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 of Mn3+ ions which occurs only at 973 K but not at 723 K [1]. 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 CO2 and 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. These results may provide some new insight about the severe deactivation of Mn-based catalysts by traces of moisture occurring during CO oxidation at RT. Furthermore, they may give an additional perspective to environmental processes that involves the interaction of moisture and CO2 with the surface of Mn-based solids and other materials as environmental interfaces. [1] G. Fierro, M. Lo Jacono, M. Inversi, R. Dragone, G. Ferraris, Appl. Cat. B, 30, 173 (2001).
A surprising formation of a rhodochrosite-like (MnCO3) phase on Co-Zn-Mn sintered spinels upon storage at room temperature and ambient air
CASALETTO Maria Pia;FIERRO Giuseppe
2016
Abstract
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 of Mn3+ ions which occurs only at 973 K but not at 723 K [1]. 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 CO2 and 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. These results may provide some new insight about the severe deactivation of Mn-based catalysts by traces of moisture occurring during CO oxidation at RT. Furthermore, they may give an additional perspective to environmental processes that involves the interaction of moisture and CO2 with the surface of Mn-based solids and other materials as environmental interfaces. [1] G. Fierro, M. Lo Jacono, M. Inversi, R. Dragone, G. Ferraris, Appl. Cat. B, 30, 173 (2001).I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
