Oxide supported metal catalysts techniques

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). 

Oxide-supported metals constitute one of the most important classes of heterogeneous catalysts, and for this reason they have been investigated by many techniques adsorption isotherms, IR of chemisorbed molecules, electron microscopy, EXAFS, etc. Flowever, the fact that they have been studied by so many methods proves that no one technique is totally satisfactory. 

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. 

In contrast, recent work (4-12) has shown that Raman spectroscopy can be used to study Ti) adsorption on oxides, oxide supported metals and on bulk metals [including an unusual effect sometimes termed "enhanced Raman scattering" wherein signals of the order of 10 - 106 more intense than anticipated have been reported for certain molecules adsorbed on silver], (ii) catalytic processes on zeolites, and (iii) the surface properties of supported molybdenum oxide desulfurization catalysts. Further, the technique is unique in its ability to obtain vibrational data for adsorbed species at the water-solid interface. It is to these topics that we will turn our attention. We will mainly confine our discussion to work since 1977 (including unpublished work from our laboratory) because two early reviews (13,14) have covered work before 1974 and two short recent reviews have discussed work up to 1977 (15,16). 

Inelastic electron tunneling spectroscopy has been shown to be a useful method for the study of chemisorption and catalysis on model oxide and supported metal catalyst systems. There are in addition a number of proven and potential applications in the fields of lubrication, adhesion (48), electron beam damage (49,50), and electrochemistry for the experimentalist who appreciates the advantages and limitations of the technique. 

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]. 

Supported metal catalysts generally show an increase in catalytic activity compared to the pure oxide or metal. Yet these systems are not well characterised, owing to the fact that such catalysts typically consist of a range of different supported metal sites, from small clusters to monolayer islands, all with non-uniform distributions in size and shape. One way to begin to understand such complex systems is to attempt to capture some essential part of the full system by developing model catalysts experimentally or using computer modelling techniques. This chapter concentrates on the latter but in the context of the relevant experimental data. 

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... 

High Resolution Electron Microscopy (HREM) has proven as a very useful technique in the structural characterisation of supported metal catalysts (383-386) in general and, in particular, of noble metal catalysts supported on ceria-based oxides (52,70,72,97,105,109,117,124,135,137,139,144,147,155,171,182-184.194.203,209, 210,218,226,234,235,387) ... 

In summary, alkali promotion of supported metal catalysts is an interesting subject that does have important technological implications in those cases where the presence of alkali has a pivotal influence on the surface chemistry of the metal phase. Fundamental studies of such systems are certainly justified. However, we should maintain a sense of proportion. Alkalis find relatively limited use as promoters in practical catalysis—indeed in some cases they act as powerful poisons. And we should not lose sight of the fact that what is actually present at the surface of the working catalyst is not an alkali metal, but some kind of alkali surface compound. This chapter deals with the application of alkali promoters to catalysis by metals, as opposed to catalysis by oxides, and, in particular, the technique of electrochemical promotion (EP), which enables us to address some pertinent issues. 

ES S studies of catalysts are described in Chapter 7. These experiments present a particular set of problems that need to be addressed. Foremost is the fact that INS is not an intrinsically surface sensitive technique. This is overcome by using large samples to maximise the number of surface sites and hydrogenous adsorbates to give the highest possible contrast. Supported metal catalysts, zeolites and oxides often have low densities, while metal powders have high densities but low surface areas. Both situations require a large volume cell to place sufficient sample in the beam. 

In this chapter, the most common techniques for preparation of supported metal catalysts will be discussed, including impregnation, coprecipitation, homogeneous deposition precipitation, and precipitation at constant pH. In principle, these techniques can all be used to attach the active phase to supports, some preferably in the form of a powder, others in the form of a pre-shaped body. First, a general description of the techniques will be presented. Then, the techniques are illustrated by specific examples of the preparation of metallic catalysts. In view of the expertise of the authors of this chapter, Pt, Au, and Ag as the active metal phases will be emphasized. The last two examples are focused on the production of propene oxide and, as a consequence, they refer to an unresolved research issue. The results on the Ag catalysis have not been published elsewhere, and are therefore treated extensively. 

T Hattori, R L Burwell, Jr., Role of carbonaceous deposits in the hydrogenation of hydrocarbons on platinum catalysts. Journal ofPhysical Chemistry 83 241-249, 1979. C A. Querini, S C Fung, Temperature programmed oxidation technique kinetics of coke-02 reaction on supported metal catalysts. Applied Catalysts A 117 53-74, 1994. 

Determination of Coke Location. The TPO technique allows the determination of the coke location on supported metal catalysts, such as naphtha reforming. Since the metal, typically platinum promoted with rhenium, iridium, tin, or germanium, has a catalytic effect for coke burning, the TPO profile displays two main peaks. The low temperature peak is due to the oxidation of the coke directly deposited on the metal particle, or in its vicinity . In this way, it is possible to study the effect of catalyst formulation and operational conditions on the formation of coke on the metal and on the support. 

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