Supported metals structure sensitivity

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

The identification of structure sensitivity would be both impossible and useless if there did not exist reproducible recipes able to generate metal nanoparticles on a small scale and under controlled conditions, that is, with narrow size and/or shape distribution onto supports. Metal nanoparticles of controlled size, shape, and structure are attractive not only for catalytic applications, but are important, for example in optics, data storage, or electronics (c.f. Chapter 5). In order not to anticipate other chapters of this book (esp. Chapter 2), remarks will therefore be confined to few examples. 

Besides supported (transition) metal catalysts, structure sensitivity can also be observed with bare (oxidic) support materials, too. In 2003, Hinrichsen et al. [39] investigated methanol synthesis at 30 bar and 300 °C over differently prepared zinc oxides, namely by precipitation, coprecipitation with alumina, and thermolysis of zinc siloxide precursor. Particle sizes, as determined by N2 physisorpt-ion and XRD, varied from 261 nm for a commercial material to 7.0 nm for the thermolytically obtained material. Plotting the areal rates against BET surface areas (Figure 3) reveals enhanced activity for the low surface area zinc... 

Since Haruta s works in the 1980s [110] CO oxidation is one of the major applications of supported gold catalysts. Interestingly, this metal/substrate combination exhibits much more pronounced structure sensitivity than the Pd, Pt, and Ir catalyzed analogues [9]. 

Besides electronic effects, structure sensitivity phenomena can be understood on the basis of geometric effects. The shape of (metal) nanoparticles is determined by the minimization of the particles free surface energy. According to Wulffs law, this requirement is met if (on condition of thermodynamic equilibrium) for all surfaces that delimit the (crystalline) particle, the ratio between their corresponding energies cr, and their distance to the particle center hi is constant [153]. In (non-model) catalysts, the particles real structure however is furthermore determined by the interaction with the support [154] and by the formation of defects for which Figure 14 shows an example. 

By using thermosensitive poly-acrylamides, it is possible to prepare cubic Pt nanocrystals (with predominant (1 0 0) facets) and tetrahedral Pt nanocrystals (rich in (111) facets). These Pt nanocrystals can be supported on oxide (alumina) and used as a catalyst in structure-sensitive reaction, NO reduction by CH4. The results proved that morphologically controlled metal nanoparticles supported on adequate support give us a novel tool to connect the worlds of surface science with that of real catalysis. 

Thus, although CO disproportionation is structure-sensitive, the CO-O2 reaction appears to be structure-insensitive at both 445 K and 518 K, provided we define correctly the number of Pd sites available for reaction at both temperatures. It should also be noted that the turnover rate at 445 K is the same on metal particles supported on 1012 a-A O, 0001 a-A O, and... 

It is well established that commercially important supported noble metal catalysts contain small metal crystallites that are typically smaller than a few nanometers. The surface of these crystallites is populated by different types of metal atoms depending on their locations on the surface, such as comers, edges, or terraces. In structure sensitive reactions, different types of surface metal atoms possess quite different properties. For example, in the synthesis of ammonia from nitrogen and hydrogen, different surface crystallographic planes of Fe metal exhibit very different activities. Thus, one of the most challenging aspects in metal catalysis is to prepare samples containing metal particles of uniform shape and size. If the active phase is multicomponent, then it is also desirable to prepare particles of uniform composition. 

The accessibility of new techniques such as EXAFS brings researchers a powerful tool for unambiguous determination of the true core metallic framework of such systems. Thus, the relationship between the parent carbonyl precursor, the support and the final metal-supported particles has been studied at the structural atomic level in some cases. This can allow differentiation of the catalytic behavior of supported metal particles with bulk-like properties from that of supported metal clusters, opening the way to understanding the mechanism of metal-catalyzed reactions and extending the concept of sensitive or insensitive structure reactions from metal aggregates to clusters. 

HREM methods are powerful in the study of nanometre-sized metal particles dispersed on ceramic oxides or any other suitable substrate. In many catalytic processes employing supported metallic catalysts, it has been established that the catalytic properties of some structure-sensitive catalysts are enhanced with a decrease in particle size. For example, the rate of CO decomposition on Pd/mica is shown to increase five-fold when the Pd particle sizes are reduced from 5 to 2 nm. A similar size dependence has been observed for Ni/mica. It is, therefore, necessary to observe the particles at very high resolution, coupled with a small-probe high-precision micro- or nanocomposition analysis and micro- or nanodiffraction where possible. Advanced FE-(S)TEM instruments are particularly effective for composition analysis and diffraction on the nanoscale. ED patterns from particles of diameter of 1 nm or less are now possible. 

Characterization of the Surfaces of Catalysts Measurements of the Density of Surface Faces for High Surface Area Supports. - It has always been a tenet of theories of catalysis that certain reactions will proceed at different rates on different surface planes of the same crystal. Experiments with metal single crystals have vindicated this view by showing that the rate of hydrogenolysis of ethane on a nickel surface will vary from one plane to another. In contrast the rate of methanation remains constant for the same planes.4 Because of this structure sensitivity of catalytic processes there is a requirement for methods of determining the number of each of the different planes which a catalyst and its support may expose at their surfaces. Electron microscopy studies of 5nm Pt particles supported upon graphite show them to be cubo-octahedra with surfaces bound by (111) and (100) planes.5 Similar studies of Pd and Pt prepared by evaporation reveal square pyramids of size 60-200 A bounded by incomplete (111) faces.6... 

To answer these questions requires some understanding of the properties of small metal particles, both structural and electronic. In this review we shall examine first the evidence relating to metal particles prepared by direct methods, e.g., vapour deposition or condensation in the gas phase. Then we shall consider whether this information can be applied to the case of supported metals where both precursor decomposition and support effects may add to the complexity of the total system. We shall then consider whether further changes in catalytic properties occur after preparation, i.e., during the catalytic reaction. Finally, we shall summarize some of the more recent evidence concerning the nature of structure sensitivity. 

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