Improving the Catalytic Performance of Cobalt for CO Preferential Oxidation by Stabilizing the Active Phase through Vanadium Promotion

Preferential oxidation of CO (COPrOx) is a catalytic reaction targeting the removal of trace amounts of CO from hydrogen-rich gas mixtures. Non-noble metal catalysts, such as Cu and Co, can be equally active to Pt for the reaction; however, their commercialization is limited by their poor stability. We have recently shown that CoO is the most active state of cobalt for COPrOx, but under certain reaction conditions, it is readily oxidized to Co₃O₄ and deactivates. Here, we report a simple method to stabilize the Co²⁺ state by vanadium addition. The V-promoted cobalt catalyst exhibits considerably higher activity and stability than pure cobalt. The nature of the catalytic active sites during COPrOx was established by operando NAP-XPS and NEXAFS, while the stability of the Co²⁺ state on the surface was verified by in situ NEXAFS at 1 bar pressure. The active phase consists of an ultra-thin cobalt-vanadate surface layer, containing tetrahedral V⁵⁺ and octahedral Co²⁺ cations, with an electronic and geometric structure that is deviating from the standard mixed bulk oxides. In addition, V addition helps to maintain the population of Co²⁺ species involved in the reaction, inhibiting carbonate species formation that are responsible for the deactivation. The promoting effect of V is discussed in terms of enhancement of CoO redox stability on the surface induced by electronic and structural modifications. These results demonstrate that V-promoted cobalt is a promising COPrOx catalyst and validate the application of in situ spectroscopy to provide the concept for designing better performing catalysts.