Oxide-supported metal catalysis

The decarbonylation of oxide-supported metal carbonyls yields gaseous products including not just CO, but also CO2, H2, and hydrocarbons [20]. The chemistry evidently involves the support surface and breaking of C - O bonds and has been thought to possibly leave C on the clusters [21]. The chemistry has been compared with that occurring in Fischer-Tropsch catalysis on metal surfaces [20] support hydroxyl groups are probably involved in the chemistry. 

The lack of calorimetric data is particularly evident in the case of the adsorption of gases on oxides or on oxide-supported metals, i.e., on solids similar to most industrial catalysts. Moreover, adsorption calorimeters are generally used at temperatures that are much lower than those usually found in industry, and it would be difficult indeed to adapt most usual adsorption calorimeters for the measurement of heats of adsorption of gases on industrial catalysts at elevated temperatures. The present success of gas chromatographic techniques for determining heats of reversible adsorption may be explained by the gap between the possibilities of the usual adsorption calorimeters and the requirements of industrial catalysis research. 

It is true, however, that many catalytic reactions cannot be studied conveniently, under given conditions, with usual adsorption calorimeters of the isoperibol type, either because the catalyst is a poor heat-conducting material or because the reaction rate is too low. The use of heat-flow calorimeters, as has been shown in the previous sections of this article, does not present such limitations, and for this reason, these calorimeters are particularly suitable not only for the study of adsorption processes but also for more complete investigations of reaction mechanisms at the surface of oxides or oxide-supported metals. The aim of this section is therefore to present a comprehensive picture of the possibilities and limitations of heat-flow calorimetry in heterogeneous catalysis. The use of Calvet microcalorimeters in the study of a particular system (the oxidation of carbon monoxide at the surface of divided nickel oxides) has moreover been reviewed in a recent article of this series (19). 

D.C. Meier, X. Lai, and D.W. Goodman, Surface chemistry of model oxide-supported metal catalysts An overview of gold on Titania, in Surface Chemistry and Catalysis, eds. A.F. Carley et al. Kluwer, New York, 2002, pp. 147-189. 

In comparison to most other methods in surface science, STM offers two important advantages (1) it provides local information on the atomic scale and (2) it does so in situ [50]. As STM operates best on flat surfaces, applications of the technique in catalysis relate to models for catalysts, with the emphasis on metal single crystals. Several reviews have provided excellent overviews of the possibilities [51-54], and many studies of particles on model supports have been reported, such as graphite-supported Pt [55] and Pd [56] model catalysts. In the latter case, Humbert et al. [56] were able to recognize surface facets with (111) structure on palladium particles of 1.5 nm diameter, on an STM image taken in air. The use of ultra-thin oxide films, such as AI2O3 on a NiAl alloy, has enabled STM studies of oxide-supported metal particles to be performed, as reviewed by Freund [57]. 

The reactivity of oxide supported metals has received considerable attention because of the importance of such systems in heterogeneous catalysis. The morphology (structure and size) of the supported particle and its stability, the interaction of the particle with the support, and the crossover of adsorbed reactants, products and intermediates between the metal and oxide phases are all important in determining the overall activity and selectivity of the system. Because of the relative insensitivity of an optical technique such as IR to pressure above the catalysts, and the flexibility of transmission and diffuse reflection measurement techniques, vibrational spectroscopy has provides a considerable amount of information on high area (powder) oxide supported metal surfaces. Particularly remarkable was the pioneering work of Eichens and Pliskin [84] in which adsorbed CO was characterised by IR spectroscopy on... 

Supported metal catalysis are employed in a variety of commercially important hydrocarbon conversion processes. Such catalysts consist, in general, of small metal crystallites (0.S to 5 nm diameter) dispersed on non-metallic oxide supports. One of the major ways in which a catalyst becomes deactivated is due to accumulation of carbonaceous deposits on its surface. Catalyst regeneration, or decoking, is normally achieved by gasification of the deposit in air at about 500°C. However, during this process a further problem is frequently encountered, which contributes to catalyst deactivation, namely particle sintering. Other factors which can contribute to catalyst deactivation include the influence of poisons such as sulfur, phosphorus, arsenic and... 

