Elucidation of Unexpectedly Weak Catalytic Effect of Doping with Cobalt of the Cryptomelane and Birnessite Systems Active in Soot Combustion

In this work the influence of cobalt doping on both properties and catalytic activity of cryptomelane and birnessite in soot combustion was investigated in detail. The investigated samples have been synthesized by a microwave-assisted hydrothermal method and cobalt was introduced in two ways-by impregnation or by addition to the precursor mixture before hydrothermal treatment. The obtained catalysts have been characterized by XRF, BET, XRD, RS, XPS and ATR-IR. Surprisingly, no distinct effect of cobalt presence on catalytic activity has been found. Most probably cobalt was localized in the position of manganese within the cryptomelane/birnessite structure or within segregated manganese-cobalt complex oxides, where its oxidation level was fixed. A series of reference manganese-cobalt mixed oxides (100-0% Mn) have been synthesized to elucidate this effect. These samples have been structurally characterized and thermal evolution of their structures was profoundly investigated. A high tendency of cobalt incorporation into the manganese oxide matrix and its subsequent stabilization in the spinel forms was proposed as an explanation of the observed lack of a promotional effect of this additive in soot combustion.