Bimetallic catalysts surface metal modifiers

In this paper we report the application of bimetallic catalysts which were prepared by consecutive reduction of a submonolayer of bismuth promoter onto the surface of platinum. The technique of modifying metal surfaces at controlled electrode potential with a monolayer or sub-monolayer of foreign metal ("underpotential" deposition) is widely used in electrocatalysis (77,72). Here we apply the theory of underpotential metal deposition without the use of a potentiostat. The catalyst potential during promotion was controlled by proper selection of the reducing agent (hydrogen), pH and metal ion concentration. 

In summary, the preparation of bimetallic catalysts by surface redox reaction using a reductant preadsorbed on the parent monometallic catalyst has been studied in detail. Unfortunately, the method is intricate and time consuming, especially if several successive operations are required. Furthermore, when the modifier has a standard electrochemical potential higher than that of the parent metal (AUCI4 deposited on Pt°), the overall reaction is a complex one involving a reduction by adsorbed reductant but also direct oxidation of the metallic parent catalyst. The relative rate of the two parallel reactions determines the catalytic properties of the resulting bimetallic catalyst. 

In summary, the technique of catalytic reduction for the preparation of bimetallic catalysts can be extensively used with a variety of parent metals and re-ductants. However, some structure sensitivities of the reduction reactions become apparent and the modifying metal can be selectively deposited on specific sites of the parent-supported metal. Furthermore, such structure sensitivity depends on the nature of the re-ductant, and a given modifier can be deposited, according to the reductant used, selectively onto different parts of the metallic surface. In fact, a bimetallic catalyst can be tailored to provide the optimum activity, selectivity and lifetime for a given reaction. 

Supported mixed metal catalysts can be prepared by almost any of the procedures described above for the production of monometallic species. The discussion concerning the surface composition of these multimetallic species presented in Chapter 12 applies to supported catalysts as well but may be modified by the presence of very small crystallites in the supported catalysts. 2> 3 The factors presented above concerning the location of the metal in the support particle are also applicable here as well and can be used to prepare bimetallic catalysts having specific distribution profiles. 

In the case of powder bulk catalysts, Cu Raney was modified by direct redox reaction between reduced copper and the salt of a noble metal M (Ru, Pt and Au) [5, 7]. Typically the Cu-M bimetallic catalysts were obtained by mixing a freshly prepared Cu Raney with an aqueous solution of the noble metal salt. When the amount of M is in excess compared to the number of copper surface atoms, it appears that ruthenium deposition is restricted to approximately 1/3 of the copper surface atoms. For platinum and gold, a deposit larger than a monolayer is obtained, indicating that subsurface copper atoms are involved in direct redox reaction. This result is explained by the lower potential difference between copper and rathenium compared to those of copper and platinum or gold [7j. However, the reactions involved in the direct redox reaction may not be as simple as indicated in Section 9.2. A typical time distribution of ion concentrations in solution during the preparation of Cu-Pt is shown in Fig. 9.1. It can be observed that platinum ions disappear very rapidly from the solution while at the same time copper... 

HNO3 functionalized carbons are used as supports for the preparation of bimetallic Pd-Bi/C catalysts. The aim is to take advantage of the oxygenated surface functions introduced on the carbon, which are expected to act as anchoring sites. Two neutral coordination complexes were selected to incorporate the two metals onto differently functionalized caibon supports. The grafted samples are then submitted to an activation treatment and characterized by SEM, XRD and XPS. It appears that the order of incorporation strongly influences the surface properties of the catalysts and thus modifies their activity in the oxidation of glucose. 

Bimetallic catalysts are generally prepared by simultaneous or consecutive reduction of corresponding precursors. In the case of simultaneous reduction the composition of the catalytically active surface is difficult to design owing to the phenomenon of segregation (refs.1-3). By the method of consecutive reduction - although not as widely applied - surface structure of the monometallic catalyst can be modified as required, by metal deposition onto the surface. This may offer an economical method for preparing small amounts of catalysts in fine chemical industry. 

Platinum is the most widely used metal catalyst and many techniques have been proposed to modify other materials to emulate its properties. Pt-based bimetallic catalysis is a possibility as the reactivity of and adsorption on clusters and surfaces can be controlled by strategically changing the composition and stracture... 

From an applied perspective, metals are probably the most important surfaces in SOMC. Whereas in SOMC on oxides we introduce the active site, in SOMC on metals the metals themselves are the active catalysts. Organometallic chemistry provides the means to modify the often unselective metal surface by introduction of organometallic complexes (most often chemically inert) to the surface and eventually by transforming the initially obtained species by thermal or chemical means. For example, the hydrogenolysis of cyclic hydrocarbons, in particular cyclohexane, on the surface of unmodified Ir particles supported on a silica carrier has been studied and clearly indicated to bimetallic mechanism of C-C bond cleavage (Scheme 4) [24, 25]. 

Activity and selectivity of monometallic Ag catalysts can be controlled by the preparation conditions leading to micro- and meso- to macroporous catalysts which are active and selective in the hydrogenation of crotonaldehyde. In Ag catalysts modified by a second metal, bimetallic sites exhibiting surface polarity and Ag particles in close contact with a partially reduced early transition metal or a rare earth element, or Ag species stabilized and incorporated in these oxides were concluded to be the active species in the working state of these catalysts. Simultaneous introduction of both metals during the sol-gel process under optimized hydrolyzing conditions could further increase the metal-promoter interaction and lead to well-tailored new hydrogenation catalysts. 

---