Ruthenium alloy

The direct anodic oxidation of methanol became much more attractive after it was shown that platinum-ruthenium alloys are catalytically much more active in this reaction than pure platinum (pure ruthenium is totally inactive in this reaction). 

Dissolution of a zinc-ruthenium alloy in hydrochloric acid leaves an explosive residue of finely divided ruthenium [1], More probably this is the hydride, which may decompose on slight stimulus, the evolved hydrogen probably igniting because of the catalytic activity of the metal. Ruthenium prepared from its compounds by borohydride reduction is especially dangerous in this respect [2],... 

Re-on-alumina catalyst, 34 9,16 -rhodium, 30 274-275 selectivity, 30 355 -ruthenium alloy films, 22 182 -ruthenium alloys, 26 77 -silica... 

Ruthenium alloyed to platinum, palladium, titanium and molybdenum have many apphcations. It is an effective hardening element for platinum and palladium. Such alloys have high resistance to corrosion and oxidation and are used to make electrical contacts for resistance to severe wear. Ruthenium-palladium alloys are used in jewelry, decorations, and dental work. Addition of 0.1% ruthenium markedly improves corrosion resistance of titanium. Ruthenium alloys make tips for fountain pen nibs, instrument pivots, and electrical goods. Ruthenium catalysts are used in selective hydrogenation of carbonyl groups to convert aldehydes and ketones to alcohols. 

Some of the materials that have been examined as catalysts include Pure Platinum, Platinum-Iridium Alloys, Various Compositions of Platinum-Rhodium Alloys, Platinum-Palladium Alloys, Platinum-Ruthenium Alloys, Platinum-Rhenium Alloys, Platinum-Tungsten Alloys, FejOj-M CVI Oj (Braun Oxide), CoO-Bi20j, CoO with AI2O3, Thorium, Cerium, Zinc and Cadmium. 

Basov, N.L., and V.M. Gryaznov, 1985, Dehydrogenation of cyclohexanol and hydrogenation of phenol into cyclohexanone on a membrane catalyst produced from a palladium-ruthenium alloy, in Membrane Catalyst Permeable to Hydrogen or Oxygen (V.M. Gryaznov, Ed.), Akad. Nauk SSSR, Inst Nefickhim. Sint, Moscow, USSR, p. 117. 

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]. 

The data of Tables 2 and 3 show that palladium-ruthenium alloys with mass % of ruthenium from 4 to 7 have high hydrogen permeability, catalytic activity toward many reactions with hydrogen evolution or consumption, and good mechanical strength [35]. Seamless tubes with a wall thickness of 100 and 60 p.m, as well as foils of 50-tim thickness made of the mentioned alloy, are commercially available in Russia. The tube of outer diameter of 1 mm and wall thickness of 0.1 mm is stable at a pressure drop of up to 100 atm and a temperature up to 900 K. The application of such tubes for membrane reactor will be discussed in next part of this section. 

Ceramic plates with palladium alloy may be joined to a stainless steel reactor shell by special welding. Anodized alumina plate 0.4 mm thick covered with palladium-ruthenium alloy by cathodic sputtering was sealed to the reactor body with phosphate adhesive [140]. Tubular ceramic supports may be joined with reactor modules through a... 

V.M. Gryaznov, A.P. Mischenko, V.P. Polyakova et al.. Palladium-ruthenium alloys as the membrane catalysts, Doki Akad. Nauk SSSR 277 624 (1973). 

M.M. Ermilova, N.V. Orekhova, L.S. Morozova, and E.V. Skakunova, Selective hydrogenation of cyclopolyolefines on membrane catalyst from palladium-ruthenium alloy. Membrane Catalysts Permeable to Hydrogen and Oxygen, Moscow, Topchiev Inst, of Petrochemical Synthesis, 1985, p. 70. 

P.P. Mardilovich, PV. Kurman. A.N. Govyadinov ei. al.. The gas permeability of anodic alumina membranes with palladium-ruthenium alloy layer, Russian J. Phys. Chem., in press. 

Ruthenium is most often combined with platinum or palladium in alloys. Electrical contacts, devices for measuring very high and very low temperatures, and medical instruments are often made from ruthenium alloys. Ruthenium is also used in alloys with other platinum family metals to make jewelry and art objects. This use is limited, however, because of the high cost of ruthenium metal. 

Electrocatalyst selection and design are the key aspects of PEM fuel cells. The most popular catalyst is platinum for the anode and the cathode in pure hydrogen cells. For direct methanol fuel cells and for hydrogen cells with carbon monoxide present, a platinum/ruthenium alloy is used. 

The method has been used to determine trace amounts of Os (6-10" %) in platinum -ruthenium alloy [5]. 

A platinum-rhodium alloy is used as a catalyst at 1100°C. Approximately equal amounts of ammonia and methane with 75 vol% air are introduced to the preheated reactor. The catalyst has several layers of wire gauze with a special mesh size (approximately 100 mesh). The Degussa process, on the other hand, reacts ammonia with methane in the absence of air using a platinum aluminum-ruthenium alloy as a catalyst at approximately 1200°C. The reaction produces hydrogen cyanide and hydrogen, and the yield is over 90%. The reaction is endothermic and requires 251 kJ/mol. 

Platinum-Ruthenium alloy films of various compositions have been sputter-deposited and characterized in half-cells and full cells. 

Electrodes were fabricated with catalyst layers containing platinum-ruthenium alloys and platinum-ruthenium oxide. Membrane electrode assemblies were fabricated with such cells, and the performance was evaluated in a full cell configuration. Although ruthenium oxide is a proton conductor and is expected to enhance the rate of proton transport from the interface during methanol oxidation, no noticeable improvement in activity of the catalyst layer was observed by addition of ruthenium oxide. The role of other metal oxides such as tungsten oxide will be investigated next year, along with evaluation of non-noble metal catalysts based on nickel, titanium, and zirconium. 

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... 

Low temperature carbon monoxide sensors based on the reversible carbon monoxide adsorptive poisoning of precious metal electrodes are also being developed by Los Alamos National Laboratory. The addition of metals such as ruthenium to the platinum electrode material greatly improves the hydrogen oxidation kinetics in the presence of CO. An amperometric sensor that senses the CO inhibition of the hydrogen oxidation can be fabricated from a platinum electrode, a proton conductor and a platinum ruthenium alloy electrode. While the... 

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