Correlation between the Properties of Surface Lattice Oxygen on NiO and Its Reactivity and Selectivity towards the Oxidative Dehydrogenation of Propane.

Modified NiO catalysts with controllable vacancies and dopants are promising for alkene production from oxidative dehydrogenation (ODH) of light alkanes, and a molecular understanding of the modification on elementary reaction steps would facilitate the design of highly efficient catalysts and catalytic processes. In this study, density functional theory (DFT) calculations was used to map out the complete reaction pathways of propane ODH on the NiO (100) surfaces with different modifiers. The results demonstrated that the presence of vacancies (O and Ni) and dopants (Li and Al) alters the electrophilicity of surface oxygen species, which in turn affects the reactivity towards C-H bond activation and the overall catalytic activity and selectivity. The strongly electrophilic O favors a radical mechanism for the first C-H activation on O followed by the second C-H activation on O-O site, whereas weak electrophilic O favors concerted C-H bond breaking over Ni-O site. The C-H bond activation proceeds through a late transition state, characterized by the almost completion of the O-H bond formation. Consequently, the adsorption energy of H adatom on O rather than p-band center or Bader charge of O has been identified to be an accurate descriptor to predict the activation barrier for C-H breaking (activity) as well as the difference between the activation barriers of propene and CH 3 CCH 3 (selectivity) of ODH.