Catalytic precious metal

Each has been recovered and used in various quantities. Rhodium, palladium, and technetium have also been recovered for potential catalytic or precious metal appHcations (34,35). 

Cost. The catalytically active component(s) in many supported catalysts are expensive metals. By using a catalyst in which the active component is but a very small fraction of the weight of the total catalyst, lower costs can be achieved. As an example, hydrogenation of an aromatic nucleus requires the use of rhenium, rhodium, or mthenium. This can be accomplished with as fittie as 0.5 wt % of the metal finely dispersed on alumina or activated carbon. Furthermore, it is almost always easier to recover the metal from a spent supported catalyst bed than to attempt to separate a finely divided metal from a liquid product stream. If recovery is efficient, the actual cost of the catalyst is the time value of the cost of the metal less processing expenses, assuming a nondeclining market value for the metal. Precious metals used in catalytic processes are often leased. 

Some catalyst supports rely on a relatively low surface area stmctural member coated with a layer of a higher surface area support material. The automotive catalytic converter monolith support is an example of this technology. In this appHcation, a central core of multichanneled, low surface area, extmded ceramic about 10 cm in diameter is coated with high surface area partially hydrated alumina onto which are deposited small amounts of precious metals as the active catalytic species. 

Precious Meta.1 Ca.ta.lysts, Precious metals are deposited throughout the TWC-activated coating layer. Rhodium plays an important role ia the reduction of NO, and is combiaed with platinum and/or palladium for the oxidation of HC and CO. Only a small amount of these expensive materials is used (31) (see Platinum-GROUP metals). The metals are dispersed on the high surface area particles as precious metal solutions, and then reduced to small metal crystals by various techniques. Catalytic reactions occur on the precious metal surfaces. Whereas metal within the crystal caimot directly participate ia the catalytic process, it can play a role when surface metal oxides are influenced through strong metal to support reactions (SMSI) (32,33). Some exhaust gas reactions, for instance the oxidation of alkanes, require larger Pt crystals than other reactions, such as the oxidation of CO (34). 

The small precious metal crystals can exist as metal crystallites or as metal oxides, both of which are catalytic (31). Rodium oxide has a tendency to react with alumina to form a soHd solution (35). To minimize this reaction, zirconia is used with the alumina (36). PubHcations regarding the TWC function of precious metals abound (37—42). 

Two classes of metals have been examined for potential use as catalytic materials for automobile exhaust control. These consist of some of the transitional base metal series, for instance, cobalt, copper, chromium, nickel, manganese, and vanadium and the precious metal series consisting of platinum [7440-06-4], Pt palladium [7440-05-3], Pd rhodium [7440-16-6], Rh iridium, [7439-88-5], Ir and mthenium [7440-18-8], Ru. Specific catalyst activities are shown in Table 3. 

The precious metals possess much higher specific catalytic activity than do the base metals. In addition, base metal catalysts sinter upon exposure to the exhaust gas temperatures found in engine exhaust, thereby losing the catalytic performance needed for low temperature operation. Also, the base metals deactivate because of reactions with sulfur compounds at the low temperature end of auto exhaust. As a result, a base metal automobile exhaust... 

The mechanism of poisoning automobile exhaust catalysts has been identified (71). Upon combustion in the cylinder tetraethyllead (TEL) produces lead oxide which would accumulate in the combustion chamber except that ethylene dibromide [106-93-4] or other similar haUde compounds were added to the gasoline along with TEL to form volatile lead haUde compounds. Thus lead deposits in the cylinder and on the spark plugs are minimized. Volatile lead hahdes (bromides or chlorides) would then exit the combustion chamber, and such volatile compounds would diffuse to catalyst surfaces by the same mechanisms as do carbon monoxide compounds. When adsorbed on the precious metal catalyst site, lead haUde renders the catalytic site inactive. 

Carrier. The metal catalyst is generally dispersed on a high surface area carrier, ie, the carrier is given a washcoat of catalyst, such that very small (2—3 nm dia) precious metal crystaUites ate widely dispersed over the surface area, serving two basic functions. It maximizes the use of the cosdy precious metal, and provides a large surface area thereby increasing gas contact and associated catalytic reactions (18). 

Toxic heavy metals and ions, eg, Pb, Hg, Bi, Sn, Zn, Cd, Cu, and Fe, may form alloys with catalytic metals (24). Materials such as metallic lead, ziac, and arsenic react irreversibly with precious metals and make the surface unavailable for catalytic reactions. Poisoning by heavy metals ordinarily destroys the activity of a precious-metal catalyst (8). 

It has been reported that below about 370°C, sulfur oxides reversibly inhibit CO conversion activity. This inhibition is greater at lower temperatures. CO conversion activity returns to normal shortly after removal of the sulfur from the exhaust (44). Above about 315°C, sulfur oxides react with the high surface area oxides to disperse the precious-metal catalytic agents and irreversibly poison CO conversion activity. 

The increasing use of sihconized coatings for weather durabiUty caused severe masking problems for the all-metal, filter mesh-like catalyst elements available in the 1970s. Interest in catalytic afterburners increased when dispersed-phase precious metal—alumin a-on-ceramic honeycomb catalysts offered economically attractive results. 

