Investigation of the Reduction/Oxidation Behavior of Cobalt Supported on Nano-ceria

The oxidation and reduction behavior of cobalt catalysts supported on nano-ceria (5–8 nm) was investigated under hydrogen, oxygen and water atmospheres. A novel quantitative isothermal reduction (QIR) technique was introduced to analyze the kinetics and activation barrier of Co reduction. CoO to Co reduction was found to be of first order in the 250–350 °C temperature range. Temperature programmed reduction and oxidation experiments were conducted and the Kissinger method was used to obtain apparent activation energies for reduction and oxidation with O₂. The apparent activation energy for CoO reduction was found to agree with that obtained from the QIR technique. Re-oxidation of Co metal was found to have a slightly lower activation energy barrier than the reduction. The reduction and oxidation behavior was further investigated with in situ XANES where the reaction order for reduction was observed to change at 450 °C. The pre-reduced samples were seen to re-oxidize under a water atmosphere, where the oxidation followed first order kinetics. Re-oxidation by water yielded a higher activation energy when compared to re-oxidation under oxygen.