1 research outputs found
Low-Temperature CO Oxidation over Combustion Made Fe- and Cr-Doped Co<sub>3</sub>O<sub>4</sub> Catalysts: Role of Dopant’s Nature toward Achieving Superior Catalytic Activity and Stability
Co<sub>3</sub>O<sub>4</sub> with a spinel structure shows unique
activity for CO oxidation at low temperature under dry conditions;
however the active surface is not very stable. In this study, two
series of Fe- and Cr-doped Co<sub>3</sub>O<sub>4</sub> catalysts were
prepared by a single-step solution combustion technique. Fe was chosen
because of its redox activity corresponding to the Fe<sup>2+</sup>/Fe<sup>3+</sup> redox couple and compared to Cr, which is mainly
stable in the Cr<sup>3+</sup> state. The catalytic activity of new
materials for low-temperature CO oxidation was correlated to the nature
of the dopant. As a function of dopant concentration, the temperature
corresponding to the 50% CO conversion (<i>T</i><sub>50</sub>) demonstrated significant differences. The maximal activity was
achieved for 15% Fe-doped Co<sub>3</sub>O<sub>4</sub> with <i>T</i><sub>50</sub> of −85 °C and remained almost
constant up to 25% Fe. In the case of Cr, the activity was observed
to be maximum for 7% of Cr with <i>T</i><sub>50</sub> of
−42 °C and significantly decreased for higher Cr loadings.
Similarly, there was a contrasting behavior in catalyst stability
too. 100% CO conversion was achieved below −60 °C for
15% Fe/Co<sub>3</sub>O<sub>4</sub> catalyst and remained unchanged
even after calcination at 600 °C. In contrast, Co<sub>3</sub>O<sub>4</sub> or 15% Cr/Co<sub>3</sub>O<sub>4</sub> catalysts strongly
deactivated after the same treatment. These differences were correlated
to the oxidation states, coordination numbers, the nature of surface
planes, and the redox properties. We observed that both Cr and Fe
were typically present in the +3 oxidation state, occupying octahedral
sites in the spinel structure. The catalysts were mainly exposed to
(111) and (220) planes on the surface. H<sub>2</sub>-TPR indicated
clear differences in the redox activity of materials due to Fe and
Cr substitutions. The reducibility of surface Co<sup>3+</sup> species
remained similar in all Fe-doped Co<sub>3</sub>O<sub>4</sub> catalysts
in contrast to nonreducible Cr-doped analogs, which shifted the reduction
temperature to the higher values. As the Fe<sup>3+</sup>/Fe<sup>2+</sup> redox couple partly substituted the Co<sup>3+</sup>/Co<sup>2+</sup> redox couple in the spinel structure, similar bond strength of Fe–O
keep redox activity of Co<sup>3+</sup> species almost unchanged leading
to higher activity and stability of Fe/Co<sub>3</sub>O<sub>4</sub> catalysts for low-temperature CO oxidation. In contrast, nonreducible
Cr<sup>3+</sup> species characterized by strong Cr–O bond substituting
active Co<sup>3+</sup> sites can make the Cr/Co<sub>3</sub>O<sub>4</sub> surface less active for CO oxidation