The catalytic activity of dioxo-molybdenum(VI)-dichloro[4,4 0 -dicarboxylato-2,2 0 -bipyridine] covalently anchored through the carboxylate function to the surface of TiO 2 has been tested for the oxidative degradation of 1-chloro-4-ethylbenzene in MeCN solution under argon and UV irradiation (k = 254 nm). After 4-5 h of photochemical reaction, the Mo complex was reoxidized in the presence of O 2 in the dark, and then the reaction was continued under argon. The reaction proceeds by the intermediate formation of 4 0 -chloroacetophenone that undergoes further decomposition to chlorobenzene, plus small amounts of oxygen-containing organochlorine compounds, CO 2 and H 2 O. Similar results were obtained for the decomposition of 4 0 -chloroacetophenone under the same conditions, which also gave chlorobenzene as one of the main products. The ratio of [final product]/ [Mo complex] increases during the decomposition of 1-chloro-4-ethylbenzene (up to 350-400% for 30-35 h of reaction), which provides evidence of a catalytic process. The probable photochemical reactions are discussed.
The reaction probability of CH 3 O 2 radicals with NO 2 , CH 4 , C 3 H 6 , and CH 3 CHO on the solid surface of KCl in flow at low pressure and temperature range of 297-353 K has been studied. The chosen conditions allowed excluding homogeneous interaction of radicals. The heterogeneous radical decay of peracetic acid served as a source of CH 3 O 2 radicals.On the basis of ESR measurements of CH 3 O 2 radicals with the above-mentioned compounds, a heterogeneous reaction mechanism has been identified.The reactivity of NO 2 was greatest for the compounds studied. The effective activation energy was evaluated to be 10.4 ± 0.8 kJ/mol for the reaction of RO 2 radicals with NO 2 and −21.3 ± 2.8 kJ/mol for methane. C
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