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

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

doi:10.1002/cphc.201402599

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

Journal Article · Mon Feb 02 00:00:00 EST 2015 · Chemphyschem, 16(2):313-321

DOI:https://doi.org/10.1002/cphc.201402599· OSTI ID:1170054

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

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.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1170054

Report Number(s):: PNNL-SA-105906; 48499; 47406

Journal Information:: Chemphyschem, 16(2):313-321, Journal Name: Chemphyschem, 16(2):313-321

Country of Publication:: United States

Language:: English

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

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