TY - JOUR
T1 - Variation in surface ionization potentials of pristine and hydrated BiVO4
AU - Crespo-Otero, Rachel
AU - Walsh, Aron
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/6/18
Y1 - 2015/6/18
N2 - Bismuth vanadate (BiVO4) is a promising material for photoelectrochemical water splitting and photocatalytic degradation of organic moieties. We evaluate the ionization potentials of the (010) surface termination of BiVO4 using first-principles simulations. The electron removal energy of the pristine termination (7.2 eV) validates recent experimental reports. The effect of water absorption on the ionization potentials is considered using static models as well as structures obtained from molecular dynamics simulations. Owing to the large molecular dipole of H2O, adsorption stabilizes the valence band edge (downward band bending), thereby increasing the ionization potentials. These results provide new understanding to the role of polar layers on complex oxide semiconductors, with importance for the design of efficient photoelectrodes for water splitting.
AB - Bismuth vanadate (BiVO4) is a promising material for photoelectrochemical water splitting and photocatalytic degradation of organic moieties. We evaluate the ionization potentials of the (010) surface termination of BiVO4 using first-principles simulations. The electron removal energy of the pristine termination (7.2 eV) validates recent experimental reports. The effect of water absorption on the ionization potentials is considered using static models as well as structures obtained from molecular dynamics simulations. Owing to the large molecular dipole of H2O, adsorption stabilizes the valence band edge (downward band bending), thereby increasing the ionization potentials. These results provide new understanding to the role of polar layers on complex oxide semiconductors, with importance for the design of efficient photoelectrodes for water splitting.
KW - density functional theory
KW - metal oxides
KW - solid-liquid interface
KW - theoretical electrochemistry
UR - http://www.scopus.com/inward/record.url?scp=84934895081&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.5b00966
DO - 10.1021/acs.jpclett.5b00966
M3 - Article
AN - SCOPUS:84934895081
SN - 1948-7185
VL - 6
SP - 2379
EP - 2383
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 12
ER -