Impact of Nanoparticle–Support Interactions in Co(3)O(4)/Al(2)O(3) Catalysts for the Preferential Oxidation of Carbon Monoxide

[Image: see text] 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.