Ruthenium bimetallic

Vinodgopal K, He Y, Ashokkumar M, Grieser F (2006) Sonochemically prepared platinum-ruthenium bimetallic nanoparticles. J Phys Chem B 110 3849-3852... 

Fig. 6.10 UV-vis absorption spectra of gold - ruthenium bimetallic nanoparticles prepared by the sonochemical co-reduction method using (a) 1 1 and (b) 1 5 gold - ruthenium compositions, respectively [45]...

Sathish Kumar P, Manivel A, Anandan S, Zhou M, Grieser F, Ashokkumar M (2010) Sonochemical synthesis and characterization of gold-ruthenium bimetallic nanoparticles. Colloids Surf A 356 140-144... 

Monometallic ruthenium, bimetallic cobalt-ruthenium and rhodium-ruthenium catalysts coupled with iodide promoters have been recognized as the most active and selective systems for the hydrogenation steps of homologation processes (carbonylation + hydrogenation) of oxygenated substrates alcohols, ethers, esters and carboxylic acids (1,2). 

Shephard, D. S., Maschmeyer, T., Sankar, G., Thomas, J. M., Ozkaya, D., Johnson, B. F. G., Raja, R., Oldroyd, R. D. and Bell, R. G. Preparation, characterization and performance of encapsulated copper-ruthenium bimetallic catalysts derived from molecular cluster carbonyl precursors, Chem. Eur. J., 1998, 4, 1214-1224. 

Iron-ruthenium bimetallic catalysts have also received considerable attention as interesting catalysts in Fischer-Tropsch synthesis [115,116]. It has been reported that the Fe-Ru alloy system results in catalysts that are more stable than monometallic iron catalysts [117], and that the hydrocarbon product distribution in CO hydrogenation can easily be modified when changing the relative proportions of the two metals [118]. 

A more detailed study into the mechanism of ruthenium bimetallic melt catalysis for alcohol/ester production has been undertaken for the ruthenium-cobalt combination. Specifically, for the triruthenium dodecacarbonyl-dicobalt octacarbonyl couple, dispersed in tetrabutyl-phosphonium bromide, we have defined the experimental limits of this catalysis, demonstrated multiple catalyst recycle (7) and most importantly, identified some of the relationships linking catalyst productivity, alcohol-ester carbon distributions, and certain key operating parameters with the catalytically active metal carbonyl species present in these reaction media. 

G.C. Bond, J.C. Slaa, Catalytic and Structural Properties of Ruthenium Bimetallic Catalysts Effects of Pretreatment on the Behaviour or Various Ru/AljOj Catalysts in AUcane Hydrogenolysis, Journal of Molecular Catalysis A 96, 163, 1995. 

Kung, C.-C., Lin, P.-Y., Buse, F.J., Xue, Y, Yu, X., Dai, L and Liu, C.-C. (2014) Preparation and characterization of three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for hydrogen peroxide based electrochemical biosensors. Biosens. Bioelectron., 52, 1-7. 

Figure 6 Classes of metal-metal interaction in ruthenium bimetallic systems bridged by polyazine bridging iigands.

K. Vinodgopal, Y. He, M. Ashokkumar, F. Grieser, SonochemicaUy prepared platinum-ruthenium bimetallic nanoparticles. J. Phys. Chem. B 110, 3849-3852 (2006)... 

An example of particular interest is the two-fold introduction of M(CO)n moieties at silicon to give HMPA adducts of organometallic analogues of silaallene. It has been shown that this reaction proceeds through the dichlorosilylene complex as intermediate. Both the iron 22 and ruthenium 23 compound and also the bimetallic complex 24 are accessible. 

Ruthenium-copper and osmium-copper clusters (21) are of particular interest because the components are immiscible in the bulk (32). Studies of the chemisorption and catalytic properties of the clusters suggested a structure in which the copper was present on the surface of the ruthenium or osmium (23,24). The clusters were dispersed on a silica carrier (21). They were prepared by wetting the silica with an aqueous solution of ruthenium and copper, or osmium and copper, salts. After a drying step, the metal salts on the silica were reduced to form the bimetallic clusters. The reduction was accomplished by heating the material in a stream of hydrogen. 