Automobile catalytic converter. Catalytic converters contain a "three-way" catalyst designed to convart CO to CO2, unbumed hydrocarbons to CO2 and H2O. and NO to N2. The activa components of the catalysts are the precious metals platinum and rhodium palladium is sometimes used as well. 

The catalytic converter on a car uses a precious-metal-based, solid catalyst, usually in the form of a monolith, to convert unburned hydrocarbons and carbon monoxide to carbon dioxide. Many different reactants are converted to two products CO2 and water. 

Recently, it is reported that Xi02 particles with metal deposition on the surface is more active than pure Ti02 for photocatalytic reactions in aqueous solution because the deposited metal provides reduction sites which in turn increase the efficiency of the transport of photogenerated electrons (e ) in the conduction band to the external sjistem, and decrease the recombination with positive hole (h ) in the balance band of Xi02, i.e., less defects acting as the recombination center[l,2,3]. Xhe catalytic converter contains precious metals, mainly platinum less than 1 wt%, partially, Pd, Re, Rh, etc. on cordierite supporter. Xhus, in this study, solutions leached out from wasted catalytic converter of automobile were used for precious metallization source of the catalyst. Xhe XiOa were prepared with two different methods i.e., hydrothermal method and a sol-gel method. Xhe prepared titanium oxide and commercial P-25 catalyst (Deagussa) were metallized with leached solution from wasted catalytic converter or pure H2PtCl6 solution for modification of photocatalysts. Xhey were characterized by UV-DRS, BEX surface area analyzer, and XRD[4]. 

The direct reductive amination (DRA) is a useful method for the synthesis of amino derivatives from carbonyl compounds, amines, and H2. Precious-metal (Ru [130-132], Rh [133-137], Ir [138-142], Pd [143]) catalyzed reactions are well known to date. The first Fe-catalyzed DRA reaction was reported by Bhanage and coworkers in 2008 (Scheme 42) [144]. Although the reaction conditions are not mild (high temperature, moderate H2 pressure), the hydrogenation of imines and/or enam-ines, which are generated by reaction of organic carbonyl compounds with amines, produces various substituted aryl and/or alkyl amines. A dihydrogen or dihydride iron complex was proposed as a reactive intermediate within the catalytic cycle. 

However, in more recent times science has made rapid strides in this direction. It is now possible to use EXAFS in situ during a catalytic reaction to examine the average coordination of metal atoms in the small particles which often exist in precious metal catalysts [2]. High resolution transmission electron microscopy has evolved to the level of atomic resolution, but can only be used ex-situ, or in situ with moderate pressures when special cells are fitted [3]. 

The catalytic activity of ln/H-ZSM-5 for the selective reduction of nitric oxide (NO) with methane was improved by the addition of Pt and Ir which catalyzed NO oxidation, even in the presence of water vapor. It was also found that the precious metal, particularly Ir loaded in/H-ZSM-5 gave a low reaction order with respect to NO, and then showed a high catalytic activity for the reduction of NO at low concentrations, if compared with ln/H-ZSM-5. The latter effect of the precious metal is attributed to the enhancement of the chemisorption of NO and also to the increase in the amount of NO2 adsorbed on in sites. 

The effects of precious metals on ln/H-ZSM-5 was found not only to simply catalyze NO oxidation but also to enhance NOx chemisorption. It is noted that NO conversion on the lr/ln/H-ZSM-5 exceeded NO2 conversion in NO2-CH4-O2 reaction on in/H-ZSM-5, when the concentration of NOx was decreased [14]. This study shows the catalytic activities of ln/H-ZSM-5 promoted by precious metals for the removal of low concentration NOx and the promotive effects of the precious metal will be discussed. 

Figure 2 shows the effect of NOx concentration on the conversion of NOx reduced by CH4 in the presence of 5% H2O. In the NO-CH4-O2 system, In/H-ZSM-5 showed low catalytic activity in the whole range of NO concentration. On the other hand, this catalyst was active for the NO2-CH4-O2 reaction, while the conversion of NO2 decreased with decreasing concentration of NO2. The catalytic activity of ln/H-ZSM-5 for the reduction of 1000 ppm NO was enhanced by the addition of Ir and R almost to the level of NO2 reduction on ln/H-ZSM-5, indicating that these precious metals worked as the catalytic sites for NO oxidation, which is a necessary step for NO reduction with CH4. With decreasing NO concentration to 100 ppm, however, the increase in NO conversion was observed on lr/ln/H-ZSM-5 and the conversion of NO exceeded that of NO2 on ln/H-ZSM-5. This can not simply be explained by the catalytic activity of Ir for NO oxidation. 

The catalytic activity for the selective reduction of NO with CH4 was significantly enhanced by the addition of precious metals, particularly Ir, to ln/H-ZSM-5. The role of added Ir was not only to promote NO oxidation which is a necessary step for NO reduction, but also to enhance the abilities of the catalyst to adsorb NO zind to increase the amount of NO2 adsorbed on In sites. 

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