Bimetallic electrocatalysis

Bimetallic Electrocatalysis The Platinum-Ruthenium and Platinum-Tin Alloys.254... 

BIMETALLIC ELECTROCATALYSIS THE PLATINUM-RUTHENIUM AND PLATINUM-TIN ALLOYS... 

These conclusions from the infrared reflectance spectra recorded with Pt and Pt-Ru bulk alloys were confirmed in electrocatalysis studies on small bimetallic particles dispersed on high surface area carbon powders.Concerning the structure of bimetallic Pt-Ru particles, in situ Extended X-Ray Absorption Fine Structure (EXAFS>XANES experiments showed that the particle is a true alloy. For practical application, it is very important to determine the optimum composition of the R-Ru alloys. Even if there are still some discrepancies, several recent studies have concluded that an optimum composition about 15 to 20 at.% in ruthenium gives the best results for the oxidation of methanol. This composition is different from that for the oxidation of dissolved CO (about 50 at.% Ru), confirming a different spatial distribution of the adsorbed species. 

Since 1976 until present time Toshima-t5q)e nanocolloids always had a major impact on catalysis and electrocatalysis at nanoparticle surfaces [47,210-213,398-407]. The main advantages of these products lie in the efficient control of the inner structure and morphology especially of bimetallic and even multimetallic catalyst systems. 

Another electro-oxidation example catalyzed by bimetallic nanoparticles was reported by D Souza and Sam-path [206]. They prepared Pd-core/Pt-shell bimetallic nanoparticles in a single step in the form of sols, gels, and monoliths, using organically modified silicates, and demonstrated electrocatalysis of ascorbic acid oxidation. Steady-state response of Pd/Pt bimetallic nanoparticles-modified glassy-carbon electrode for ascorbic acid oxidation was rather fast, of the order of a few tens of seconds, and the linearity was observed between the electric current and the concentration of ascorbic acid. 

Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ, Lucas CA, Wang GF, Ross PN, Markovic NM. 2007b. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Mater 6 241-247. 

Chang SC, Ho Y, Weaver MJ. 1992. Applications of real-time infrared spectroscopy to electrocatalysis at bimetallic surfaces. I. Electrooxidation of formic acid and methanol on bismuth-modified platinum (111) and platinum (100). Surf Sci 265 81-94. 

Markovic NM, Radmilovic V, Ross PN. 2003. Physical and electrochemical characterization of bimetallic nanoparticle electrocatalysts. In Wieckowski A, Savinova E, Vayenas C, eds. Catalysis and Electrocatalysis at Nanoparticle Surfaces. New York Marcel Dekker, pp. 311-342. 

Ross PN. 1998. The science of electrocatalysis on bimetallic surfaces. In Lipkowski J, Ross PN Jr, editors. Electrocatalysis. New York Wiley-VCH. pp. 43-74. 

The PtRu bimetallic system has been the catalyst of choice for MeOH oxidation in acid elecfrolyfes since its discovery by workers at Shell in the early 1960s2 In practice, PtRu lowers the overpotential for MeOH oxidation by >200 mV compared to pure Pt. The MeOH oxidation reaction on Pt and PtRu is probably the most studied reaction in fuel cell electrocatalysis due to its ease of sfudy in liquid electrolytes and the many possible mechanistic pathways. In recent years, the deposition of PtRu particles onto novel carbon supports and the novel PtRu particle preparation routes have proved popular as a means to demonstrate superiority over conventional PtRu catalysts. 

In this paper we report the application of bimetallic catalysts which were prepared by consecutive reduction of a submonolayer of bismuth promoter onto the surface of platinum. The technique of modifying metal surfaces at controlled electrode potential with a monolayer or sub-monolayer of foreign metal ("underpotential" deposition) is widely used in electrocatalysis (77,72). Here we apply the theory of underpotential metal deposition without the use of a potentiostat. The catalyst potential during promotion was controlled by proper selection of the reducing agent (hydrogen), pH and metal ion concentration. 

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