Platinum active automotive exhaust

As an introductory example we take one of the key reactions in cleaning automotive exhaust, the catalytic oxidation of CO on the surface of noble metals such as platinum, palladium and rhodium. To describe the process, we will assume that the metal surface consists of active sites, denoted as We define them properly later on. The catalytic reaction cycle begins with the adsorption of CO and O2 on the surface of platinum, whereby the O2 molecule dissociates into two O atoms (X indicates that the atom or molecule is adsorbed on the surface, i.e. bound to the site ) ... 

A very important aspect of gas sensors in automotive exhaust-gas environments is aftertreatment of the electrodes to control a specific sensor behavior. For example, to measure nonequilibrium raw emissions, the sensor needs excellent catalytic ability. Various methods are known to improve electrodes in Zr02-based sensors. One well known method is to increase the active platinum surface area and the three-phase boundary area by partial reduction of zirconia close to the electrode. This occurs when the ceramic is exposed to a reducing atmosphere at high temperatures or when an electrical cathodic current is applied through the electrode and electrolyte. A similar effect can be achieved by chemical etching of the elec-... 

A ceramic (cordierite) monolith-type three-way automotive exhaust catalyst was used for laboratory-simulated sintering and activity tests and was characterized at Aliieo-Signa1 Materials Research Center. The catalyst contained platinum and rhodium at a weight ratio of 5 to and a total noble metal loading of approximately 1.1 weight percent based on the weight of the... 

The parameters that affect the degradation of supported platinum and palladium automotive exhaust catalysts are investigated. The study includes the effects of temperature, poison concentration, and hed volume on the lifetime of the catalyst. Thermal damage primarily affects noble metal surface area. Measurements of specific metal area and catalytic activity reveal that supported palladium is more thermally stable than platinum. On the other hand, platinum is more resistant to poisoning than palladium. Electron microprobe examinations of poisoned catalyst pellets reveal that the contaminants accumulate almost exclusively near the skin of the pellet as lead sulfate and lead phosphate. It is possible to regenerate these poisoned catalysts by redistributing the contaminants throughout the pellet. 

Platinum and palladium have high activities for total oxidation. This property is exploited in automotive exhaust catalysis. Automobile exhaust contains toxic gases such as CO, NO, and hydrocarbons which contribute to formation of photochemical smog and acid rain. Since 1978, catalysts based on platinum, rhodium, and sometimes palladium, supported on a monolithic carrier, are applied to convert exhaust gases to less harmful products. The so-called threeway catalyst enables the following three overall reactions... 

Not all catalysts need the extended smface provided by a porous structure, however. Some are sufficiently active so that the effort required to create a porous catalyst would be wasted. For such situations one type of catalyst is the monolithic catalyst. Monolithic catalysts are normally encountered in processes where pressure drop and heat removal are major considerations. Typical examples include the platinum gauze reactor used in the ammonia oxidation portion of nitric acid manufacture and catalytic converters used to oxidize pollutants in automobile exhaust. They can be porous (honeycomb) or non-porous (wire gauze). A photograph of a automotive catalytic converter is shown in Figure CD 11-2. Platinum is a primary catalytic material in the monolith. 

The catalytic layer of monolithic automotive reactors usually consist of active metals (Pt, Pd, Rh) supported on alumina. One of the most important problems set by these catalysts is the decrease in their activity after thermal exposure to the exhaust gas itself (Ref.l). It is well known that this thermal deactivation is directly related to the sintering of the active components. Moreover, this modification of the supported metal is drastically enhanced by structural changes of the support. Thus using TEM experiments, Chu et al (Ref. 2) have reported rapid sintering of platinum during the structural transition Y-AI2O3 to (X-AI2O3. 

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