Platinum catalyst phosphoric acid

T. Ito, K. Kato, S. Kamitomai, M. Kamiya, "Organization of Platinum Loading Amount of Carbon-Supported Alloy Cathode for Advanced Phosphoric Acid Fuel Cell," in Fuel Cell Seminar Abstracts, 1990 Fuel Cell Seminar, Phoenix, AZ, November 25-28, 1990. J.S. Buchanan, G.A. Hards, L. Keck, R.J. Potter, "Investigation into the Superior Oxygen Reduction Activity of Platinum Alloy Phosphoric Acid Fuel Cell Catalysts," in Fuel Cell Seminar Abstracts, Tucson, AZ, November 29-December 2, 1992. 

J.S. Buchanan, G.A. Hards, L. Keck, R.J. Potter, Investigation into the Superior Oxygen Reduction Activity of Platinum Alloy Phosphoric Acid Fuel Cell Catalysts, in Fuel Cell Seminar Abstracts, Tucson, AZ, November 29-December 2, 1992. 

Buchanan J.S., Hards G.A., Keck L., and Potter R.J. (1992) Investigation into the superior oxygen reduction activity of platinum alloy phosphoric acid fuel cell catalysts, Fuel Cell Seminar Abstracts, Tucson, Arizona, U.S. 

Phosphoric acid fuel cells (PAFC) use liquid phosphoric acid as an electrolyte - the acid is contained in a Teflon-bonded silicon carbide matrix - and porous carbon electrodes containing a platinum catalyst. The PAFC is considered the "first generation" of modern fuel cells. It is one of the most mature cell types, the first to be used commercially, and features the most proven track record in terms of commercial applications with over 200 units currently in use. This type of fuel cell is typically used for stationary power generation, but some PAFCs have been used to power large vehicles such as city buses. 

For more than 10 years (138-143) it has been known that by reaction of dispersed Pt on soot with nonnoble metals of Group IV B and V B dispersed alloys are formed. Treating Pt-impregnated carbons, to which salts of these metals had been added, at 900°C in inert atmosphere (Ar) leads to formation of highly dispersed Pt-Cr or Pt-V alloys. The metal salt is reduced to the metal by the soot and forms the respective platinum alloy in situ. These alloy crystallites are reported to be highly active catalysts for phosphoric acid fuel cells. 

Agglomeration of Pt crystallites due to Brownian motion can really be observed and it can also be shown that, indeed, the interaction between the Pt particles and the supporting soot in the presence of the electrolyte, phosphoric acid, is weak enough to allow for relatively free movement of the Pt particles. This fast process obviously is also the reason for the nonobservability of slower surface diffusion-induced Ostwald ripening. Fortunately alloy catalysts composed of platinum and nonnoble metals seem to show a reduced tendency to agglomeration as their deterioration and activity loss is much slower than that of the pure platinum catalyst. 

Phosphoric acid fuel cell (PAFC)—Phosphoric acid electrolyte with platinum catalyst. It can use hydrocarbon fuel and is suited for stationary applications. It can generate both electricity and steam. As many as 200 units in sizes ranging from 200 kW to 1 mW are in operation. 

Phosphoric acid fuel cells rely on expensive components and, like pems, use platinum catalysts to accelerate the chemical reactions at the electrodes. Finally, they have not achieved the level of sales needed to significantly reduce manufacturing costs. For these reasons, UTC Fuel Cells is phasing out production of phosphoric acid fuel cells in favor of pem fuel cell technology, which is likely to be significantly less expensive. 

Second, molten carbonate fuel cells have electric efficiencies of 47 to 50 percent or more, which significantly reduces their fuel costs for stationary applications compared with both phosphoric acid and pem fuel cells, whose overall efficiency when running on natural gas might not exceed 35 to 40 percent. Third, high temperatures allow relatively inexpensive nickel to be used as a catalyst rather than pricey platinum, which is required by the lower-temperature fuel cells. Fourth, these fuel cells are far more tolerant of carbon monoxide, which can poison the electrochemical reaction of pem... 

