 348 of Young, Hydrothermal Synthesis of Manganese Oxide with Tunnel Structure, Recent Analytical Techniques for Petroleum Analysis. Such substances are also disclosed in US Pat. No. 5,340,562 to O'Young et al. In addition, α-MnO It is disclosed in No. 562. In addition, α-MnO It is disclosed in No. 562. In addition, α-MnO₂The form of is disclosed in McKenzie, Birnessite, Cryptomellene, and the Synthesis of Some Other Oxides and Hydroxides of Manganese, Mineralogical Magazine, December 1971, Vol. 38, pp. 493-502. For the purposes of the present invention, α-MnO₂Is Holland Ore (BaMn)₈O₁₆ XH₂O), cryptomelen (KMn)₈O₁₆ XH₂O), manjiroite (NaMn)₈O₁₆ XH₂O) and coronado ore (PbMn)₈O₁₆ XH₂O) is specified to be included. O'Young discloses that these materials have a three-dimensional skeletal tunnel structure (both incorporated herein by reference, U.S. Pat. Nos. 5,340,562 and O'Young, oxidation with a tunnel structure. Hydrothermal synthesis of manganese). For the purposes of the present invention, α-MnO₂Has a 2x2 tunnel structure and is thought to contain Holland ore, cryptomelene, mandylote and coronado ore.<u style="single">Abstract of the invention</u>The present invention relates to devices, methods and compositions for treating atmospheres. For the purposes of the present invention, the atmosphere is defined as a mass of air surrounding the earth. The present invention is directed to devices and related methods for treating the atmosphere, including the vehicle and means for moving the vehicle from one place to another through the atmosphere, eg, a motor. The vehicle comprises at least one atmospheric contact vehicle surface and a contaminant treatment composition located on the surface thereof. Atmospheric contact surfaces are the surfaces of vehicle components that are in direct contact with the atmosphere. Preferred and useful atmospheric contact surfaces include the surface of the body, the surface of the baffle plate, the surface of the grill, the back of the mirror, and the surface of the components "below the hood". The preferred atmospheric contact surface is typically located within the body of the engine, i.e., the vehicle near the engine compartment. The surface is preferably a cooling means comprising a coolant wall enclosure, eg, an inflow path for a liquid or gas through a tube, or a housing on which fins are located to facilitate heat transfer and an outer surface. Is the surface of. A preferred atmospheric contact surface comprises a finned outer surface and is an air intake, also referred to as a radiator, an outer surface of an air conditioner condenser, a radiator fan, an engine oil cooler, a transmission oil cooler, a power steering fluid cooler, and an intercooler or aftercooler. Selected from the surface of the built-in cooler. The most preferred atmospheric contact surfaces are the outer surfaces of air conditioner condensers and radiators due to their large surface area and relatively high ambient operating temperatures up to about 40 ° C to 135 ° C and typically 110 ° C. .. An advantage of the present invention is that an atmospheric contact surface useful for supporting the contaminant treatment composition may be the surface of an existing vehicle component. No additional filters or equipment is required to support the contaminant treatment composition. Accordingly, the devices and methods of the present invention may be positioned on top of existing components of a new car or refurbished on an old car. Can be done. Refurbishment can include coating an existing vehicle surface with a suitable contaminant treatment composition that comes into contact with atmospheric air as the vehicle is driven through the atmosphere. The present invention is directed to compositions, methods and articles for treating contaminants in the air. Such contaminants are typically 0-400 ppb, more typically 1-300 ppb, and even more typically 1-200 ppb ozone; 0-30 ppm, and even more typically 1-20 ppm. Carbon monoxide; as well as 2 to 3000 ppb unsaturated hydrocarbon compounds such as C₂~ About C₂₀-Olefins and partially oxygenated hydrocarbons such as alcohols, aldehydes, esters, ethers, ketones and analogs can be included. Typical hydrocarbons that can be processed include, but are not limited to, propylene, butylene, formaldehyde and other wind-carried hydrocarbon gases and vapors. Other contaminants present can include nitrogen oxides and sulfur oxides. The national ambient air quality standard is 120 ppb for ozone and 9 ppm for carbon monoxide. Contaminant treatment compositions include catalytic compositions useful for contacting the conversion of contaminants present in the atmosphere to non-unpleasant substances. Alternatively, an adsorption composition for adsorbing contaminants, which can be destroyed upon adsorption or stored for further treatment later, can be used as the contaminant treatment composition. Catalytic compositions can be used that can aid in the conversion of contaminants to harmless or less harmful compounds. Useful and preferred catalytic compositions contact oxygen-producing ozone reactions, carbon monoxide-producing carbon monoxide reactions, and / or water and carbon dioxide-producing hydrocarbon reactions. Contains the composition. Specific and preferred catalysts for contacting hydrocarbon reactions are low molecular weight unsaturated hydrocarbons with 2-20 carbons and at least one double bond, such as C.₂~ About C₈It is useful for contacting the reaction of monoolefins. Such low molecular weight hydrocarbons have been identified as being sufficiently reactive to cause smog. Special olefins that can be reacted include propylene and butylene. Useful and preferred catalysts can contact the reaction of both ozone and carbon monoxide, and preferably ozone, carbon monoxide and hydrocarbons.<u style="single">ozone</u> Useful and preferred catalytic compositions for treating ozone are manganese compounds containing oxides such as Mn.₂O₃And MnO₂The preferred composition comprises a composition comprising₂Containing, and cryptomelene is most preferred. Other useful and preferred compositions are MnO₂And a mixture of CuO. Specific and preferred compositions are CuO and MnO₂Hopcarite containing and even more preferably MnO₂, CuO and Al₂O₃Includes and sold by Carus Chemical Co.^(R)Consists of including. The alternative composition comprises a refractory metal oxide support on which a contactably useful amount of palladium component is dispersed and preferably also contains a manganese component. Catalysts containing a noble metal component, preferably a platinum component, on a co-precipitated zirconia and manganese oxide support are also useful. The use of this co-precipitated support has been found to be particularly effective in allowing the platinum component to be used to treat ozone. Yet another composition that can result in the conversion of ozone to oxygen is carbon, as well as carbon, manganese dioxide, and Carulite.^(R)And / or contains palladium or platinum supported on top of hopcarite. Manganese supported on refractory oxides such as alumina has also been found to be useful.<u style="single">Carbon monoxide</u> --- A useful and preferred catalytic composition for treating carbon monoxide comprises a refractory metal oxide on which a contactally effective amount of platinum and / or palladium components, preferably platinum components are dispersed. Contains a composition consisting of. The most preferred catalytic composition for treating carbon monoxide comprises a refractory metal oxide, preferably a reduced platinum group component supported on top of titania. Useful catalytic materials include noble metal components such as platinum group components including metals and their compounds. Such metals can be selected from platinum, palladium, rhodium and ruthenium, gold and / or silver components. Platinum will also result in a catalytic reaction of ozone. Catalysts comprising a noble metal component, preferably a platinum component on a support of co-precipitated zirconia and manganese dioxide, are also useful. Preferably, this catalyst embodiment has been reduced. Other useful compositions capable of converting carbon monoxide to carbon dioxide include a platinum component supported on a support comprising carbon, or manganese dioxide. Preferred catalysts for treating such contaminants have been reduced. Another catalyst useful for treating carbon monoxide is a platinum group metal component, preferably a platinum component, a fire resistant oxide support, preferably alumina and titania, and preferably a tungsten component and rhenium in the form of a metal oxide. It contains at least one metal component selected from the components.<u style="single">hydrocarbon</u> --C as mentioned above₂~ About C₂₀-Olefin and typically C₂~ C₈-A useful and preferred catalytic composition for treating unsaturated hydrocarbons containing mono-olefins such as propylene and partially oxygenated hydrocarbons is above for use in contacting carbon monoxide reactions. Found to be of the same type as described in, and preferred compositions for unsaturated hydrocarbons are reduced platinum and / or palladium components, as well as refractory metal oxide supports for platinum components. Consists of including. A preferred refractory metal oxide support is titania. Other useful compositions capable of converting hydrocarbons to carbon dioxide and water include a platinum component supported on a support comprising carbon, or manganese dioxide. Preferred catalysts for treating such contaminants have been reduced. Another composition useful for converting hydrocarbons is a platinum group metal component, preferably a platinum component, a fire resistant oxide support, preferably alumina and titania, and preferably a tungsten component and rhenium in the form of a metal oxide. It contains at least one metal component selected from the components. The combination of platinum and palladium components results in improved CO conversion in increasing costs, and is most preferred if higher conversions are desirable and cost increases are acceptable.<u style="single">Ozone and carbon monoxide</u> --- A useful and preferred catalyst capable of treating both ozone and carbon monoxide comprises a support on which a noble metal component is dispersed, such as a refractory metal oxide support. The refractory oxide support can comprise a support component selected from the group consisting of ceria, alumina, silica, titania, zirconia, and mixtures thereof. Co-precipitates of zirconia and manganese oxide are also useful as supports for precious metal catalytic components. Most preferably, this support is used with a platinum component, and the catalyst is in reduced form. This single catalyst has been found to effectively treat both ozone and carbon monoxide. Other useful and preferred noble metal components consist of noble metal components selected from palladium and also platinum components, with palladium being preferred. The combination of the palladium component and the ceria support provides an effective catalyst for treating both ozone and carbon monoxide. Other useful and preferred catalysts for treating both ozone and carbon monoxide are platinum group components, preferably platinum and / or palladium components, on titania or on a combination of zirconia and silica. It preferably contains a platinum component. The combination of platinum and palladium components results in improved CO conversion in increasing costs, and is most preferred if higher conversions are desirable and cost increases are acceptable. Other useful compositions capable of converting ozone to oxygen and carbon monoxide to carbon dioxide include a platinum component supported on carbon or on a support comprising manganese dioxide. The preferred catalyst has been reduced.<u style="single">Ozone, carbon monoxide and hydrocarbons</u> Ozone, carbon monoxide, and hydrocarbons, typically low molecular weight olefins such as those mentioned above (C)₂~ About C₂₀) And typically C₂~ C₈-Useful and preferred catalysts capable of treating mono-olefins and partially oxygenated hydrocarbons include supports in which noble metal components are dispersed, preferably refractory metal oxide supports. Consists of. The refractory oxide support can consist of a support component selected from the group consisting of ceria, alumina, titania, zirconia and mixtures thereof, with titania being most preferred. Useful and preferred noble metal components consist of noble metal components selected from platinum group components, including palladium and / or platinum components, with platinum being most preferred. It has been found that the combination of platinum component and titania support provides the most effective catalyst for treating ozone, carbon monoxide and low molecular weight gaseous olefin compounds. The combination of platinum and palladium components results in improved CO and hydrocarbon conversions in increasing costs, and is most preferred if higher conversions are desirable and cost increases are acceptable. It is preferable to reduce the platinum group component with an appropriate reducing agent. Other useful compositions capable of converting ozone to oxygen, carbon monoxide to carbon dioxide, and hydrocarbons to carbon dioxide are carbon, a support comprising manganese dioxide, or manganese oxide and zirconia. Contains a platinum component supported on a support comprising a co-precipitate. The preferred catalyst has been reduced. The above composition can be imparted by coating on the surface of at least one atmospheric contact vehicle. Particularly preferred compositions are contacted with ozone, carbon monoxide and / or the destruction of unsaturated low molecular weight olefinic compounds under ambient or ambient operating conditions. The surrounding conditions are atmospheric conditions. Ambient operating conditions mean conditions such as the temperature of the atmospheric contact surface during normal operation of the vehicle, without the use of additional energy directed at heating the contaminant treatment composition. Certain atmospheric contact surfaces, such as grills or baffles, can be at the same or similar temperature as the atmosphere. Preferred catalysts for contacting ozone reactions are 5-30 It was found that ozone reactions could be contacted under ambient conditions as low as ° C. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It has been found that the reaction of ozone can be contacted under the ambient conditions of such a low region. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It has been found that the reaction of ozone can be contacted under the ambient conditions of such a low region. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It has been found that the reaction of ozone can be contacted under the ambient conditions of. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It has been found that the reaction of ozone can be contacted under the ambient conditions of. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It was found that they could be contacted. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C It was found that they could be contacted. Atmospheric contact surfaces can have an ambient atmosphere and higher temperatures due to the operating nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C The contact surface can have an ambient atmosphere and a higher temperature due to the driving nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C The contact surface can have an ambient atmosphere and a higher temperature due to the driving nature of the components lying beneath the surface. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C There is a possibility. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C There is a possibility. For example, preferred atmospheric contact surfaces are the surfaces of air conditioner condensers and radiators due to their high surface area. If the vehicle uses an air intake cooler, these are preferred due to their high surface area and operating temperature of ambient ~ 250 ° F. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C Preferred for ambient ~ 250 ° F operating temperature. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C Preferred for ambient ~ 250 ° F operating temperature. Normally, during ambient operating conditions, the surfaces of these components increase to higher temperature levels than the ambient environment due to the nature of their operation. After the vehicle has warmed up, these components are typically at temperatures up to about 130 ° C and typically in the range of 40 ° C to 110 ° C. The temperature range of these atmospheric contact surfaces helps to increase the conversion rate ratio of ozone, carbon monoxide and hydrocarbon catalysts supported on such surfaces. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C And helps to increase the conversion rate ratio of hydrocarbon catalysts. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalyst compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C And helps to increase the conversion rate ratio of hydrocarbon catalysts. Air intake coolers operate at temperatures up to about 130 ° C and typically between 60 ° C and 130 ° C. The various catalyst compositions can be combined and the combined coating can be applied to the atmospheric contact surface. Instead, different surfaces or different parts of the same surface can be coated with different catalytic compositions. The methods and devices of the present invention are designed to be capable of treating contaminants in ambient atmospheric conditions or in ambient operating conditions of the atmospheric contact surface of the vehicle. The present invention is such contamination even in ambient conditions, typically at a vehicle surface temperature of at least 0 ° C, preferably 10 ° C to 105 ° C, and even more preferably 40 ° C to 100 ° C. It is particularly useful for treating ozone by coating the automotive atmosphere contact surface with a suitable catalyst that is useful for destroying objects. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C Especially useful for. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C Especially useful for. Carbon monoxide is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. Low molecular weight hydrocarbons, typically unsaturated hydrocarbons with at least one unsaturated bond, such as C₂~ About C₂₀Olefin and typically C₂~ C₈The mono-olefin is preferably treated at an atmospheric contact surface temperature of 40 ° C to 105 ° C. The percent conversion of ozone, carbon monoxide and / or hydrocarbons depends on the temperature and air velocity of the atmospheric air relative to the atmospheric contact surface, as well as the temperature of the atmospheric contact surface. Thus, in the most preferred embodiments, the present invention at least reduces ozone, carbon monoxide and / or hydrocarbon levels present in the atmosphere without the addition of any mechanical features or energy sources to existing vehicles, especially automobiles. Can bring about letting. In addition, the catalytic reaction occurs under the normal ambient driving conditions experienced by the surfaces of these automotive elements, so no changes are required in the way the vehicle is built or driven. Although the devices and methods of the present invention are generally directed towards treating atmospheres, it is recognized that variants of the device are designed for use in treating volumes of air in closed spaces. There will be. For example, vehicles with atmospheric contact surfaces that support pollutant treatment compositions can be used to treat air in factories, mines and tunnels. Such devices may include vehicles used in such an environment. Although preferred embodiments of the present invention are directed to the destruction of contaminants at the ambient operating temperature of the atmospheric contact surface, it is also possible to treat contaminants having a contact reaction temperature higher than the ambient temperature of the atmospheric contact surface or the ambient operating temperature. Also desirable. Such contaminants include hydrocarbons and nitrogen oxides and carbon monoxide that bypass or are not treated on atmospheric contact surfaces. These contaminants can typically be treated at higher temperatures in the range of at least 100 ° C to 450 ° C. This can be achieved, for example, by using an auxiliary heated catalyst surface. Auxiliary heated surface means that there is a supplementary means of heating the surface. A preferred auxiliary heated surface is a single body of electrically heated catalyst of a type known to those of skill in the art, such as the surface of a metal honeycomb of an electrically heated catalyst. Electricity is self It can be supplied by a battery or generator present in the vehicle. The catalyst composition is a three-way catalyst (TWC) comprising any well-known oxidation and / or reduction catalyst, preferably a noble metal supported on a refractory oxide support such as platinum, palladium, rhodium and the like. ) Is fine. Auxiliary heated catalyst surfaces can be used in combination with the atmospheric contact surface of the vehicle to further treat contaminants, and preferably downstream thereof. As mentioned earlier, the adsorption composition can also be used to adsorb contaminants such as hydrocarbons and / or granular objects for subsequent oxidation or subsequent removal. Useful and preferred adsorption compositions include zeolites, other molecular sieves, carbon, and Group IIA alkaline earth metal oxides such as calcium oxide. Hydrocarbons and granular objects can be adsorbed at 0 ° C to 110 ° C and can be subsequently treated by desorption, followed by a catalytic reaction or combustion. It is preferable to coat the area of the vehicle with a relatively high surface area that is exposed to a large flow of atmospheric air as the vehicle is driven through the environment. For automobiles used on land, particularly preferred atmospheric contact surfaces are on the roofs of radiators, fan blades, air conditioner condensers or heat exchangers, air intake coolers, engine oil coolers, transmission oil coolers, and truck cabs. Includes the type of wind deflector used. Most preferably, the atmospheric contact surface is the surface of the radiator. The radiator has a large surface area to facilitate cooling of the internal combustion engine fluid refrigerant. By applying the catalyst so as to be supported over the radiator surface, the advantage of a large honeycomb-like surface area can be obtained, and usually there is little or no effect on the cooling function of the radiator. The high honeycomb-like surface area makes it possible to maximize contact between the air flowing through the radiator's honeycomb-like design and the catalyst. In addition, radiators in many cars are positioned behind air conditioner condensers. , And thereby protected by an air conditioner condenser. The present invention includes a method for coating a contaminant treatment composition on an atmospheric contact surface of an automobile. In particular, the present invention includes methods for coating the catalytic composition onto finned elements such as radiators, air conditioner condensers, and air intake coolers. Calculations suggest that there are a sufficient number of vehicles in areas of traffic congestion that significantly impact the contaminants treated according to the present invention. For example, there are about 8 million cars in the air quality control area of the South Coast of South California. It was calculated that if each car travels 20 miles daily, all air in the area up to an altitude of 100 feet can be circulated through the radiator in a week.