Clusters bimetallic

Composite clusters, alloyed or bilayered, are of great interest because they enlarge the number of the possible types of clusters. It is therefore important to be able to select the conditions of the synthesis of composite metal clusters containing M and M in variable proportions, with either an alloyed or a core/shell structure. Actually, when a mixed solution of two ionic precursors M and M is irradiated or chemically reduced, both situations of alloyed or bilayered cluster formation may be encountered without clear prediction. 

In many cases, even though and M are both readily reduced by radiolytic radicals (reactions (1,7,8)), a further electron transfer from the more electronegative atoms (for example M ) to the more noble ions (E°(M VM ) E°(M /M°)) systematically favors the reduction into M . 

If the ionic precursors are plurivalent, an electron transfer is possible as well between the low valencies of both metals, so increasing the probability of segregation. Reaction (33) has been observed directly by pulse techniques for 

Bimetallic cluster compounds containing coinage metals and peripheral Fe(CO)4 groups have been synthesized and show a considerable structural variety. Particularly interesting are the clusters of composition [M4 Fe(CO)4 4] (M = Ag, Au). Clusters of other stoichiometry have been isolated with M = The metal 

The main difference lies in the Ag-Ag distance which in the calculations is ca. 0.2 A shorter than in the experiment. It should be noted, however, that changes 

The charge transfer from M to Fe is well illustrated by the orbital interaction scheme between Ag4 and four Fe(CO)4 units (Fig. 14). The 4d orbitals of Ag4 are highly stabilized by the interaction with the Fe(CO)4 groups and provide the first clear evidence of the electron flow, because the rather localized d orbitals are very 

The bonding mechanism described for the bimetallic [M4 Fe(CO)4 4] clusters is not restricted to the tetramers. The largest carbonylated Ag-Fe cluster synthesized so far is [Agi3 Fe(CO)4 8] (Fig. 15). The cluster core consists of 12 Ag 

Spin-polarized LDA all-electron scalar-relativistic calculations were performed 

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Cryophotochemical techniques have been developed that (i) allow a controlled synthetic approach to mini-metal clusters 112), Hi) have the potential for "tailor-making small, bimetallic clusters (mini-alloy surfaces) 114,116), Hi) permit the determination of relative extinction-coefficients for naked-metal clusters 149), and iv) allow naked-cluster, cryophotochemical experiments to be conducted in the range of just a few atoms or so 112,150,151). 

Codeposition of Group-iB and Transition Metals To Give Bimetallic Clusters. 

Sulfided bimetallic clusters which mimic the metal composition of commercial hydrodesulfurization (HDS) catalysts have been prepared and their homogeneous catalytic behavior studied. Reaction of thiophenol with [Mo2Co2(/z4-S)... 

A MgO-supported W—Pt catalyst has been prepared from IWsPttCOIotNCPh) (i -C5H5)2l (Fig. 70), reduced under a Hs stream at 400 C, and characterized by IR, EXAFS, TEM and chemisorption of Hs, CO, and O2. Activity in toluene hydrogenation at 1 atm and 60 C was more than an order of magnitude less for the bimetallic cluster-derived catalyst, than for a catalyst prepared from the two monometallic precursors. 

MgO-supported model Mo—Pd catalysts have been prepared from the bimetallic cluster [Mo2Pd2 /z3-CO)2(/r-CO)4(PPh3)2() -C2H )2 (Fig. 70) and monometallic precursors. Each supported sample was treated in H2 at various temperatures to form metallic palladium, and characterized by chemisorption of H2, CO, and O2, transmission electron microscopy, TPD of adsorbed CO, and EXAFS. The data showed that the presence of molybdenum in the bimetallic precursor helped to maintain the palladium in a highly dispersed form. In contrast, the sample prepared from the monometallie precursors was characterized by larger palladium particles and by weaker Mo—Pd interactions. ... 

We have found EXAFS to be a very effective method for obtaining structural information on bimetallic cluster catalysts (8,12-15,17) These types of catalysts, and bimetallic catalysts in general, have been the subject of extensive research in the EXXON laboratories since the 1960 s (18-25). In this paper we present a brief review of the results of some ofour EXAFS investigations on bimetallic cluster catalysts. 

In the analysis of EXAFS data on bimetallic clusters, we consider two EXAFS functions, one for each component of the clusters (8,12-15.17). If the treatment is limited to contributions of near-est neighbor backscattering atoms, each of the functions will consist of two terms. For a bimetallic cluster composed of elements a and b, the EXAFS associated with element a is given by the expression ... 

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. 

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). 

We plan to make studies on palladium-copper, iridium-copper, and platinum-copper catalysts to extend our investigation of the effect of varying miscibility of the components on the structural features of the bimetallic clusters present. With these additional systems, the whole range from complete immiscibility to total miscibility of copper with the Group VIII metal will be encompassed. 

Bimetallic clusters of platinum and iridium can be prepared by coimpregnating a carrier such as silica or alumina with an aqueous solution of chloroplatinic and chloroiridic acids (22,34). After the Impregnated carrier is dried and possibly calcined at mild conditions (250°-270 C), subsequent treatment in flowing hydrogen at elevated temperatures (300 -500°C) leads to formation of the bimetallic clusters. 

