Ruthenium alloys surface oxidation

MVD of ruthenium on Pt(llO) has been shown to provide an ideal system for the study of the promotion of electrocatalytic reactions on a well-characterized Pt-Ru alloy surface [85,86]. In transfer studies, XPS, LEISS, and LEED have been used to characterize the Pt(110)-Ru alloy system, and TPD and stripping voltammetry used to investigate the chemisorption behavior of CO, and the promotion of CO electro-oxidation as a function of incorporated ruthenium. The facile incorporation of ruthenium in the relatively open-packed Pt(110)-(1 x 2) surface provided an ideal model for the alloy system. It is also interesting to note also that the clean Pt(llO) surface exhibits the highest hydrogen oxidation currents of the three basal planes of platinum [108]. 

High catalyst activity and utilization of sputtered thin films was demonstrated in operating fuel cells. Optimal sputter-deposition conditions for platinum-ruthenium alloys have been determined. The effect of composition on the performance of Pt-Ru films was studied, and optimal composition has been determined. Novel methods of enhancing surface area and improving porosity have been identified. Co-sputtered ruthenium oxide has been demonstrated not to have any significant beneficial effect on the activity of the catalyst layers. While cost presents a major obstacle to commercialization of DMFCs for mobile applications, this project demonstrates novel means to reduce the catalyst costs in DFMC fuel cells. Efficiency enhancements that are also necessary for DMFCs to be viable will be addressed... 

The interaction of CO with alloy or bimetallic surfaces is of special interest because of the importance of bimetallic catalysts in both the electrochemical and gas-phase oxidation of CO. Platinum-ruthenium alloys have long been known to be superior catalysts for the electrochemical CO oxidation, but the details of their catalytic action are still disputed. We will have more to say about the mechanism of the electrocatalytic CO oxidation on both metals and alloys in section III.8, in particular about the relevant ab initio quantum-chemical studies. Here, we will simply discuss how the chemisorption properties of CO on PtRu depend on the stmcture and composition of the bimetallic surface. 

The interaction of CO with alloy or bimetallic surfaces is of special interest because of the importance of bimetallic catalysts in both the electrochemical and gas-phase oxidation of CO. Platinum-ruthenium alloys have long been known to be superior catalysts for the electrochemical CO oxidation, but the details of their catalytic action are still disputed. 

In agreement with previous observations on PtRu alloy surfaces [18, 20, 67, 339], ruthenium-modified Pt surfaces exhibit a substantial electrocatalytic enhancement toward the oxidation of adsorbed CO, demonstrated by the shift of the CO oxidation peak to more negative values [112, 116, 180]. FTIR spectra on the CO-covered electrodes indicate that the electrocatalytic activity of the Ru-modified Pt(lll) for CO oxidation is slightly higher than that of a 50 50 Pt/Ru alloy [116]. 

However, the intermediate product during the oxidation of methanol makes the catalysis complicated, and the reaction rate for making CO out of methanol solution is slow. Moreover, a second metal such as Ruthenium (Ru) is required, which is explained by the bifunctional mechanism. In other words, activation of water or surface oxides at lower potentials makes the CO absorption bond weaker on the PtRu alloy catalyst. In the meantime, oxidative methanol dehydrogenation occurs on Pt by oxygen-like species on Ru, so that species on Pt-Ru pair sites enables the continuous oxidation of CO to CO. ... 

Petrii and Entin [54, 57, 78, 150, 180, 243] investigated the adsorption and electrochemical characteristics of platinum and ruthenium alloys in detail. The optimum alloy compositions for oxidation of methanol at various temperatures were determined, the anodic oxidation reactions of various compounds of the alloys were investigated, the stability of the alloys after prolonged use was investigated, and the characteristics of platinum— ruthenium alloys prepared by various methods (skeletal electrodes, electro-lytically mixed deposits on a platinum and titanium carbide bases, powders deposited by sodium borohydride, smooth alloys) were compared. It was found that heat treatment of platinum - ruthenium alloys at 800 C in an atmosphere of inert gas led to loss of their high catalytic properties and formation of catalysts which behave similarly to platinum. This phenomenon is explained by diffusion of ruthenium atoms from the surface layer into the volume. 

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. 

In the late 1960s it was discovered (Entina, 1968 Binder et al., 1972) that a strong synergy effect exists in the platinum-ruthenium system. Alloys of these two metals are two to three orders of magnitude more active catalytically for the anodic oxidation of methanol than pure platinum, whereas pure ruthenium is altogether inactive for this reaction. Prolonged exploitation of such anodes is attended by a gradual decrease in catalytic activity of the alloys because of slow anodic dissolution of ruthenium from the surface layer. A similar simation is seen for platinum-tin alloys, which... 

While many studies have been performed for the oxidation of methanol and carbon monoxide on supported catalyst systems [66,99-103] and Pt-Ru bulk alloys [61,104— 107], relatively few studies have been initiated on single-crystal platinum surfaces modihed with ruthenium. Of those performed these have largely involved the investigation of platinum single crystals modihed by ruthenium dosed electro-chemically [92,93] or spontaneously [80-82,90,91] from aqueous chloride solutions. This approach is discussed in Section 5.4. 

In contrast, the effect of the adsorbed and alloyed ruthenium on the electrooxidation of CO has shown that promotion of the reaction is only evident if ruthenium is present in the top surface layer. Hence the mediation of the oxidizing species by top-layer ruthenium in the provision of Pt-Ru ensembles, rather than the modification of CO adsorption by ruthenium, promotes the electro-oxidation reaction [85,86]. 

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