Supported catalysts metal-support interaction

In general, encapsulated metal particles were observed on all graphite-supported catalysts. According to Ref. [4] it can be the result of a rather weak metal-graphite interaction. We mention the existence of two types of encapsulated metal particles those enclosed in filaments (Fig. 1) and those encapsulated by graphite. It is interesting to note that graphite layers were parallel to the surface of the encapsulated particles. 

B. Catalysts Formed by Interaction of Organometallic Compounds of Transition Metals with Oxide Supports... 

Electrochemical promotion or NEMCA is the main concept discussed in this book whereby application of a small current (1-104 pA/cm2) or potential ( 2 V) to a catalyst, also serving as an electrode (electrocatalyst) in a solid electrolyte cell, enhances its catalytic performance. The phenomenology, origin and potential practical applications of electrochemical promotion, as well as its similarities and differences with classical promotion and metal-support interactions, is the main subject of this book. 

It will also be shown that the absolute electrode potential is not a property of the electrode but is a property of the electrolyte, aqueous or solid, and of the gaseous composition. It expresses the energy of solvation of an electron at the Fermi level of the electrolyte. As such it is a very important property of the electrolyte or mixed conductor. Since several solid electrolytes or mixed conductors based on ZrC>2, CeC>2 or TiC>2 are used as conventional catalyst supports in commercial dispersed catalysts, it follows that the concept of absolute potential is a very important one not only for further enhancing and quantifying our understanding of electrochemical promotion (NEMCA) but also for understanding the effect of metal-support interaction on commercial supported catalysts. 

Consequently the absolute potential is a material property which can be used to characterize solid electrolyte materials, several of which, as discussed in Chapter 11, are used increasingly in recent years as high surface area catalyst supports. This in turn implies that the Fermi level of dispersed metal catalysts supported on such carriers will be pinned to the Fermi level (or absolute potential) of the carrier (support). As discussed in Chapter 11 this is intimately related to the effect of metal-support interactions, which is of central importance in heterogeneous catalysis. 

The second phenomenon, i.e. the change in catalytic activity or selectivity of the active phase with varying catalyst support, is usually termed metal-support interaction. It manifests itself even when the active phase has the same dispersion or average crystallite size on different... 

This implies that Electrochemical Promotion or NEMCA is an electrochemically controlled metal-support interaction. It also implies that metal-support interactions on these supports can be viewed as a self-driven wireless NEMCA system, such as the one explored by Cavalca, Haller and Vayenas for the CH3OH oxidation system under catalyst-counter electrode short-circuit conditions where gaseous 02 replenishes O2 in the YSZ support at the vicinity of the counter electrode.24... 

The good qualitative agreement between eUwR variation and O0 variation shown in Figure 11.11 for the various supports used, underlines again the common promotional mechanism of electrochemically promoted and metal-support interaction promoted metal catalysts. 

In dispersed metal-support systems (Fig. 11.2 right), one can vary pe(M) - M-e(S) by varying the support or by doping the support with aliovalent cations. This is known in the literature as dopant-induced metal-support interactions (DIMSI).8,11,41,42 Thus one can again vary the electrochemical potential and thus the coverage of backspillover O2 on the supported catalyst surface. 

An important question frequently raised in electrochemical promotion studies is the following How thick can a porous metal-electrode deposited on a solid electrolyte be in order to maintain the electrochemical promotion (NEMCA) effect The same type of analysis is applicable regarding the size of nanoparticle catalysts supported on commercial supports such as Zr02, Ti02, YSZ, Ce02 and doped Zr02 or Ti02. What is the maximum allowable size of supported metal catalyst nanoparticles in order for the above NEMCA-type metal-support interaction mechanism to be fully operative ... 

