Metal oxide bulk doping catalysts

However, the correlation of the electrical properties of the bulk phase with the catalytic properties of the essentially heterogeneous catalyst surface is a classical difficulty. This may be one of the reasons why no general correlation between these properties is found when a variety of different metal oxide catalysts is compared. A close relationship is often shown, on the other hand, when a particular catalyst is modified or doped with minor amounts of an additional metal oxide. It is very likely that the correlation is successful in this case, because the nature of surface sites is not essentially changed. 

Pd-doped catalysts have been produced by USS [82]. The fingerprint of Pd adopting the octahedral coordination of Fe in LaFeo,95Pdo,o503 has been observed in the XANES spectra of the material prepared by spray synthesis (27m /g) similarly to the preparation by the amorphous citrate method (14m /g) [17,82]. In contrast, the flame-made material of the same composition (22m /g) exposed metallic Pd particles on LaFeOs similarly to preparation by solution combustion. The different nature of the Pd species obtained by changing the synthesis method dramatically influences their catalytic performance, since PdO nanoparticles exposed at the surface of the mixed oxide exhibit catalytic activity, whereas Pd—O species in the bulk of the mixed oxide are inactive, at least in the case of methane oxidation [27]. In contrast to LaFeOs, LaMnOs did not allow Pd to adopt the octahedral coordination irrespective of synthesis method. Therefore, the coordination of Pd strongly depends on both the composition of the perovskite-type oxide and the synthesis method. 

Metal oxides, either bulk, doped, supported or mixed, are widely used as catalysts in chemical industry. Catalytic behavior of these materials, in terms of activity and selectivity, is related to their acid/base properties. 

By doping a primary catalyst component with lower-valent metal cations, additional oxygen vacancies will be created which facilitate the incorporation of electrophilic oxygen species chemisorbed on the surface into the bulk where they will not oxidize adsorbed methyl radicals. Also, the promoter oxide should be basic, not be reducible, oxidizablc, or easily volatiz-ablc. It should form a mixed oxide with the main component which may be possible if the ionic radii arc similar. According to these rules, the expert system proposes as potential catalyst components combinations of substances with appropriate chemical and physico-chemical properties (Table 2). Many of these systems already have been described in the literature... 

The first part of this article specifically deals with representative laboratoiy applications to fine chemistry of clearly identified, unaltered KIO, excluding its modified forms (cation-exchanged, doped by salt deposition, pillared, etc.) and industrial uses in bulk. This illustrative medley shows the prowess of KIO as a strong Brpnsted acidic catalyst. The second part deals with cation-exchanged (mainly Fe ") montmorillonite. Clayfen and claycop, versatile stoichiometric reagents obtained by metal nitrate deposition on KIO, are used in oxidation and nitration reactions. They are treated under Iron(III) Nitrate-KlO Montrrufrillonite Clay and Copperfll) Nitrate-KlO Bentonite Clay. 

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