Selective oxidative dehydrogenation (ODH) of, in particular, alcohols to aldehydes, is the process with paramount importance in chemical industries. Recently, vanadium oxide species supported at ceria have been shown to give some amazing features in such reactions. In the current work, we performed total energy density functional theory (DFT) calculations corrected by on-site Coulomb interaction (DFT+U) and London dispersion of the Grimme DFT-D type1 to study the reactivity of VOx/CeO2(111) for ODH of benzyl alcohol (BA) to benzaldehyde (BAD) by using the VASP package2,3. Elaborate calculations on various reaction pathways suggested that the oxidation of BA to BAD at monomeric VOx/CeO2(111) has remarkable catalytic activities, such as the low H-cleavage barriers. However, comparing with clean CeO2(111), dimeric and trimeric VOx/CeO2(111) do not possess any improved activities. Detailed studies told us that these high activities of CeO2 supported monomeric VOx originate from both structural and electronic effects. The three-dimensional monomeric VOx clusters sitting at surface can help to facilitate the H-cleavage. Especially, unique electronic 'hole' of monomeric VOx acts as some kind of magnet to seize the hydrogen from BA. These results may help us obtain a better view of ODH reactions, and facilitate design of more effective catalysts for similar reaction systems as well.References(1) Grimme, S. J. Comput. Chem. 2006  , 27, 1787-1799.(2) Kresse, G.; Furthm�ller, J. Comput. Mater. Sci. 1996  , 6, 15-50.(3) Kresse, G.; Hafner, J. Phys. Rev. B 1994  , 49, 14251-14269.

Electronic "hole" induced ultrahigh activity of CeO<sub>2</sub> supported monomeric VO<sub>x</sub> for selective oxidative dehydrogenation of benzyl alcohol

248th National Meeting (2014)

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Electronic "hole" induced ultrahigh activity of CeO2 supported monomeric VOx for selective oxidative dehydrogenation of benzyl alcohol

Electronic "hole" induced ultrahigh activity of CeO₂ supported monomeric VO_x for selective oxidative dehydrogenation of benzyl alcohol