Support materials most adapted for stabilizing clusters on surfaces are oxide materials. They reveal a relatively large band gap and thus the characteristic, discrete electronic levels of the clusters are maintained to a certain extent. Furthermore, the interaction of the clusters with oxide surfaces, especially with their defects may be substantial and trapping of the clusters is feasible. Oxide supported metal particles are also relevant in industrial catalysis. 

The electron microscopes can be divided into two types (166) scanning electron microscopes (SEM), which use a 10-nm electron beam at the specimen surface, and transmission electron microscopes (TEM). With current TEMs, resolution of about 0.2 nm can be achieved, provided very thin (<20 nm) samples are available. With conventional inorganic oxide-supported metal catalysts, particles of approximately 1 nm can be detected. Scanning transmission electron microscopes (STEM) use a high brightness dark-field emission gun to produce a probe about 0.3 nm in diameter and combine the techniques of SEM and TEM. Further experimental and theoretical aspects of electron microscopy applied to catalysis have been reviewed recently (113, 167-169). 

S. Bernal, J.J. Calvino, J.M. Gatica, C. L6pez-Cartes, and J.M. Pintado, Chemical and Nano-Structural Aspects of the Preparation and Characterisation of Ceria and Ceria-Based Mixed Oxide Supported Metal Catalysts, in A. Trovarelli (ed.), Catalysis by Ceria and Related Materials, Imperial College Press, London, p.85, 2002. 

Bernal, S. Calvino, J.J. and Gatica, J.M. in " Chemical and nanostructural aspects of the preparation and characterization of ceria and ceria-based mixed oxide-supported metal catalysts , in Catalysis by Ceria and Related Materials, eds A. Trovarelli, Catalytic Science Series, Vol 2, Imperial College Press, London, 2002, page 85. 

Ceria-zirconia mixed oxide-supported metal nanoparticles are attractive catalysts in low-temperature WGS, CO preferential oxidation (PROX), or three-way catalysis. It was observed that after redox cycles (reduction at 1173K and then oxidation at 823 K), the reducibility of these catalysts was enhanced substantially, which greatly affected their catalytic performance. HAADF studies showed that the pyrochlore-type cation sublattice in the reduced Ce Zr O was retained in the fully oxidized mixed oxide with a Ce Zr Og stoichiometry as far as the oxidation temperature did not exceed 823 K. However, it is not clear whether compositional heterogeneity occurred at the atomic level in Ce Zr Og. Trasobares and coworkers addressed this issue by aberration-corrected STEM, atomic-resolution EELS mapping, and EELS image simulations [66], They synchronously acquired EELS and HAADE signals in... 

Supported molecular species. Although there are several examples of intact oxide-supported metal clusters acting as catalysts at relatively low temperatures, e.g., alkene isomerization at < 100 C, there is at least one example whereby, for specific combinations of metal, support, pre-treatment, reaction conditions, etc., catalysis can be carried out at up to 275°C. At this temperature, on the basis of the structural characterization at present available, the structure of the cluster is maintained. The catalytic properties of such stable support-... 

The mechanism and rate of hydrogen peroxide decomposition depend on many factors, including temperature, pH, presence or absence of a catalyst (7—10), such as metal ions, oxides, and hydroxides etc. Some common metal ions that actively support homogeneous catalysis of the decomposition include ferrous, ferric, cuprous, cupric, chromate, dichromate, molybdate, tungstate, and vanadate. For combinations, such as iron and... 

G.L. Haller, and D.E. Resasco, Metal-Support Interaction Group VIII Metals and Reducible Oxides, Advances in Catalysis 36, 173-235 (1989). 

The interactions between metals and supports in conventional supported metal catalysts have been the focus of extensive research [12,30]. The subject is complex, and much attention has been focused on so-called strong metal-support interactions, which may involve reactions of the support with the metal particles, for example, leading to the formation of fragments of an oxide (e.g., Ti02) that creep onto the metal and partially cover it [31]. Such species on a metal may inhibit catalysis by covering sites, but they may also improve catalytic performance, perhaps playing a promoter-like role. 

It is evident that the supported clusters have a strong affinity for hydride ligands provided by the support. The process by which the support delivers these ligands is referred to in the catalysis literature as reverse hydrogen spillover. The opposite process (spillover), well known for supported metals [36], is shown by the theoretical results to be a redox process in reverse spillover, the support hydroxyl groups oxidize the cluster. 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

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