Effect of crystallite size on the performance and phase transformation of Co3O4/Al2O3 catalysts during CO-PrOx – an in situ study

The preferential oxidation of carbon monoxide has been identified as an effective route to remove trace amounts of CO (approx. 0.5–1.0 vol%) in the H2-rich reformate gas stream after the low-temperature water–gas shift. Instead of noble metal-based catalysts, Co3O4-based catalysts were investigated in this study as cheaper and more readily available alternatives. This study aimed at investigating the effect of crystallite size on the mass- and surface area-specific CO oxidation activity as well as on the reduction behaviour of Co3O4. Model Co3O4 catalysts with average crystallite sizes between 3 and 15 nm were synthesised using the reverse micelle technique. Results from the catalytic tests revealed that decreasing the size of the Co3O4 crystallites increased the mass-specific CO oxidation activity in the 50–200 °C temperature range. On the other hand, the surface area-specific CO oxidation activity displayed a volcano-type behaviour where crystallites with an average size of 8.5 nm were the most active within the same temperature range. In situ characterisation in the magnetometer revealed that the Co3O4 crystallites are partially reduced to metallic Co above 225 °C with crystallites larger than 7.5 nm showing higher degrees of reduction under the H2-rich environment of CO-PrOx. In situ PXRD experiments further showed the presence of CoO concurrently with metallic fcc Co in all the catalysts during the CO-PrOx runs. In all experiments, the formation of fcc Co coincided with the formation of CH4. Upon decreasing the reaction temperature below 250 °C under the reaction gas, both in situ techniques revealed that the fcc Co previously formed is partially re-oxidised to CoO.