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Title: Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

Abstract

Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of 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 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absence of the 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 voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.

Authors:
; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1170054
Report Number(s):
PNNL-SA-105906
48499; 47406
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemphyschem, 16(2):313-321
Country of Publication:
United States
Language:
English
Subject:
TiO2, point-defects, STM, DFT, SIMS; Environmental Molecular Sciences Laboratory

Citation Formats

Yoon, Yeohoon, Du, Yingge, Garcia, Juan C., Zhu, Zihua, Wang, Zhitao, Petrik, Nikolay G., Kimmel, Gregory A., Dohnalek, Zdenek, Henderson, Michael A., Rousseau, Roger J., Deskins, N. Aaron, and Lyubinetsky, Igor. Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110). United States: N. p., 2015. Web. doi:10.1002/cphc.201402599.
Yoon, Yeohoon, Du, Yingge, Garcia, Juan C., Zhu, Zihua, Wang, Zhitao, Petrik, Nikolay G., Kimmel, Gregory A., Dohnalek, Zdenek, Henderson, Michael A., Rousseau, Roger J., Deskins, N. Aaron, & Lyubinetsky, Igor. Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110). United States. doi:10.1002/cphc.201402599.
Yoon, Yeohoon, Du, Yingge, Garcia, Juan C., Zhu, Zihua, Wang, Zhitao, Petrik, Nikolay G., Kimmel, Gregory A., Dohnalek, Zdenek, Henderson, Michael A., Rousseau, Roger J., Deskins, N. Aaron, and Lyubinetsky, Igor. Mon . "Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)". United States. doi:10.1002/cphc.201402599.
@article{osti_1170054,
title = {Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)},
author = {Yoon, Yeohoon and Du, Yingge and Garcia, Juan C. and Zhu, Zihua and Wang, Zhitao and Petrik, Nikolay G. and Kimmel, Gregory A. and Dohnalek, Zdenek and Henderson, Michael A. and Rousseau, Roger J. and Deskins, N. Aaron and Lyubinetsky, Igor},
abstractNote = {Using combination of STM, DFT and SIMS, we explored the interplay and relative impact of surface vs. subsurface defects on the surface chemistry of rutile TiO2. STM results show that surface O vacancies (VO’s) are virtually absent in the vicinity of positively-charged subsurface point-defects. This observation is consistent with DFT calculations of 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 is employed, which is observed to be suppressed around them. DFT results attribute this to a perceived absence of the 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 voided of any charged point-defects, whereas prevalent VO’s are largely responsible for mediation of the redox chemistry at reduced TiO2(110) surface.},
doi = {10.1002/cphc.201402599},
journal = {Chemphyschem, 16(2):313-321},
number = ,
volume = ,
place = {United States},
year = {Mon Feb 02 00:00:00 EST 2015},
month = {Mon Feb 02 00:00:00 EST 2015}
}