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 Mn 1.7 Ga 1.3 O 4 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 Mn 1.7 Ga 1.3 O 4+ 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 Mn 3+ 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 cm 3 (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 Mn 1.7 Ga 1.3 O 4+ δ was studied in detail by TPR, in situ XRD and XPS. It was found that the hydrogen reduction of Mn 1.7 Ga 1.3 O 4+ δ proceeds in two steps. In the first step, excess oxygen is removed, Mn 1.7 Ga 1.3 O 4+ δ → Mn 1.7 Ga 1.3 O 4 . In the second step, Mn 3+ cations are reduced to Mn 2+ in the spinel structure with a release of manganese oxide as a single crystal phase, Mn 1.7 Ga 1.3 O 4 → Mn 2 Ga 1 O 4 + MnO.