Abstracto‐Xylene combustion in air over a Pt/γ‐Al2O3 catalyst was investigated in a laboratory reactor at low concentrations typical for depollution applications. The results evidenced a slightly negative influence of o‐xylene concentration on combustion rate. A kinetic model of the combustion process was developed by using the Langmuir‐Hinshelwood mechanism, assuming the surface reaction between adsorbed oxygen atoms and adsorbed o‐xylene molecules as controlling step. The rate expression includes the influences of o‐xylene and water adsorption on the active centers of the catalyst. The estimation of rate expression parameters is based on o‐xylene conversion measurements obtained under conditions free of influences of physical steps.
The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and hafnium(IV) phthalocyaninate-capped derivatives. Electronic structures of their 1e-oxidized and 1e-electron-reduced forms were experimentally studied by electron paramagnetic resonance (EPR) spectroscopy and UV−vis−near-IR spectroelectrochemical experiments and supported by density functional theory (DFT) calculations. The investigated hybrid molecular systems that combine a transition metal (pseudo)clathrochelate and a Zr/Hf-phthalocyaninate moiety exhibit quite rich redox activity both in the cathodic and in the anodic region. These binuclear compounds and their precursors were tested as potential catalysts in oxidation reactions of cyclohexane and the results are discussed.
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