Small metal particles transmission electron microscopy

However, in more recent times science has made rapid strides in this direction. It is now possible to use EXAFS in situ during a catalytic reaction to examine the average coordination of metal atoms in the small particles which often exist in precious metal catalysts [2]. High resolution transmission electron microscopy has evolved to the level of atomic resolution, but can only be used ex-situ, or in situ with moderate pressures when special cells are fitted [3]. 

Characterization of the Ru/KY and Ru/NaY catalysts used in this study by transmission electron microscopy showed that the metal was well-dispersed within the zeolite as particles small enough to fit inside the supercages, less than 1 nm in diameter. 

There are many ways in which small metal particles can be created and examined (Section 3.2). When the gold particles are supported, the first step is to determine their mean size and size distribution for this there is no real substitute for transmission electron microscopy (TEM). The various energetic and electronic properties then need to be examined, and the bases of the available experimental techniques will be briefly rehearsed in Section 3.3. Of particular interest is the point at which the change from metallic to nonmetallic behaviour occurs as size is decreased, because this corresponds very roughly to the point at which catalytic activity (at least for oxidation of carbon monoxide) starts to rise dramatically. Relevant experimental results and theoretical speculations are reviewed in Section 3.4. 

Since the number of atoms on the surface of a bulk metal or metal oxide is extremely small compared to the number of atoms in the interior, bulk materials are often too costly to use in a catalytic process. One way to increase the effective surface area of a valuable catalytic material like a transition metal is to disperse it on a support. Figure 5.1.5 illustrates how Rh metal appears when it is supported as nanometer size crystallites on a silica carrier. High-resolution transmission electron microscopy reveals that metal crystallites, even as small as 10 nm, often expose the common low-index faces commonly associated with single crystals. However, the surface to volume ratio of the supported particles is many orders of magnitude higher than an equivalent amount of bulk metal. In fact, it is not uncommon to use catalysts with 1 nm sized metal particles where nearly every atom can be exposed to the reaction environment. 

For supported metal catalysts, no simple calculation is possible. A direct measurement of the metal crystallite size or a titration of surface metal atoms is required (see Example 1.3.1). TWo common methods to estimate the size of supported crystallites are transmission electron microscopy and X-ray diffraction line broadening analysis. Transmission electron microscopy is excellent for imaging the crystallites, as illustrated in Figure 5.1.5. However, depending on the contrast difference with the support, very small crystallites may not be detected. X-ray diffraction is usually ineffective for estimating the size of very small particles, smaller than about 2 nm. Perhaps the most common method for measuring the number density of exposed metal atoms is selective chemisorption of a probe molecule like H2, CO, or O2. 

The introduction in catalysis of bimetallic formulations created an important area of application of microanalysis in transmission electron microscopy. In particular, with selective hydrogenation and postcombustion catalysts, where the metallic particle sizes are several nanometres, the STEM can be used to determine the composition particle by particle and thus confirm the success of the preparation. Figure 9.16 shows the analysis of individual particles in a bimetallic preparation. It is easy to detect the existence of genuinely bimetallic particles and others containing only platinum. It should, however, be noted that this analysis, obtained on a few nanometer sized particles, concerns only a very small quantity of the catalyst (in the present case approximately 10" g of metal ). As we have noted, it is dangerous to extrapolate only one result of this type to the solid as a whole. A statistical analysis of the response of a very large number of particles, in addition to a preliminary study of the chemical composition at different scales, can be used to confirm that this case indeed concerns two groups of particles. 

The characteristics of reforming catalysts make them one of the most frequent cases where EXAFS is used. The very small metallic particles cannot be detected in transmission electron microscopy the long range order required for XRD analysis is absent, and the low metal contents make XPS analysis difficult. The observation of XANES structures at Pi and Re thresholds can be used to determine the electronic state. Some examples of reference compounds are shown in Figure 11.10. In particular a sharp peak (called a white line for historical reasons) is visible at the edge with an intensity related to the oxidisation state of the element. This peak in the absorption coefficient is a consequence of the existence of the empty electron states close to zero binding energy. 

It is not surprising therefore that the optical properties of small metal particles have received a considerable interest worldwide. Their large range of applications goes from surface sensitive spectroscopic analysis to catalysis and even photonics with microwave polarizers [9-15]. These developments have sparked a renewed interest in the optical characterization of metallic particle suspensions, often routinely carried out by transmission electron microscopy (TEM) and UV-visible photo-absorption spectroscopy. The recent observation of large SP enhancements of the non linear optical response from these particles, initially for third order processes and more recently for second order processes has also initiated a particular attention for non linear optical phenomena [16-18]. Furthermore, the paradox that second order processes should vanish at first order for perfectly spherical particles whereas experimentally large intensities were collected for supposedly near-spherical particle suspensions had to be resolved. It is the purpose of tire present review to describe the current picture on the problem. 

Figure 2. Transmission Electron Microscopy (TEM) picture of small gold metallic particles. The shape of the particles approaches that of perfect spheres...

The results that have been obtained with the catalysts after reduction and passivation are the same as those after calcination, i.e. the textural and structural properties of the support material have completely been retained after the treatments (as determined with nitrogen physisorption. X-ray diflfiaction and transmission electron microscopy). Information concerning the metallic nickel particles has been obtained with X-ray diffraction and transmission electron microscopy. Diflractograms of the catalysts after passivation are shown in Fig. 8. The observed features are exactly the same as for the oxidic systems (Fig. 4) only very broad and low diffractions are visible for the catalyst ex citrate, whereas sharp, intense peaks with a broad onset are observed for the catalyst ex nitrate. Consequently the nickel particles of the catalyst ex citrate have resisted sintering during the reduction treatment, thereby conserving the high dispersion of the catalyst. These results were confirmed by transmission electron microscopy measurements (not shown) only very small nickel nanoparticles situated inside the mesopores were found for the catalyst ex citrate. 

The adherence of small particles of precious metals to the surface of the support can be assessed by transmission electron microscopy. It has been observed that mild ultrasonic treatment of the catalyst in a liquid, such as ethanol, can remove precious metal particles from the surface of the support. After applying a drop of the suspension resulting from the ultrasonic treatment on the carbon films used as specimen support the precious metal particles released from the support show up on the carbon support film. Especially dark-field techniques are useful to indicate the presence of precious metal particles on the carbon support film. 

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