<u style="single">[Simple explanation of drawings]</u>FIG. 1 is a schematic side view of a truck showing an engine with a grill, an air conditioner condenser, an electrically heated catalyst, an air intake cooler, a radiator, a fan and a wind spill plate on the roof of the truck cab. FIG. 2 is a partial schematic of an automobile showing a grill, an air conditioner condenser, a radiator and a fan. FIG. 3 is a front view of the radiator. FIG. 4 is a front view of the air conditioner condenser. FIG. 5 is a front view of the type of wind sway plate illustrated in FIG. FIG. 6 is a front view of the truck of FIG. FIG. 7 is a partial cross-sectional view of a coated finned cooling element. FIG. 8 is a photograph of the coated radiators from Examples 1 and 2. 9-14 and 16-17 are graphs of CO conversion vs. temperature when different catalysts in Examples 4, 9-12, 14 and 15 are used. FIG. 15 is a graph of propylene conversion rate vs. temperature based on Example 14. FIG. 18 is a graph of ozone conversion rate vs. temperature based on Example 17. FIG. 19 is an IR spectrum for cryptomelene. FIG. 20 is an XRD pattern for cryptomelene shown as 2θ, the number of counts vs. Bragg angle using the square root scale. FIG. 21 is a graph of CO and hydrocarbon conversion rate vs. temperature based on Example 30.<u style="single">Detailed description of preferred embodiments</u>The present invention relates to devices and methods for cleaning a useful atmosphere by a vehicle having means for transporting the vehicle through the atmosphere. As the vehicle moves through the atmosphere, at least one atmospheric contact surface comprising a contaminant treatment composition (eg, a catalyst or adsorbent) located on the surface is in contact with the atmospheric air. As atmospheric air encounters contaminant treatment compositions, various contaminants, including particulate matter and / or gaseous contaminants carried into the air, are removed by the contaminant treatment composition located on the atmospheric contact surface. It can be contacted or adsorbed. It will be appreciated by those skilled in the art that the vehicle may be any suitable vehicle having a translational means for advancing the vehicle, such as a car, sail, belt, truck or analog. Such means include any suitable power means, such as an engine using fossil fuels such as gasoline or diesel fuel, ethanol, methanol, gas engines powered by fuels such as methane gas, wind forces such as wind driven. It can be powered by the power of a sail or propeller, the power of the sun, or the power of electricity, such as in a battery-powered vehicle. Vehicles include cars, trucks, buses, trains, boats, ships, planes, airships, balloons and analogues. The atmospheric contact surface may be any suitable surface that encounters and contacts air as the vehicle travels through the atmosphere. Preferably in an automobile, preferably a car, truck and bus, the contact means is a surface positioned towards the front of the vehicle and can come into contact with air as the vehicle travels forward. A useful contact surface should have a relatively large surface area. The preferred contact surface is at least partially surrounded by the vehicle. The preferred atmospheric contact surface is located under the hood and within the body of the vehicle, typically near the engine, i.e. the engine compartment. The surface is preferably a wall enclosure of the refrigerant in which fins for promoting heat transfer are located, such as a tube or a house. The outer surface of the cooling means, including a flow path for the liquid or gas through the tongue and the outer surface. Useful contact surfaces are means for cooling fluids such as liquids and / or gases used in vehicles, such as air conditioner condensers, radiators, charge coolers, engine oil coolers, transmission oil coolers, power. Includes the steering fluid cooler, fan cover, and outer surface of the radiator fan, all of which are located and supported within the vehicle housing. A useful contact surface on the outside of the vehicle is typically located on the front of the housing and supported grill, or a wind deflector generally supported on the roof of a large truck cab. Is fine. The contact surface is preferably a front-facing surface, a side-facing surface, or a top or bottom-facing surface of the vehicle. The front-facing surface is a fin-like surface of the radiator and condenser elements that faces the front of the vehicle and faces the sides, top and bottom of the vehicle. Even a surface directed away from and toward a surface of a vehicle in contact with air, such as the rear surface of a fan blade, can be an atmospheric contact surface. Airplane engine surfaces such as wings, propellers and jet engine components such as turbine rotors and / or stators can be coated. Preferred atmospheric contact surfaces in automobiles are located on engine cooling elements such as automotive radiators, air conditioner condensers, air intake coolers, also known as intercoolers or aftercoolers, engine oil coolers and transmission oil coolers. .. Such elements typically have a high surface area structure associated with them, with improved heat transfer. The high surface area is useful for maximizing contact between atmospheric air and the contaminant treatment composition. All such elements are well known in automotive technology. Robert, subscribed herein by reference.<u style="single">Bosch Automobile Handbook</u>, Second Edition, pages 301-303, 320 and 349-351. This reference illustrates a truck's diesel engine with radiators, intercoolers and fans. Such elements can be coated by the contaminant treated surfaces of the present invention. Radiators and intercoolers typically operate at temperatures above the temperature of the atmospheric air. For radiator and fin design, Taylor,<u style="single">Internal combustion engine in theory and practice</u>, Volume 1: Thermo Dynamics, Fluid Flow, Performance, Second Edition, Rev. The MIT Press, 1985, pp. 304-306, and also 392 for aftercoolers. The upper pages in Taylor are incorporated herein by reference. Published in 1993 by the Automotive Engineering Association<u style="single">Minutes of the 1993 Vehicle Heat Management System Meeting</u>See also the collection of articles in SAE P: 263. The following articles are incorporated herein by reference. By Eichlseder and Raab of Steyr Damler Puchag<u style="single">Cooling system calculation and design</u>And by the Collette of Valeo Thermique Moteur<u style="single">Intake air cooler for passenger cars</u>SAE Article No. 931088; Kern and Eitel of Behr GmbH and Co.<u style="single">Current status and future development of aluminum radiator technology for cars and trucks</u>SAE Article No. 931092; Rolling and Cummings of Behr of America, Inc. and Schweizer of Behr GmbH &amp; Co.<u style="single">Air mixing vs. refrigerant flow to control intake air temperature and vehicle heating air conditioning system</u>SAE Article 931112 entitled. The above paper includes a description of radiators, air conditioners and air intake cooler structures for use in automobiles. By the El-Bourini and Chen of Calsonic Technical Center, starting on page 379 and subscribing herein by reference.<u style="single">Development of engine cooling module using air flow management technology</u>See also SAE Article 931115 entitled. Of interest are Appendix 1 and 2, which illustrate typical radiator and capacitor structures useful in automotive applications. By Smith, Valeo Engine Cooling Inc., which discloses an air intake cooler and subscribes herein by reference.<u style="single">Concerns about the durability of aluminum air against aluminum intake coolers</u>See also SAE Article 931125 entitled. The present invention will be understood by those skilled in the art by reference to FIGS. 1-7 attached. FIG. 1 illustrates a track 10 that graphically includes various vehicle elements, including an atmospheric contact surface. These surfaces include the surfaces of the grill 12, the air conditioner condenser 14, the air intake cooler 25, the radiator 16 and the radiator fan 18. The truck also has a wind deflector 20 with a front deflecting surface 22. It is recognized that these various elements can have different relative positions on different vehicles. Explaining with reference to FIGS. 1-4, preferred contact surfaces are the front 13 and side 15 surfaces of the air conditioner condenser 14, the front 17 and side 19 surfaces of the radiator 16, the corresponding surfaces of the air intake cooler 25, and Includes front 21 and back 23 surfaces of radiator fan 18. These surfaces are located within the truck housing 24. They are typically under the hood 24 between the front 26 of the truck and the engine 28. The air conditioner condenser, air intake cooler, radiator and radiator fan can be directly or indirectly supported by the housing 24 or a frame (not shown) within the housing. FIG. 2 shows a schematic diagram of the automobile assembly as a whole. The corresponding elements in Figures 1 and 2 have a common reference number. The car includes a housing 30. There is an automobile front 32 with a supported grill 12 above the front of the housing 30. The air conditioner condenser 14, the radiator 16, and the radiator fan 18 can be positioned in the housing 30. Explaining the embodiments in FIGS. 1, 2 and 6, the grill 12, the air conditioner condenser 14, the air intake cooler 25, and the radiator 16; the front and back of the radiator fan 18; Also, the contact surfaces on at least one front and side of the wind deflector 20 can have contaminant treatment compositions located on them. The grill 12 can have a suitable grill net type design that provides an opening 36 through which air flows through the truck 12 as it is driven and travels through the atmosphere. These openings are defined by the grill net 38. The grill net 38 has a front grill surface 40 and a side grill surface 42. Front and side grill mesh surfaces 40 and 42 can be used as atmospheric contact surfaces for placing contaminant treatment compositions on them. Explained with reference to FIGS. 1 and 4, the air conditioner condenser 14 includes a plurality of air conditioner condenser fins 44. In addition, there is an air conditioner fluid conduit 46 that guides the air conditioner fluid through the condenser 14. The front and side surfaces of the air conditioner fins 44, as well as the front surfaces of the air conditioner conduit 46, can be atmospheric contact surfaces that position the contaminant treatment composition on them. As shown, the front 21 and back 23 surfaces of the radiator fan 18 can be contact surfaces to support the contaminant treatment composition. The most preferred atmospheric contact surface is on the radiator 16 as shown in FIG. A typical radiator 16 has a front radiator surface 17 as well as a plurality of radiator corrugated plates or fins 50 located in the corresponding radiator plate or fin channel 52 that pass through the radiator 16. It is preferable to coat the front surface 17, the side surface of the radiator plate 50, and the surface of the channel 52. The radiator is most preferred because it is located within the housing 24 or 30 and is protected from the front by at least the grill 12 and preferably the air conditioner condenser 14. In addition to getting air into the hood room 34 as the car moves through the atmosphere, the radiator fan 18 blows air into and through channels 52. Pull in. Therefore, the radiator 16 is positioned and protected by the grill 12, the air conditioner condenser 19, and is in the front of the radiator fan 18. In addition, as shown above, radiators have a large surface area for heat transfer purposes. According to the present invention, the contaminant treatment composition can be effectively positioned and utilized on such a large surface area without significantly adversely affecting the heat transfer function of the radiator. it can. The above description is specifically directed to and describes the use of atmospheric treatment surfaces on devices such as radiator 16 and air conditioner condenser 14. As shown above, the atmospheric contact surface is another suitable means for cooling the engine fluid, including well-known parts, such as the air intake cooler 25 cited above as well as the engine oil cooler, transmission oil. Can be above the cooler and power steering oil cooler. A common attribute of all such cooling means is the housing or the conduit through which the fluid flows. The housing includes a wall having an inner surface in contact with the fluid and typically an outer surface in contact with the atmosphere within the frame of the vehicle and typically within the engine compartment. In order to effectively transfer heat from the fluid in these various devices, there are fins or plates extending from the outer surface of the cooling, housing or conduit. Useful and preferred embodiments of each of these cooling means are illustrated in FIG. FIG. 7 is a schematic cross-sectional view of the cooling element 60 of the coated fins. This element includes the housing or conduit defined by the housing or conduit wall 62. A passage or chamber 64 through which a fluid, such as an oil or cooling liquid or air conditioner fluid, flows is located within the conduit. Such fluids are shown as reference letter 66. The walls of the housing include an inner surface 68 and an outer surface 70. A plate or fin 72 is located and attached to the outer surface. According to the present invention, on the outer surface 70 and on the fins or plates 72 There is a contaminant treatment composition 74 that can be positioned in. During operation, the air stream contacts the contaminant treatment composition to allow various contaminants to be treated. Applicants are hereby referring to the commonly assigned patent application entitled "Contaminant Treatment Devices and Methods of Making them" in Agent Document No. 3794/3810, filed as US Serial No. 08 / 537,208. To join. In addition, all of the devices of the invention and embodiments of the methods of use thereof can further incorporate replaceable contaminant treatment devices as disclosed therein, as required. The contaminant treatment composition can also be positioned on the outer surface of the vehicle. As shown, such compositions should be located on the grill 12 and, in the case of the trucks shown in FIGS. 1 and 6, on the wind deflector surface 22 on the front of the wind deflector 20. Can be done. In addition, the contaminant treatment composition can be positioned on the front of the mirror 54 as well as any variety of front facing surfaces. The use of an air intake cooler 25 represents a particularly effective atmospheric contact surface on which the contaminant treatment composition can be supported. The operating temperature can be as high as 25 ° F. At such temperatures, the catalytic compositions of the present invention can more effectively treat ozone, hydrocarbons, and carbon monoxide contaminants. Compositions containing noble metals such as platinum, palladium, gold or silver components are particularly useful. Instead, the catalyst comprises a manganese compound such as manganese dioxide and a copper compound such as copper oxide such as Carulite or hopcalite. During normal operation, the vehicle moves forward with the front 26 of the vehicle 10 first in contact with the atmospheric air. Typically, the vehicle is about 1, per hour for a jet plane. It travels through the air at speeds of up to 000 miles. Land and water vehicles typically travel at speeds of up to 300 miles per hour, and more typically up to 200 miles per hour, and cars up to 100 miles per hour and typically. Moves at a speed of 5 to 75 miles per hour. Marine vehicles, such as ships, typically move through water at speeds of up to 30 miles per hour and typically 2 to 20 miles per hour. According to the methods of the invention, the relative velocity (or surface velocity) between the atmosphere contact surface and the atmosphere is 0 per hour when the vehicle, typically a car or land-based vehicle, moves through the atmosphere. ~ 100 miles, and typically 2 to 75 miles per hour In a car, typically 5 to 60 miles per hour. Surface velocity is the velocity of air relative to the pollutant treated surface. In a vehicle such as a truck 10 having a radiator fan 18, the fan draws atmospheric air through a grill 12, an air conditioner condenser 14, an air intake cooler 25 and / or a radiator 16. This is in addition to the air flowing across these elements as the car moves through the atmosphere. When the car is idling, the relative surface velocity of the air drawn into the radiator is in the range of about 5-15mph. As the car moves through the atmosphere, the radiator fan relaxes the flow of air through the radiator. When a typical car is moving through the atmosphere at a speed close to 70 mph, the air inlet velocity is about 25 mph. Depending on the design of the car using the radiator fan, the car will have the same low surface speed as when the fan is used during idling up to about 100% of the surface speed corresponding to the speed of the car. However, typically, the surface velocity of the air relative to the atmospheric contact surface is 0.1 to 1.0 of the idling surface velocity + the velocity of the vehicle, and more typically 0.2 to 0. Equal to 8 times. According to the present invention, a large amount of air can be treated at a relatively low temperature. This happens when the vehicle moves through the atmosphere. The high surface area components of a vehicle, such as radiators, air conditioner condensers and intake air coolers, typically have a large front surface area that encounters airflow. However, these devices are relatively narrow, typically in the range of about 3/4 to about 2 inches deep of 1 inch and typically 3/4 to 1 + 1/2 inches. It is in the range of depth. The linear velocity of the air in the atmosphere in contact with the front surface of such a device is typically in the range of up to 20, and more typically 5 to 15 miles per hour. An indicator of the amount of air processed as air flows across the components of a contacted vehicle is commonly referred to as spatial velocity or, more precisely, volumetric spatiotemporal velocity (VHSV). This is measured as the volume of air per hour flowing across the volume of the catalyst article (corresponding to the volume of the contacted element). It is based on cubic feet of catalyst substrate divided by cubic feet per hour of air. The volume of the catalyst substrate is the depth or axial length of the front area multiplied by the air flow direction. Instead, volumetric time-spatial velocity is the number of catalyst volumes based on the volume of catalyst article processed per hour. Due to the relatively short axial depth of the contacted elements of the present invention, the spatial velocity is relatively high. The volumetric spatiotemporal velocity of air that can be processed according to the present invention can be a million or more vice versa. The surface velocity of air for these elements at 5 miles per hour can result in a high inverse temporal spatial velocity of 300,000. According to the present invention, the catalyst is 250,000-750,000 and typically 300,000-600, It is designed to treat contaminants in the atmosphere at speeds in the opposite time range of 000. This is achieved even at relatively low ambient temperatures, and at ambient operating temperatures of vehicle elements containing contaminant treatment compositions according to the present invention. The ambient operating temperature of the atmosphere in contact with the surface can vary depending on whether the surface is located near a heat source in the vehicle or is the surface of an element that serves to cool parts of the vehicle. However, the contact surfaces such as the grill 12 and the wind sway plate 20 are in ambient conditions. During typical operation, the means for cooling operates at a temperature higher than the ambient temperature, and the surfaces of the contact surfaces such as the air conditioner condenser 14, the radiator 16 and the air intake cooler 25 are 130 ° C. And typically can be in the range up to 105 ° C, and typically 10 ° C to 105 ° C, more typically 40 ° C to 100 ° C, and 10 ° C to It can be 75 ° C. The air intake cooler 25 typically operates at temperatures between 75 ° C and 130 ° C. The amount of contact surface can vary according to the air conditioner condenser, radiator and air intake cooler, and typically has 20-2,000 square feet, and the fan blade 18 is 0. when considering the front and back surfaces. It has 2 to about 40 square feet. The contaminant treatment composition is preferably a catalyst composition or an adsorption composition. A useful and preferred catalytic composition is one that can contactally trigger the reaction of the target contaminant at the air velocity of the air as it contacts the surface and at the temperature of the surface at the point of contact. Typically, these catalyzed reactions are 0 ° C to 130 ° C, more typically 20 ° C to 105 ° C, and even more typically about 40 ° C to 100 °. Will be in the temperature range at the atmospheric contacting surface of C. As long as some reaction occurs, there is no limit to the efficiency of the reaction. Preferably, there is a conversion efficiency of at least 1% with the highest conversion efficiency possible. Useful conversion efficiencies are preferably at least about 5% and most preferably at least about 10%. The preferred conversion depends on the particular contaminant and contaminant treatment composition. When ozone is treated with the catalytic composition on the atmospheric contact surface, the conversion efficiency is greater than about 30% -40%, preferably greater than 50%, and even more preferably greater than 70%. Is preferable. The preferred conversion for carbon monoxide is greater than 30% and preferably greater than 50%. The preferred conversion efficiency for hydrocarbons and partially oxygenated hydrocarbons is at least 10%, preferably at least 15%, and most preferably at least 25%. These conversion rate ratios are particularly preferred when the atmospheric contact surface is in ambient operating conditions up to about 110 ° C. These temperatures are the surface temperatures typically experienced during normal operation of atmospheric contact surfaces of vehicles, including the surfaces of radiators and air conditioner condensers. Conversion efficiency is greater than 90% and even more preferably in the presence of auxiliary heating of the atmospheric contact surface, such as by having an electrically heated catalytic monolith, grid, screen, gauze or analog. Is preferably greater than 95%. Conversion efficiency is the catalyst composition It is based on the molar% of certain pollutants in the air that react in the presence of. The ozone treatment catalyst composition is a manganese compound such as manganese dioxide, such as non-stoichiometric manganese dioxide (eg, MnO)._(1.5-2.0)) And / or Mn₂O₃including. Nominal MnO₂The preferred manganese dioxide, called manganese dioxide, has a chemical formula such that the molar ratio of manganese to oxide is about 1.5-2.0, eg Mn.