Jithin John Varghese

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 (Ce0.83Ni0.17O1.83) at typical ODH conditions. Only one-third of the surface oxygens, adjacent to the dopant, were selective for propene formation. Moreover, activated oxygen (O22–*) 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.

Propane oxidative dehydrogenation (ODH) was studied over VOx/CeO2 nanoparticle catalysts for various vanadia nuclearities using Density Functional Theory simulations. On monomers and dimers, propene formation involved V=O, bridged (V–O–Ce, V–OV) and ceria surface oxygens but with low selectivity, while on trimers and possibly higher oligomers it was kinetically favourable over ceria surface oxygens, with higher selectivity than on monomers and dimers. On trimer, overoxidation via acetone formation was inhibited, but at the expense of overall catalyst reactivity. Doping of ceria support with Ni induced strong Ni–VOx interactions, stabilizing the vanadia monomer. The V–O–Ni bridged oxygen was less accessible for overoxidation, resulting in an increase in activation energy barrier for acetone formation by 0.69 eV on VO2/Ce0.89Ni0.11O2(1 1 1), while there was a minimal impact on V3O6/Ce0.89Ni0.11O2 (1 1 1). Hence, transition metal doping of ceria support is a potential strategy to improve propene selectivity over VOx/CeO2 catalysts for a wide range of V loadings.