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Title: Structure and reactivity of highly reduced titanium oxide surface layers on TiO 2: A first-principles study

Abstract

Titanium oxide structures featuring highly reduced TiO x films on top of nearly stoichiometric TiO 2 hold promise for applications ranging from photocatalysis to resistance switching devices. In this article, we focus on titanium monoxide (TiO) layers on anatase TiO 2 (001) and use first principles calculations to investigate their structure and properties as well as their interface with liquid water. We find that only a single TiO layer can grow epitaxially on anatase (001) and subsequent growth leads to the formation of TiO islands. The TiO layers decrease the work function and enhance the surface conductivity in comparison to pure anatase, two features that can improve the TiO 2 performance in photocatalytic hydrogen evolution but are thermodynamically unstable relative to pure TiO 2 in humid/aqueous environment. Furthermore, first principles molecular dynamics simulations of the TiO (001)-water and anatase (001)-water interfaces show that unlike the multilayer structure of interfacial water on the anatase surface, a very dense and tightly packed first water layer is present on the surface of TiO, which could represent the first stage of partial surface reoxidation.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
  1. Beijing Computational Science Research Center, Beijing (China); Princeton Univ., NJ (United States)
  2. Beihang Univ., Beijing (China)
  3. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
Science Challenge Project; National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1594489
Alternate Identifier(s):
OSTI ID: 1573513
Grant/Contract Number:  
[SC0007347; TZ2018004; 51572016; U1930402; 11747167; 11847213; 51861130360; NAFR1180242]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
[ Journal Volume: 151; Journal Issue: 18]; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wen, Bo, Liu, Li-Min, and Selloni, Annabella. Structure and reactivity of highly reduced titanium oxide surface layers on TiO2: A first-principles study. United States: N. p., 2019. Web. doi:10.1063/1.5126961.
Wen, Bo, Liu, Li-Min, & Selloni, Annabella. Structure and reactivity of highly reduced titanium oxide surface layers on TiO2: A first-principles study. United States. doi:10.1063/1.5126961.
Wen, Bo, Liu, Li-Min, and Selloni, Annabella. Fri . "Structure and reactivity of highly reduced titanium oxide surface layers on TiO2: A first-principles study". United States. doi:10.1063/1.5126961.
@article{osti_1594489,
title = {Structure and reactivity of highly reduced titanium oxide surface layers on TiO2: A first-principles study},
author = {Wen, Bo and Liu, Li-Min and Selloni, Annabella},
abstractNote = {Titanium oxide structures featuring highly reduced TiOx films on top of nearly stoichiometric TiO2 hold promise for applications ranging from photocatalysis to resistance switching devices. In this article, we focus on titanium monoxide (TiO) layers on anatase TiO2 (001) and use first principles calculations to investigate their structure and properties as well as their interface with liquid water. We find that only a single TiO layer can grow epitaxially on anatase (001) and subsequent growth leads to the formation of TiO islands. The TiO layers decrease the work function and enhance the surface conductivity in comparison to pure anatase, two features that can improve the TiO2 performance in photocatalytic hydrogen evolution but are thermodynamically unstable relative to pure TiO2 in humid/aqueous environment. Furthermore, first principles molecular dynamics simulations of the TiO (001)-water and anatase (001)-water interfaces show that unlike the multilayer structure of interfacial water on the anatase surface, a very dense and tightly packed first water layer is present on the surface of TiO, which could represent the first stage of partial surface reoxidation.},
doi = {10.1063/1.5126961},
journal = {Journal of Chemical Physics},
number = [18],
volume = [151],
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
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