₈O₁₆Have. Manganese dioxide MnO up to 100% by weight₂Can be used in catalytic compositions for treating ozone. Alternative compositions available include manganese dioxide, as well as copper oxide alone or compounds such as copper oxide and alumina. A useful and preferred manganese dioxide is α-manganese dioxide, which nominally has a molar ratio of manganese to oxygen of 1-2. Useful manganese dioxide is found in US Pat. No. 5,340,562 to O'Young et al.; Zeolite and columnar clay structures submitted before the Petrochemical Subcommittee of the New York City Council of the American Chemistry Association, August 25-30, 1991. In O'Young, hydrothermal synthesis of manganese oxide with a tunnel structure, submitted at the Symposium on Progress in the Body, beginning on page 342, and McKenzie, Birnessite, cryptomelene and some others. Synthesis of Manganese Oxides and Hydroxides, Mineralogical Magazine, December 1971, Vol. 38, pp. 493-502. The preferred α-manganese dioxide for the purposes of the present invention is Holland ore (BaMn).₈O₁₆ XH₂O), cryptomelen (KMn)₈O₁₆ XH₂O), manjiroite (NaMn)₈O₁₆ XH₂O) and coronado ore (PbMn)₈O₁₆ XH₂O) is a good 2x2 tunnel structure. The manganese dioxide of the present invention is preferably 150 m.²Greater than / g, more preferably 200m²Greater than / g, and more preferably 220m²Greater than / g, BET N₂It has a surface area measured by adsorption. The upper area is 300m²/ g, 325m²/ g or more 350m²It may be as high as 3 / g. Preferred substances are 200-350 m²/ g, preferably 200-275m²/ g and most preferably 220-250m²It is in the range of / g. The composition preferably comprises the binder described below, and the preferred binder is a polymeric binder. The composition can further contain a noble metal component, and the preferred noble metal component is an oxide of the noble metal, preferably an oxide of a platinum group metal and most preferably an oxidation of palladium or platinum, also referred to as palladium black or platinum black. It is a thing. The amount of palladium or platinum black may be in the range of 0-25%, and useful amounts are in the range of about 1-25 and 5-15% by weight based on the weight of the manganese and noble metal components. The use of compositions containing the cryptomelene form of α-manganese oxide, and also containing a polymeric binder, is a concentration range of 0 to 400 parts per billion (ppb) and a reciprocal time space of 300,000 to 650,000. It has been found that in the air flow moving across the radiator at a rate, it is possible to result in ozone conversion rates greater than 50%, preferably greater than 60% and most preferably 75-85%. When replacing a portion of cryptomelene with up to 25% and preferably 15-25% by weight of palladium black (PdO), the ozone conversion ratio under the above conditions is 95 ~ using a powder reactor. It will be in the 100% range. Preferred cryptomelene manganese dioxide is typically K₂It has 1.0 to 3.0% by weight potassium as O, and the crystal size is in the range of 2 to 10 and preferably less than 5 nm. It can be calcined at 250-550 ° C and preferably in a temperature range below 500 ° C and above 300 ° C for at least 1.5 hours and preferably at least 2 to about 6 hours. Preferred cryptomelene can be made according to the articles and patents cited above to O'Young and McKenzie. Cryptomelene is MnCl₂, Mn (NO)₃)₂, MnSO₄And Mn (CH)₃COO)₂It can be made by reacting a manganese salt containing a salt selected from the group consisting of with a permanganate compound. Cryptomellene is made with potassium permanganate, Holland ore is made with barium permanganate, coronado ore is made with lead permanganate, and manjiroite is sodium permanganate. Made using. It is recognized that α-manganese useful in the present invention can include one or more Holland ore, cryptomelene, manjiroite or coronado ore compounds. Even when making cryptomelene, small amounts of other metal ions, such as sodium, may be present. Useful methods for producing α-manganese dioxide are described in the above references, which are incorporated herein by reference. The preferred α-manganese for use according to the invention is cryptomelene. Preferred cryptomelene is "clean" or substantially free of inorganic anions, especially on the surface. Such anions will include chlorides, sulfates and nitrates introduced during the method for producing cryptomelene. An alternative method for making clean cryptomelene is to react manganese carboxylate, preferably manganese acetate, with potassium permanganate. The use of such substances that have already been calcined has been found to be "clean". The use of substances containing inorganic anions can result in the conversion of ozone to oxygen up to about 60%. The use of cryptomelene with a "clean" surface results in conversion rates in excess of about 80%. It is believed that the carboxylate is incinerated and removed during the firing process. However, the inorganic anions remain on the surface even during firing. Inorganic anions such as sulfate can be washed away with an aqueous solution or a slightly acidic aqueous solution. Preferably, the α-manganese dioxide is a clean α-manganese dioxide. Cryptomeren is washed at about 60 ° C to 100 ° C for about half an hour and a significant amount of sulfatea Nion can be removed. This wash also reduces the level of potassium present. The nitrate anion can be removed in a similar manner. "Clean" α-manganese dioxide is characterized as having an IR spectrum as shown in FIG. 19 and in an X-ray diffraction (XRD) pattern as shown in FIG. Such cryptomelene is preferably 200 m.²Greater than / g and even more preferably 250m²Has a surface area greater than / g. The overview of the IR spectrum for the most preferred cryptomelene, shown in FIG. 19, is characterized by the absence of peaks attributed to carbonate, sulfate and nitrate groups. Expected peaks for carbonate groups appear in the wavenumber region of 1320 to 1520, and for sulfate groups in the wavenumber region of 950 to 1250. FIG. 20 is a powder X-ray diffraction pattern for the high surface area cryptomelene produced in Example 23. The X-ray pattern for cryptomelene useful in the present invention is characterized by a wide range of peaks originating from a small crystallite size (~ 5-10 nm). CuK as shown in Figure 20_αThe rough peak position (± 0.15 ° 2θ) and rough intensity (± 5) for cryptomelene using radiation are 2θ / relative intensity-12.1 / 9; 18/9; 28.3 / 10; 37.5 / 100; 41.8 / 32; 49.7 / 16; 53.8 / 5; 60.1 / 13; 55.7 / 38; and 68.0 / 23. A preferred method of making cryptomelene useful in the present invention consists of mixing an aqueous acidic manganese salt solution with a potassium permanganate solution. The acidic manganese salt solution preferably has a pH of 0.5-3.0 and is acidified using any common acid, preferably acetic acid at concentrations of 0.5-5.0 and even more preferably 1.0-2.0. Can be done. The mixture forms a slurry, which is agitated in the temperature range of 50 ° C to 110 ° C. The slurry is filtered and the filtrate is dried over a temperature range of 75 ° C to 200 ° C. The cryptomelene crystals produced are typically 200 m.²/ g ~ 350m²It has a surface area in the range of / g. Another useful composition containing manganese dioxide is a composition containing manganese dioxide and a small amount of silica, typically up to 2%, even more typically up to 1%, and preferred amounts are It is 0.4 to 0.8% based on the weight of manganese dioxide and silica. It has been found that the presence of a preferred amount of silica results in the microcrystalline form of manganese dioxide, especially the cryptomelene form of manganese dioxide. It is speculated that the presence of a small amount of particularly preferred range of silica may provide certain advantages to the compositions of the present invention. The presence of silica is believed to make the composition more hydrophobic, especially when used as a coating on a substrate, eg, a coating on a radiator. Second, the presence of silica in the coating composition containing manganese dioxide is believed to increase the pH and aid in the compatibility of manganese dioxide with the latex binder. Preferred and useful compositions for use as coating materials include cryptomelene and silica. Such substances are 200-340 and preferably 220-250 m.²Includes cryptomelene with a surface area of / g, 1-3% by weight potassium, less than 0.1% by weight sulfur, and 13-18% by weight of measured ignition loss primarily due to moisture. The pH of the composition is about 3. Surface area is measured by BET nitrogen adsorption and desorption test. As the amount of sulfur decreases, the pH typically increases slightly. In addition, the pH typically increases with the amount of potassium present, and the preferred amount of potassium is 1.2-2.8% by weight. Other useful compositions include manganese dioxide and, if necessary, copper oxide and alumina, and manganese dioxide and, if present, copper oxide and at least one noble metal component supported on the alumina, such as a platinum group metal component. Including. Useful compositions include up to 100, 40-80 and preferably 50-70% by weight manganese dioxide, and 10-60 and typically 30-50% copper oxide. Useful compositions have about 60% manganese dioxide and about 40% copper oxide, Hopcalite; as well as 60-75% by weight manganese dioxide, 11-14% copper oxide and 15-16% aluminum oxide. Carulite reported to be^(R)Includes (sold by Carus Chemical Co.). Carulite^(R)Surface area is about 180m²It is reported to be / g. Baking at 450 ° C does not significantly affect activity and only about 50% Carulite^(R)Reduces the surface area of. It is preferable to calcin the manganese compound at 300 ° C to 500 ° C and more preferably 350 ° C to 450 ° C. Baking at 550 ° C causes a large loss of surface area and ozone treatment activity. Carulite after ball milling with acetic acid^(R)Baking and coating on the substrate can improve the adhesion of the coating to the substrate. Other compositions for treating ozone can include manganese dioxide components and noble metal components such as platinum group metal components. Manganese dioxide can also support noble metal components, although both components are contactively active. The platinum group metal component is preferably palladium and / or a platinum component. The amount of the platinum group metal compound is preferably in the range of about 0.1 to about 10% by weight (based on the weight of the platinum group metal) of the composition. Preferably, if platinum is present, it is in an amount of 0.1-5% by weight, and a useful and preferred amount based on the volume of the contaminant treatment catalyst is about 0.5-based on the volume of the supporting object. About 70g / ft³Is the range of. The amount of the palladium component preferably ranges from about 2 to about 10% by weight of the composition, and a useful and preferable amount based on the contaminant treatment catalyst volume is from about 10 to about 250 g / ft.³Is the range of. Various useful and preferred contaminant treatment catalyst compositions, in particular compositions containing contactally active components such as noble metal catalyst components, can include suitable support materials such as refractory oxide supports. Preferred refractory oxides can be selected from the group consisting of silica, alumina, titania, ceria, zirconia and chromia and mixtures thereof. More preferably, the support is at least one activated high selected from the group consisting of alumina, silica, titania, silica-alumina, silica-zirconia, alumina silicate, alumina zirconia, alumina-chromia and alumina-ceria. It is a surface area compound. The refractory oxide is in bulk granular form, typically having a particle size in the range of about 0.1 to about 100 and preferably 1 to 10 μm, or also a particle size in the range of about 1 to about 50 and preferably about 1 to about 10 nm. Any suitable form may be used, including the form of a sol having. A preferred titania sol support consists of titania with a particle size in the range of about 1 to about 10, and typically about 2 to 5 nm. A co-precipitate of manganese oxide and zirconia is also useful as a preferred support. This composition may be made as cited in US Pat. No. 5,283,041 incorporated herein by reference. Briefly, this co-precipitated support material is preferably 5:95 to 95: 5, preferably 10:90 to 75:25, even more preferably 10:90 to 50:50, and most preferably 15. It consists of a ratio based on the weight of manganese and zirconium metals from: 85 to 50:50. A useful and preferred embodiment consists of a 20:80 Mn: Zr weight ratio. U.S. Pat. No. 5,283,041 describes a preferred method for making co-precipitates of manganese oxide and zirconia components. U.S. Pat. No. 5,283, As cited in No. 041, zirconia oxide and manganese oxide substances are suitable zirconium oxide precursors such as zirconium oxynitrate, zirconium acetate, zirconium oxychloride or zirconium oxysulfate, and suitable manganese oxide precursors. For example, mixing an aqueous solution of manganese nitrate, manganese acetate, manganese dichloride or manganese dibromide, adding a sufficient amount of base such as ammonium hydroxide to obtain a pH of 8-9, forming a precipitate. It can be produced by filtering, washing with water, and drying at 450 ° C to 500 ° C. Useful supports for catalysts for treating ozone are selected from refractory oxide supports, preferably alumina and silica-alumina, and more preferred supports are from about 1-10% by weight silica and A silica-alumina support containing 90-99% by weight of alumina. Useful refractory oxide supports for catalysts containing platinum group metals for treating carbon monoxide are selected from alumina, titania, silica-zirconia, and manganese-zirconia. Preferred supports for catalytic compositions for treating carbon monoxide are zirconia-silica supports as cited in US Pat. No. 5,145,825, US Pat. No. 5,283, Manganese-zirconia supports, as cited in No. 041, and high surface area alumina. Titania is most preferred for the treatment of carbon monoxide. Reduced catalysts with titania supports resulted in greater carbon monoxide conversion than the corresponding non-reducing catalysts. Hydrocarbons such as low molecular weight hydrocarbons, especially low molecular weight olefinic hydrocarbons having about 2 to about 20 carbons and typically 2 to about 8 carbon atoms, as well as partially oxygenated hydrocarbons. The support for the catalyst for treating is preferably selected from refractory metal oxides containing alumina and titania. For catalysts for treating carbon monoxide, reduced catalysts result in higher hydrocarbon conversion rates. The titania support found to be useful is particularly preferred, as the titania support provides a catalytic composition with an enhanced ozone conversion and a significant conversion of carbon monoxide and low molecular weight olefins. High surface area macroporous refractory oxide, preferably 150 m²Greater than / g and preferably about 150-350, preferably 200-300, and even more preferably 225-275 m²Surface area in the range of / g; porosity in the range of greater than 0.5 cc / g, typically 0.5-4.0 and preferably about 1-2 cc / g as measured based on the mercury porosity method; as well as 0.1 Alumina and titania with a particle size range of ~ 10 μm are also useful. Useful substance is about 260m²Versal with a surface area of / g, a porosity of 1.4-1.5 cc / g and supplied by La Roche Industries GL alumina. A preferred refractory support for platinum group metals, preferably platinum and / or palladium, for use in treating carbon monoxide and / or hydrocarbons is titania dioxide. Titania can be used in the form of bulk powder or in the form of titania sol dioxide. Nano-particle size (nanometer) titania is also useful. The catalyst composition can be made by adding platinum nitrate, preferably in the form of a solution, with a platinum group metal such as titania sol, and the sol is most preferred. The resulting slurry can then be coated on a suitable substrate such as an atmospheric contact surface such as a radiator, metal integral substrate or ceramic substrate. A preferred platinum group metal is a platinum compound. The platinum titania sol catalyst obtained from the above procedure has high activity for carbon monoxide and / or hydrocarbon oxidation at ambient operating temperature. Metallic components other than the platinum component that can be combined with titania sol include gold, palladium, rhodium, silver components and mixtures thereof. It has also been found that the reduced platinum group components, preferably the platinum components on titanium catalysts shown to be preferred for treating carbon monoxide, are also useful and preferred for treating hydrocarbons, especially olefinic hydrocarbons. Was done. A preferred titania sol support consists of titania with a particle size in the range of about 1 to about 10, and typically about 2 to 5 nm. Preferred bulk titania is about 25-120m²/ g, and preferably 50-100m²It has a surface area of / g; and a particle size of about 0.1-10 μm. Specific and preferred bulk titania supports are 45-50 m²It has a surface area of / g, a particle size of about 1 μm, and is marketed as P-25 by DeGussa. Useful nano-grain size titania consists of particle sizes ranging from about 5 to 100 and typically greater than 10 and up to 50 nm. Preferred silica-zirconia supports consist of 1-10% silica and 90-99% zirconia. Preferred support particles have a high surface area, eg 100-500 square meters (m) per gram, to enhance the dispersion of one or more catalytic metal components on them.²/ g) surface area, preferably 150-450m²/ g, more preferably 200-400m²Has / g. Preferred refractory metal oxide supports also have high porosity with pores up to a radius of about 145 nm, eg about 0.75 to 1.5 cubic centimeters (cm) per gram.