Palladium catalysts thermal stability

Heck C-C coupling reactions were also facilitated by the presence of a palladium catalyst when Pd was deposited on a tubular membrane of porous glass. Thus, the coupling of iodobenzene with allyl alcohol affording 3-phenylpropionaldehyde in the presence of this Pd catalyst had several advantages - the ease of catalyst manufacture, mechanical strength, thermal stability, and resistance to organic solvents [46],... 

Because of their convenient preparation from palladium(II) salts and stable NHC-precursors (vide supra), paUadium(ll) complexes were first examined as potential catalysts for Heck-type reactions. Due to the high thermal stability, temperatures up to 150°C can be used to activate even less reactive substrates, like, e.g., aryl chlorides. Inunobilization of such catalysts has been shown recently (vide infra) ... 

Palladium catalyst stability, recovery and recycle are the key to viable commercial technology. Continuous palladium recovery and recycle at 99.9% efficiency is critical to the economics of the process. Traditional catalyst recovery methods fail since the adipic acid precursor, dimethyl hex- -enedioate, is high boiling and the palladium catalytic species are thermally unstable above 125 C. Because of this problem, a non-traditional solvent extraction approach to catalyst recovery has been worked out and implemented at the pilot plant scale. Since patents have not issued, process detail on catalyst separation, secondary palladium recovery, and product recovery cannot be included in this review. 

Diaminobutyl dendrimers (DAB-POPAM) were functionalised with terminal diphenylphosphanyl groups and employed as catalysts in the Heck coupling of bromobenzene and styrene to give stilbene. Owing to their greater thermal stability, these dendritic palladium catalysts afforded higher yields than conventional palladium catalysts. In addition, the dendritic catalyst could be completely recovered by precipitation after addition of diethyl ether [7]. 

Automobile and Hydrocarbon Emissions. The oxidation of carbon monoxide and hydrocarbons is catalyzed by platinum/palladium/rhodium on alumina. If catalyst poisons such as lead and phosphorus are not present, the major problems become initiation of oxidation at low temperature, thermal stability at high temperature, resistance to thermal schock, and a high external surface area catalyst configuration. 

Najera et al. [92] have reported that for the coupling of aryl halides with organoboronic adds, complexes 23-26 are adequate catalysts, giving TONs between 102 and 10s. These pallada-cycles exhibit greater aerial and thermal stability than palladium]0) complexes. 

The key reaction of this 1-octanol process is telomerization of butadiene with a palladium complex catalyst. Known attempts to commercialize the palladium complex-catalyzed telomerization have failed, in spite of great efforts, for the following reasons (1) palladium complex catalysts are thermally unstable and tbe catalytic activity markedly decreases when, as a means of increasing the thermal stability, the ligand concentration is increased (2) a sufficiently high reaction rate to satisfy industrial needs cannot be obtained (3) low selectivity and (4) distillative separation of reaction products and unreacted butadiene from the reaction mixture causes polymeric products to form and the palladium complex to metallize. Kuraray succeeded in 1991 in commercializing the production of 1-octanol using hydrodimerization of butadiene. 

For the telomerization of butadiene, distillative separation methods cannot be employed to separate the product from the reaction mixture containing catalyst, because the palladium complex catalyst has not such a high thermal stability... 

These catalysts are more active in some cases than complexes generated from the same ligands and either palladium salts or dba adducts. In general, palladacycles have a higher thermal stability compared to the Pd/phosphine system and precipitation of palladium black is reduced. 

Indeed, the aged 1-500 and SGI-500 catalysts kept, respectively, 60 % and 69 % of their initial metallic dispersion values, whereas 86 % of the initial metallic dispersion was kept on the aged SG-500 catalyst (Table 1). In order to investigate the metal-support interaction suspected to be responsible of this improved thermal stability, XPS measurements were performed on the supported palladium catalysts. 

On the other hand, cerium has been shown to be an effective oxygen reservoir, enhancing the activity of many oxidation catalysts. Due to this property, cerium oxide is also considered to potentially enhance the thioresistance of the catatysts. This aspect is of great practical importance, since the use of palladium catalysts is hindered by the poisonous effect of sulphur compoimds, often present in off gases. Most works dealing with ceria-zirconia catalysts have been carried out with catalysts prepared by coprecipitation methods, whereas in this work an ahemative procedure, based on the incipient wetness technique is used to incorporate ceria to the zirconia support. The aim is to maintain the advantages of zirconia supports, especially the thermal stability. 

As it can be observed in Fig. 4, when only methane is added to the feed, catalyst A shows the best behaviour, followed by catalysts B and U. According to this, the addition of cerium to the zirconium hydroxide increases the activity of the zirconia-supported palladium catafysts. Comparing the performance of the cerium-containing catalysts, it is remarkable that catalyst B presents a poorer performance, than catalyst A (slightly lower initial conversion and foster deactivation). This result suggests that the interaction between Pd and Ce, revealed in the TPR experiments, does not enhance the activity of the active phase (Pd). In contrast, the interaction Ce-Zr in catalysts A increases the thermal stability, considered as the main foctor for preventing catalyst deactivation in these reactions [9]. 

Fresh and thermally aged catalysts containing mixtures of platinum and palladium were laboratory tested for the oxidation of carbon monoxide, propane, and propylene. For both monolithic and particulate catalysts, resistance to thermal deactivation was optimum when palladium content was 80%. Full-scale vehicle tests confirmed these findings. Catalysts of this composition were developed which, on the basis of durability tests at Universal Oil Products and General Motors, appeared capable of meeting the 1977 Federal Emissions Standards with as little as 0.56 g noble metal per vehicle. The catalyst support was thermally-stabilized, low density particulate. 

Thermal Stability. Our initial work on catalyst degradation processes was designed to answer qualitatively several simple yet vital questions. This report is organized similarly. The question naturally arises whether platinum or palladium is best for automotive emission control. One aspect... 

---