The role of Ru and Sn on the methanol oxidation over Pt was investigated for three different systems viz. Pt covered with adatom layers of Ru and Sn, electro-codeposited Pt-Ru and carbon supported Pt-Ru. By following the oxide growth on the Pt-promoter metal electrodes with ellipsometry it was found that in the presence of methanol the surface oxides of the promotor metal are no longer present on the surface. This supports the bifunctional model of the promotor action. DEMS measurements at Pt with submonolayer coverage of Ru or Sn revealed that the current efficiency of the methanol oxidation to CO 2 is increased in the presence of Ru or Sn and that the onset potential of the oxidation keeps lowering with increasing amounts of the promoting metal. On electrodeposited Pt-Ru systems the adsorption of methanol already takes place at potentials in the hydrogen range. These results seem to point to an electronic (ligand) effect. This is further corroborated by activity measurements at carbon supported Pt-Ru with very small particles, which show a tenfold higher activity compared with the Ru-free system.It is concluded that the promoting action of Ru and Sn may involve both a bifunctional and an electronic (ligand) effect.

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To obtain the surface content of Ru in rough electrocodeposited PtRu electrodes, the mass change of a Pt electrode during Ru deposition was measured with the electrochemical quartz crystal microbalance (EQCMB). It is shown that there is a correlation between the potential of the surface oxide reduction peak of the PtRu electrode and the surface Ru content. With the EQCMB also the methanol oxidation and oxide formation on both Pt and PtRu were studied. Implications for the oxidation of CO and CH 3OH are discussed, in the context of which some IR experiments on CO and PtRu are presented as well.

Abstract-The oxidation of submonolayers of Ru and Sn on Pt in sulfuric acid was monitored with ellipsometry.In the presence of methanol the oxides on Ru and Sn disappear but the Pt-oxide is not affected by methanol.This signifies that Ru and Sn are present in their zero valent state during the methanol oxidation.DEMS measurements showed that both metals enhance methanol oxidation. The promoting role of these metals is explained with the bifunctional mechanism.

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