³/ g), preferably about 0.9-1.2 cm³A pore size range with / g and a porosity of at least about 50% is provided by pores with a radius of 5-100 nm. Useful ozone treatment catalysts include at least one noble metal component dispersed on a suitable support, eg, a refractory oxide support. The composition is 0.1-20.0% by weight, preferably 0.5-15% by weight, on a support such as a refractory oxide support, based on the weight of the noble metal (metal and not oxide) and support. Includes% precious metals. Palladium is preferably used in an amount of 2 to 15, even more preferably 5 to 15, and even more preferably 8 to 12% by weight. Platinum is preferably used in an amount of 0.1 to 10, more preferably 0.1 to 5.0, and even more preferably 2 to 5% by weight. Palladium is most preferred for contacting the reaction of ozone to generate oxygen. The support material can be selected from the groups mentioned above. In a preferred embodiment, the bulk manganese component as described above, or the manganese component dispersed on the same or different refractory oxide support as the noble metal preferably palladium component, may be additionally present. .. Up to 80, preferably up to 50, even more preferably 1 to 40, and even more preferably 5 to 35% by weight of manganese components can be present based on the weight of the palladium and manganese metals in the contaminant treatment composition. .. In another way, there are preferably about 2-30 and preferably 2-10% by weight of manganese content. Catalyst loading is 20-250 grams (g / ft) per cubic foot of catalyst capacity³) And preferably about 50-250 grams of palladium. The catalyst capacity is the total capacity of the finished catalyst composition and therefore includes the total capacity of the air conditioner condenser or radiator including the void space provided by the gas flow passage. In general, higher palladium loadings result in higher ozone conversion rates, i.e., higher percentages of ozone decomposition in the air stream being processed. The conversion of ozone to oxygen achieved by the palladium / manganese catalyst on the alumina support composition at a temperature of about 40 ° C to 50 ° C has an ozone concentration in the range of 0.1 to 0.4 ppm and a surface velocity. Was about 50 mol% if was about 10 miles per hour. Lower conversions were achieved with the use of platinum catalysts on alumina. Of particular interest is the use of a support consisting of the co-precipitated products of manganese oxide and zirconia, preferably selected from platinum and palladium and most preferably used to support the noble metal which is platinum. There is. Platinum is of particular interest as it has been found to be particularly effective when platinum is used on this co-precipitated support. The amount of platinum may be in the range of 0.1-6, preferably 0.5-4, more preferably 1-4, and most preferably 2-4% by weight, based on the metallic platinum and the co-precipitated support. The use of platinum to treat ozone has been found to be particularly effective on this support. In addition, as discussed below, this catalyst is useful for treating carbon monoxide. Preferably, the noble metal is platinum and the catalyst is reduced. Other useful catalysts for the catalytic conversion of ozone to oxygen are described in US Pat. Nos. 4,343,776 and 4,405,507, both of which are incorporated herein by reference. Useful and most preferred compositions are commonly assigned and filed on February 25, 1994, US Serial No. 08/202, which is incorporated herein by reference. 397, now described in US Pat. No. 5,422,331 entitled "Lightweight Low Pressure Ozonolytic Catalyst for Airplane Applications". Other compositions that can result in the conversion of ozone to oxygen include carbon, as well as carbon, manganese dioxide, and Carulite.^(R)And / or contains palladium or platinum supported on top of hopcarite. Manganese supported on top of refractory oxides as mentioned above has also been found to be useful. The carbon monoxide treatment catalyst preferably comprises at least one selected from at least one noble metal component, preferably a platinum and / or palladium component, with the platinum component being most preferred. The combination of platinum and palladium components results in improved CO conversion at an increased cost, and is most preferred if a higher conversion is desirable and the cost increase is acceptable. The composition comprises 0.01-20% by weight, and preferably 0.5-15% by weight of noble metal components on a suitable support such as a refractory oxide support, and the amount of noble metal is noble metal (metal and It is based on the weight of the support (not the metallic component). Platinum is most preferably used in an amount of 0.01-10% by weight, even more preferably 0.1-5% by weight, and most preferably 1.0-5.0% by weight. Palladium is useful in an amount of 2 to 15, preferably 5 to 15, and even more preferably 8 to 12% by weight. The preferred support is titania, and as mentioned above, titania sol is most preferred. When loaded onto a single structure, such as a radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150, and even more preferably 10-100 grams, per cubic foot of catalyst capacity. g / ft³) Platinum and / or 20-250 per catalytic volume and preferably 50-250 grams (g / ft)³) Palladium. Approximately 25-100g / ft when using a combination of platinum and palladium³Platinum and 50 ~ 250g / ft³Palladium is present. A preferred composition is about 50-90 g / ft³Platinum and 100 ~ 225g / ft³Contains palladium. The preferred catalyst has been reduced. A coated core sample from an automobile radiator with a platinum composition of 1-6% by weight (based on metal) on titania with a conversion of 5-80 mol% from carbon monoxide to carbon dioxide. Achieved when using carbon monoxide concentration at a temperature of 25-90 ° C and a space velocity of 300,000-500,000 opposite times. Also, carbon monoxide with a conversion of 5 to 65 mol% from carbon monoxide to carbon dioxide at temperatures up to about 95 ° C using a platinum composition of 1.5 to 4.0% by weight on an alumina support. Achieved when the concentration was about 15-25 ppm and the space velocity was about 300,000 opposite times. Lower conversion was achieved by palladium on the ceria support. Alternative and preferred catalytic compositions for treating carbon monoxide include manganese oxide and noble metal components supported on the co-precipitates mentioned above for zirconia. The co-precipitate is produced as described above. The preferred ratio of manganese to zirconia is 5:95 to 95: 5; 10: 90 to 75:25; 10: 90 to 50:50; and 15: 85 to 25:75, and the preferred co-precipitate is 20. Has: 80 manganese oxide vs. zirconia. The percentage of platinum supported on the platinum metal-based co-precipitate is 0.1-6, preferably 0. It is in the range of 5 to 4, more preferably 1 to 4, and most preferably 2 to 4% by weight. Preferably, the catalyst is reduced. The catalyst can be reduced in powder form or after it has been coated on a support substrate. Other useful compositions capable of converting carbon monoxide to carbon dioxide include a platinum component supported on a support containing carbon, or manganese dioxide. Hydrocarbons, typically unsaturated hydrocarbons, and more typically unsaturated monoolefins with 2 to about 20 carbon atoms and especially 2 to 8 carbon atoms, and partials of the types mentioned above. The catalyst for treating an oxygenated hydrocarbon preferably contains at least one noble metal component selected from platinum and palladium, with platinum being most preferred. The combination of platinum and palladium components results in improved hydrocarbon conversions under increased costs, and is most preferred if higher conversions are desirable and cost increases are acceptable. Useful catalytic compositions include those described for use in treating carbon monoxide. The composition for treating hydrocarbons comprises 0.01-20% by weight, and preferably 0.5-15% by weight of noble metal components on a suitable support such as a refractory oxide support, and the amount of noble metal , Based on the weight of precious metals (not metallic components) and supports. Platinum is most preferably used in an amount of 0.01-10% by weight, even more preferably 0.1-5% by weight, and most preferably 1.0-5% by weight. When loaded onto a single structure such as an automotive radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150 per cubic foot of catalyst capacity, and even more preferably 10-100 grams. (g / ft Used in an amount of 0-5% by weight. When loaded onto a single structure, eg, an automotive radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150 per cubic foot of catalyst capacity, and even more preferably 10-100 grams. (g / ft Used in an amount of 0-5% by weight. When loaded onto a single structure, eg, an automotive radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150 per cubic foot of catalyst capacity, and even more preferably 10-100 grams. (g / ft Used in an amount of 0-5% by weight. When loaded onto a single structure, eg, an automotive radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150 per cubic foot of catalyst capacity, and even more preferably 10-100 grams. (g / ft Used in an amount of 0-5% by weight. When loaded onto a single structure, eg, an automotive radiator or other atmospheric contact surface, the catalyst loading is preferably about 1-150 per cubic foot of catalyst capacity, and even more preferably 10-100 grams. (g / ft³) Platinum. Approximately 25-100g / ft when using a combination of platinum and palladium³Platinum and 50 ~ 250g / ft³Palladium is present. A preferred composition is about 50-90 g / ft³Platinum and 100 ~ 225g / ft³Contains palladium. Preferred refractory oxide supports are preferably metal oxide refractories selected from ceria, silica, zirconia, alumina, titania and mixtures thereof, with alumina and titania being most preferred. Preferred titania is characterized as described above, and titania sol is most preferred. The preferred catalyst has been reduced. Testing on coated automotive radiators resulted in the conversion of low molecular weight monoolefins such as propylene to water and carbon dioxide, and 1.5-4 wt% platinum on alumina or titania supports has a propylene concentration of about 10 ppm. It was 15-25% when it was propylene and the space velocity was 320,000 reverse times. These catalysts were not reduced. Catalytic reduction improves conversion. Catalysts useful for the oxidation of both carbon monoxide and hydrocarbons generally include those mentioned above as useful for treating either carbon monoxide or hydrocarbons. The most preferred catalysts found to have good activity for the treatment of both carbon monoxide and hydrocarbons such as unsaturated olefins include a platinum component supported on a preferred titania support. This composition preferably comprises a binder and 0.8-1. It can be coated on a suitable support structure in an amount of 0 g / in. Preferred platinum concentrations range from 2 to 6 and preferably 3 to 5% by weight of platinum metal on the titania support. A useful and preferred substrate cell density is equal to about 300-400 cells per square inch. The catalyst is preferably reduced as a powder or on a coated article using a suitable reducing agent. Preferably, the catalyst is reduced at 200-500 ° C for 1-12 hours in a gas stream consisting of about 7% hydrogen and the remaining nitrogen. The most preferred reduction or formation temperature is 400 ° C for 2-6 hours. This catalyst has been found to maintain high activity after long exposures at high temperatures up to 100 ° C in air or moist air. A useful catalyst capable of treating both ozone and carbon monoxide is selected from at least one noble metal component on a suitable support, eg, a refractory oxide support, most preferably palladium, platinum and mixtures thereof. Contains precious metals. The combination of platinum and palladium components results in improved CO conversion at an increased cost, and is most preferred if a higher conversion is desirable and the cost increase is acceptable. Useful refractory oxide supports include ceria, zirconia, alumina, titania, silica, and mixtures thereof, including mixtures of zirconia and silica as described above. The manganese oxide and zirconia co-precipitates mentioned above are also useful and preferred as supports. The composition comprises 0.1 to 20.0, preferably 0.5 to 15, and even more preferably 1 to 10% by weight of the noble metal component on the support, based on the weight of the noble metal and support. Palladium is preferably used in an amount of 2 to 15 and even more preferably 3 to 8% by weight. Platinum is preferably 0. It is used in an amount of 1 to 6 and even more preferably 2 to 5% by weight. A preferred composition is one in which the refractory component comprises ceria and the noble metal component comprises palladium. This composition resulted in a relatively high ozone and carbon monoxide conversion. More specifically, testing of this composition on a coated radiator was performed with a surface contact at 95 ° C. with a surface velocity of 5 miles per hour for an air stream containing 16 ppm carbon monoxide. It resulted in a conversion rate of 21% of carbon monoxide in. The same catalyst, but the flow is 0. It contained 25 ppm ozone and resulted in a 55% ozone conversion rate with an air flow surface velocity of 10 miles per hour when the treated surface was 25 ° C. A composition comprising a noble metal, preferably a platinum group metal, more preferably a noble metal selected from platinum and palladium components, and most preferably a platinum component and a co-precipitate of manganese oxide and zirconia described above is also preferred. The noble metal-containing catalysts mentioned above in the form of catalyst powder or coating on a suitable substrate are in reduced form. Preferred reduction conditions include those mentioned above, and the most preferred conditions are 250-350 ° C. for 2-4 hours in a reducing gas consisting of 7% hydrogen and 93% nitrogen. This catalyst has been found to be particularly useful in treating both carbon monoxide and ozone. Other compositions useful for converting ozone to oxygen and carbon monoxide to carbon dioxide include carbon, manganese dioxide, or a platinum component supported on a refractory oxide support, and if required. It has an additional manganese component accordingly. Useful and preferred catalysts capable of treating ozone, carbon monoxide and hydrocarbons, and partially oxygenated hydrocarbons are noble metal components on suitable supports such as refractory oxide supports, preferably. Contains platinum component. The combination of platinum and palladium components results in improved CO conversion at an increased cost, and is most preferred if a higher conversion is desirable and the cost increase is acceptable. Useful refractory oxide supports include ceria, zirconia, alumina, titania, silica, and mixtures thereof, including mixtures of zirconia and silica as described above. Supports containing the above-mentioned co-precipitates of manganese oxide and zirconia are also useful. The composition is 0.1-20, preferably 0., based on the weight of the noble metal and the support. It contains 5-15, and more preferably 1-10% by weight, of noble metal components on the refractory support. When conversion of hydrocarbon components to carbon dioxide and water is required, platinum is the most preferred catalyst and is preferably used in an amount of 0.1-5 and even more preferably 2-5% by weight. In certain embodiments, there may be a combination of the catalysts described above as well as catalysts containing catalysts particularly preferred for the treatment of ozone, eg, catalysts containing a manganese component. The manganese component can be combined with the platinum component if necessary. Manganese and platinum can be on the same or different supports. Up to 80, preferably up to 50, even more preferably 1-40, and even more preferably 10-35% by weight of manganese components can be present based on the weight of the noble metal and manganese in the contaminant treatment composition. The catalyst loading is the same as described above for ozone catalysts. A preferred composition is one in which the refractory component comprises an alumina or titania support and the noble metal component comprises a platinum component. Testing of such compositions coated on a radiator has a surface velocity of gas flow of approximately 10 miles per hour with an air dew point of 35 ° F (320, reverse time). When the surfaces were brought into contact at 95 ° C (with a spatiotemporal velocity of 000), carbon monoxide conversion was 68-72%, ozone conversion was 8-15%, and propylene conversion was 17-18%. In general, the percentage conversion rate decreases as the contact surface temperature decreases and the spatial velocity of the surface velocity of the atmospheric airflow above the pollutant contact surface increases. Catalytic activity, especially those for treating carbon monoxide and hydrocarbons, can be further enhanced by reducing the catalyst in forming gases such as hydrogen, carbon monoxide, methane or hydrocarbons and nitrogen gases. Alternatively, the reducing agent may be in liquid form such as hydrazine, formic acid and formate such as sodium formate solution. The catalyst can be reduced as a powder or after coating on a substrate. The reduction can be carried out at 150 to 500 ° C., preferably 200 to 400 ° C. for 1 to 12 hours, preferably 2 to 8 hours. In a preferred method, the coated article or powder can be reduced at 275-350 ° C. for 2-4 hours in a gas containing 7% hydrogen in nitrogen. Alternative compositions for use in the methods and devices of the present invention include noble metal components such as contactally active substances selected from the group consisting of platinum group metal components, gold and silver components, as well as tungsten and rhenium components. Contains metal components selected from the group consisting of. The relative amount of contact-active material to tungsten and / or rhenium components based on the weight of the metal is 1: 25-15: 1. Compositions containing a tungsten component and / or a rhenium component preferably contain tungsten and / or rhenium in the form of an oxide. Oxides can be obtained by producing a composition using tungsten or rhenium salts, and subsequently the composition can be calcined to produce tungsten and / or rhenium oxide. The composition can include additional components such as a support such as a refractory oxide support, a manganese component, carbon, and a co-precipitate of manganese oxide and zirconia. Useful refractory metal oxides are alumina, series Includes mosquitoes, titania, ceria, zirconia, chromia and mixtures thereof. The composition can additionally include a binder material, such as a metallic sol, such as an alumina or titania sol, or a polymeric binder that can be supplied in the form of a polymeric latex binder. In a preferred composition, there are 0.5 to 15, preferably 1 to 10, and most preferably 3 to 5% by weight of contactally active material. Preferred contactally active substances are platinum group metals, with platinum and palladium being more preferred, and platinum being most preferred. The amount of the tungsten and / or rhenium component based on the metal is in the range of 1 to 25, preferably 2 to 15, and most preferably 3 to 10% by weight. The amount of binder can vary from 0 to 20% by weight, preferably 0.5 to 20, more preferably 2 to 10, and most preferably 2 to 5% by weight. No binder is required in this composition, depending on the support material. Preferred compositions are 60-98.5% by weight refractory oxide support, 0.5-15% by weight contactally active material, 1-25% by weight tungsten and / or rhenium component, and 0-10% by weight. Includes binder. The composition containing the tungsten component and the rhenium component can be calcined under the conditions described above. In addition, this composition can be reduced. However, as shown in the examples below, the composition does not necessarily have to be reduced, and the presence of the tungsten and / or rhenium components is comparable to carbon monoxide and compositions containing reduced platinum group metals. It can provide a conversion of hydrocarbons. The contaminant treatment compositions of the present invention preferably contain a binder that acts to bond the composition and provide adhesion to the atmospheric contact surface. Preferred binders are 0. A polymeric binder used in an amount of 5-20, more preferably 2-10, and most preferably 2-5% by weight. Preferably, the binder is a polymeric binder, which may be a thermosetting or thermoplastic polymeric binder. Polymeric binders can have suitable stabilizers and anti-aging agents known in polymer technology. The polymer may be a plastic or elastomeric polymer. The slurry of the catalyst composition is preferably a thermosetting, elastomeric polymer introduced as a latex into the catalyst into an aqueous slurry. Upon application and heating of the composition, the binder material can bridge and provide a suitable support that enhances its adhesion to the substance of the coating, the atmospheric contact surface, and under the vibrations encountered in automobiles. Gives structural stability. The use of a preferred polymeric binder allows the contaminant treatment composition to adhere to the atmospheric contact surface without the need for an undercoat layer. Binders can include water resistant additives to improve water resistance and adhesion. Such additives can include fluorocarbon emulsions and petroleum wax emulsions. Useful polymeric compositions include polyethylene, polypropylene, polyolefin copolymers, polyisoprenes, polybutadienes, polybutadiene copolymers, chlorinated rubbers, nitrile rubbers, polychloroprenes, ethylene-propylene-diene elastomers, polystyrenes, polyacrylates, polymethacrylates, polyacrylonitriles. , Poly (vinyl ester), poly (vinyl halide), polyamide, cellulose polymer, polyimide, acrylic, vinyl acrylic and styrene acrylic, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, poly (phenylene oxide), poly ( Phenylene sulfide), fluorinated polymers such as poly (tetrafluoroethylene), polyvinylidene fluoride, poly (vinyl fluoride) and chloro / fluorocopolymas. -Includes, for example, ethylene chlorotrifluoroethylene copolymers, polyamides, phenolic and epoxy resins, polyurethanes, and silicone polymers. The most preferred polymeric material is an acrylic polymeric latex as described in the attached examples. Particularly preferred polymers and copolymers are vinyl acrylic polymers and ethylene vinyl acetate copolymers. A preferred vinyl acrylic polymer is a bridging polymer sold by the National Starch and Chemical Company as Xlink 2833. It is described as a vinyl acrylic polymer with a Tg of -15 ° C, a 45% solid, a pH of 4.5 and a viscosity of 300 cps. In particular, it is pointed out that it has vinyl acetate CAS No. 108-05-4 in the concentration range less than 0.5%. It is pointed out that it is a vinyl acetate copolymer. Other preferred vinyl acetate copolymers sold by the National Starch and Chemical Company include Dur-O-Set E-623 and Dur-O-Set E-646. It has been pointed out that Dur-O-Set E-623 is an ethylene vinyl acetate copolymer having a Tg of 0 ° C, a 52% solid, a pH of 5.5 and a viscosity of 200 cps. It has been pointed out that Dur-O-Set E-646 is an ethylene vinyl acetate copolymer having a Tg of -12 ° C, a 52% solid, a pH of 5.5 and a viscosity of 300 cps. A useful and preferred binder is the bridging acrylic copolymer sold by the National Starch and Chemical Company as X-4280. It has a pH of 2.6; a boiling point of 212 ° F, a pseudo-solid point of 32 ° F; a specific density of 1.060; Described as a milky white aqueous emulsion with a viscosity of 100 cps. An alternative and useful binder is the use of zirconium compounds. Zirconyl acetate is the preferred zirconium compound used. Zirconia is believed to act as a high temperature stabilizer, promote catalytic activity, and improve catalytic adhesion. Upon firing, a zirconium compound such as zirconyl acetate is believed to be a binder ZrO₂Will be converted to. Various useful zirconium compounds are ZrO in the catalyst₂Contains acetates, hydroxides, nitrates, etc. to generate When zirconyl acetate is used as the catalyst of the present invention, ZrO unless the radiator coating is fired.