Supported metal catalysts size effect

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 ... 

In many catalytic systems, nanoscopic metallic particles are dispersed on ceramic supports and exhibit different stmctures and properties from bulk due to size effect and metal support interaction etc. For very small metal particles, particle size may influence both geometric and electronic structures. For example, gold particles may undergo a metal-semiconductor transition at the size of about 3.5 nm and become active in CO oxidation [10]. Lattice contractions have been observed in metals such as Pt and Pd, when the particle size is smaller than 2-3 nm [11, 12]. Metal support interaction may have drastic effects on the chemisorptive properties of the metal phase [13-15]. Therefore the stmctural features such as particles size and shape, surface stmcture and configuration of metal-substrate interface are of great importance since these features influence the electronic stmctures and hence the catalytic activities. Particle shapes and size distributions of supported metal catalysts were extensively studied by TEM [16-19]. Surface stmctures such as facets and steps were observed by high-resolution surface profile imaging [20-23]. Metal support interaction and other behaviours under various environments were discussed at atomic scale based on the relevant stmctural information accessible by means of TEM [24-29]. 

Based on TEM studies of supported metal catalysts, several workers have concluded that their catalysts were made of two-dimensional discs or rafts , where virtually all atoms are at the particle surface. However, sample tilting experiments in TEM have shown that great care should be exercised in the interpretation of TEM images of small particles (<2 nm in size), since phase contrast effects may dominate and variations in the particle contrast with specimen orientation can occur as a result of amplitude contrast effects (Treacy and Howie 1980). Sample tilting is therefore necessary to ensure correct interpretations of TEM images of metal-particle catalysts. This will be discussed further in the following sections. 

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. 

For supported-metal catalysts, the questions of interaction with and location of the metal on the support are of important concern, since these factors may be instrumental in determining, for example, the metal particle size and size distribution, the particle size stability to thermal and chemical treatments, and the accessibility of the metal to the reactants of the catalytic process. That these questions are amenable to study using the Mbssbauer effect is the topic of this section. 

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 in the case of CO oxidation, the reduction of NO by CO depends on the heterogeneity of the supported model catalyst. The effect of size and shape of the metal particles has been addressed with Pd/MgO(l 00) model catalysts [88, 90, 91, 168]. 

The efficiency and selectivity of a supported metal catalyst is closely related to the dispersion and particle size of the metal component and to the nature of the interaction between the metal and the support. For a particular metal, catalytic activity may be varied by changing the metal dispersion and the support thus, the method of synthesis and any pre-treatment of the catalyst is important in the overall process of catalyst evaluation. Supported metal catalysts have traditionally been prepared by impregnation techniques that involve treatment of a support with an aqueous solution of a metal salt followed by calcination (4). In the Fe/ZSM-5 system, the decomposition of the iron nitrate during calcination produces a-Fe2(>3 of relatively large crystallite size (>100 X). This study was initiated in an attempt to produce highly-dispersed, thermally stable supported metal catalysts that are effective for synthesis gas conversion. The carbonyl Fe3(CO) was used as the source of iron the supports used were the acidic zeolites ZSM-5 and mordenite and the non-acidic, larger pore zeolite, 13X. 

This study was initiated in an attempt to produce highly-dispersed, thermally-stable, zeolite-supported metal catalysts and to investigate the effect of acidity and pore size of the zeolite on the products obtained from synthesis gas conversion. As a result of this study, several conclusions can be made. 

The recent accomplishments of near-edge X-ray absorption spectroscopy in catalysis studies are already quite impressive, in particular if one considers the limited availability of suitable X-ray spectrometers. Developments of catalytic interest have concerned the Shell Higher Olefin process, size effects, metal-support interaction, mono- and bimetallic catalysts (in particular the PtRe/Al203 system), the reactivity of supported metal catalysts, dynamical and in situ catalyst studies, and a variety of oxide and sulfide catalysts. Other catalytic problems are now coming within easy experimental reach, such as the study of sulfur poisoning and the nature of coking. 

This paper examines the hydrogenation of aniline, /Moluidinc. and 4-fcrt-butylanilinc over a series of 2.5 % Rh/Si02 catalysts, comparing reaction rates and product selectivities. Further studies concentrated on examining support particle size and average metal crystallite size effects on /Moluidinc hydrogenation and the support pore size effects on 4-tert-butylaniline hydrogenation. 

Thus, complex high-area catalysts are typically not the best for fundamental investigations at the atomic or molecular level. Although many broadly important characteristics of heterogeneous catalysis, such as metal particle size effects, support effects, metal—support interaction, and the influence of the promoters and poisons... 

Three aspects of the performance of supported catalysts are also discussed in this Chapter. With the development of techniques, as outlined above, for the characterization of supported metal catalysts, it seems timely to survey studies of crystallite size effect/structure sensitivity with special reference to the possible intrusion of adventitious factors (Section 5). Recently there has been considerable interest in the existence of (chemical) metal-support interactions and their significance for chemisorption and catalytic activity/ selectivity (Section 6). Finally, supported bimetallic catalysts are discussed for various reactions not involving hydrocarbons (hydrocarbon reactions over alloys and bimetallic catalysts have already been reviewed in this Series with respect to both basic research and technical applications ). References to earlier reviews (including some on techniques) that complement material in this Chapter are given in the appropriate sections. It might be useful, however, to note here some topics not discussed that also form part of the vast subject of supported metal and bimetallic catalysts and for which recent reviews are available, viz, spillover, catalyst deactivation, the growth and... 

The scope of the present paper is to emphasize that the interactions between support, metal and atmosphere are responsible for both the physical (size distribution, shape of the crystallites, wettability of the substrate by the crystallites and vice versa), the chemical and the catalytic (suppression of chemisorption, increased activity for methanation, etc.) manifestations of the supported metal catalysts. In the next section of the paper, a few experimental results concerning the behaviour of iron crystallites on alumina are presented to illustrate the role of the strong chemical interactions between the substrate and the compounds of the metal formed in the chemical atmosphere. Surface energetic considerations, similar to those already employed by the author (7,8), are then used to explain some of the observed phenomena. Subsequently, the Tauster effect is explained as a result of the migration, driven by strong interactions,... 

---