Apparent Metal-Support Effects

In summary, apparent metal-support interactions may arise through the operation of a specific particle size effect, or of bifunctionality or spillover, or through the support acting as a source or sink of a catalytic poison. Deliberately added promoters constitute an additional complication. Real interactions not due to these or similar causes may be attributed either to electronic or geometric effects, the latter embracing possible differences in crystal habit, or to the creation of phases which contain the active component in some form but which are hard to reduce. 

Is it known that the rate of hydrogenolysis reactions are extremely sensitive to effects of alloying, surface contamination, poisoning, etc. Consequently, in all cases where supported metals are used there must be concern as to whether apparent particle size effects are due to structure sensitivity or to some minor contamination effect. In the few cases where clean single crystal surfaces have been used there is evidence of a structure effect.338 However, the maximum change in activity between different crystal faces seems to be about a factor of 10. For Ni single crystals the (100) surface is more active than the (111) surface. A similar conclusion has been reached for oriented Ni powder samples.339... 

This paper focuses on the influence of the support on the H/D exchange of CP over supported Pt catalysts. It will be shown that kinetics and selectivities are largely affected by the support material. Particle size effects are separated from support effects. The activity shows a compensation effect, and the apparent activation energy and pre-exponential factor show an isokinetic relationship . This can be explained by different adsorption modes of the CP on the metallic Pt surface. The change in adsorption modes is attributed to a change in the electronic structure of the Pt particles, which in turn is induced by changes in the acid/base properties of the support. 

As is shown in Figure 6 (experiments) and Table 4 (Monte-Carlo analysis), a general trend is that Pt catalysts with supports of higher acidity lead to a higher contribution of the a-T)1 (Dl) and di-o-T)2 (D2) intermediates. As the ASA and LTL supports have similar metal particle sizes, this cannot be explained by particle size effects. Apparently, acidic supports enhance... 

Fig. 4.38. The effects of various pretreatments (oxidative and reductive) on CO oxidation on a 40-nm Pt/ceria model catalyst prepared by colloidal lithography as measured by the temperature of 50% of CO conversion and the apparent activation energy from the Arrhenius plot. CO reduction was made in 0.5% CO for Ih at 573K, H2 oxidation (a-treatment) was done at a = Ph2/(.Ph.2 + P02) = 0.33 at 573 K for 1 h, and finally /3 = CO oxidation (/3-treatment) was done in the O-rich regime (oxidative conditions), /3 = Pco/ Pco + P02) = 0.2 with 0.3% CO and 1.2% O2 at temperatures between 300 and 673 K. It is seen that reduction leads to a lower Tbo and activation energy, while sustained CO oxidation leads to an increase of the activation energy, which is not recovered by reductive treatments. The latter is explained in terms of strong-metal-support interactions (SMSI) and particle reshaping (see text)...

Various supported platinum group metal systems have been tested for the SCR process.101 Among them, supported platinum systems appear to be the most active when jointly considering the NOx reduction level achieved and the temperature range at which the catalyst is active, while palladium, rhodium and iridium also show catalytic activity for the process and Rh and Ir apparently present higher selectivity to N2.101>i03-i07 Support effects are observed which generally depend on the type of hydrocarbon employed, the presence or absence of SO2 in the reactant mixture or the type of impurities present in the support.101 In this respect, a variety of materials like SiC>2, AI2O3, ZrC>2, sulphated alumina, zeolitic materials and activated carbons have been employed as supports of the metals and tested for the process.101-112... 

The action of nickel is so much more powerful than that of alumina that the dehydrating action of the latter is practically eliminated when catalysts containing mixtures of reduced nickel and alumina are used. In fact, the alumina apparently only acts as a support for the active metal. However, comparative measurements have shown that the oxides of aluminium, iron, magnesium, and calcium may act as strong promoters for nickel catalysts. This effect has been explained as a mechanical effect, viz., the development of a large surface by which relatively more active metal is effectively exposed.10 When only small amounts of oxide are present the effect is predominantly that of support. The increased addition of oxide may increase the catalytic activity up to a certain point beyond which it only serves to dilute the catalyst and reduce its selectivity. Other explanations of the promoter action postulate the removal of catalyst poisons by the oxide, or regeneration of the active metallic catalyst by oxidations and reductions.20... 

Of course, the bonding of the support to the metal particle will affect the ease of sintering, and may also affect the electronic properties of the metallic particle. Thus, strong support effects are the subject of much current research. The support 1102 has the most pronounced support effect because it is capable of shuttling electrons to and from the metallic particle. This is apparently due to the fact that TiO or U02 (Ti + or Ti" +) is available on the surface. 

For several years the Homogeneous Reactor Project has supported investigations of an exploratory nature to determine the influence of radiation effects on pressure vessel steels [148, 149, 150]. Although it is not yet possible to give definitive answers to many of the questions posed, it has become apparent that radiation effects in steels depend upon a large number of factors, and the unusual properties of irradiated metals may force a reappraisal of the usual standards for predicting service performance from mechanical property data. 

There is a wide variety of solid electrolytes and, depending on their composition, these anionic, cationic or mixed conducting materials exhibit substantial ionic conductivity at temperatures between 25 and 1000°C. Within this very broad temperature range, which covers practically all heterogeneous catalytic reactions, solid electrolytes can be used to induce the NEMCA effect and thus activate heterogeneous catalytic reactions. As will become apparent throughout this book they behave, under the influence of the applied potential, as active catalyst supports by becoming reversible in situ promoter donors or poison acceptors for the catalytically active metal surface. 

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