Alloys copper-ruthenium

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Thus the palladium alloy with 53% copper proved to be more permeable than palladium [37]. However, the maximal operating temperature for membranes of this alloy is 623 K. Palladium-ruthenium alloys are more thermostable and may be used up to 823 K. At the increase in ruthenium content from 1 to 9.4 at.%, the hydrogen permeability of the alloys attained a maximum at a ruthenium content of about 4.5%. The long-term strength of this alloy at 823 K after service for lOOOhr was greater by a factor of almost 5 than that of pure palladium [35]. 

It was discovered that the ability of metals to form solid solutions (alloys) in the bulk is not necessary for a bimetallic system to be of interest as a catalyst. An example is the ruthenium-copper system, in which the two components are virtually completely immiscible in the bulk. This system exhibits an effect of the copper (in particular, selective inhibition of hydrocarbon hydrogenoly-sis) similar to that exhibited by the nickel-copper system, in which the components are completely miscible. Although ruthenium and copper do not form solid solutions in the bulk, they do exhibit a strong interaction at copper-ruthenium interfaces. The copper tends to cover the surface of the ruthenium, analogous to a chemisorbed layer. As a result, the copper has a marked effect on the chemisorption and catalytic properties of the ruthenium. 

Green CL, Kucemak A (2002) Determination of the platinum and ruthenium surface areas in platinum-ruthenium alloy electrocatalysts by underpotential deposition of copper. 1. Unsupported catalysts. J Phys Chem B 106 1036-1047... 

The trend in CVD metallization is toward greater use of copper, and the refractory metals and their silicides in multilayered metallization designs, typically consisting of metal-silicide contacts, refractory-metal barriers, and copper or an aluminum alloy as the principal interconnect metal. Other metals deposited by CVD such as chromium, molybdenum, platinum, rhodium, and ruthenium are also actively considered for use as conductors. 

Because of- the similarity in the backscattering properties of platinum and iridium, we were not able to distinguish between neighboring platinum and iridium atoms in the analysis of the EXAFS associated with either component of platinum-iridium alloys or clusters. In this respect, the situation is very different from that for systems like ruthenium-copper, osmium-copper, or rhodium-copper. Therefore, we concentrated on the determination of interatomic distances. To obtain accurate values of interatomic distances, it is necessary to have precise information on phase shifts. For the platinum-iridium system, there is no problem in this regard, since the phase shifts of platinum and iridium are not very different. Hence the uncertainty in the phase shift of a platinum-iridium atom pair is very small. 

Ruthenium and copper are not miscible hence, homogeneous alloy particles will not be formed in supported Ru-Cu catalysts. As copper has a smaller surface free energy than ruthenium, we expect that if the two metals are present in one particle, copper will be at the surface and ruthenium in the interior (see also Appendix 1). This is indeed what chemisorption experiments and catalytic tests suggest [40], EXAFS, being a probe for local structure, is of particular interest here because it investigates the environment of both Ru and Cu in the catalysts. 

Let us first consider what EXAFS might tell us in the case of bimetallic particles that are not too small - say a few nanometer in diameter. For a truly homogeneous alloy with a 50 50 composition, EXAFS should see a coordination shell of nearest neighbors with 50% Cu and 50% Ru around both ruthenium and copper atoms. If, on the other hand, the particle consists of an Ru core surrounded by a Cu shell of monatomic thickness, we expect that the Ru EXAFS shows Ru as the dominant neighbor, because only Ru atoms in the layer directly below the surface are in contact with Cu. The Cu EXAFS should see both Cu neighbors in the surface and Ru neighbors from the layer underneath, with a total coordination number smaller than that of the Ru atoms. The latter situation is indeed observed in Ru-Cu/Si02 catalysts, as we shall see below. 

Other metals, such as copper, nickel, or silver, have been used as electrode materials in connection with specific applications, such as the detection of amino acids or carbohydrates in alkaline media (copper and nickel) and cyanide or sulfur compounds (silver). Unlike platinum or gold electrodes, these electrodes offer a stable response for carbohydrates at constant potentials, through the formation of high-valence oxyhydroxide species formed in situ on the surface and believed to act as redox mediators (40,41). Bismuth film electrodes (preplated or in situ plated ones) have been shown to be an attractive alternative to mercury films used for stripping voltammetry of trace metals (42,43). Alloy electrodes (e.g., platinum-ruthenium, nickel-titanium) are also being used for addressing adsorption or corrosion effects of one of their components. The bifunctional catalytic mechanism of alloy electrodes (such as Pt-Ru or Pt-Sn ones) has been particularly useful for fuel cell applications (44). 

Following the development of sponge-metal nickel catalysts by alkali leaching of Ni-Al alloys by Raney, other alloy systems were considered. These include iron [4], cobalt [5], copper [6], platinum [7], ruthenium [8], and palladium [9]. Small amounts of a third metal such as chromium [10], molybdenum [11], or zinc [12] have been added to the binary alloy to promote catalyst activity. The two most common skeletal metal catalysts currently in use are nickel and copper in unpromoted or promoted forms. Skeletal copper is less active and more selective than skeletal nickel in hydrogenation reactions. It also finds use in the selective hydrolysis of nitriles [13]. This chapter is therefore mainly concerned with the preparation, properties and applications of promoted and unpromoted skeletal nickel and skeletal copper catalysts which are produced by the selective leaching of aluminum from binary or ternary alloys. 

Since the ability to form bulk alloys was not a necessary condition for a system to be of interest as a catalyst, it was decided not to use the term alloy in referring to bimetallic catalysts in general. Instead, terms such as bimetallic aggregates or bimetallic clusters have been adopted in preference to alloys. In particular, bimetallic clusters refer to bimetallic entities which are highly dispersed on the surface of a carrier. For systems such as ruthenium-copper, it appears that the two components can interact strongly at an interface, despite the fact that they do not form solid solutions in the bulk. In this system the copper is present at the surface of the ruthenium, much like a chemisorbed species. 

The crystal structures of metallic ruthenium and copper are different, ruthenium having a hexagonal close-packed structure and copper a face-centered cubic structure (7). Although the ruthenium-copper system can hardly be considered one which forms alloys, bimetallic ruthenium-copper aggregates can be prepared that are similar in their catalytic behavior to alloys such as nickel-copper (3,4,8). 

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