₂Will not be generated. Good adhesion was achieved at a "calcination" temperature of only 120 ° C, so zirconyl acetate is not decomposed into zirconium oxide, but instead pollutants such as Carulite.^(R)It is believed to have produced acetate produced from a bridged network with particles and ball mill milling with acetic acid. Therefore, the use of any zirconium-containing compound in the catalyst of the present invention is not limited to zirconia. In addition, the zirconium compound can be used with other binders such as the polymeric binders mentioned above. Alternative contaminant treatment catalyst compositions can include activated carbon compositions. The carbon composition comprises activated carbon, binders such as polymeric binders, and optionally conventional additives such as defoamers and analogs. Useful activated carbon compositions include 75-85% by weight of activated carbon, such as "coconut shell" carbon or carbon from wood, and an acrylic binder having a binder, such as a defoaming agent. Useful slurries contain 10-50% by weight solids. Activated carbon can contact the reduction of ozone to oxygen and adsorb other contaminants. The contaminant treatment catalyst composition of the present invention can be produced by any suitable method. Preferred methods are disclosed in US Pat. No. 4,134,860, which is incorporated herein by reference. According to this method, a refractory oxide support such as activated alumina, titania or activated silica alumina is jet ground and impregnated with a catalytic metal salt, preferably a noble metal salt solution, and at a suitable temperature, typically about. From 300 ° C to about 600 ° C, preferably from about 350 ° C to about 550 ° C, and even more preferably from about 400 ° C to about 500 ° C to about 0. Bake for 5 to about 12 hours. The palladium salt is preferably palladium nitrate or palladium amine such as palladium tetraamine acetate, or palladium tetraamine hydroxide. The platinum salt preferably contains platinum hydroxide dissolved in an amine. In certain and preferred embodiments, the calcined catalyst is reduced as described above. In the ozone treatment composition, a manganese salt such as manganese nitrate can then be mixed with alumina-supported palladium that has been dried and calcined in the presence of deionized water. The amount of water added should be up to the point of initial wetness. See the method outlined in US Pat. No. 4,134,860 cited and incorporated above. The point of initial wetness is that the amount of liquid added is the lowest concentration at which the powdered mixture is sufficiently dry to absorb essentially all liquids. In this manner, a suitable manganese salt such as Mn (NO) in water₃)₂Can be added to the calcined and supported catalyst noble metal. The mixture is then calcined at a suitable temperature, preferably 400-500 ° C. for about 0.5-about 12 hours. Instead, the supported catalyst powder (ie, palladium supported on top of alumina) is combined with a liquid, preferably water, to form a slurry, which is then combined with a solution of manganese salt, such as Mn (NO).₃)₂Can be added. Preferably, a refractory support such as activated alumina, more preferably a manganese component and palladium supported on activated silica-alumina, is mixed with an appropriate amount of water to 15-40% and preferably 20-35. A slurry with a weight% solid is produced. The combined mixture can be coated on a carrier such as a radiator, and the radiator is dried in air under suitable conditions, for example 50 ° C to 150 ° C, for 1 to 12 hours. The substrate supporting the coating is then placed under suitable conditions, typically 300 ° C to 550 ° C, preferably 350 ° C to 500 ° C, more preferably 350 ° C to 450 ° C and most preferably. Heating in an oxygen-containing atmosphere at 400 ° C to 500 ° C, preferably in air for about 0.5 to about 12 hours, can help calcin the components and fix the coating to the substrate atmosphere contact surface. .. If the composition further contains a noble metal component, it is preferably reduced after firing. The method of the present invention comprises producing a mixture containing at least one platinum group metal component, a gold component, a silver component, a manganese component and a contact-active substance selected from a mixture thereof, as well as water. The contactally active material can be on a suitable support, preferably a refractory oxide support. Crush this mixture and thenIt can then be fired as needed and reduced when using the noble metal catalytic material. The firing step can be performed prior to grinding and adding the polymeric binder. It is also preferred to reduce the catalytically active material prior to grinding, calcining and adding the polymeric binder. The slurry comprises a carboxylic acid compound or a polymer containing a carboxylic acid group or a derivative thereof in an amount that provides a pH of about 3-7, typically 3-6. Preferably, the acid comprises 0.5-15% by weight glacial acetic acid based on the contactally active material and the weight of acetic acid. A suitable amount of water can be added to achieve the desired solid concentration and / or viscosity slurry. Percent solids are typically 20-50 and preferably 30-40% by weight. The preferred medium is deionized water (DI). Acetic acid can be added in producing a mixture of water and a contactally active material that may be calcined. Instead, acetic acid can be added with the polymeric binder. A preferred composition for treating ozone using manganese dioxide as a catalyst is approximately 1, which is mixed with 2,250 g of deionized water and 75 g of acetic acid. It can be made using 500 g of manganese dioxide. The mixture is combined in a 1 gallon ball mill and ball milled for about 4 hours until about 90% of the particles are less than 8 micrometers. Drain the ball mill and add 150 g of polymeric binder. The mixture is then blended on a roll mill for 30 minutes. The resulting mixture is ready to be coated on a suitable substrate, eg, an automobile radiator, according to the method described below. The compatibility of the components of the slurry, including the catalytic material and the polymeric binder, eg, a latex emulsion, is desirable in order to maintain slurry stability and uniformity. For the purposes of the present invention, compatibility means that the binder and catalytic material remain as a mixture of separate particles in the slurry. If the polymeric binder is a latex emulsion and the catalytic materials have an electrical charge that repels them from each other, they are compatible, and the slurry is stable and in a liquid vehicle such as an aqueous fluid such as water. Has a uniform distribution of catalytic material and polymer latex. If the catalyst material and the latex emulsion particles do not repel each other, irreversible agglomeration of latex will occur on the catalyst material. Therefore, these substances are incompatible, and the latex comes out of the emulsion. Compatibility between high surface area catalysts and organic latex binders is a key property in producing stable and uniform slurries. Irreversible agglomeration will occur if the catalyst and latex emulsion particles do not repel each other. The result of this would be an unstable, non-uniform slurry that would result in a poor adhesive coating. The surface charge plays an important role, although the mutual repulsion of the catalyst and binder particles is controlled by various physical factors. Since latex emulsion particles are typically negatively charged, catalytic particles must be charged as well. However, zeta potential measurements are₂Has been shown to be slightly negatively or even positively charged, and as a result, irreversible pseudo-solidification of the catalyst and latex occurs (ie, the catalyst and latex are not compatible). It has been found that while the methods described above add acetic acid provide certain advantages to the slurry of the invention, eg viscosity control, it does not improve compatibility and can even be detrimental to the stability of the aged slurry. Was done. If the catalytic material is positively or slightly negatively charged, improved compatibility can be achieved by making the slurry more basic. The pH of the slurry can be controlled depending on the acidity of the catalytic material, and the preferred pH level is at least 6, preferably at least 7, and even more preferably at least 8.5. In general, the slurry should not be too alkaline, and the preferred upper limit is about 11. The preferred range is 8.5-11. Latex emulsion and MnO₂It is important to maintain the pH of the slurry containing (cryptomerene) at 8.5. If the pH drops below 8.5 for a long period of time (days), the binder and catalyst will irreversibly solidify. Despite the large negative charge on the cryptomelene particles at this pH, the long-term stability of cryptomelene containing the slurry was difficult to achieve. Preferred binders are poly (acrylic) derivative based binders, and particularly preferred binders with long-term stability under these conditions are National as x-4280 acrylic latex. Acrylic latex sold by Starch. The difficulty of achieving long-term compatibility even for basic slurries containing negatively charged latex and catalytic particles is that surface charge is important, but it is the only factor that determines binder / catalytic compatibility. Indicates that it is not. Other factors that play a role include emulsion particle size, surfactant packaging, and the like. The method of the present invention comprises raising the pH of the ball mill ground catalyst slurry to pH 8.5 and preferably to 9 in order to improve stability. Alternative methods for improving slurry stability include adding a surfactant, eg, a polymeric dispersant, to the slurry in lieu of or in addition to increasing the pH. In the second case, binder / catalytic compatibility is achieved by adding a polymeric acrylate-induced dispersant (approximately 3% solid-state basis) instead of increasing the pH. However, the results are the same in that the catalytic particles are given a large negative charge that can repel similarly charged latex particles. The dispersant can be added during or after the ball mill milling operation. Not all dispersants work equally well, despite the large negative charge generated on the catalyst particles. Preferred dispersants include polymers containing carboxylic acid groups or derivatives thereof such as esters and salts. Preferred dispersants include Accusol 445 (from Rohm and Haas) and Colloid 226/35 (from Rhone-Poulenc). An overview of useful dispersants and dispersant technologies can be found in Surfactants &amp; Specialties published by Rhone-Poulenc, which is incorporated herein by reference.<u style="single">Additive technology for dispersants</u>Presented inside. Useful polymeric dispersants include sodium polyacrylate and Colloid.^TMContains, but is not limited to, anionic copolymer sodium salts sold by Rhone-Poulenc as polymeric dispersants. Again, surface charge is an important factor in determining catalyst / binder compatibility, but it is not the only factor. Dispersants in general (especially Colloid) 226) does do a good job of stabilizing, as a wider variety of latex binders (eg acrylics, styrene acrylics, and EVAs) are compatible. Long-term compatibility issues can be addressed by increasing the amount of dispersant, raising the pH somewhat, or both. The method described above enhances compatibility and results in a stable catalytic slurry. Both methods generate a large negative surface charge on the catalyst particles, which in turn stabilizes the catalyst in the presence of similarly charged (anionic) latex emulsion particles. For both systems, good adhesion was observed with a 10 wt% loading of the polymeric binder (on a solid basis) (ie, the catalyst cannot be wiped off the surface of the coated single body). At 5%, the adhesion is not very good, so the optimal loading is probably somewhere in between. These methods are MnO₂Although shown to improve the compatibility of latex slurries, the invention is not limited to systems that use negatively charged latex emulsions. Those skilled in the art will appreciate that slurry compatibility can be achieved as well by using cationic latex emulsions and stabilizing catalytic particles using cationic surfactant and / or dispersant packages. There will be. Polymeric slurries of the invention, in particular polymeric latex slurries, can contain conventional additives such as thickeners, biocides, oxidants and the like. The contaminant treatment compositions of the present invention can be applied to the surface of an atmospheric contact vehicle by any suitable means such as spray coating, powder coating, or brushing or immersing the surface in a catalytic slurry. Atmospheric contact surfaces are preferably cleaned to remove surface stains, especially oils that can result in poor adhesion to the surface of the contaminant treatment composition. When possible, it is preferable to heat the substrate on which the surface is located to a temperature high enough to volatilize or burn off the surface debris and oil. If the substrate on which the atmospheric contact surface is present is made of a material capable of withstanding high temperatures, such as an aluminum radiator, the substrate surface is a catalyst composition, preferably an ozone, carbon monoxide and / or hydrocarbon catalyst. It can be processed in such a way as to improve adhesion to the composition. One method is to heat the aluminum substrate, eg, a radiator, to a sufficient temperature in the air for a time sufficient to form a thin layer of aluminum oxide on the surface. This helps clean the surface by removing oils that can be harmful to adhesions. In addition, if the surface is aluminum, the radiator is 0. By heating at 350 ° C to 500 ° C, preferably 400 to 500 ° C and even more preferably 425 to 475 ° C for 5 to 24 hours, preferably 8 to 24 hours and even more preferably 12 to 20 hours. It has been found that a sufficient layer of oxidized aluminum can be produced. In some cases, sufficient adhesion without the use of an undercoat layer was achieved when the aluminum radiator was heated in air at 450 ° C for 16 hours. This method is particularly useful when applying a coating to a new surface, such as a radiator or air conditioner condenser, prior to assembly of the vehicle, whether it is the original device or a replacement. Adhesion is improved by applying an undercoat or precoat to the substrate. Useful undercoats or precoats include the types of refractory oxide supports discussed above, and alumina is preferred. Preferred undercoats for increasing adhesion between the atmospheric contact surface and the overcoat of the ozone catalyst composition are incorporated herein by reference, commonly assigned U.S. Pat. No. 5,422, It is stated in No. 331. The undercoat layer is disclosed as consisting of a fine granular refractory metal oxide and a mixture of sol selected from silica, alumina, zirconia and titania sol. According to the method of the present invention, the surface on an existing vehicle can be coated while a substrate such as a radiator, radiator fan or air conditioner condenser is positioned on the vehicle. The catalyst composition can be applied directly to the surface. If additional adhesion is desired, an undercoat can be used as described above. If it is practical to separate the radiator from the vehicle, support materials such as activated alumina, silica-alumina, bulk titania, titanium sol, silica zirconia, manganese zirconia and others as mentioned above in the slurry. Can be formed on the substrate and coated with silica sol on the substrate to improve adhesion. The precoated substrate can subsequently be coated with soluble noble metal salts such as platinum and / or palladium salts and, if desired, manganese nitrate. The coated substrate was then allowed to calcin the palladium and manganese components in the air in the oven to produce their oxides (0. at 350 ° C to 550 ° C). Can be heated for 5-12 hours). The present invention can include an adsorption composition supported on an atmospheric contact surface. The adsorption composition can be used to adsorb gaseous contaminants such as hydrocarbons and sulfur dioxide and granular objects such as granular hydrocarbons, soot, pollen and fungi. Useful supported compositions can include adsorbents such as zeolites for adsorbing hydrocarbons. Useful zeolite compositions are described in Publication No. WO 94/27709, published December 8, 1994 and entitled Nitrous Oxide Degradation Catalyst, which is incorporated herein by reference. Particularly preferred zeolites are β-zeolites and dealuminated zeolite Y. Carbon preferably activated carbon can be produced in a carbon adsorption composition containing activated carbon and a binder such as a polymer known in the art. The carbon adsorption composition can be applied to the atmospheric contact surface. Activated carbon can adsorb hydrocarbons, volatile organic compounds, bacteria, pollen and analogs. Yet another adsorption composition is SO₃Can contain components capable of adsorbing. Especially useful SO₃The adsorbent is calcium oxide. Calcium oxide is converted to calcium sulfate. The calcium oxide adsorption composition can also include vanadium or platinum catalysts that can be used to convert sulfur dioxide to sulfur trioxide. Sulfur trioxide is then adsorbed on calcium oxide to produce calcium sulphate. In addition to the treatment of atmospheric air containing contaminants under ambient or ambient operating conditions, the present invention presents a conventional three-way catalyst supported on an electrically heated catalyst as known in the art. Is intended for catalytic oxidation and / or reduction of hydrocarbons, nitrogen dioxide and residual carbon monoxide. The electrically heated catalyst can be positioned on top of the electrically heated catalyst unit 56 illustrated in FIG. Such electrically heated catalytic substrates are disclosed in references such as US Pat. Nos. 5,308,591 and 5,317,869, which are incorporated herein by reference. For the purposes of the present invention, the electrically heated catalyst should be of suitable thickness to suit the flow direction, preferably 1/8 "to 12" and even more preferably 0.5 to 3 "thickness. It is a metal honeycomb having. If the electrically heated catalyst must fit in a tight space, it is 0.25 ~ 1. A thickness of 5 inches is fine. A preferred support is a single carrier of the type having multiple narrow parallel gas flow passages extending through the carrier from the inlet surface to the outlet surface of the carrier, yet these passages enter from the front 26 and are single. It is open for airflow through 56 towards fan 20. Preferably the passages are essentially straight from their inlets to their outlets, and the catalyst material is coated as a washcoat and as a result the gas flowing through the passages is defined by the walls that come into contact with the catalyst material. Has been done. The flow path of the single carrier may be any suitable cross-sectional shape and size such as trapezoid, rectangle, quadrangle, sine curve, hexagon, oval, circular, or corrugated and flat as known in the art. It is a thin-walled channel that can be formed from a metal component that is. Such a structure can include about 60-600 or more gas inlet openings (cells) per square inch cross section. The single body can be made from any suitable material and can preferably be heated by applying an electric current. A useful catalyst to impart is a three-way catalyst (TWC) as described above, which can enhance the oxidation of hydrocarbons and carbon monoxide and the reduction of nitrogen oxides. Useful TWCs are described in US Pat. Nos. 4,714,694, 4,738,947, 5,010,051, 5,057,483 and 5,139,992. The present invention will be further described by the following examples, which are not intended to limit the scope of the invention. It is stated in issue 992. The present invention will be further described by the following examples, which are not intended to limit the scope of the invention. It is stated in No. 992. The present invention will be further described by the following examples, which are not intended to limit the scope of the invention.