Catalytic activity, water formation, and sintering: Methane activation over Co- and Fe-doped MgO nanocrystals

Microstructure, structure, and compositional homogeneity of metal oxide nanoparticles can change dramatically during catalysis. Considering the different stabilities of cobalt and iron ions in the MgO host lattice [M. Niedermaier et al., J. Phys. Chem. C 123, 25991 (2019)], we employed MgO nanocube powders with or without transition metal admixtures for the oxidative coupling of methane (OCM) reaction to analyze characteristic differences in catalytic activity and sintering behavior. Undoped MgO nanocrystals exhibit the highest C₂ selectivity and retain the nanocrystallinity of the starting material after 24 h time on stream. For the Co-Mg-O nanoparticle powder, which exhibits the highest activity and CO_x selectivity and where OCM-induced coarsening is strongest, we found that the Co²⁺ ions remain homogeneously distributed over the MgO lattice. Trivalent Fe ions migrate to the surface of Fe-Mg-O nanoparticles where they form a magnesioferrite phase (MgFe₂O₄) with a characteristic impact on catalytic performance: Fe-Mg-O is initially less selective than MgO despite its lower activity. An increase in C₂ selectivity and a decrease in the CO₂/CO ratio with time on stream are attributed to the increasing fraction of coarsened particles that become depleted in redox active Fe. Surface water is a by-product of the OCM reaction, favors mass transport across the particle surfaces, and serves as a sintering aid during catalysis. The characteristic changes in size and morphology of MgO, Co-doped, and Fe-doped MgO particles can be consistently explained by activity and C₂ selectivity trends. The original morphology of the nanocubes as a starting material for the OCM reaction does not impact the catalytic activity.