Heterogeneous catalyst particles microscopy

Analytical Electron Microscopy of Heterogeneous Catalyst Particles... 

High resolution electron microscopy has recently demonstrated the capability to directly resolve the atomic structure of surfaces on small particles and thin films. In this paper we briefly review experimental observations for gold (110) and (111) surfacest and analyse how these results when combined with theoretical and experimental morphological studies, influence the interpretation of geometrical catalytic effects and the transfer of bulk surface experimental data to heterogeneous catalysts. 

Application of transmission electron microscopy (TEM) techniques on heterogeneous catalysis covers a wide range of solid catalysts, including supported metal particles, transition metal oxides, zeolites and carbon nanotubes and nanofibers etc. 

Theoretical models based on first principles, such as Langmuir s adsorption model, help us understand what is happening at the catalyst surface. However, there is (still) no substitute for empirical evidence, and most of the papers published on heterogeneous catalysis include a characterization of surfaces and surface-bound species. Chemists are faced with a plethora of characterization methods, from micrometer-scale particle size measurement, all the way to angstrom-scale atomic force microscopy [77]. Some methods require UHV conditions and room temperature, while others work at 200 bar and 750 °C. Some methods use real industrial catalysts, while others require very clean single-crystal model catalysts. In this book, I will focus on four main areas classic surface characterization methods, temperature-programmed techniques, spectroscopy and microscopy, and analysis of macroscopic properties. For more details on the specific methods see the references in each section, as well as the books by Niemantsverdriet [78] and Thomas [79]. 

One of the major uses of transmission electron microscopy in the area of catalysts is the measurement of particle size distributions for supported metals. Chemical techniques can only effectively be used to obtain a global value for the dispersion. By observing the particles directly in transmission electron microscopy, it is possible to check the heterogeneity, and detect the existence of bimodal size distributions. Figure 9.8 shows an example of metallic particles distributed in a zeolite. 

The use of transmission electron microscopy in heterogeneous catalysis centers around particle size distribution measurement, particle morphology and structural changes in the support. Consideration is given to the limitations of conventional electron microscopy and how modifications to the instrument enable one to conduct in-situ experiments and be in a position to directly observe many of the features of a catalyst as it participates in a reaction. In order to demonstrate the power of the in-situ electron microscopy technique examples are drawn from areas which impact on aspects of catalyst deactivation. In most cases this information could not have been readily obtained by any other means. Included in this paper is a synopsis of the methods available for preparing specimens of model and real catalyst systems which are suitable for examination by transmission electron microscopy. 

Analytical electron microscopy (AEM) permits the determination of the elemental composition of a solid catalyst at the microscopic level by energy-dispersive detection of the electron-induced X-ray emission (EDX). Energy dispersive spectroscopy (EDS) is sensitive for elements with atomic numbers Z > 11. For lighter elements (Z < 11), electron energy loss spectroscopy (EELS) is applied. An example is shown in Figure 7 (bottom), which exhibits the elemental composition by EDX of two individual Pt/Rh particles on a carbon film. This analysis clearly demonstrates the heterogeneous composition of the alloy particles. 

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