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Band positions of anatase (001) and (101) surfaces in contact with water from density functional theory.

Published version
Peer-reviewed

Type

Article

Change log

Authors

Geiger, Julian 
May, Matthias M 

Abstract

Titanium dioxide in the anatase configuration plays an increasingly important role in photo(electro)catalytic applications due to its superior electronic properties when compared to rutile. In aqueous environments, the surface chemistry and energetic band positions upon contact with water determine charge-transfer processes over solid-solid or solid-electrolyte interfaces. Here, we study the interaction of anatase (001) and (101) surfaces with water and the resulting energetic alignment by means of hybrid density functional theory. While the alignment of band positions favors charge-transfer processes between the two facets for the pristine surfaces, we find the magnitude of this underlying driving force to crucially depend on the water coverage and the degree of dissociation. It can be largely alleviated for intermediate water coverages. Surface states and their passivation by dissociatively adsorbed water play an important role here. Our results suggest that anatase band positions can be controlled over a range of almost 1 eV via its surface chemistry.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

Publisher

AIP Publishing

Rights

All rights reserved
Sponsorship
Engineering and Physical Sciences Research Council (EP/P022596/1)
International Exchanges grant IE161814 of the Royal Society. German National Academy of Sciences Leopoldina, grant LPDS 2015-09 German Research Foundation, project 434023472