Metal/support catalysts

F. W. Kaiser and S. Pelters, Comparison of Metal Supported Catalysts with Different Cell Geometries, SAE 910837, Society of Automotive Engineers, Warrendale, Pa., 1991. 

JOVANOVIC, G., Sacrittichai, P., Toppinen, S., Microreactors systems for dechlorination of p-chlorophenol on palladium based metal support catalyst theory and experiment, in Proceedings of the 6th International Conference on Microreaction Technology, IMRET 6, 11-14 March 2002, pp. 314-325, AIChE Pub. No. 164, New Orleans (2002). 

If microwave heating leads to enhanced reactions rates, it is plausible to assume that the active sites on the surface of the catalyst (micro hot spots) are exposed to selective heating which causes some pathways to predominate. In the case of metal supported catalysts, the metal can be heated without heating of the support due to different dielectric properties of both catalyst components. The nonisothermal nature of the microwave-heated catalyst and the lower reaction temperature affects favorably not only reaction rate but also selectivity of such reactions. 

Describe, in general, an enantioselective hydrogenation mechanism in the presence of a chiral-modified metal/support catalyst. 

In this chapter, we discussed some general results obtained using a new route of preparation method of metallic supported catalysts by using colloidal oxide chemistry... 

Several reasons can be considered for using metal binary carbonyl precursors in the preparation of metal supported catalysts ... 

The following sections detail and update the more relevant aspects concerning the use of binary carbonyl metal complexes in the preparation of tailored metal supported catalysts. In several cases, we discuss the use of other pertinent carbonyl... 

The M(C0)6 (M = Cr, Mo, W) stable carbonyls have been used to prepare metal supported catalysts of elements of group 6 that have been used as catalysts in several reactions, such as metathesis, water-gas shift, CO hydrogenation and olefin hydrogenation and polymerization [15-24]. Table 8.2 compiles several examples in which M(CO)s (M = Cr, Mo, W) compounds are used as an alternative for preparing chromium-molybdenum or tungsten-based catalysts. 

Exploiting Surface Chemistry to Prepare Metal-Supported Catalysts by Organometallic Chemical Vapor Deposition... 

In this chapter we report on the gas-phase preparation of metal-supported catalysts, that is on the deposition of dispersed metallic nanoparhcles onto a surface. Taking most of the examples from the thoroughly studied chemistry of the [Mo(CO)is]/oxide support system, we successively consider (i) surface organometallic chemistry issues, (ii) the methods used to avoid chemical contaminahon of the deposit and (iii) the competition between nucleation and growth. 

General Trends in Metal Complex/Surface Reactivity, and Further Requirements for Metal-Supported Catalyst Preparation... 

When we are interested in the reproducible preparation of metal-supported catalysts it is also necessary to integrate the mesoscopic scale. Indeed, the deposit needs to be homogeneous, with particles anchored not only on all the support grains but also in their porosity. The use of CVD-fluidized bed reactors, for which we have gained some experience [85, 86], is one of the most elegant ways to master a process that fulfils these requirements under relatively mild conditions. 

The preparation of precious metal supported catalysts by the HTAD process is illustrated by the synthesis of a wide range of silver on alumina materials, and Pt-, Pt-Ir, Ir-alumina catalysts. It is interesting to note that the aerosol synthesis of alumina without any metal loading results in a material showing only broad reflections by XRD. When the alumina sample was calcined to 900°C, only reflections for a-alumina were evident. The low temperature required for calcination to the alpha-phase along with TEM results suggest that this material was formed as nano-phase, a-alumina. Furthermore, the use of this material for hexane conversions at 450°C indicated that it has an exceptionally low surface acidity as evidenced by the lack of any detectable cracking or isomerization. 

In the mentioned studies the selective hydrogenations were made with the aim to obtain kinetical data, and the catalysts characterization was scarce. On the other hand, It is known that metal supported catalysts exhibit important particle size and support effects in the selectivity patterns (ref. 7). 

An important consideration for the electronics of semiconductor/metal supported catalysts is that the work function of metals as a rule is smaller than that of semiconductors. As a consequence, before contact the Fermi level in the metal is higher than that in the semiconductor. After contact electrons pass from the metal to the semiconductor, and the semiconductor s bands are bent downward in a thin boundary layer, the space charge region. In this region the conduction band approaches the Fermi level this situation tends to favor acceptor reactions and slow down donor reactions. This concept can be tested by two methods. One is the variation of the thickness of a catalyst layer. Since the bands are bent only within a boundary layer of perhaps 10-5 to 10 6 cm in width, a variation of the catalyst layer thickness or particle size should result in variations of the activation energy and the rate of the catalyzed reaction. A second test consists in a variation of the work function of the metallic support, which is easily possible by preparing homogeneous alloys with additive metals that are either electron-rich or electron-poor relative to the main support metal. 

Most commonly a freshly reduced metal or metal-supported catalyst will have a layer of oxygen, either strongly chemisorbed or fully oxidized, on its surface. Because of this it is common practice in hydrogenation reactions to pretreat the catalyst in a stream of H2 in the reactor to remove all traces of surface oxygen before performing the catalytic reactions. Also, throughout the years catalytic scientists have dealt with the problem of pyrophoric metals by intentionally blanketing the catalyst with a carefully controlled amount of O2 or CO2 after reduction to prevent bulk oxidation. These protective layers are removed by reduction and/or heat treatment in order to permit catalysis to occur. 

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