In Situ Study of Reduction of Mn x Co 3- x O 4 Mixed Oxides: The Role of Manganese Content.

A series of Mn-Co mixed oxides with a gradual variation of the Mn/Co molar ratio were prepared by coprecipitation of cobalt and manganese nitrates. The structure, chemistry, and reducibility of the oxides were studied by X-ray diffraction (XRD), X-ray absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR). It was found that at concentrations of Mn below 37 atom %, a solid solution with a cubic spinel structure is formed. At concentrations above 63 atom %, a solid solution is formed on the basis of a tetragonal spinel, while at concentrations in a range of 37-63 atom %, a two-phase system, which contains tetragonal and cubic oxides, is formed. To elucidate the reduction route of mixed oxides, two approaches were used. The first was based on a gradual change in the chemical composition of Mn-Co oxides, illustrating slow changes in the TPR profiles. The second approach consisted in a combination of in situ XRD and pseudo- in situ XPS techniques, which made it possible to directly determine the structure and chemistry of the oxides under reductive conditions. It was shown that the reduction of Mn-Co mixed oxides proceeds via two stages. During the first stage, (Mn, Co) ₃ O ₄ is reduced to (Mn, Co)O. During the second stage, the solid solution (Mn, Co)O is transformed into metallic cobalt and MnO. The introduction of manganese cations into the structure of cobalt oxide leads to a decrease in the rate of both reduction stages. However, the influence of additional cations on the second reduction stage is more noticeable. This is due to crystallographic peculiarities of the compounds: the conversion from the initial oxide (Mn, Co) ₃ O ₄ into the intermediate oxide (Mn, Co)O requires only a small displacement of cations, whereas the formation of metallic cobalt from (Mn, Co)O requires a rearrangement of the entire structure.