Recently we reported EXAFS results on bimetallic clusters of iridium and rhodium, supported on silica and on alumina (15). The components of this system both possess the fee structure in Efie metallic state, as do the components of the platinum-iridium system. The nearest neighbor interatomic distances in metallic iridium and rhodium are not very different (2.714A vs. 2.690A). From the results of the EXAFS measurements, we concluded that the interatomic distances corresponding to the various atomic pairs (i.e., iridium-iridium, rhodium-rhodium, and iridium-rhodium) in the clusters supported on either silica or alumina were equal within experimental error. Since the Interatomic distances of the pure metals differ by only 0.024A, the conclusion is not surprising. 

Extended X-ray absorption fine structure (EXAFS) studies have been very useful for obtaining structural information on bimetallic cluster catalysts. The application to bimetallic systems is a particularly good one for illustrating the various factors which have an influence on EXAFS. Moreover, the applicability of EXAFS to this area has been very timely, in view of the enormous interest in bimetallic systems in both catalytic science and technology. 

The results of the EXAFS studies on supported bimetallic catalysts have provided excellent confirmation of earlier conclusions (21-24) regarding the existence of bimetallic clusters in these catalysts. Moreover, major structural features of bimetallic clusters deduced from chemisorption and catalytic data (21-24), or anticipated from considerations of the miscibility or surface energies of the components (13-15), received additional support from the EXAFS data. From another point of view, it can also be said that the bimetallic catalyst systems provided a critical test of the EXAFS method for investigations of catalyst structure (17). The application of EXAFS in conjunction with studies employing ( mical probes and other types of physical probes was an important feature of the work (25). 

The Effect of Support-Metal Precursor Interactions on the Surface Composition of Supported Bimetallic Clusters... 

The effect of precursor-support interactions on the surface composition of supported bimetallic clusters has been studied. In contrast to Pt-Ru bimetallic clusters, silica-supported Ru-Rh and Ru-Ir bimetallic clusters showed no surface enrichment in either metal. Metal particle nucleation in the case of the Pt-Ru bimetallic clusters is suggested to occtir by a mechanism in which the relatively mobile Pt phase is deposited atop a Ru core during reduction. On the other hand, Ru and Rh, which exhibit rather similar precursor support interactions, have similar surface mobilities and do not, therefore, nucleate preferentially in a cherry model configuration. The existence of true bimetallic clusters having mixed metal surface sites is verified using the formation of methane as a catalytic probe. An ensemble requirement of four adjacent Ru surface sites is suggested. 

It has generally been assumed that the most important consideration in the surface enrichment of one metal in preference to another in a supported bimetallic cluster is based on differences in the enthalpies of sublimation of the metals which comprise the cluster. In most cases, the surface composition is enriched in the metal having the lower enthalpy of sublimation (1 ). 

The role played by the support of influencing the surface composition of supported bimetallic clusters has only recently begun to receive some attention. Miura, a ( ) have shown that the nature of the support can play an important role in determining not only the surface composition of the supported bimetallic clusters but also the morphology of the particles. For silica-supported Pt-Ru... 

In order to verify the presence of bimetallic particles having mixed metal surface sites (i.e., true bimetallic clusters), the methanation reaction was used as a surface probe. Because Ru is an excellent methanation catalyst in comparison to Pt, Ir or Rh, the incorporation of mixed metal surface sites into the structure of a supported Ru catalyst should have the effect of drastically reducing the methanation activity. This observation has been attributed to an ensemble effect and has been previously reported for a series of silica-supported Pt-Ru bimetallic clusters ( ). 

Surface Composition Measurements. The surface composition and metal dispersion for a series of silica (Cab-O-Sll) supported Ru-Rh bimetallic clusters are summarized In Table I. Surface enrichment In Rh, the element with the lower heat of sublimation, was not observed over the entire bimetallic composition range. In fact, to within the experimental limit of error of the measurements, surface compositions and catalyst compositions were nearly equal. A small local maximum In the dispersion was observed for the catalyst having a surface composition of 50% Rh. 

Metal dispersions were observed to decrease as the concentration of Ru was Increased. This same trend was observed for the Ru-Rh catalysts and was in marked contrast to observations on silica-supported Ft-Ru catalysts W. In this case a large Increase in dispersion was obtained as a result of bimetallic clustering in the cherry model configuration. 

The surface-catalyst composition data for the silica-supported Ru-Rh cuid Ru-Ir catalyst are shown in Figure 1. A similcir plot for the series of silica-supported Pt-Ru bimetallic catalysts taken from ref. P) is included for comparison purposes. Enthalpies of sublimation for Pt, Ru, Rh and Ir are 552, 627, 543, and 648 KJ/mole. Differences in enthalpies of sublimation (a<75 KJ/mole) between Pt and Ru cind between Rh and Ru are virtually identical, with Pt euid Rh having the lower enthalpies of sublimation. For this reason surface enrichment in Pt for the case of the Pt-Ru/Si02 bimetallic clusters cannot be attributed solely to the lower heat of sublimation of Pt. Other possibilities must also be considered. 

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