Conclusions
The results presented in the previous sections demonstrate the importance of point defects at the surface of oxide materials in determining the chemical activity of deposited metal atoms or clusters. A single Pd atom in fact is not a good catalyst of the cyclization reaction of acetylene to benzene except when it is deposited on a defect site of the MgO(100) surface. A detailed analysis of the reaction mechanism, based on the calculation of the activation barriers for the various steps of the reaction, and of a study of the preferred site for Pd binding, based on the MgO/Pd/CO adsorption properties, has shown that the defects which are most likely involved in the chemical activation of Pd are the oxygen vacancies, or F centers, located at the terraces of the MgO surface and populated by two (neutral F centers) or one (charged paramagnetic F+ centers) electrons.
This combined theoretical-experimental approach shows the potentiality of generating defective surfaces to modify the chemical activity of supported nano-aggregates for catalytic applications. It also shows the importance to obtain an atomistic control on the species deposited on the surface for the proper characterization of their activity. Through a specifically designed experimental apparatus which makes it possible to deposit size-selected metal clusters it has become possible to study the properties of a supported cluster as a function of its size. This opens new, unprecedented perspectives for the understanding of size-dependent activity and selectivity of a supported metal catalyst. To reach this ambitious goal theory plays a role which cannot be overlooked.
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Pacchioni, G., Giordano, L., Ferrari, A.M., Abbet, S., Heiz, U. (2001). Role of Point Defects in the Catalytic Activation of Pd Atoms Supported on the MgO Surface. In: Lipscomb, W.N., et al. Theoretical Aspects of Heterogeneous Catalysis. Progress in Theoretical Chemistry and Physics, vol 8. Springer, Dordrecht. https://doi.org/10.1007/0-306-47667-3_7
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