Applied Surface Science, Vol.422, 990-996, 2017
The role of high oxygen vacancy concentration on modification of surface properties and H2S adsorption on the rutile TiO2 (110)
In this work, spin-polarized DFT + U method has been employed to investigate adsorption properties of H2S on the rutile TiO2 (110) surface with a high coverage of bridging oxygen vacancies (BOVs). The influence of different BOV coverage (theta-BOVs) on the surface electronic structure is examined. Defected states increase within the band gap with theta-BOVs increasing from 1/8 to 4/8 monolayer (ML). The high defected surface with theta-BOVs =4/8 ML is determined to have a desired band structure and noticeable visible light response. In addition, H2S adsorption behaviors are noticeably affected by different H2S coverage (theta-H2S). Particularly, it is found molecular adsorption at theta-H2S <= 1/8 ML and dissociative adsorption at the higher theta-H2S. The maximization of spontaneous dissociation of H2S can be realized when the BOVs are all covered by H2S molecules. This work gains mechanistic insights into BOVs in tuning the surface properties and provides a guide for the effective utilization of the active surface sites on the rutile TiO2 (110) in the field of H2S splitting. (C) 2017 Elsevier B.V. All rights reserved.
Keywords:H2S dissociative adsorption;Rutile TiO2 (110);Bridging oxygen vacancies;DFT plus U calculation