<u style="single">Example</u>Example 1 (Reference Example) 1993 Nissan Altima radiator core (Nissan part number 21460-1E400) is heat-treated in air at 450 ° C for 16 hours to clean and oxidize the surface, then a water slurry containing silica-alumina. Was partially coated with a high surface area silica-alumina undercoat by pouring through a radiator groove, blowing out excess using an air gun, drying at room temperature using a fan, and then firing at 450 ° C (drying load =). 0.23g / in³). Silica-alumina slurry is a high surface area calcined SRS-II alumina (Davison) with acetic acid (0.5% based on alumina) and water (about 20% for all solids), 90% &lt;4 μm. Prepared by ball mill grinding to particle size. The ball mill ground material was then blended with Nalco silica sol (# 91SJ065-28% solid) in a 25% / 75% ratio. SRS-11 Alumina is xSiO₂ YAl₂O₃ ZH₂It has an O structure, and 92 to 95% by weight of Al after activation.₂O₃And 4-7% by weight is SiO₂It is stipulated that. BET surface area is a minimum of 260m after firing²It is specified as / g. Pd / Mn / Al by impregnating high surface area SRS-II alumina (Davison) with an aqueous solution containing sufficient tetraamine palladium acetate to the point of initial wetness.₂O₃A catalytic slurry (nominal 10 wt% palladium on alumina) was prepared. The resulting powder was dried and then calcined at 450 ° C. for 1 hour. The powder is then subjected to high shear manganese nitrate (5.5 wt% MnO on alumina powder).₂Was mixed with an aqueous solution (equivalent to) and diluted water sufficient to give a 32-34% solid slurry. The radiator was coated with slurry, dried in air using a fan, and then fired in air at 450 ° C. for 16 hours. This ozone destruction catalyst is made of palladium on high surface area SRS-II alumina (dry load = 1 ft of radiator volume).³263g per) and manganese dioxide (drying load = 142g / ft)³) Was included. Figure 8 shows a coolant tank, also known as a header, and a reassembled partially coated radiator. The ozone-destroying performance of the coated catalyst is measured by blowing an air stream containing a given concentration of ozone through the radiator groove at a surface speed typical of operating speed, and then measuring the concentration of ozone exiting the back of the radiator. It was decided by doing. The air used was at about 20 ° C and had a dew point of about 35 ° F. The coolant was circulated through the radiator at a temperature of about 50 ° C. The ozone concentration was in the range of 0.1 to 0.4 ppm. Ozone conversion was measured and it was 43% at linear air velocity (surface velocity) equal to 12.5 miles per hour; 33% at 25mph; 30% at 37.5mph and 24% at 49mph. .. Example 2 (Reference Example) A portion of the same radiator used in Example 1 without catalyst coating was similarly evaluated for ozone destruction performance (ie standard experiment). No ozone conversion was observed. Example 3 (Reference example) After heat treatment in air at 450 ° C for 60 hours, Lincoln A variety of different ozone-destructive catalyst compositions (ie different catalysts; catalyst loadings, binder formulations and heat treatments) are applied to the TownCar radiator core (part # F1VY-8005-A) in succession as 6 "x6" square patches. Coated. Some of the radiator patches were pre-coated with high surface area alumina or silica-alumina prior to coating the catalyst and fired at 450 ° C. The actual coating was carried out by pouring a water slurry containing a specific catalyst formulation through a radiator groove, blowing out an excess using an air gun, and drying with a fan at room temperature, as in Example 1. The radiator core was then dried to 120 ° C or 120 ° C and then calcined to 400-450 ° C. The radiator core was then reattached to its plastic tank and the ozone destructive performance of the various catalysts was determined as described in Example 1 at a radiator surface temperature of about 40-50 ° C and a surface velocity of 10 mph. Table I summarizes the various catalysts coated on the radiator. The preparation of the catalyst slurry will be described in detail below. Pt / Al₂O₃Catalyst (nominal Al₂O₃Top 2 wt% Pt) solubilized in amine H₂Pt (OH)₆Derived from (17.9% Pt), 114g of platinum salt solution dissolved in 520g of water 1000g of Condea SBA-150 high surface area (about 150m)²Prepared by impregnating alumina powder (defined as / g). Subsequently, 49.5 g of acetic acid was added. The powder was then dried at 110 ° C for 1 hour and calcined at 550 ° C for 2 hours. A catalytic slurry was then prepared by adding 875 g of powder to 1069 g of water and 44.6 g of acetic acid in a ball mill and grinding the mixture to a particle size of 90% &lt;10 μm. (Patches 1 and 4). The carbon-catalyzed slurry was a formulation purchased from Grant Industries, Inc., Elmwood Park, NJ (29% solid). Carbon comes from the coconut shell. Contains an acrylic binder and a defoaming agent. (Patches 8 and 12). Carulite^R200 catalysts (CuO / MnO₂) Is the first 1000g Carulite^R200 (purchased from Carus Chemical Co., Chicago, IL) was prepared by ball milling with 1500 g of water to a particle size of 90% &lt;6 μm. Carucite^R200 is 60-75 weight percent MnO₂, 11-14% CuO and 15-16% Al₂O₃Is specified to contain. The resulting slurry was diluted to about 28% solid and then mixed with 3% (based on solid) Nalco # 1056 silica sol or 2% (based on solid) National Starch # x4260 acrylic copolymer. (Patches 5, 9 and 10). Pd / Mn / Al₂O₃The catalytic slurry (nominal 10% by weight palladium on alumina) was prepared as described in Example 1. (Patches 2, 3 and 6). IW (initial wetness) Pd / Mn / Al₂O₃Catalyst (nominal 8% palladium and 5.5% MnO based on alumina₂) Was similarly prepared by first impregnating high surface area SRS-II alumina (Davison) with an aqueous solution containing tetraamine palladium acetate to the point of initial wetting. After drying, the powder was calcined at 450 ° C. for 2 hours and then the powder was reimpregnated with an aqueous solution containing manganese nitrate to the point of initial wetting. After drying again and firing at 450 ° C. for 2 hours, the powder was mixed in a ball mill with acetic acid (3% by weight of catalyst powder) and water sufficient to make a 35% solid slurry. The mixture was then ground to a particle size of 90% &lt;8 μm. (Patches 7 and 11). SiO₂/ Al₂O₃Pre-coated slurry was prepared as described in Example 1 (patches 3 and 11). Al₂O₃Pre-coating slurry is made by ball milling high surface area Condea SBA-150 alumina with acetic acid (5% by weight based on alumina) and water (about 44% total solid) to a particle size of 90% &lt;10 μm. Prepared (patches 9 and 12). The results are summarized in Table I. For patch # 4, the conversion of carbon monoxide after being on the vehicle for 5,000 miles was also measured under the conditions listed in Example 1. No conversion was observed at a radiator temperature of 50 ° C and a linear velocity of 10 mph.<img file="JP4065026B2_D0001.tif" /><img file="JP4065026B2_D0002.tif" />Example 4 (Reference Example) 1993 Nissan Altima radiator core (Nissan part number 21460-1E400) is heat-treated in air at 450 ° C for 16 hours, then water slurry containing alumina is poured through the radiator groove and used with an air gun. The excess was blown out, dried at room temperature using a fan, and then partially coated with Condea high surface area SBA-150 alumina by firing at 400 ° C (drying load = 0.86 g / in).³). Alumina pre-coated slurry was prepared as described in Example 3. The radiator was then subsequently coated with 7 CO destructive catalysts (Table II) in 2 "x 2" square patches. Each coating was applied by pouring a water slurry containing a particular catalyst formulation through a radiator groove, blowing out excess with an air gun and drying at room temperature with a fan. Carulite^RAnd 2% Pt / Al₂O₃The catalysts (patches # 4 and # 6, respectively) were prepared according to the method described in Example 3. 3% Pt / ZrO₂/ SiO₂The catalyst (patch # 3) is initially 510g of zirconia / silica frit (95% ZrO)₂/ 5% SiO₂-Magnesium Elektron XZ0678/01) was prepared by firing at 500 ° C for 1 hour. H solubilized with 480 g of deionized water, 468 g of the resulting powder, 42 g of glacial acetic acid and amine.₂Pt (OH)₆A catalytic slurry was prepared by adding 468 g of a platinum salt solution (18.2% Pt) derived from. The resulting mixture was milled in a ball mill for 8 hours to a particle size of 90% less than 3 μm. 3% Pt / TiO₂The catalyst (patch # 7) is 500 g of TiO in a regular blender.₂H solubilized with (Degussa P25), 500 g deionized water, 12 g concentrated ammonium hydroxide and amine₂Pt (OH)₆It was prepared by mixing 82 g of a platinum salt solution (18.2% Pt) derived from. After blending for 5 minutes to a particle size of 90% less than 5 μm, 32.7 g of Nalco 1056 silica sol and enough deionized water to reduce the solid content to about 22% were added. The resulting mixture was blended in a roll mill and all ingredients were mixed. 3% Pt / Mn / ZrO₂Catalytic slurry (patch # 5), in a ball mill, 70 g of manganese / zirconia frit (Magnesium Elektron XZ0719 / 01), 100 g, containing 20 weight percent manganese and 80 weight percent zirconium coprecipitate based on metal weight. H solubilized with deionized water, 3.5 g acetic acid and amine₂Pt (OH)₆It was prepared by combining 11.7 g of platinum salt solution (18.2% Pt) derived from. The resulting mixture was ground for 16 hours to a particle size of 90% 10 μm. 2% Pt / CeO₂The catalyst (patch # 1) was solubilized with amines in 490 g of alumina-stabilized high surface area ceria (Rhone Poulenc).₂Pt (OH)₆It was prepared by impregnating with 54.9 g of platinum salt solution (18.2% Pt) dissolved in deionized water (total volume -155 mL). The powder was dried at 110 ° C for 6 hours and calcined at 400 ° C for 2 hours. A catalytic slurry was then prepared by adding 491 g of powder to 593 g of deionized water in a ball mill and grinding the mixture for 2 hours to a particle size of 90% less than 4 μm. 4.6% Pd / CeO₂The catalyst (patch # 2) was similarly prepared using 209.5 g (180 mL) of tetraamine palladium acetate solution via initial wet impregnation. After applying all seven catalysts, the radiator was calcined at 400 ° C. for about 16 hours. After mounting the radiator core in a plastic tank, an air stream containing CO (about 16ppm) is blown through the radiator groove at a linear face velocity of 5mph (space velocity of 315,000 / h), and then of the radiator. The CO destruction performance of various catalysts was determined by measuring the concentration of CO leaving the back surface. The radiator temperature was about 95 ° C and the air flow had a dew point of about 35 ° F. The results are summarized in Table II. Ozone destruction performance is 25 ° C, 0.25 ppm ozone and 135.2 L / min flow rate and 640,000 / h hourly space. Measured as described in Example 1 at a line velocity of 10 mph with velocity). The air used had a dew point of 35 ° F. The results are summarized in Table II. Figure 9 shows the CO conversion rate for temperature for patch numbers 3, 6 and 7. An air stream containing propylene (about 10 ppm) is blown through the radiator groove at a line velocity of 5 mph with a flow rate of 68.2 L / min and a temporal space velocity of 320,000 / h, and then the concentration of propylene leaving the back of the radiator. The catalyst was also examined for propylene breakdown by measuring. The radiator temperature was about 95 ° C and the air flow had a dew point of about 35 ° F. The results are summarized in Table II.<img file="JP4065026B2_D0003.tif" />Example 5 (Reference Example) This example summarizes the technical results from the road vehicle tests conducted in February and March 1995 in the Los Angels area. The purpose of the test was to measure the catalytic ozonolysis efficiency on a catalyst-mounted radiator under actual operating conditions. The Los Angels (LA) area was pre-selected as the most suitable test site because of its measurable ozone content during this March test period. In addition, LA limits special driving routes that are typical of morning and afternoon peak and off-peak driving. Two catalyst compositions were evaluated: 1) Carulite^R200 (CuO / MnO purchased from Carus Chemical Company₂/ Al₂O₃); And 2) Pd / Mn / Al prepared as described in Example 3.₂O₃(77g / ft³Pd). Both catalysts were patched onto an older model Cadillac V-6 engine aluminum radiator. The radiator was an aluminum replacement for the copper-brass OEM radiator on the Chevrolet Caprice test vehicle. 1/4 Teflon located on the car immediately after each catalyst patch and after the uncoated part of the radiator (control patch)^R A PTFE sampling wire was attached on the outside. The amount of ambient (catalyst in) ozone was measured via a sampling line placed in front of the radiator. Ozone concentration was measured using two Dasibi Model 1003AH ozone monitors placed in the backseat of the car. The temperature probe was mounted directly (using epoxy) on each radiator test patch within a few inches of the sampling line. One air velocity probe was mounted on the front of the radiator, between the two patches. Data from ozone analyzers, temperature probes, air velocity probes and vehicle speedometers were collected using a personal computer in the trunk and downloaded to a floppy disk. The overall results from the study are summarized in Table III below. Each catalyst (Carulite^RAnd Pd / Mn / Al₂O₃), The results in the case of low temperature idling, high temperature idling and road driving are reported. Data were collected on two separate trips to LA in February and March 1995. The first trip was interrupted only a few days later due to low ambient ozone. Although somewhat higher during the second trip in March, the perimeter still averaged only about 40 ppb. The best ozone was encountered during the last three days of the test (March 17-20). The peak amount was about 100 ppb. In general, no trend in conversion rate with respect to ozone concentration was noticed. Except for the cold idling results, the results reported in Table III are averages from at least 11 different experiments (actual range of values is shown in parentheses). Only data corresponding to inlet ozone concentrations above 30 ppb were included. Freeway data was not included as the ambient volume decreased below 20 ppb. In the case of the low temperature idling test, only two experiments were completed. Cold idling refers to the data collected before the thermostat switch enters and pumps warm coolant to the radiator during idling immediately after the car starts. Overall, the ozone conversion was very high for both catalysts, with the highest values during high temperature idling. This can be attributed to the higher temperatures and lower surface velocities associated with idling. Cold idling gave the lowest conversion rate due to the relatively low ambient temperature of the radiator surface. The results during operation were intermediate between the results of high temperature and low temperature idling. The radiator was warm, but cooler and faster than encountered under high temperature idling conditions. Carulite in general^RThe ozone conversion rate measured in the case of is Pd / Mn / Al.₂O₃Was higher than the conversion rate measured in the case of (eg, 78.1 vs. 63.0% during operation). But for high temperature idling and driving experiments, Carulite^RThe average temperature of the catalyst is typically Pd / Mn / Al₂O₃It was 40 ° F higher than the catalyst and the average radiator surface velocity was typically 1 mph lower. Overall, the results show that ozone can be decomposed at high conversion rates under typical operating conditions.<img file="JP4065026B2_D0004.tif" />Automotive test results were generally consistent with new activity measured in the laboratory prior to radiator installation. Pd / Mn / Al at room temperature (about 25 ° C), 20% relative humidity (absolute water vapor amount 0.7%) and surface velocity equivalent to 10mph₂O₃And Carulite^RIn the case of, the conversion rates in the laboratory were 55 and 69%, respectively. Increasing the relative humidity to 70% (absolute water vapor 2.3%) at room temperature (about 25 ° C) reduced the conversion rates to 38 and 52%, respectively. The low temperature idling (70 ° F) conversions measured at 9mph plane velocities were 48 and 67%, respectively, suggesting that the humidity encountered during the test was low. The surface velocity of the air entering the radiator was low. At an average operating speed of approximately 20 mph (typical of short section operation), the surface speed of the radiator was only about 13 mph. Even at freeway velocities above 60 mph, radiator surface velocities were only about 25 mph. The fan significantly affects the control of the air flowing through the radiator. During idling, the fan typically pulled about 8mph. Example 6 (Reference example) 100 g of Carulite^R Carulite by impregnating 200 powders (ground in a blender) with 69.0 g of aqueous solution (12.6% Pd) containing tetraamine palladium acetate to the point of initial wetting.^RA catalyst of top 8 weight percent Pd was prepared. The powder was dried overnight at 90 ° C and then calcined at 450 ° C or 550 ° C for 2 hours. The resulting 92 g of calcined catalyst was then combined with 171 g of deionized water in a ball mill to make a 35% solid slurry. After grinding for 30 minutes to a particle size where 90% is 9 μm, 3.1 g of National Starch x4260 acrylic latex binder (50% solid) is added and the resulting mixture is ground for an additional 30 minutes to disperse the binder. It was. Carulite^RCompositions containing 2, 4 and 6 weight percent Pd on the catalyst were similarly prepared and evaluated. The catalyst was evaluated for ozonolysis at room temperature and at a space velocity of 630,000 / h using wash-coated 300 cpsi (cells per square inch) ceramic honeycomb. The catalyst sample was prepared as listed above. The results are summarized in Table IV. As you can see, 4 and 8% Pd / Carulite fired to 450 ° C^RThe catalyst gave comparable initial and 45 minute ozone conversion rates (about 62 and 60%, respectively). These results show Carulite under the same test conditions^REquivalent to the result of only. The 2 and 4% Pd catalysts calcined to 550 ° C gave significantly lower conversions after 45 minutes (47%). This is attributed to the loss of surface area at higher firing temperatures. The 6% catalyst was also calcined to 550 ° C but did not show a significant decrease in activity.<img file="JP4065026B2_D0005.tif" />Example 7 (Reference Example) A series of tests was performed to evaluate various catalytic compositions containing a palladium component to treat air containing 0.25 ppm ozone. The air was in ambient conditions (23 ° C; 0.6% water). The composition was coated on a 300 cell cordierite flow-through honeycomb per inch with a washcoat loading of approximately 2 g per cubic inch of substrate. A coated monolith containing various supported palladium catalysts was loaded into a 1 diameter stainless steel tube and airflow was passed perpendicular to the open surface of the honeycomb at a space velocity of 630,000 / h. And at the outlet, the ozone concentration was measured. The one alumina carrier used was characterized as described in Example 1 (has a surface area of about 300 m).²/ g) SRS-II gamma alumina (purchased from Davison). About 58m²Low surface area thetaalumina, characterized by a surface area of / g and an average pore radius of about 80 angstroms, was also used. E-160 Alumina is about 180m²Gamma alumina characterized by a surface area of / g and a pore radius of approximately 47 angstroms. The ceria used is about 120m²It had a surface area of / g and an average pore radius of about 28 angstroms. Silica to alumina ratio of about 250 to 1 and about 430 m²Dealuminated beta zeolite with a surface area of / g was also used. Carbon, about 850m²Microporous charcoal, characterized by a surface area of / g, was also used as a carrier. Finally purchased from Rhone-Poulenc, about 110m²Titania (DT51 grade), characterized by a surface area of / g, was also used as a carrier. The results are summarized in Table V, which includes the relative weight percent of the various catalytic components, the load on the honeycomb, the initial ozone conversion rate and the conversion rate after 45 minutes.<img file="JP4065026B2_D0006.tif" />Example 8 (Reference Example) The following is a Carulite containing a vinyl acetate latex binder.^RA formulation of slurries, used in radiator coatings, which results in excellent catalyst adhesion to aluminum radiators. 1000g Carulite^R 200, 1500 g of deionized water and 50 g of acetic acid (Carulite)^R5%) was combined in a 1 gallon ball mill and ground for 4 hours to a particle size where 90% was 7 μm. After draining the resulting slurry from the mill, 104 g (based on 5% solid) of National Starch Dur-O-Set E-646 crosslinked EVA copolymer (48% solid) was added. A sufficient blend of binders was achieved by rotating the slurry on a mill for several hours without the use of a grinding medium. The slurry was coated on a piece of aluminum substrate (eg, a radiator) and then dried at 30 ° C for 30 minutes to give good adhesion (ie the coating could not be wiped). Higher curing temperatures (up to 150 ° C) can be used if desired. Example 9 (Reference Example) The carbon monoxide conversion rate was investigated by coating various titania-supported platinum compositions on a ceramic honeycomb as described in Example 6. Catalyst load is about 2g / in³The test was performed using an air stream with 16 ppm carbon monoxide (dew point 35 ° F) at a space velocity of 315,000 / h. The catalyst composition is on the honeycomb with 7% H₂And a forming gas with 93% N was used and reduced at 300 ° C. for 3 hours. TiO₂Compositions containing 2 and 3 weight percent platinum on P25 titania; and 2 and 3 weight percent platinum on DT52 grade titania. DT51 Grade Titania is purchased from Rhone-Poulenc and is approximately 110m²It had a surface area of / g. DT52 Grade Titania is purchased from Rhone-Poulenc and is approximately 210m²It was a tungsten-containing titanaa with a surface area of / g. P25 grade titania is purchased from Degussa and has a particle size of about 1 μm and about 45-50 m.²Characterized to have a surface area of / g. The results are shown in Fig. 10. Example 10 (Reference Example) Example 10 relates to the evaluation of the CO conversion rate for a composition containing alumina, ceria and zeolite. The carrier is characterized as described in Example 7. The composition to be evaluated comprises 2 weight percent platinum on low surface area thetaalumina; 2 weight percent platinum and ceria; 2 weight percent platinum on SRS-II gamma alumina and 2 weight percent platinum on beta zeolite. That's right. The results are shown in Fig. 11. Example 11 (Reference Example) 1993 Nissan listed in Example 4 containing 2 weight percent platinum on SRS-II gamma alumina and ZSM-5 zeolite. The CO conversion rate with respect to temperature was measured for the composition coated on the Altima radiator and examined using the same method for examining CO as used in Example 4. The results are shown in Fig. 9. Example 12 (Reference Example) Slowly add 0.659 g of a solution of amine-solubilized platinum hydroxide solution with 17.75 wt% platinum (based on metallic platinum) to 20 g of 11.7 wt% water slurry of titania sol in a glass beaker. , Stirred using a magnetic stirrer. A metal monolith cored sample of 1 inch diameter x 1 inch length and 400 cells (cpsi) per square inch was immersed in the slurry. Air was blown onto the coated monolith to clean the grooves and the monolith was dried at 110 ° C for 3 hours. At this point, the monolith was reimmersed in the slurry and the steps of air blowing the groove and drying at 110 ° C were repeated. The twice coated monolith was calcined at 300 ° C for 2 hours. The uncoated metal monolith weighed 12.36 g. After the first soaking, it weighs 14.06g, after the first drying it is 12.6g, after the second soaking it is 14.38g, after firing it is 13.05g and the total weight of 0.69g Showed an increase. Coated monolith is based on metal 72g / ft³It has platinum and is called 72 Pt / Ti. The catalyst was evaluated at a gas flow rate of 36.6 liters per minute in an air stream containing 20 ppm carbon monoxide. After this initial evaluation, the catalytic core was reduced in a molding gas with 7% hydrogen and 93% nitrogen at 300 ° C. for 12 hours to treat an air stream containing 20 ppm carbon monoxide, and the evaluation was repeated. It was. The coated and reduced monolith is referred to as 72 Pt / Ti / R. The slurries listed above were then evaluated using a cored sample from a (cpsi) ceramic monolith having 400 cells per square inch, which was 40 g per cubic foot of 5: 1 weight ratio of platinum to rhodium and cubic inches. Pre-coated with 2.0 g of ES-160 (alumina) per, the core has 11 cells x 10 cells x 0.75 inch long monolith, referred to as 33Pt / 7Rh / Al, immersed in the slurry listed above. , Air blown to clean the ditch. The monolith was dried at 110 ° C for 3 hours and calcined at 300 ° C for 2 hours. The catalytic substrate containing the first platinum and rhodium layers weighed 2.19 g. After the first soaking, it weighs 3.40 g, after firing it is 2.38 g, showing a total weight increase of 0.19 g, which is equal to 0.90 g per cubic inch of platinum / titania slurry. The immersed ceramic core contains 74 platinum per cubic foot based on platinum metal and is referred to as 74Pt / Ti // Pt / Rh. The results are shown in Fig. 12. Example 13 (Reference Example) The titania Kamishirokane catalyst described in Example 12 mentioned above was used in an air stream containing 4 ppm propane and 4 ppm propylene. The airflow had a space velocity of 650,000 standard time space velocity. The platinum and titanium catalysts contained 72 g of platinum per cubic foot of the catalyst and substrate used. It was evaluated on a ceramic honeycomb as listed in Example 13. Measured results for propylene conversion are 16.7% at 65 ° C; 19% at 70 ° C; It was 23.8% at 75 ° C; 28.6% at 80 ° C; 35.7% at 85 ° C; 40.5% at 95 ° C and 47.6% at 105 ° C. Example 14 (Reference Example) Example 14 is an example of a platinum component on a titania carrier. This example shows the excellent activity of platinum supported on titania for carbon monoxide and hydrocarbon oxidation. The evaluation was performed using a catalyst prepared from colloidal titania sol and forming a composition containing 5.0 weight percent platinum component based on the weight of platinum metal and titania. Platinum was added to titania in the form of an amine-solubilized platinum hydroxide solution. It was added to colloidal titania slurry or titania powder to prepare platinum and titania-containing slurry. The slurry was coated on a ceramic monolith with 400 cells (cpsi) per square inch. The sample had a coating amount varying from 0.8 to 1.0 g / in. The coated monolith was calcined in air at 300 ° C. for 2 hours and then reduced. The reduction was carried out in a gas containing 7% hydrogen and 93% nitrogen at 300 ° C. for 12 hours. The colloidal titania slurry contained 10% by weight titania in an aqueous medium. Titania had a nominal particle size of 2-5 nm. The carbon monoxide conversion was measured in an air stream containing 20 ppm CO. The flow rate of carbon monoxide in various experiments ranges from 300,000 VHSV to 650,000 VHSV in space at ambient temperatures up to 110 ° C. The air used was purified air from an air cylinder, and when moisture was added, the air was passed through a water bath. When moisture was studied, the relative humidity was varied from 0 to 100% at room temperature (25 ° C). Carbon monoxide-containing airflow to a ceramic monolith coated with a catalytic composition, 650, It was passed using a space velocity of 000 / h. Figure 13 shows a study using air with 20 ppm CO to measure the carbon monoxide conversion with temperature, using a reducing gas containing 7% hydrogen and 93% nitrogen as mentioned above. In use, titania-supported platinum (Pt / Ti-R) reduced at 300 ° C for 12 hours is compared to a non-reduced titania-supported platinum-catalyzed (Pt / Ti) coating. FIG. 13 shows the significant advantages of using a reduced catalyst. FIG. 14 shows the reduced titania-supported platinum with various carriers including tin oxide-supported platinum (Pt / Sn), zinc oxide-supported platinum (Pt / Zn) and ceria-supported platinum (Pt / Ce) for comparison. A comparison is shown. All samples were reduced under the conditions shown above. The flow rate of carbon monoxide in the air was 650,000 shsv. As can be seen, the reduced colloidal titania top platinum has significantly higher conversion results than platinum on various other carrier materials. Hydrocarbon oxidation was measured using a 6 ppm propylene air mixture. A propylene air stream was passed through the catalytic monolith at a space velocity of 300,000 vhsv at temperatures varying from room temperature to 110 ° C. The propylene concentration was determined before and after the catalyst using a flame ionized detector. The results are summarized in Figure 15. The carriers used were 5% by weight platinum metal and yttrium oxide Y by weight. It was 000shsv. As can be seen, the reduced colloidal titania top platinum has significantly higher conversion results than platinum on various other carrier materials. Hydrocarbon oxidation was measured using a 6 ppm propylene air mixture. A propylene air stream was passed through the catalytic monolith at a space velocity of 300,000 vhsv at temperatures varying from room temperature to 110 ° C. The propylene concentration was determined before and after the catalyst using a flame ionized detector. The results are summarized in Figure 15. The carriers used were 5% by weight platinum metal and yttrium oxide Y by weight. It was 000shsv. As can be seen, the reduced colloidal titania top platinum has significantly higher conversion results than platinum on various other carrier materials. Hydrocarbon oxidation was measured using a 6 ppm propylene air mixture. A propylene air stream was passed through the catalytic monolith at a space velocity of 300,000 vhsv at temperatures varying from room temperature to 110 ° C. The propylene concentration was determined before and after the catalyst using a flame ionized detector. The results are summarized in Figure 15. The carriers used were 5% by weight platinum metal and yttrium oxide Y by weight.₂O₃Met. Comparisons were made between reduced and non-reduced catalysts. As shown in FIG. 15, catalytic reduction resulted in a significant improvement in propylene conversion. The titania-supported platinum catalysts listed above were reduced at 500 ° C. for 1 hour in a molding gas containing 7% hydrogen and 93% nitrogen. Carbon monoxide conversion was evaluated at a flow rate of 500,000 vhsv in air at 0 percent relative humidity. Evaluation was performed to determine if the reduction of the catalyst was reversible. The catalyst was first evaluated for its ability to convert carbon monoxide at 22 ° C. As shown in FIG. 16, the catalyst initially converted about 53% of carbon monoxide and dropped to 30% after about 200 minutes. At 200 minutes, the air and carbon monoxide were heated to 50 ° C, and the carbon monoxide conversion increased to 65%. The catalyst was further heated to 100 ° C. in air and carbon monoxide, held at 100 ° C. for 1 hour, and then cooled to room temperature (about 25 ° C.) in air. Initially, the conversion rate dropped to about 30% over a period of about 225-400 minutes. The evaluation was continued at 100 ° C for up to 1200 minutes, at which point the conversion was measured to be about 40%. Parallel studies were performed at 50 ° C. At about 225 minutes, the conversion rate was about 65%. After 1200 minutes, the conversion rate actually rose to about 75%. This example shows that reduction of the catalyst permanently improves catalytic activity. Example 15 (Reference Example) Example 15 is used to show ozone conversion of platinum and / or palladium components supported on a manganese oxide / zirconia coprecipitate at room temperature. This example also shows a platinum catalyst that catalyzes the conversion of ozone to oxygen and at the same time oxidizes carbon monoxide to hydrocarbons. Manganese oxide / zirconia mixed oxide powders with weights of 1: 1 and 1: 4 were prepared based on Mn and Zr metals. The coprecipitate was prepared according to the method disclosed in US Pat. No. 5,283,041 cited above. 3% and 6% Pt catalysts on manganese / zirconia (1: based on weight 4 Mn vs. Zr) was prepared as described in Example 4. SBA-150 gamma alumina (10% based on the weight of the mixed oxide powder) is added as a binder in the form of a 40% water slurry containing acetic acid (5% by weight of the alumina powder), 90% is &lt;10 μm. Grinded to grain size. The 6 weight percent Pd catalyst was prepared by impregnating manganese / zirconia frit (1: 1 Mn vs. Zr by weight) with an aqueous solution containing tetraamine palladium acetate to the point of initial wetting. After drying and then calcining the powder at 450 ° C. for 2 hours, the catalyst was mixed in a ball mill with Nalco # 1056 silica sol (10% by weight of catalyst powder) and enough water to make a slurry of about 35% solid. The mixture was then ground to a particle size of 90% &lt;10 μm. 7% H for various samples₂And 93% N₂It was reduced at 300 ° C. for 3 hours using a molding gas having. An evaluation was made to determine the conversion rate of ozone on a coated radiator mini-core from the 1993 Altima radiator, which is approximately 1/2 inch x 7/8 inch x 1 inch deep. For evaluation, use a 1-inch diameter stainless steel tube as described in Example 7 at room temperature, and use room air (laboratory supply air) with an inlet ozone concentration of 0.25 ppm at a space velocity of 630,000 / h. It was done using. The results are shown in Table VI.<img file="JP4065026B2_D0007.tif" />As can be seen from Table VI, cores 1 and 2 with only 3% platinum produced high ozone conversion rates initially and after 45 minutes for both reduced and non-reduced catalysts. Cores 3 and 4 with a 6% platinum concentration also gave excellent results, but not as good as the 3% platinum results. Cores 5-7 represent a variety of other carrier materials that have undergone ozone conversion in use. Core 5 had palladium on the manganese oxide / zirconia coprecipitate, resulting in lower than expected but still significant ozone conversion. The evaluation of cores 6 and 7 also produced significant ozone conversion using a noble metal-free coprecipitate, but again not as well as using platinum as a catalyst. Core 8 was platinum on a calcined but unreduced zirconia / silica carrier, and core 9 was platinum on a reduced zirconia / silica carrier. Both cores 8 and 9 gave some conversion, but again not as good as the conversion obtained with platinum on the coprecipitate. Furthermore, for 3% and 6% platinum on the manganese / zirconia carrier, the carbon monoxide conversion was evaluated on the 39cpsi radiator minicore described above. Samples that were reduced and not reduced were evaluated. For illustration purposes, platinum and Carulite on reduced and non-reduced zirconia / silica carriers^RThe platinum above is also shown. As can be seen from FIG. 17, the results of 3% reduced platinum on the manganese / zirconia carrier are high compared to other embodiments. Example 16 (Reference Example) Ozone conversion by blowing an air stream containing ozone (0.25 ppm) through a radiator groove at a linear velocity (630,000 spatial velocity) of 10 mph and then measuring the concentration of ozone exiting the back of the radiator. The rates were measured at room temperature and 80 ° C. on an uncoated 1995 Ford Contour radiator. The airflow had a dew point of about 35 ° F. The heated coolant did not circulate through the radiator, but the air stream was heated with heating tape when needed to obtain the desired radiator temperature. Uncoated 0.75 (L) x0.5 (W) x1.0 (D) Ford in a 1 diameter stainless steel tube as described in Example 7. Additional testing was completed with the Taurus radiator "Mini Core". The air stream was heated with a heating tape to obtain the desired radiator temperature. No ozone degradation was observed up to 120 ° C for both tests. Example 17 (Reference Example) Reduced 3% Pt / TiO in the absence of CO and in the presence of 15 ppm CO₂For catalysts, ozone conversion was measured at various temperatures. Degussa P25 grade titania is used as the carrier, which has a particle size of about 1 μm and about 45-50 m.²Characterized by having a surface area of / g. The catalyst is coated on a 300 cpsi ceramic (cordierite) honeycomb with 7% H₂And 93% N₂It was reduced on the honeycomb at 300 ° C. for 3 hours using a molding gas having. The test was performed as previously described in Example 7. The air stream (35 ° F dew point) was heated with a heating tape to obtain the desired temperature. As can be seen from FIG. 18, an increase of about 5% in absolute ozone conversion was observed at 25-80 ° C. The presence of CO improves the conversion rate of ozone. Example 18 (Reference Example) 100 g of Versal GL alumina obtained from La Roche Industries Inc. is impregnated with about 28 g of Pt amine hydroxide (Pt (A) salt) diluted in water to form a solution of about 80 g. It was. 5 g of acetic acid was added to fix Pt on the surface of alumina. After mixing for half an hour, water was added to make the catalyst about 40% solid, so that the catalyst impregnated with Pt was made into a slurry. The slurry was ball milled for 2 hours. Particle size was measured at 90% to be less than 10 microns. The catalyst is coated on a 400 cpsi ceramic substrate with a length of 1.5 diameter x 1.0 and dried to approximately 0.65 g / in.³Was obtained. The catalyst was then dried at 100 ° C and calcined at 550 ° C for 2 hours. This catalyst is placed in dry air at a temperature of 60-100 ° C as described in Example 21.₃H₆I investigated about oxidation. The above fired Pt / Al₂O₃Some of the samples were also reduced in 7% H2 / N2 at 400 ° C. for 1 hour. The reduction step was carried out by raising the catalyst temperature from 25 to 400 ° C at a H2 / N2 gas flow rate of 500 cc / min. The rising temperature was about 5 ° C / min. Cool the catalyst to room temperature and C the catalyst as described in Example 21.₃H₆I investigated about oxidation. Example 19 (Reference Example) 6.8 g of ammonium tungstate was dissolved in 30 cc of water, the pH was adjusted to 10, and the solution was impregnated on 50 g of Versal GL alumina (La Roche Industries Inc.). The material was dried at 100 ° C and calcined at 550 ° C for 2 hours. Al₂O₃The above approximately 10% by weight of metal W was cooled to room temperature and impregnated with 13.7 g of Pt amine hydroxide (18.3% Pt). 2.5 g of acetic acid was added and mixed well. Water was then added to make the catalyst a slurry containing 35% solid. The slurry is then coated on a 400 cpsi 1.5 x1.0 diameter ceramic substrate, dried and then 0.79 g / in.³The results were given with the catalytic washcoat loading of. The coated catalyst was then dried and calcined at 550 ° C for 2 hours. In the calcined form of the catalyst, in the temperature range of 60 to 100 ° C, C₃H₆And examined in dry air. Example 20 (Reference Example) 6.8 g of perrhenic acid (36% Re in solution) was further diluted in water to obtain a 10 g% perrhenic acid solution. The solution was impregnated on 25 g of Versal GL alumina. The impregnated alumina was dried and the powder was calcined at 550 ° C for 2 hours. Impregnated Al₂O₃A powder of 10 weight percent Re based on the metal above was then further impregnated with 6.85 g of a Pt amine hydroxide solution (18.3% Pt metal in the solution). 5 g of acetic acid was added and mixed for half an hour. A slurry was prepared by adding water to make it 28% solid. The slurry is ball milled for 2 hours, coated on a 400 cpsi ceramic substrate with a length of 1.5 "diameter x 1.0" and 0.51 g / in after drying.³The catalyst wash coat load of the above was obtained. The catalyst-coated substrate was dried at 100 ° C and calcined at 550 ° C for 2 hours. 60ppm C in the fired form of the catalyst₃H₆And using dry air, the examination was carried out in the temperature range of 60 to 100 ° C. Example 21 (Reference Example) The catalysts of Examples 18, 19 and 20 were examined in a microreactor. The dimensions of the catalyst sample were 0.5 "diameter and 0.4" length. The supply gas is 60 ppm C in dry air in the temperature range of 25-100 ° C.₃H₆Consists of. C₃H₆Was measured under steady state conditions at 60, 70, 80, 90 and 100 ° C. The results are summarized in Table VII.<img file="JP4065026B2_D0008.tif" />From the table, the addition of W or Re oxide is Pt / Al in the calcined form.₂O₃It is clear that the activity of was enhanced. Baked Pt / Al₂O₃C₃H₆The conversion rate was significantly improved when the catalyst was reduced at 400 ° C. for 1 hour. Improved activity was also observed for catalysts calcined by the insertion of W or Re oxides. Example 22 (Example of the present invention) This is MnSO₄Is an example of the preparation of high surface area cryptomelene using. Mole ratio: KMnO₄: MnSO₄: Acetic acid was 1: 1.43: 5.72. The number of moles of Mn in the solution before mixing is: 0.44 M KmnO₄0.50M MnSO₄Met. FW KMnO₄= 158.04g / mol FW MnSO₄ H₂O = 169.01g / mol FW C₂H₄O₂The steps were less than = 60.0 g / mol: 3.50 mol (553 g) of KMnO in 1.8.05 L of deionized water.₄Was made and heated to 68 ° C. Using 2.1260 grams of glacial acetic acid, 10.5 L of 2N acetic acid was made by diluting to 10.5 L with deionized water. The density of this solution is 1.01 g / mL. 3.5.00 mol (846 grams) of manganese sulfate hydrate (MnSO)₄ H₂O) was weighed, dissolved in 10,115 g of the above 2N acetic acid solution and heated to 40 ° C. 4. The solution from step 3 was added to the solution from step 1 over 15 minutes with constant stirring. After the addition was completed, heating of the slurry was started according to the following heating rate: 1:06 pm 69.4 ° C1: 07 pm 71.2 ° C1: 11 pm 74.5 ° C1: 15 pm 77.3 ° C1: 18 pm 80.2 ° C1: At 23 pm 83.9 ° C1: 25 pm 86.7 ° C1: 28 pm 88.9 ° C5.1: 28 pm, remove approximately 100 mL of slurry from the container, immediately filter on the Büchner funnel, wash with 2 L of deionized water and wash. It was then dried in the oven at 100 ° C. The sample is 259m²It was determined to have a BET Multi-Point surface area of / g. Example 23 (Example of the present invention) This is Mn (CH)₃COO)₂Is an example of the preparation of high surface area cryptomelene using. Mole ratio: KMnO₄: Mn (CH₃CO₂)₂: Acetic acid was 1: 1.43: 5.72. FW KMnO₄= 158.04g / mol Aldrich Lot # 08824MGFW Mn (CH)₃CO₂)₂ H₂O = 245.09g / Mol Aldrich Lot # 08722HGFW C₂H₄O₂= 60.0 g / mol 1.4.6 L of 2.0 mol (316 g) of KMnO in deionized water₄Was made and heated to 60 ° C by heating on a hot plate. 6.0 L of 2N acetic acid was made by diluting to 6.0 L with deionized water using 2.720 grams of glacial acetic acid. The density of this solution is 1.01 g / mL. 3.2.86 mol (700 grams) of manganese (II) acetate tetrahydrate [Mn (CH)₃CO₂)₂ 4H₂O] was weighed and dissolved in 5780 g of the above 2N acetic acid solution (in the reactor). It was heated to 60 ° C in the reactor. 