Promotion, electrochemical promotion and metal-support interactions are three, at a first glance, independent phenomena which can affect catalyst activity and selectivity in a dramatic manner. In Chapter 5 we established the (functional) similarities and (operational) differences of promotion and electrochemical promotion. In this chapter we established again the functional similarities and only operational differences of electrochemical promotion and metal-support interactions on ionic and mixed conducting supports. It is therefore clear that promotion, electrochemical promotion and metal-support interactions on ion-conducting and mixed-conducting supports are three different facets of the same phenomenon. They are all three linked via the phenomenon of spillover-backspillover. And they are all three due to the same underlying cause The interaction of adsorbed reactants and intermediates with an effective double layer formed by promoting species at the metal/gas interface (Fig. 11.2). 

Consequently the proven functional identity of classical promotion, electrochemical promotion and metal-support interactions should not lead the reader to pessimistic conclusions regarding the practical usefulness of electrochemical promotion. Operational differences exist between the three phenomena and it is very difficult to imagine how one can use metal-support interactions with conventional supports to promote an electrophilic reaction or how one can use classical promotion to generate the strongest electronegative promoter, O2, on a catalyst surface. Furthermore there is no reason to expect that a metal-support-interaction-promoted catalyst is at its best electrochemically promoted state. Thus the experimental problem of inducing electrochemical promotion on fully-dispersed catalysts remains an important one, as discussed in the next Chapter. 

Having discussed the functional equivalence of classical promotion, electrochemical promotion and metal-support interactions on 02 -conducting and mixed electronic-ionic conducting supports, it is useful to also address and systematize their operational differences. This is attempted in Figure 11.15 The main operational difference is the promoter lifetime, Tpr, on the catalyst surface (Fig. 11.15). 

Figure 11.15. Operational range of classical promotion, electrochemical promotion and metal-support interactions in terms of the promoter lifetime on the catalyst surface.

B.L. Mojet, J.T. Miller, D.E. Ramaker, and D.C. Koningsberger, A new model describing the metal-support interaction in noble metal catalysts, J. Catal. 186, 373-386 (1999). 

On the other hand, as already discussed in Chapter 11 in connection to the effect of metal-support interactions, it appears that a fully dispersed noble metal catalyst on porous YSZ is already at a NEMCA or electroche-mically-promoted state, i.e. it is covered by an effective double layer of promoting backspillover O2 ions. This can explain both the extreme catalytic activity ofZr02- and Ti02- supported commercial catalysts, as well as the difficulty so far to induce NEMCA on fully dispersed noble metal catalysts deposited on YSZ. 

Thus not only promotion and electrochemical promotion is catalysis in the presence of a double layer but apparently the same applies for supported catalysts undergoing metal-support interactions (Chapter 11). 

Since then Electrochemical Promotion of Catalysis has been proven to be a general phenomenon at the interface of Catalysis and Electrochemistry. More than seventeen groups around the world have made important contributions in this area and this number is reasonably expected to grow further as the phenomenon of electrochemical promotion has very recently been found, as analyzed in this book, to be intimately related not only to chemical (classical) promotion and spillover, but also to the heart of industrial catalysis, i.e. metal-support interactions of classical supported catalysts. 

The utility of a SiKa x-ray source in the study of catalyst systems, and especially its utility in the observation of previously undetected metal-support interactions has been demonstrated. Scanning Auger microprobe data were also useful in understanding the quantitative changes observed by XPS. Finally, the ability to treat materials in a controlled manner, and perform the subsequent analyses without exposure to the ambient atmosphere, made the experiment possible. 

To Illustrate the utility of the technique, we have addressed the question of the anomalous chemlsorptlve behavior of tltanla-supported group VIII metals reduced at high temperatures. The suppression of strong H2 chemisorption on these catalysts has been ascribed to a strong-metal-support Interaction (SMSI) ( ). It has also been found that the reaction activity and selectivity patterns of the catalysts are different In normal and SMSI states... 

Huizinga, T., "Metal Support Interactions in Pt and Rh AI2O3 and T102 Catalysts," Ph.D. Thesis, Eindhoven University of Technology, 1983. 

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