title: Anticorrelation between surface and subsurface point defects and the impact on the redox chemistry of TiO2(110).
abstract: By using a combination of scanning tunneling microscopy (STM), density functional theory (DFT), and secondary-ion mass spectroscopy (SIMS), we explored the interplay and relative impact of surface versus subsurface defects on the surface chemistry of rutile TiO2 . STM results show that surface O vacancies (VO ) are virtually absent in the vicinity of positively charged subsurface point defects. This observation is consistent with DFT calculations of the impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 was employed and was observed to be suppressed around them. DFT results attribute this to a perceived absence of intrinsic (Ti), and likely extrinsic interstitials in the nearest subsurface layer beneath inhibited areas. We also postulate that the entire nearest subsurface region could be devoid of any charged point defects, whereas prevalent surface defects (VO ) are largely responsible for mediation of the redox chemistry at the reduced TiO2 (110).
authors.affiliation: Fundamental and Computational Sciences Directorate and Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352 (USA).
authors.forename: Yeohoon
authors.initials: Y
authors.lastname: Yoon
authors.forename: Yingge
authors.initials: Y
authors.lastname: Du
authors.forename: Juan C
authors.initials: JC
authors.lastname: Garcia
authors.forename: Zihua
authors.initials: Z
authors.lastname: Zhu
authors.forename: Zhi-Tao
authors.initials: ZT
authors.lastname: Wang
authors.forename: Nikolay G
authors.initials: NG
authors.lastname: Petrik
authors.forename: Gregory A
authors.initials: GA
authors.lastname: Kimmel
authors.forename: Zdenek
authors.initials: Z
authors.lastname: Dohnalek
authors.forename: Michael A
authors.initials: MA
authors.lastname: Henderson
authors.forename: Roger
authors.initials: R
authors.lastname: Rousseau
authors.forename: N Aaron
authors.initials: NA
authors.lastname: Deskins
authors.forename: Igor
authors.initials: I
authors.lastname: Lyubinetsky
keywords: density functional calculations; metal oxides; oxygen; scanning probe microscopy; surface chemistry