10.1021/jz501635f.s001
Nathan
Z. Koocher
Nathan
Z.
Koocher
John Mark P. Martirez
John
Mark P. Martirez
Andrew M. Rappe
Andrew M.
Rappe
Theoretical
Model of Oxidative Adsorption of Water
on a Highly Reduced Reconstructed Oxide Surface
American Chemical Society
2015
Reduced Reconstructed Oxide SurfaceHighly
H 2 evolution
surface conduction band edge
TiO 2 surface
surface Ti species
H 2O oxidizes
Ti adatoms
2015-12-17 04:53:35
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Theoretical_Model_of_Oxidative_Adsorption_of_Water_on_a_Highly_Reduced_Reconstructed_Oxide_Surface/2041053
Highly reduced surface reconstructions
of BaTiO<sub>3</sub> (001)
have been found to be composed of a TiO<sub>2</sub> surface covered
with Ti adatoms occupying surface interstitial sites. We predict the
reactivity of these highly oxophilic and reduced surface Ti species
through density functional theory, where we calculate the adsorption
of H<sub>2</sub>O on the (√5 × √5)<i>R</i>26.6° TiO<sub>2</sub>–Ti<sub>3/5</sub> reconstruction.
H<sub>2</sub>O serves as the primary O source and oxidizing agent.
We demonstrate that H<sub>2</sub>O oxidizes some of the Ti adatoms,
shifting their occupied 3d states to the surface conduction band edge.
We find that, due to the high concentration of reduced Ti species
on the surface, a dissociative adsorption of water on the reconstructed
surface can also lead to the formation of surface hydrides, which
serve as a precursor for H<sub>2</sub> evolution. This suggests that
the reconstructed surface may be an attractive single-phase hydrogen
evolution catalyst.