Impact of surface-active site heterogeneity and surface hydroxylation in Ni doped ceria catalysts on oxidative dehydrogenation of propane

Using periodic Density Functional Theory calculations, propane oxidative dehydrogenation (ODH) and overoxidation over bare and hydroxylated Ni-doped CeO₂ nanorods with predominantly exposed (1 1 0) facets were studied. Ab-initio thermodynamics-based surface phase analysis and computational Raman spectroscopic analysis predicted an 8.3 % surface oxygen vacancy concentration (Ce_0.83Ni_0.17O_1.83) at typical ODH conditions. Only one-third of the surface oxygens, adjacent to the dopant, were selective for propene formation. Moreover, activated oxygen (O₂^2–*) favored the formation of overoxidation products over propene. A monolayer hydroxyl coverage from water dissociation was stable at typical ODH conditions. This reduced the activation energy barrier for propene formation by 0.38 eV, increased the barrier for undesired acetone formation by 0.54 eV, and increased the barrier for propene activation by 0.6 eV. These promotional effects were due to the destabilization and induced hyperconjugation effects in the C₃ adsorbates due to surface hydroxylation. Hence, surface hydroxylation (Lewis Base addition) is a potential strategy to improve propene selectivity.