Catalysts bimetallic, structure

Dynamic Monte Carlo simulations have been employed to study the effect of the bimetallic catalyst structure and CO mobility in a simple model for the electrochemical oxidation of CO on Pt-Ru alloy electrodes. The Pt-Ru surface was modeled as a square lattice of surface sites, which can either be covered by CO or OH, or be empty. The important reactions taken into account in the model reflect the generally accepted bifunctional model, in which the OH with which CO is... 

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. 

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). 

Waszczuk et al., 2001b Tong et al., 2002]. Because Ru is deposited as nanosized Ru islands of monoatomic height, the Ru coverage of Pt could be determined accurately. In that case, the best activity with regard to methanol oxidation was found for a Ru coverage close to 40-50% at 0.3 and 0.5 V vs. RHE. However, the structure of such catalysts and the conditions of smdy are far from those used in DMFCs. Moreover, the surface composition of a bimetallic catalyst likely depends on the method of preparation of the catalyst [Caillard et al., 2006] and on the potential [Blasini et al., 2006]. 

Ffirai and Toshima have published several reports on the synthesis of transition-metal nanoparticles by alcoholic reduction of metal salts in the presence of a polymer such as polyvinylalcohol (PVA) or polyvinylpyrrolidone (PVP). This simple and reproducible process can be applied for the preparation of monometallic [32, 33] or bimetallic [34—39] nanoparticles. In this series of articles, the nanoparticles are characterized by different techniques such as transmission electronic microscopy (TEM), UV-visible spectroscopy, electron diffraction (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) or extended X-ray absorption fine structure (EXAFS, bimetallic systems). The great majority of the particles have a uniform size between 1 and 3 nm. These nanomaterials are efficient catalysts for olefin or diene hydrogenation under mild conditions (30°C, Ph2 = 1 bar)- In the case of bimetallic catalysts, the catalytic activity was seen to depend on their metal composition, and this may also have an influence on the selectivity of the partial hydrogenation of dienes. 

The surface structure and characteristics (density and acidity) of the hydroxyl groups presented in Fig. 13.21 (using CrystalMaker 2.1.1 software) give very useful information to understand the reactivity of the surface of the particles, particularly when adsorption of another complex is desired to synthesize a bimetallic catalyst, or to control the interaction with an oxide carrier (the deposition step). The isoelectric point calculated with the model (5.9) is in fair agreement with the experimental value (4.3). 

The different strategies used to obtain bimetalhc catalysts have been well classified by Alexeev and Gates, who analyzed the structural properties of different catalysts as a function of the preparation method [3]. These authors have classified the bimetallic catalysts as described in the next four subsections. 

On the other hand, hi- or multi-metallic supported systems have been attracting considerable interest in research into heterogeneous catalysis as a possible way to modulate the catalytic properties of the individual monometalUc counterparts [12, 13]. These catalysts usually show new catalytic properties that are ascribed to geometric and/or electronic effects between the metalUc components. Of special interest is the preparation of supported bimetallic catalysts using metal carbonyls as precursors, since the milder conditions used, when compared with conventional methods, can render catalysts with homogeneous bimetallic entities of a size and composition not usually achieved when conventional salts are employed as precursors. The use of these catalysts as models can lead to elucidation of the relationships between the structure and catalytic behavior of bimetalUc catalysts. 

In bimetallic catalysts, Cu-Ru is an important system. Combinations of the Group Ib metal (Cu) and Group VIII metal (Ru)-based catalysts are, for example, used for the dehydrogenation of cyclohexane to aromatic compounds and in ethane hydrogenolysis involving the rupture of C-C bonds and the formation of C-H bonds (Sinfelt 1985). Here we elucidate the structural characteristics of supported model Cu-Ru systems by EM methods, including in situ ETEM. 