4. The solution from 1. was added to the solution from 3. while keeping the slurry at 62-63 ° C. After the addition was complete, the slurry was gently heated according to: 3:58 pm 82.0 ° C 4:02 pm 86.5 ° C 4:06 pm 87.0 ° C 4:08 pm 87.1 ° C then 10 L of deionized water Was pumped into the container to quench the slurry. This cooled the slurry to 58 ° C at 4:13 pm. The slurry was filtered on the Buchner funnel. The resulting filter cake was re-slurried in 12 L of deionized water and then stirred overnight in a 5 gallon bucket using a mechanical stirrer. The washed product was refiltered in the morning and then dried in the oven at 100 ° C. The sample is 296m²It was determined to have a BET multipoint surface area of / g. The resulting cryptomelene is characterized by the XRD pattern in FIG. It appears to have an IR spectrum similar to the spectrum shown in FIG. Example 24 (Example of the present invention) The following is a description of the ozone test method for determining the percent ozone decomposition used in this example. Percent ozone destroyed by the catalyst sample was measured using a test device including an ozone generator, a gas flow controller, a water whisk, a cold mirror dew point hygrometer and an ozone detector. Ozone was generated on the spot using an ozone generator in a flowing gas stream containing air and water vapor. The ozone concentration was measured using an ozone detector, and the water content was determined using a dew point hygrometer. The sample flowed at about 1.5 L / min at 25 ° C and was examined using an inlet ozone concentration of 4.5-7 parts per million (ppm) in a gas stream with a dew point of 15 ° C-17 ° C. The sample was examined as particles with a particle size of -25 / + 45 mesh held between glass wool stoppers in a 1/4 "inner diameter Pyrex glass tube. The test sample filled a 1 cm portion of the glass tube. Sample test. Generally took 2 to 16 hours to reach a steady state of conversion. At the start of the test, the sample typically gave conversions close to 100% and slowly declined to "averaged" conversions. It remained constant for a long time (48 hours). After the steady state is obtained, the equation:²It was determined to have a BET multipoint surface area of / g. Ozone destruction tests on the samples showed a conversion rate of 85%. Comparison with the test of the sample of Example 23 showed that no benefit in ozone conversion was realized from the washing and calcination of the sample of Example 23. Example 26 (Example of the present invention) A sample of high surface area cripromelene was obtained from a commercial supplier and modified by calcination and / or washing. As received and modified powders were examined for ozonolytic performance according to the method of Example 24 and characterized by powder X-ray diffraction, infrared spectroscopic analysis and BET surface area measurements by nitrogen adsorption. Example 26a (Example of the Invention) A commercially supplied sample of high surface area cryptomelene (Chemetals, Inc., Baltimore, MD) was washed in deionized water at 60 ° C. for 30 minutes, filtered, rinsed and 100%. Oven dried at ° C. The ozone conversion of the as-received sample was 64% compared to 79% for the washed material. It was determined by nitrogen adsorption and powder X-ray diffraction measurements that cleaning did not change the surface area or crystal structure of this material, respectively (223 m).²/ g cryptomelene). However, infrared spectroscopic analysis showed the disappearance of peaks at 1220 and 1320 wavenumbers in the spectrum of the washed sample, indicating the removal of sulfate anions. Example 26b (Example of the Invention) Commercially supplied samples of high surface area cryptomelene (Chemetals, Inc., Baltimore, MD) were calcined at 300 ° C for 4 hours and at 400 ° C for 8 hours. The ozone conversion of the material as received was 44% compared to 71% for the sample calcined at 300 ° C and 75% for the sample calcined at 400 ° C. Sintering did not significantly change the surface area or crystal structure of the 300 ° C or 400 ° C sample (334 m).²/ g cryptomelene). Trace amount of Mn in 400 ° C sample₂O₃Was detected. Sintering causes dehydroxylation of these samples. Infrared spectroscopy shows a decrease in the intensity of the absorption band with wave numbers of 2700 to 3700 specified for the surface hydroxyl group. Example 27 (Example of the present invention) It is found that the addition of Pd black (containing Pd metal and oxide) to the high surface area cryptomelene significantly improves the ozone decomposition performance. (1) Commercially obtained cryptomelene (300 ° C calcined sample described in Example 26b) and (2) High surface area cryptomelene powder synthesized in Example 23 and calcined at 200 ° C for 1 hour. A sample containing Pd black powder physically mixed with was prepared. Samples were prepared by mixing Pd black powder and cryptomelene in a dry state at a ratio of 1: 4 by weight. The dry mixture was shaken until the color was uniform. An amount of deionized water giving a solid content of 20-30% was added to the mixture in the beaker, thus forming a suspension. The agglomerates in the suspension were mechanically broken using a stirring rod. Bransonic suspension^R It was sonicated in a Model 5210 ultrasonic cleaner for 10 minutes and then oven dried at 120-140 ° C for about 8 hours. The ozone conversion of commercially available cryptomelene calcined at 300 ° C was 71% as measured on a powder reactor (Example 26b). A sample of this product was mixed with 20 weight percent Pd black to give 88% conversion. Cryptomelene samples prepared as in Example 23 and calcined at 200 ° C had a conversion of 85%. Performance improved to 97% with the addition of 20 weight percent Pd Black. Example 28 (Example of the Invention) 1500 g of high surface area manganese dioxide (cryptomerene purchased from Chemetals) and 2250 g of deionized water are combined in a 1 gallon ball mill and ground for 1.5 hours to a particle size where 90% is 7 μm. did. After draining the resulting slurry from the mill into another 1 gallon container, sufficient KOH (20% solution in deionized water) was added to raise the pH to about 9.5. Additional KOH was added over the next few days to maintain a pH of 9.5. Then 294g (based on 10% solid) National Starch x-4280 Acrylic latex polymer (51% solid) was added. Sufficient blending of the binder was achieved by rotating the container containing the slurry on a two-roll machine. The vessel did not contain a grinding medium such as a ceramic milling ball. Slurries prepared according to this method were coated on a variety of substrates and showed excellent adhesion. Such substrates included a porous monolithic carrier (eg, a ceramic honeycomb), on which the coating was applied by immersing the honeycomb in a slurry. The slurry was also spray coated on the aluminum radiator. The slurry was also dip-coated on the small radiator mini-core of the type listed above. In addition, a polyfiber filter of the type used for air filtration media) was coated by dipping or spraying. Samples were typically coated with a loading that could vary from 0.15 to 1.5 grams per cubic inch. Samples were typically air dried for at least 2 hours until dried at 30 ° C. Excellent catalytic adhesion was obtained in each case (ie the coating could not be wiped). Higher drying temperatures (up to 150 ° C) can be used if desired. Latex cures during drying. Example 29 (Example of the Invention) 3.20 g (based on 3% solid) of Rhone-Poulenc Colloid 226 polymer dispersion obtained in Example 1 and ball mill ground 96.56 g of catalytic colloid (before KOH addition). The agent was added. After rotating the mixture on a roll mill for several hours, 7.31 g (based on 10% solid) National Starch x-4280 Acrylic latex polymer (51% solid) was added. Sufficient blending of the binder was achieved by rotating the container containing the slurry on a double roll machine as in Example 28. The container did not contain a grinding medium such as a ceramic grinding ball. Slurries prepared according to this method were coated on a variety of substrates and showed excellent adhesion. Such substrates included a porous monolithic carrier (eg, a ceramic honeycomb), on which the coating was applied by immersing the honeycomb in a slurry. The slurry was also dip-coated on the small radiator mini-core of the type listed above. Samples were typically coated with a loading that could vary from 0.15 to 1.5 grams per cubic inch. Samples were typically air dried for at least 2 hours until dried at 30 ° C. Excellent catalytic adhesion was obtained in each case (ie the coating could not be wiped). Higher drying temperatures (up to 150 ° C) can be used if desired. Latex cures during drying. Example 30 (Reference Example) 8.9 grams of deionized water was added to 1.1 grams of TiO2 nanopowder in a beaker. Ammonia / water concentrate was added to adjust the pH to 9.5. A solution of amine-solubilized platinum hydroxide with 17.75 weight percent platinum (based on metallic platinum) was added slowly with mixing to give 5 weight percent platinum on titania. Then add a mixed solution of palladium nitrate containing 20% by weight based on the palladium metal on Titania 14. Obtained 3% palladium. A 1-inch diameter x 1-inch long metal monolith cored sample per square inch to 400 cells (cpsi) was immersed in the slurry. Air was blown onto the coated monolith to clean the grooves and the monolith was dried at 110 ° C for 3 hours. At this point the monolith was reimmersed in the slurry and the steps of air blowing the groove and drying at 110 ° C were repeated. The twice coated monolith was calcined at 300 ° C for 2 hours. After this initial evaluation, the catalytic core was reduced in a molding gas with 7% hydrogen and 93% nitrogen at 300 ° C. for 12 hours. Catalyst 20ppm carbon monoxide and C₁Was evaluated in an air stream containing 20 ppm of hydrocarbons based on. Hydrocarbons were evaluated in the presence of 20 ppm CO. The evaluated hydrocarbon is ethylene C at a gas flow rate of 36.6 liters per minute, which corresponds to 300,000 standard time space velocity (SHSV).₂=; Propene C₃=; and Pentene C₅It was =. The airflow was at 30% relative humidity (RH). The results are shown in FIG.<u style="single">The main features and aspects of the present invention are as follows.</u><u style="single">1. A method of treating an atmosphere comprising moving the vehicle through the atmosphere, wherein the vehicle consists of at least one atmospheric contact surface and a group consisting of a catalytic composition and an adsorption composition located on the surface. A method having a contaminant treatment composition comprising a selected active substance, a polymeric binder and a dispersant.</u><u style="single">2. A method of treating an atmosphere comprising moving the vehicle through the atmosphere, wherein the vehicle comprises at least one atmospheric contact surface and an active material selected from the group consisting of a catalytic composition and an adsorption composition. The contaminated treatment composition comprises a contact-active substance selected from a platinum component and a palladium component, wherein the contaminated treatment composition is located on the surface thereof. Method.</u><u style="single">3. The method according to paragraph 2, wherein the contaminant treatment composition is at least one composition selected from the group consisting of catalyst compositions and adsorption compositions.</u><u style="single">Four. The method of paragraph 3, further comprising the step of adding a polymeric binder to the contaminant treatment composition.</u><u style="single">Five. The method according to paragraph 1 or 4, further comprising the step of adding a polymeric latex binder to the contaminant treatment composition.</u><u style="single">6. The method of paragraph 5, wherein the polymeric binder comprises a polymeric composition comprising a polymer selected from the group consisting of thermoplastic and thermosetting polymers.</u><u style="single">7. Polymeric binders are polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, poly (vinyl). Ester), poly (vinyl halide), polyamide, cellulose polymer, thermoplastic polyester, thermosetting polyester, poly (phenylene oxide), poly (phenylene sulfide), fluorinated polymer, polyamide, phenol resin and epoxy resin, polyurethane , The method of claim 5, comprising a polymeric composition comprising a polymer selected from the group consisting of silicone polymers, polyimides, acrylics, styrene acrylics, poly (vinyl alcohols) and ethylene vinyl acetate copolymers.</u><u style="single">8. 8. The method according to paragraph 1 or 3, wherein the catalytic composition comprises a refractory oxide support, a manganese component, carbon, and a support material selected from the group consisting of co-precipitates of manganese oxide and zirconia. ..</u><u style="single">9. 8. The method of paragraph 8, wherein the contactally active material is selected from at least one platinum group metal component, a gold component, a silver component, and said method further comprises the step of reducing the catalytic composition.</u><u style="single">Ten. 9. The method of paragraph 9, wherein the contactally active substance is selected from the palladium and platinum components and mixtures thereof.</u><u style="single">11. 11. 8. The method of paragraph 8, wherein the refractory oxide is selected from the group consisting of alumina, silica, titania, ceria, zirconia, chromia and mixtures thereof.</u><u style="single">12. The method of paragraph 11, wherein the refractory oxide is titania sol.</u><u style="single">13. The method according to paragraph 1 or 3, further comprising the step of firing the catalyst composition.</u><u style="single">14. The method according to paragraph 1, wherein the catalyst composition comprises a manganese component.</u><u style="single">15. 15. The method of paragraph 1 or 3, further comprising the step of contacting at least one contaminant in an atmosphere selected from the group consisting of ozone, carbon monoxide and hydrocarbons.</u><u style="single">16. The method according to paragraph 1 or 3, further comprising the step of maintaining the surface at a temperature of about 20 to about 105 ° C.</u><u style="single">17. 17. The method of paragraph 1 or 3, wherein the atmospheric contact surface comes into direct contact with the atmosphere as the vehicle moves through the atmosphere.</u><u style="single">18. 18. The method of paragraph 1 or 3, wherein the relative speed between the atmospheric contact surface and the atmosphere as the vehicle travels through the atmosphere is up to 100 miles per hour.</u><u style="single">19. The method according to paragraph 1 or 3, further comprising a step of heating the atmospheric contact surface and a step of contacting carbon monoxide and / or hydrocarbons in the atmosphere.</u><u style="single">20. Item 1 or 3 where the atmospheric contact surface is selected from the group consisting of the outer surfaces of air conditioner condensers, radiators, radiator fans, air intake coolers, wind deflectors, engine oil coolers, transmission oil coolers and power steering fluid coolers The method described in.</u><u style="single">twenty one. The method according to paragraph 1, wherein the dispersant is a polymeric acid or a derivative thereof.</u><u style="single">twenty two. A device for treating an atmosphere comprising a vehicle, wherein the vehicle comprises a means of transport, at least one atmosphere contact vehicle surface, and a contaminant treatment composition located on the surface. An apparatus in which a contaminant treatment composition comprises an active substance, a polymeric binder and a dispersant selected from the group consisting of catalyst compositions and adsorption compositions located on the surface.</u><u style="single">twenty three. A device for treating an atmosphere comprising a vehicle, wherein the vehicle comprises a means of transport, at least one atmosphere contact vehicle surface, and an active material selected from the group consisting of a catalyst composition and an adsorption composition. Containing a contaminant treatment composition comprising, the contaminant treatment composition is located on said surface, and the catalytic composition comprises a contactally active substance comprising a platinum component and a palladium component. A device consisting of.</u><u style="single">twenty four. 22 or 23, wherein the catalyst composition comprises a refractory oxide support, a manganese component, carbon, and a support material selected from the group consisting of co-precipitates of manganese oxide and zirconia. ..</u><u style="single">twenty five. The device according to paragraph 24, wherein the refractory oxide support is titania.</u><u style="single">26. Steps to produce a mixture consisting of a platinum component and a palladium component supported on a catalytic support, the mixture is essentially dry enough to absorb all the solutions.</u><u style="single">Steps to dry the mixture,</u><u style="single">Steps to bake the composition,</u><u style="single">A step of producing a slurry containing a mixture and a liquid, and a step of coating the atmospheric contact surface of an automobile with the slurry.</u><u style="single">A method consisting of.</u><u style="single">27. 26. The method of paragraph 26, further comprising the step of reducing the composition.</u><u style="single">28. Containing catalytic material selected from the group consisting of manganese oxide and noble metal components; refractory oxide supports and supports selected from the group consisting of co-precipitates of manganese oxide and zirconia; binders; and dispersants. Composition.</u><u style="single">29. 28. The composition according to paragraph 28, further comprising a water resistant additive selected from the group consisting of waxes and fluorocarbons.</u><u style="single">30. 28. The composition according to paragraph 28, wherein there is at least one catalytic material selected from the group consisting of manganese oxide, platinum components, and palladium components and mixtures thereof.</u><u style="single">31. 28. The composition according to paragraph 28, wherein the dispersant is a polymeric acid or a derivative thereof.</u><u style="single">32. 28. The composition according to paragraph 28, wherein the binder is a polymeric binder selected from the group consisting of acrylic and vinyl acetate polymers and copolymers.</u><u style="single">33. Binders are polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, poly (vinyl ester) , Poly (vinyl halide), polyamide, cellulose polymer, thermoplastic polyester, thermosetting polyester, poly (phenylene oxide), poly (phenylene sulfide), fluorinated polymer, polyamide, phenol resin and epoxy resin, polyurethane, silicone 28. The composition of claim 28, comprising a polymeric composition comprising a polymer selected from the group consisting of polymers, polyimides, acrylics, styrene acrylics, poly (vinyl alcohols) and ethylene vinyl acetate copolymers.</u><u style="single">34. A device for treating an atmosphere comprising a vehicle, wherein the vehicle comprises a means of transport, at least one atmosphere contact vehicle surface, and a contaminant treatment composition located on the surface. Contaminant treatment composition is MnO</u>_{<u style="single">2</u>}<u style="single">, A device comprising a polymeric binder and a dispersant.</u><u style="single">35. 34. The apparatus according to paragraph 34, wherein the contaminant treatment composition further comprises a platinum group component.</u><u style="single">36. The device according to paragraph 35, wherein the platinum group component is reduced.</u><u style="single">37. 35. The apparatus of paragraph 35, wherein the contaminant treatment composition further comprises a refractory support.</u><u style="single">38. MnO</u>_{<u style="single">2</u>}<u style="single">Is α-MnO</u>_{<u style="single">2</u>}<u style="single">The device according to paragraph 34.</u><u style="single">39. α-MnO</u>_{<u style="single">2</u>}<u style="single">38. The apparatus of paragraph 38, wherein the device comprises up to 2% by weight silica.</u><u style="single">40. α-MnO</u>_{<u style="single">2</u>}<u style="single">38. The device according to paragraph 38, wherein is selected from the group consisting of Holland ore, cryptomelene, mandylote and coronado ore.</u><u style="single">41. α-MnO</u>_{<u style="single">2</u>}<u style="single">Is about 200 ~ 350m</u>^{<u style="single">2</u>}<u style="single">The device according to paragraph 40, which is a cryptomelene having a surface area of / g.</u><u style="single">42. A step of producing a mixture comprising at least one platinum group metal component, a contactly active substance selected from a gold component, a silver component and a manganese component, and water.</u><u style="single">Steps to grind this mixture,</u><u style="single">Steps to adjust the pH of the composition to at least 8.5, as well as</u><u style="single">Steps to add the polymeric binder to the mixture</u><u style="single">A method consisting of.</u><u style="single">43. A step of producing a mixture comprising at least one platinum group metal component, a contactly active substance selected from a gold component, a silver component and a manganese component, and water.</u><u style="single">Steps to add dispersant,</u><u style="single">Steps to grind this mixture, as well</u><u style="single">Steps to add the polymeric binder to the mixture</u><u style="single">A method consisting of.</u><u style="single">44. A step of producing a slurry comprising the mixture and the liquid, and</u><u style="single">Step of coating the automobile atmosphere contact surface with the slurry</u><u style="single">The method according to paragraph 42 or 43, further comprising:</u><u style="single">45. 44. The method of paragraph 44, wherein the contactally active substance further comprises a support.</u><u style="single">46. 28. The method of claim 45, further comprising the step of calcining the contactally active material prior to adding the polymeric binder.</u><u style="single">47. 46. The method of paragraph 46, further comprising the step of reducing a contactally active substance.</u>