Chemical deactivation, platinum catalysts

Catalyst poisoning. The more or less permanent deactivation of a catalyst by chemical reaction with a contaminant. Sulfur will poison platinum catalysts vanadium will poison zeolyte catalysts. 

Chemical deactivation by adsorbed impurities or reaction products was identified as a primary cause of catalyst deactivation [42,43,45-48,50]. Deactivation of platinum catalysts in l-methoxy-2-propanol oxidation was attributed to polymeric species formed by aldol-dimerization and detected by chromatographic... 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

Platinum is generally acknowledged as the most effective catalyst for the electroreduction of oxygen in a wide range of conditions (e.g. fuel cells). In the instance of aqueous HC1 electrolysis, the basic drawback is corrosion or deactivation of the catalyst during cell shutdown, owing to chemical attack from HC1 and chlorine that diffuse across the membrane. 

Cerium-zirconium mixed metal oxides are used in conjunction with platinum group metals to reduce and eliminate pollutants in automotive emissions control catalyst systems. The ceria-zirconia promoter materials regulate the partial pressure of oxygen near the catalyst surface, thereby facilitating catalytic oxidation and reduction of gas phase pollutants. However, ceria-zirconia is particularly susceptible to chemical and physical deactivation through sulfur dioxide adsorption. The interaction of sulfur dioxide with ceria-zirconia model catalysts has been studied with Auger spectroscopy to develop fundamental information regarding the sulfur dioxide deactivation mechanism. 

The release of VOCs into the environment has widespread environmental imph-cations. Pollution by VOCs has been linked to the increase in photochemical smog and ozone depletion. In addition, many VOCs are themselves toxic and/or carcinogenic. The US Clean Air Act of 1990 was one of the first measures to call for a 90% reduction in the emissions of 189 toxic chemicals, with 70% of these classed as VOCs, by 1998. Hence, in recent years, the development of effective technologies for the removal of VOCs from the atmosphere has increased in importance with the introduction of legislation to control their release. Various methods have been proposed, and one of the best is heterogeneous catalytic oxidation. This has the advantage over the more common original thermal oxidation process, since it requires less supplementary fuel and is therefore a less expensive process. However, the characteristics of the catalyst selected for this process are of vital importance for successful operation, and potential problems such as lifetime and deactivation must be solved if catalytic oxidation is to be employed universally. Catalysts currently in use include noble metals, notably platinum and palladium, and those based on metal oxides, however, irrespective of the type of catalyst, the most important characteristics are activity and selectivity for total oxidation. 

Ammonia decomposition over Fe, Cu, Ag, Au, and Pt Hydrolysis of starch to glucose catalyzed by acids Mixture of coal gas and air makes a platinum wire white hot Measurements on the rate of H2O2 decomposition Selective oxidation of ethanol to acetic acid over platinum Comprehensive paper on the H2 + O2 reaction on platinum foils, including reaction rates, deactivation, reactivation, and poisoning Definition of catalysis, catalyst, and catalytic force First quantitative analysis of reaction rates Systematic studies on the concentration dependence of reaction rates First concise monograph on chemical kinetics Definition of order of reaction Arrhenius equation k = u exp (-Ea/RT)... 

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