Stability of adsorbed water on TiO2-TiN interfaces. A first-principles and ab initio thermodynamics investigation

Thumbnail Image
5923.pdf(1.34 MB)
Accepted Version
jp8b03520_si_001.pdf(7.02 MB)
Supporting Information
Gutiérrez Moreno, José Julio
Fronzi, Marco
Lovera, Pierre
O'Riordan, Alan
Nolan, Michael
Journal Title
Journal ISSN
Volume Title
ACS Publications
Research Projects
Organizational Units
Journal Issue
Titanium nitride (TiN) surfaces can oxidize, and the growth of a TiOx layer on the surface along with the likely presence of water in the surrounding environment can modify the properties of this widely used coating material. The present density functional theory study, including Hubbard + U correction (DFT+U), investigates the stability of adsorbed water at TiO2-TiN interfaces with different defects that serve as a model for an oxide layer grown on a TiN surface. Surface free energy calculations show the stability of a perfect TiN-TiO2 interface at regular O pressures, while oxygen vacancy-rich TiO1.88-TiN is more favorable at reducing conditions. An isolated water is preferentially adsorbed dissociatively at perfect and oxygen -defective interfaces, while molecular adsorption is more stable at higher coverages. The adsorption energy is stronger at the oxygen-defective interfaces which arise from the high concentration of reduced Ti3+ and strong interfacial atomic relaxations. Ab initio atomistic thermodynamics show that water will be present at high coverage on TiO2-TiN interfaces at ambient conditions, and the pristine interface is only stable at very low pressure of O and H2O. The results of these DFT+U simulations are important for the fundamental understanding of wettability of interfacial systems involving metal oxides.
Sputtered titanium nitride , Augmented-wave method , Clay brick facade , Oxygen vacancies , Biomedical applications , Oxidation mechanism , TiN thin films , Density functional theory , Van der Waals , CeO2
Gutiérrez Moreno, J. J., Fronzi, M., Lovera, P., O'Riordan, A. and Nolan, M. (2018) 'Stability of adsorbed water on TiO2-TiN interfaces. A first-principles and ab initio thermodynamics investigation', Journal of Physical Chemistry C, 122(27), pp. 15395-15408. doi: 10.1021/acs.jpcc.8b03520
Link to publisher’s version
© 2018, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry C, after technical editing by the publisher. To access the final edited and published work see: