Catalyst supported platinum

There are several advantages for the use of S-ZrOj as a catalyst support in PEMFC applications. Because of its hydrophilicity, it has been suggested that this type of fuel cell catalyst would be well suited for low-relative humidity conditions and possibly simplify fuel cell components to operate without the use of a humidifier. Due to the proton conductivity across the surface of the material, less Nafion iono-mer needs to be cast to form the TPBs. Platinum utilization increases as the S-ZrOj support acts as both the platinum and proton conductor and better gas diffusion to the catalyst site results from the decreased blockage of Nafion ionomer (Liu et al., 2006a,b). It is beheved that within porous carbon catalyst supports, platinum deposited within the pores may not have proton conductivity due to the perfluorosul-fonated ionomer unahle to penetrate into the pores. Thus, a TPB which is necessary for a catalyst active site will not be formed. Therefore, the S-ZrOj support has an additional benefit over porous carbon material supports in that by using the S-ZrOj as a support for platinum catalysts, the surface of the support can act as a proton conductor and platinum deposited anywhere on the surface of the support will provide immediate access to the electron and proton pathways thereby requiring less Nafion. Thus the use of S-ZrOj in fuel cell MEA components may potentially lower the cost of materials substantially, as the catalytic metals and membrane materials are among the most costly in a PEMFC. However, like most metallic oxides, the downside of their use stems from their relatively low electron conductivity and low surface areas that results in poor platinum dispersion. 

Reduction of the aromatic nuclei contained in catalytic C-9 resins has also been accomplished in the molten state (66). Continuous downward concurrent feeding of molten resin (120°C softening point) and hydrogen to a fixed bed of an alumina supported platinum—mthenium (1.75% Pt—0.25% Ru) catalyst has been shown to reduce approximately 100% of the aromatic nuclei present in the resin. The temperature and pressure required for this process are 295—300°C and 9.8 MPa (lOO kg/cni2), respectively. The extent of hydrogenation was monitored by the percent reduction in the uv absorbance at 274.5 nm. 

Several processes are available for the recovery of platinum and palladium from spent automotive or petroleum industry catalysts. These include the following. (/) Selective dissolution of the PGM from the ceramic support in aqua regia. Soluble chloro complexes of Pt, Pd, and Rh are formed, and reduction of these gives cmde PGM for further refining. (2) Dissolution of the catalyst support in sulfuric acid, in which platinum is insoluble. This... 

Standard Test Methodfor Surface Area of Catalysts. (D3663—78) Standard Test Method for Hydrogen Chemisorption on Supported Platinum on Alumina Catalysts. (D3908-80) American Society for Testing and Materials (ASTM), Philadelphia, PA. 

Many workers (5,6,7,87) have compared various metals for the selective hydrogenation of lower acetylenes to olefins, and it was always found that palladium was by far the most selective. This conclusion concurs with the usual synthetic experience, but under special circumstances other metals, such as platinum, may prove more useful (35,63). The catalyst support may also have an influence (21,65). Carbon, calcium carbonate, and barium sulfate are frequently used supports. Examples of some differences are noted later,... 

A platinum catalyst supported on AI2O3 is used for the oxidation of sulfur dioxide ... 

AXB) shows time courees of amounts of evolved hydrogen and decalin conversions with caibon-supported platinum-based catalysts unda" supeiheated liquid-film conditions. Enhancement of dehydrogenation activities for decalin was realized by using fiiese composite catalysts. The Pt-W / C composite catalyst exhibited the hipest reaction rate at the initial stage, whereas the Pt-Re / C composite catalyst showed the second highest reaction rate in addition to low in sensitivity to retardation due to naphthaloie adsorbed on catalytic active sites [1-5], as indicated in Fig. 2(A) ). 

Figure 5. X-ray absorption spectrum of a silica supported platinum-iridium catalyst at 100 K in the region of the L absorption edges of platinum and iridium. Reproduced with permission from Ref. 13. Copyright 1982, American Institute of Physics.

While the discovery of the catalytic properties of zeolites was driven by the desire to improve industrial prcKessing, the development of emission control catalysts was necessitated by governmental fiat. The first requirement was for 90+% removal of CO and of hydrocarbons, a goal which could not be met by oxidation with base metal oxides. To achieve the required spedfications during automobile operations, it was necessary to develop supported platinum catalysts. Originally the support was alumina in pellet form. Later platinum on cordierite was used in honeycomb form, containing 200-400 square channels per square inch. 

P 15] Cyclohexene was purified prior to use in a micro reactor experiment [11]. As catalyst, standard platinum supported on alumina powder with platinum contents... 

It was found in the 1960s that disperse platinum catalyst supported by certain oxides will in a number of cases be more active than a similar catalyst supported by carbon black or other carbon carrier. At platinum deposits on a mixed carrier of WO3 and carbon black, hydrogen oxidation is markedly accelerated in acidic solutions (Hobbs and Tseung, 1966). This could be due to a partial spillover of hydrogen from platinum to the oxide and formation of a tungsten bronze, H WOj (0 < a < 1), which according to certain data has fair catalytic properties. 

It was seen when studying mixed systems Pt-WOj/C and Pt-Ti02/C that with increasing percentage of oxide in the substrate mix the working surface area of the platinum crystallites increases, and the catalytic activity for methanol oxidation increases accordingly. With a support of molybdenum oxide on carbon black, the activity of supported platinum catalyst for methanol oxidation comes close to that of the mixed platinum-ruthenium catalyst. 

The choice of the metals is strictly related to the catalytic application. As we shall show later, the catal54ic reaction most commonly investigated with polymer supported M / CFP catalysts is hydrogenation (Table 3). The overwhelming majority of catalytic studies concerns the hydrogenation of alkenes and by far the most commonly employed metal is palladium, followed by platinum. Examples of rhodium and ruthenium hydrogenation catalysts supported on pol5uneric supports are very rare. 

Bergamaski K, Pinheiro ALN, Teixeira-Neto E, Nart EC. 2006. Nanoparticle size effects on methanol electrochemical oxidation on carbon supported platinum catalysts. J Phys Chem B 110 19271-19279. 

Andreaus B, Maillard F, Kocylo J, Savinova ER, Eikerling M. 2006. Kinetic modeling of CO monolayer oxidation on carbon-supported platinum catalyst nanoparticles. J Phys Chem B 110 21028-21040. 

Frelink T, Visscher W, vanVeen JAR. 1995. Particle-size effect of carbon-supported platinum catalysts for the electrooxidation of methanol. J Electroanal Chem 382 65-72. 

Hanson FV, Boudart M. 1978. The reaction between H2 and O2 over supported platinum catalysts. J Catal 53 56-67. 

Perrichon, V., Retailleau, L., Bazin, P. et al. (2004) Metal dispersion of Ce02—Zr02 supported platinum catalysts measured by H2 or CO chemisorption, Appl. Catal. A, 260, 1. 

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