Vickerman and Ertl (1983) have studied H2 and CO chemisorption on model Cu-on-Ru systems, where the Cu is deposited on single-crystal (0001) Ru, monitoring the process using LEED/Auger methods. However, the applicability of these studies carried out on idealized systems to real catalyst systems has not been established. Significant variations in the electronic structure near the Eermi level of Cu are thought to occur when the Cu monolayer is deposited on Ru. This implies electron transfer from Ru to Cu. Chemical thermodynamics can be used to predict the nature of surface segregation in real bimetallic catalyst systems. 

In the presence of a large excess of EtO ion, the bimetallic catalyst is fully saturated with EtO as shown by structure I in Scheme 5.3. Incremental additions of a carboxylate substrate would cause the gradual conversion of I into the 1 1 productive complex II, but further additions would yield the unproductive complex III. As expected from this mechanism a bell-shaped profile is observed in a plot of initial rate versus substrate concentration related to the catalyzed ethanolysis of 16 (Figure 5.5). The fairly good quality of the fit supports the validity of Scheme 5.3. Further confirmation comes from the finding that benzoate anions behave as competitive inhibitors of the reaction. Since the reaction product of the ethanolysis of 16 is also a benzoate anion, product inhibition is expected. Indeed, only four to five turnovers are seen in the ethanolysis of 16 before product inhibition shuts down the reaction. The first two turnovers are shown graphically in Figure 5.6. 

Figure 9.4 A modular approach to chiral ligand design using metal-directed heteroleptic self-assembly of chiral bidentate SALs 5 and bimetallic catalysts 6 incorporating both structural (Ms) and catalytic metals (M ).

Trost et al. [11] reported another impressive example of bimetallic catalysts in which a Zn-Zn homobimetallic complex (17, Scheme 7) serves as an effective catalyst for direct aldol reactions [11-13]. The proposed structure of the catalyst was verified by mass spectrometry and the best ratio of Et2Zn and the ligand. The chemical yield was moderate in the reaction of methyl ketones (1) (Scheme 7, top) [11,12], but a highly atom-economic system was achieved when a-hydroxylated ketones (10) were used as a substrate (Scheme 7, bottom) [13]. Excellent diastereo- and enantioselectivity were obtained under mild conditions. In contrast to the case of Shibasaki s heteropolymetallic catalyst, syn-1,2-diols (syn-11) were obtained as the major diastereomers. 

From a true catalytic point of view, what is looked for are so-called synergetic effects , i.e., a reciprocal influence between two or more components so as to obtain a material whose activity exceeds that of the pure components [74]. This usually involves intimate electronic interaction between the various components so that their electronic structures become profoundly modified. It is well possible that a metal deprived of part of its valence electrons may behave as the element on its left in the Periodic Table [75]. However, the theory of synergetic effects is still in its infancy in electrochemistry. Predictions for a bimetallic catalyst with two non-interacting sites obtained by combining two metals with different adsorption energies are that... 

A brief overview of bimetallic catalysts is presented. Electronic vs. ensemble effects are discussed, and literature is reviewed on single crystal bimetallics, and supported bimetallic clusters. Bimetallic cluster compounds are considered as models. Structural considerations, effects of potential poisons, particles from bimetallic cluster compounds, and catalytic activity/selectivity studies are briefly reviewed and discussed. 

Another non-conventional preparative route to bimetallic catalysts has been developed where metal atoms (vapors) have been trapped at low temperature in solvating media. (A review has recently appeared).(17) By solvating two metals at the same time (eg. Co in toluene and Mn in toluene), followed by warming, bimetallic clusters/particles form. In the presence of a catalyst support, surface -OH groups can have a dramitic affect on the structure of the small bimetallic cluster produced. For example, with Co and Mn, a layered structure of MnOx covered by Co° in a particle of about 25 A was formed.(iS) With Fe and Co combinations, a layer of FeOx followed by Fe°Co° alloy and a surface rich in Co° was formed. (19)... 

Table I. A Brief Summary of Literature Relating Generally to Structural Elucidations of Bimetallic Catalysts...

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