Supported bimetallic catalysts

Z. Knor, and J. Sotola, Supported Bimetallic Catalysts, Coll. Czech. Chemical Comm. 

Hi ly dispersed supported bimetallic catalysts with bimetallic contributions have been prepared from molecular cluster precursors containing preformed bimetallic bond [1-2]. For examples, extremely high dispersion Pt-Ru/y-AUOa could be prepared successfully by adsorption of Pt2Ru4(CO)ison alumina [2]. By similar method, Pt-Ru cluster with carbonyl and hydride ligands, Pt3Ru6(CO)2i(p3-H)(p-H)3 (A) was used in this work to adsorb on MgO support. The ligands were expectedly removable from the metal framework at mild conditions without breaking the cluster metal core. 

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). 

All of the supported bimetallic catalysts studied show a sharp drop in methanatlon activity when the Ru/M ratio falls below four. 

Supported bimetallic catalysts find many industrial applications. Examples include Pt and Rh in automobile exhaust conversion catalysts and Pt and Re (or Pt and Sn or Pt and Ir) in naphtha reforming catalysts. 

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... 

TPR of supported bimetallic catalysts often reveals whether the two metals are in contact or not. The TPR pattern of the 1 1 FeRh/SiOi catalyst in Fig. 2.4 shows that the bimetallic combination reduces largely in the same temperature range as the rhodium catalyst does, indicating that rhodium catalyzes the reduction of the less noble iron. This forms evidence that rhodium and iron are well mixed in the fresh catalyst. The reduction mechanism is as follows. As soon as rhodium becomes metallic it causes hydrogen to dissociate atomic hydrogen migrates to iron oxide in contact with metallic rhodium and reduces the oxide instantaneously. 

J. Margitfalvi, S. Szabo, andF. Nagy, Supported bimetallic catalysts prepared by controlled surface reactions. Stud. Surf. Sci. Catal. 27, 373-409 (1983). 

Supported bimetallic catalysts have gained unquestionable importance in subjects such as refining, petrochemistry and fine chemistry since their earliest use in the 1950s [1, 2]. The catalytic behavior of such a system is influenced by the size of the metal particles and by the interactions among them and with the support and other catalyst components. The second metal may influence the first metal through electronic interactions or by modifying the architecture of the active site. Very often, the interactions between the two metals are complex and largely unknown, and consequently the preparation procedure critically influences the nature of the catalytic system obtained. 

Synthesis of Supported Bimetallic Catalysts from Molecular Cluster Precursors... 

Another work on the Hquid phase hydrogenation of acetophenone is that of Casagrande et al. The reaction was studied over a series of silica-supported bimetallic catalysts with various Ru/Cr atomic ratios, which were prepared by reduction at room temperature with aqueous sodium tetrahydroborate. The nanostructured catalysts are very active in the low-pressure hydrogenation of acetophenone, although the selectivity towards 1-phenylethanol did not surpass 22% at 90% conversion. The addition of chromium salts to the starting solution gave rise to... 

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. 

Fig. 2 Potential reaction scheme for the catalytic hydrogenation of nitrates over a supported bimetallic catalyst showing catalysed steps and the formation of products and intermediates.

Preparation of Supported Bimetallic Catalysts Containing Gold... 

The preparation of a successful supported bimetallic catalyst is quite a difficult proposition. The main problem is to ensure that the two components reside in the same particle in the finished catalyst, and to know that it is so. The main physical techniques to characterise bimetallic particles are hydrogen chemisorption, XRD, TEM, EDX, XPS, XAFS,197Au Mossbauer (Section 3.3) and CO chemisorption coupled by IR spectroscopy (Section 5.3). The characterisation of bimetallic catalysts is not always thoroughly done, and there is the further complication of structural changes (particularly of the surface) during use. In situ or post-operative characterisation would reveal them, but it is rarely done. 

Supported bimetallic catalysts can be made by adsorption of a bimetallic precursor such as molecular cluster compounds, colloidal particles or dendrimer-stabilised particles. In several cases, homogeneous bimetallic particles have been found where the compositions lie within the miscibility gap of the bulk alloy (e.g. with PtAu particles). This suggests that when the particles are small enough and do not possess metallic properties, the normal rules do not apply. 

Surface redox reactions represent a relatively new approach for preparing supported bimetallic catalysts. Three main techniques have already been identified ... 

Of particular interest was the fact that the bimetallic cluster catalysts, i.e., RuNiY and RuCuY, had considerably better metal dispersions than the pure NiY and CuY catalysts. Further, the zeolite-supported bimetallic catalysts were more resistant to sintering during methanation than those supported on alumina. Particle-size measurement indicated, however, that most of the bimetallic clusters were too large to be located inside the zeolite pores. 

Furthermore, it was clearly shown that noble metals, rhodium in particular, play an active role in promoting the OSC of the support [1,3-6,31]. It was shown for example that only Rh can really promote OSC on alumina catalysts [32,33]. Nevertheless the situation changes when ceria is added to alumina. A comparative study of alumina and ceria-alumina supported bimetallic catalysts [32,33] demonstrated the differences between those systems. Ceria-alumina catalysts were shown to have higher OSC values which do not depend on the composition of the bimetallic (Fig. 7.3). 

The essential application of LEISS analysis concerns supported bimetallic catalysts. For these solids, XPS analysis can no longer be considered as a surface analysis. The sizes of the particles present on the surface of these catalysts are around a nanometre, similar to the mean free path of the photoelectrons that determines the thickness probed by XPS. Certain pairs of elements do not lend themselves to LEISS analysis. This is the case, for example, with Pt-Rc for which the mass difference of the two metals is small compared to the resolution. One example of a pair that lends itself to LEISS analysis is provided by a study of Pt-Sn reforming catalysts. LEISS is ten times more sensitive for platinum than for tin. Despite this, an intensity of the tin peak at least comparable to that of platinum can be observed on a catalyst with a Pl/Sn ratio of three (Fig. 6.5), This study can be used to show a surface segregation of tin that is dilTicult to detect by XPS because of the small size of the platinum particles (2 nm). 

Three aspects of the performance of supported catalysts are also discussed in this Chapter. With the development of techniques, as outlined above, for the characterization of supported metal catalysts, it seems timely to survey studies of crystallite size effect/structure sensitivity with special reference to the possible intrusion of adventitious factors (Section 5). Recently there has been considerable interest in the existence of (chemical) metal-support interactions and their significance for chemisorption and catalytic activity/ selectivity (Section 6). Finally, supported bimetallic catalysts are discussed for various reactions not involving hydrocarbons (hydrocarbon reactions over alloys and bimetallic catalysts have already been reviewed in this Series with respect to both basic research and technical applications ). References to earlier reviews (including some on techniques) that complement material in this Chapter are given in the appropriate sections. It might be useful, however, to note here some topics not discussed that also form part of the vast subject of supported metal and bimetallic catalysts and for which recent reviews are available, viz, spillover, catalyst deactivation, the growth and... 

Iron-Platinum or Palladium. - The nature of supported bimetallic catalysts can be probed by determining the chemical state of one metallic component,... 

Some Reactions over Supported Bimetallic Catalysts... 

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