Surprising formation of a rhodochrosite-like (MnCO3) phase on Co-Zn-Mn sintered spinels upon storage at room temperature and ambient air

A detailed XPS investigation, supported by XRD analysis, was performed on Co-Zn-Mn oxide-based spinels as a function of cobalt concentration and calcination temperature (723 and 973 K). Results revealed for the first time that a recarbonation occurred under ambient conditions but only for the Co-containing materials calcined at 973 K. Indeed, such effect was not observed for the homologous preparations at 723 K. This evidence was quite surprising because the solids calcined at 973 K, for which a sintering occurred as reflected by the low surface areas, were supposed to be almost inert under ambient conditions. Such an intriguing recarbonation chemistry, leading even to a bulky rhodochrosite-like (MnCO3) phase in the cobalt most enriched samples, arises from the combined effect of the calcination treatment at high temperature and the presence of cobalt ions. The spinels calcined at higher temperature are characterized by a high surface defectivity, due to anionic vacancies produced by a partial self-reduction of a fraction ofMn3+ions that occurs only at 973 K but not at 723 K. Consequently, the presence of anionic vacancies and the incomplete coordination of the outermost layers promoted a higher reactivity of the solids calcined at 973 K with CO2and moisture from ambient air. However, a carbonate phase was absent in the sample at 973 K with no cobalt. This suggests that the presence of cobalt is another crucial factor for the recarbonation process to take place. Cobalt ions appear to play a catalytic role. An attempt is made to provide a reasonable explanation of this intriguing recarbonation chemistry, trying to shed some more light on the rather complex chemistry behind the attack of moisture and CO2 to oxide solid surfaces. These results, as a whole, may provide new insight on phenomena observed in the case of some Mn-based catalysts, as the severe deactivation by traces of moisture occurring in hopcalite during CO oxidation at RT. They may also give an additional perspective to environmental processes that involves the interaction of moisture and CO2with the surface of Mn-based solids or other materials as environmental interfaces.