When the ruthenium EXAFS for the ruthenium-copper catalyst is compared with the EXAFS for a ruthenium reference catalyst containing no copper, it is found that they are not very different. This indicates that the environment about a ruthenium atom in the bimetallic catalyst is on the average not very different from that in the reference catalyst. This result is consistent with the view that a ruthenium-copper cluster consists of a central core of ruthenium atoms with the copper atoms present at the surface. 

This discussion of EXAFS on ruthenium-copper clusters has emphasized qualitative aspects of the data analysis. A quantitative data analysis, yielding information on the various structural parameters of interest, has also been made and published (8). Of particular Interest was the finding that the average compo tion of the first coordination shell of ruthenium and copper atoms about a ruthenium atom was about 90% ruthenium, while that about a copper atom was about 50% ruthenium. Details of the methods Involved in the quantitative analysis of EXAFS data on bimetallic clusters can be obtained from our original papers (8.12-15). 

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. 

Other one-pot preparations of bimetallic nanoparticles include NOct4(BHEt3) reduction of platinum and ruthenium chlorides to provide Pto.sRuo.s nanoparticles by Bonnemann et al. [65-67] sonochemical reduction of gold and palladium ions to provide AuPd nanoparticles by Mizukoshi et al. [68,69] and NaBH4 reduction of dend-rimer—PtCl4 and -PtCl " complexes to provide dend-rimer-stabilized PdPt nanoparticles by Crooks et al. [70]. 

PtRu nanoparticles can be prepared by w/o reverse micro-emulsions of water/Triton X-lOO/propanol-2/cyclo-hexane [105]. The bimetallic nanoparticles were characterized by XPS and other techniques. The XPS analysis revealed the presence of Pt and Ru metal as well as some oxide of ruthenium. Hills et al. [169] studied preparation of Pt/Ru bimetallic nanoparticles via a seeded reductive condensation of one metal precursor onto pre-supported nanoparticles of a second metal. XPS and other analytical data indicated that the preparation method provided fully alloyed bimetallic nanoparticles instead of core/shell structure. AgAu and AuCu bimetallic nanoparticles of various compositions with diameters ca. 3 nm, prepared in chloroform, exhibited characteristic XPS spectra of alloy structures [84]. 

There has been great interest in the preparation of bimetallic transition metal cluster complexes containing palladium.899-902 Bimetallic palladium-ruthenium clusters have been shown to be good precursors to supported bimetallic catalysts.903,904... 

Iglesia, E., Soled, S. L., Fiato, R. A., and Via, G. H. 1993. Bimetallic synergy in cobalt-ruthenium Fischer-Tropsch synthesis catalysts. J. Catal. 143 345-68. 

Hsu et al. [15] applied a bimetallic catalyst comprising rhodium and ruthenium for the hydrogenation to combine the high selectivity of the rhodium complex with the lower cost of the ruthenium complex. When the amount of each metal is identical, the catalytic activity of the bimetallic complex catalyst system was similar to that of the single rhodium-complex catalyst, containing... 

The first deals with small islands of silver on a ruthenium substrate. One may look at this sample as a, perhaps somewhat far-fetched, model of a supported catalyst or a bimetallic surface. As metal layers are almost never in perfect registry with the substrate, they possess a certain amount of strain. Goodman and coworkers [46] used these strained metal overlayers as model systems for bimetallic catalysts. Here we look first at the electronic properties of the Ag/Ru(001) system as studied by UPS. 

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. 

Comparison of the Cu K-edge EXAFS signals for the monometallic Cu/Si02 and the bimetallic Ru-Cu/Si02 catalyst, on the other hand, provides clear evidence for the proximity of ruthenium to copper atoms in the latter. This is seen in the different shape of the measured EXAFS signal and the distorted inverse transform of the first coordination shell. Note that the intensity of the latter is weaker for the bimetallic catalyst, while the region between k=8 and k=15 A-1 has become more important, which points to the presence of a scattering atom heavier than copper in the first coordination shell. The reduced intensity in the Cu Fourier transform of the bimetallic catalyst is indicative of a lower coordination of the copper, which is characteristic of surface atoms. 

Another useful bimetallic for fuel cell electrodes is Pt/Ru. Ruthenium is readily oxidized to Ru02 by calcination after it is impregnated. The PZC of ruthenium oxide is unknown. Propose a comprehensive sequence of experiments with which the SEA method can be applied for the synthesis of a Pt/Ru bimetallic catalyst supported on carbon. The goal is to have intimate contact between the Pt and Ru phases in the final, reduced catalyst. 

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