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The role of Ti3+ interstitials in TiO2(110) reduction and oxidation

Michael Bowker1 and Roger A Bennett2

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Here we describe results which teach us much about the mechanism of the reduction and oxidation of TiO2(110) by the application of scanning tunnelling microscopy imaging at high temperatures. Titania reduces at high temperature by thermal oxygen loss to leave localized (i.e.  Ti3+) and delocalized electrons on the lattice Ti, and a reduced titania interstitial that diffuses into the bulk of the crystal. The interstitial titania can be recalled to the surface by treatment in very low pressures of oxygen, occurring at a significant rate even at 573 K. This re-oxidation occurs by re-growth of titania layers in a Volmer–Weber manner, by a repeating sequence in which in-growth of extra titania within the cross-linked (1 × 2) structure completes the (1 × 1) bulk termination. The next layer then initiates with the nucleation of points and strings which extend to form islands of cross-linked (1 × 2), which once again grow and fill in to reform the (1 × 1). This process continues in a cyclical manner to form many new layers of well-ordered titania. The details of the mechanism and kinetics of the process are considered.


PACS

61.72.J- Point defects and defect clusters

82.65.+r Surface and interface chemistry; heterogeneous catalysis at surfaces

68.35.Dv Composition, segregation; defects and impurities

81.65.Mq Oxidation

Subjects

Surfaces, interfaces and thin films

Condensed matter: structural, mechanical & thermal

Chemical physics and physical chemistry

Dates

Issue 47 (25 November 2009)

Received 18 May 2009, in final form 8 June 2009

Published 5 November 2009


An Erratum for this article has been published in 2010 J. Phys.: Condens. Matter 22 059801


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