CO oxidation by oxygen of the catalyst and by gas-phase oxygen over (0.5–15)%CoO/ZrO2

详细

CO adsorption on (0.5–15)%CoO/ZrО₂ catalysts has been investigated by temperature-programmed desorption and IR spectroscopy. At 20°С, carbon monoxide forms carbonyl and monodentate carbonate complexes on Co_m²⁺O_n^2- clusters located on the surface of crystallites of tetragonal ZrO₂. With an increasing CoO content of the clusters, the amount of these complexes increases and the temperature of carbonate decomposition, accompanied by CO₂ desorption, decreases from 400 to 304°С. On the 5%CoO/ZrО₂ sample, the carbonyls formed on the Со²⁺ and Со⁺ cations and Со⁰ atoms decompose at 20, 90, and 200–220°С, respectively, releasing CO. At 20°С, they are oxidized by oxygen to monodentate carbonates, which decompose at 180°С. Adsorbed oxygen decreases the temperature of their decomposition on oxidation sites by ~40°C, and the sample remains in an oxidized state ensuring the possibility of subsequent CO adsorption and oxidation. The rate of the oxidation of 5%CoO/ZrО₂ containing adsorbed CO by oxygen is higher than the rate of the oxidation of the same sample reduced by carbon monoxide, because the latter reaction is an activated one. In view of the properties of the complexes, it can be concluded that the carbonates decomposing at 180°С are involved in CO oxidation by oxygen from the gas phase in the presence of hydrogen, a process occurring at 50–200°С. The rate-limiting step of this process the decomposition of the carbonates, which is characterized by an activation energy of 77–94 kJ/mol.