Impact of Nanoparticle–Support Interactions in Co3O4/Al2O3 Catalysts for the Preferential Oxidation of Carbon Monoxide

Different supporting procedures were followed to alter the nanoparticle-support interactions (NPSI) in two Co 3 O 4 /Al 2 O 3 catalysts, prepared using the reverse micelle technique. The catalysts were tested in the dry preferential oxidation of carbon monoxide (CO-PrOx) while their phase stability was monitored using four complementary in situ techniques, viz., magnet-based characterization, PXRD, and combined XAS/DRIFTS, as well as quasi in situ XPS, respectively. The catalyst with weak NPSI achieved higher CO 2 yields and selectivities at temperatures below 225 °C compared to the sample with strong NPSI. However, relatively high degrees of reduction of Co 3 O 4 to metallic Co were reached between 250 and 350 °C for the same catalyst. The presence of metallic Co led to the undesired formation of CH 4 , reaching a yield of over 90% above 300 °C. The catalyst with strong NPSI formed very low amounts of metallic Co (less than 1%) and CH 4 (yield of up to 20%) even at 350 °C. When the temperature was decreased from 350 to 50 °C under the reaction gas, both catalysts were slightly reoxidized and gradually regained their CO oxidation activity, while the formation of CH 4 diminished. The present study shows a strong relationship between catalyst performance (i.e., activity and selectivity) and phase stability, both of which are affected by the strength of the NPSI. When using a metal oxide as the active CO-PrOx catalyst, it is important for it to have significant reduction resistance to avoid the formation of undesired products, e.g., CH 4 . However, the metal oxide should also be reducible (especially on the surface) to allow for a complete conversion of CO to CO 2 via the Mars-van Krevelen mechanism.