O.A. Bulavchenko

Low- and high-temperature oxidation of Mn1.5Al1.5O4 in relation to decomposition mechanism and microstructure

Spinel-like Mn1.5Al1.5O4 is an unstable compound whose decomposition is induced by partial oxidation of Mn2+ ions in the temperature range of 300–800 °C in air. According to XRD, two spinel-like phases, Mn0.4Al2.4O4 and Mn2.8Al0.2O4, are formed during both cooling and heating of Mn1.5Al1.5O4. In this paper, we have studied microstructural changes of Mn1.5Al1.5O4 to understand its decomposition mechanism. During heating, low-temperature oxidation takes place and decomposition proceeds via a nucleation and growth mechanism. As a result slightly Al-doped β-Mn3O4 nanoparticles are formed on the surface of the parent spinel particles. On the contrary, cooling leads to high-temperature oxidation that results preferably in spinodal decomposition and formation of alternating Mn- and Al-rich lamellas of nanosized thickness. The present study provides a fundamental reference for the nanostructure design of a Mn–Al–O system and probably some other ones subjected to oxidative decomposition.

Nonstoichiometric oxygen in Mn–Ga–O spinels: reduction features of the oxides and their catalytic activity

The subject of this study was the content of oxygen in mixed oxides with the spinel structure Mn1.7Ga1.3O4 that were synthesized by coprecipitation and thermal treatment in argon at 600–1200 °C. The study revealed the presence of excess oxygen in “low-temperature” oxides synthesized at 600–800 °C. The occurrence of superstoichiometric oxygen in the structure of Mn1.7Ga1.3O4+δ oxide indicates the formation of cationic vacancies, which shows up as a decreased lattice parameter in comparison with “high-temperature” oxides synthesized at 1000–1200 °C; the additional negative charge is compensated by an increased content of Mn3+ cations according to XPS. The low-temperature oxides containing excess oxygen show a higher catalytic activity in CO oxidation as compared to the high-temperature oxides, the reaction temperature was 275 °C. For oxides prepared at 600 and 800 °C, catalytic activity was 0.0278 and 0.0048 cm3 (CO) per g per s, and further increase in synthesis temperature leads to a drop in activity to zero. The process of oxygen loss by Mn1.7Ga1.3O4+δ was studied in detail by TPR, in situ XRD and XPS. It was found that the hydrogen reduction of Mn1.7Ga1.3O4+δ proceeds in two steps. In the first step, excess oxygen is removed, Mn1.7Ga1.3O4+δ → Mn1.7Ga1.3O4. In the second step, Mn3+ cations are reduced to Mn2+ in the spinel structure with a release of manganese oxide as a single crystal phase, Mn1.7Ga1.3O4 → Mn2Ga1O4 + MnO.

Structure and Chemistry of Cu–Fe–Al Nanocomposite Catalysts for CO Oxidation

High-active Fe–Al and Cu–Fe–Al nanocomposite catalysts were synthesized by fusion of aluminium, iron, and copper salts and then tested in the oxidation of CO. It was found that the activity of Fe–Al catalysts depends on the Fe concentration and the maximum is achieved when the Fe2O3 content is approximately 82xa0wt%. The addition of Cu leads to a significant increase in activity. Using adsorption techniques, X-ray diffraction, X-ray absorption spectroscopy, and Fourier-transform infrared spectroscopy, morphology, structure, and chemistry of the catalysts were studied. It was shown that the Fe–Al catalysts consist of Fe2O3 and Al2O3 phases mainly. Alumina is in an amorphous state whereas iron oxide forms nanoparticles with the protohematite structure. The Al3+ cations partially dissolute in the Fe2O3 lattice. X-ray absorption spectroscopy indicated that the Cu–Fe–Al catalysts in addition contain CuO and CuFe2O4 oxides in an amorphous state.Graphical Abstract