The PAFC is based on an immobilized phosphoric acid electrolyte. The matrix universally used to retain the acid is silicon carbide, and the catalyst for both the anode and cathode is platinum [8], The active layer of platinum catalyst on a carbon-black support and a polymer binder is backed by a carbon paper with 90% porosity, which is reduced to some extent by a Teflon binder [6,9]. 

Alkaline fuel cells (AFC) — The first practical -+fuel cell (FC) was introduced by -> Bacon [i]. This was an alkaline fuel cell using a nickel anode, a nickel oxide cathode, and an alkaline aqueous electrolyte solution. The alkaline fuel cell (AFC) is classified among the low-temperature FCs. As such, it is advantageous over the protonic fuel cells, namely the -> polymer-electrolyte-membrane fuel cells (PEM) and the - phosphoric acid fuel cells, which require a large amount of platinum, making them too expensive. The fast oxygen reduction kinetics and the non-platinum cathode catalyst make the alkaline cell attractive. 

Some of other effective platinum catalysts are sulfided platinum on carbon120 or platinum catalysts with inhibitors such as bis(2-hydroxyethyl)sulfide,121 morpholine,122 polyamines,123 phosphorous acid,105 phosphoric acid,124 and dicyandiamide.96 Dicy-andiamide was originally used as an effective inhibitor for Raney Ni, as described above (see eq. 9.50).113 Hydrogenations of halonitrobenzenes with use of these platinum catalysts are summarized in Table 9.5. In one patent, it is claimed that ethano-lamine is a better inhibitor than morpholine for Pt-C. Thus, 3,4-dichloronitrobenzene was hydrogenated over Pt-C modified with iron oxide in the presence of 1.2 mol% ethanolamine to give 3,4-dichloroaniline containing only 235 ppm of 4-chloroaniline, compared to 548 ppm with morpholine as the inhibitor.125... 

The next advance in development of PAFC binary-alloy cathode electrocatalysts was the use of Pt-Cr alloys.27 In this patent, it was disclosed that with the platinum-vanadium alloy in 99 % phosphoric acid at 194 °C and at an electrode potential 0.9 volts, over 67 % by weight of the vanadium had dissolved in the first 36 hours. In the case of Pt-Cr, only 37 % had dissolved under the same conditions. It is not clear from the descriptions in these patents whether or not there is any unreacted vanadium or chromium present in the catalyst because it is not identified that all of the vanadium or all of the chromium was initially alloyed with the platinum. It is conceivable that significant amounts of the non-noble metal components are not fully reacted. 

In order to evaluate the performance advantages of alloying platinum with 3d transition metals, Buchanan, Keck, el al.s examined platinum with first-row transition elements to examine whether or not there were significant improvements in the performance of the alloys in hot phosphoric acid as oxygen reduction catalysts. They concluded that alloying platinum with the first-row transition elements significantly increases the performances above that for platinum alone. 

In Section 3, the slow rate of the ORR at the Pt/ionomer interface was described as a central performance limitation in PEFCs. The most effective solution to this limitation is to employ dispersed platinum catalysts and to maximize catalyst utilization by an effective design of the cathode catalyst layer and by the effective mode of incorporation of the catalyst layer between the polymeric membrane electrolyte and the gas distributor/current collector. The combination of catalyst layer and polymeric membrane has been referred to as the membrane/electrode (M E) assembly. However, in several recent modes of preparation of the catalyst layer in PEFCs, the catalyst layer is deposited onto the carbon cloth, or paper, in much the same way as in phosphoric acid fuel cell electrodes, and this catalyzed carbon paper is hot-pressed, in turn, to the polymeric membrane. Thus, two modes of application of the catalyst layer - to the polymeric membrane or to a carbon support - can be distinguished and the specific mode of preparation of the catalyst layer could further vary within these two general application approaches, as summarized in Table 4. 

Class 3 additives are materials such as phosphoric acid and citric acid that can compete with the metal for adsorption sites. While Class 1 and Class 2 additives can control the depth and amount of metal adsorbed leading either to uniform or egg shell catalysts. Class 3 species interfere with platinum adsorption and can give entirely different adsorption profiles. This approach is used, specifically, for the preparation of egg white and egg yolk type catalysts. Fig. 13.11 shows that the platinum distribution is displaced from the surface of the... 

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