Imaging consecutive steps of O 2 reaction with hydroxylated TiO 2(110)

Identification of HO 2 and terminal OH intermediates

Yingge Du, N. Aaron Deskins, Zhenrong Zhang, Zdenek Dohnálek, Michel Dupuis, Igor Lyubinetsky

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

We report the results of a combined experimental and theoretical investigation of the reaction of molecular oxygen with a partially hydroxylated TiO 2(110) surface. The consecutive steps of both primary and secondary site-specific reactions have been tracked with high-resolution scanning tunneling microscopy (STM). We have directly imaged stable, adsorbed hydroperoxyl (HO 2) species, which is believed to be a key intermediate in many heterogeneous photochemical processes but generally metastable and "elusive" until now. We also found terminal hydroxyl groups, which are another critical but never previously directly observed intermediates. Conclusive evidence that O 2 reacts spontaneously with a single bridging OH group as an initial reaction step is provided. The experimental results are supported by density functional theory (DFT) calculations that have determined the energies and configurations of these species. Reported observations provide a base for a consistent description of the elementary reaction steps and offer molecular-level insight into the underlying reaction mechanisms. Tthe results are also expected to have important implications for various catalytic systems involving the interconversion of O 2 and H 2O.

Original languageEnglish
Pages (from-to)666-671
Number of pages6
JournalJournal of Physical Chemistry C
Volume113
Issue number2
DOIs
Publication statusPublished - Jan 15 2009

Fingerprint

Molecular oxygen
Scanning tunneling microscopy
Hydroxyl Radical
Density functional theory
Imaging techniques
scanning tunneling microscopy
density functional theory
high resolution
oxygen
configurations
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Imaging consecutive steps of O 2 reaction with hydroxylated TiO 2(110) : Identification of HO 2 and terminal OH intermediates. / Du, Yingge; Deskins, N. Aaron; Zhang, Zhenrong; Dohnálek, Zdenek; Dupuis, Michel; Lyubinetsky, Igor.

In: Journal of Physical Chemistry C, Vol. 113, No. 2, 15.01.2009, p. 666-671.

Research output: Contribution to journalArticle

Du, Yingge ; Deskins, N. Aaron ; Zhang, Zhenrong ; Dohnálek, Zdenek ; Dupuis, Michel ; Lyubinetsky, Igor. / Imaging consecutive steps of O 2 reaction with hydroxylated TiO 2(110) : Identification of HO 2 and terminal OH intermediates. In: Journal of Physical Chemistry C. 2009 ; Vol. 113, No. 2. pp. 666-671.
@article{afd638695e5d41a3bc640e046b5c6ac6,
title = "Imaging consecutive steps of O 2 reaction with hydroxylated TiO 2(110): Identification of HO 2 and terminal OH intermediates",
abstract = "We report the results of a combined experimental and theoretical investigation of the reaction of molecular oxygen with a partially hydroxylated TiO 2(110) surface. The consecutive steps of both primary and secondary site-specific reactions have been tracked with high-resolution scanning tunneling microscopy (STM). We have directly imaged stable, adsorbed hydroperoxyl (HO 2) species, which is believed to be a key intermediate in many heterogeneous photochemical processes but generally metastable and {"}elusive{"} until now. We also found terminal hydroxyl groups, which are another critical but never previously directly observed intermediates. Conclusive evidence that O 2 reacts spontaneously with a single bridging OH group as an initial reaction step is provided. The experimental results are supported by density functional theory (DFT) calculations that have determined the energies and configurations of these species. Reported observations provide a base for a consistent description of the elementary reaction steps and offer molecular-level insight into the underlying reaction mechanisms. Tthe results are also expected to have important implications for various catalytic systems involving the interconversion of O 2 and H 2O.",
author = "Yingge Du and Deskins, {N. Aaron} and Zhenrong Zhang and Zdenek Dohn{\'a}lek and Michel Dupuis and Igor Lyubinetsky",
year = "2009",
month = "1",
day = "15",
doi = "10.1021/jp807030n",
language = "English",
volume = "113",
pages = "666--671",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Imaging consecutive steps of O 2 reaction with hydroxylated TiO 2(110)

T2 - Identification of HO 2 and terminal OH intermediates

AU - Du, Yingge

AU - Deskins, N. Aaron

AU - Zhang, Zhenrong

AU - Dohnálek, Zdenek

AU - Dupuis, Michel

AU - Lyubinetsky, Igor

PY - 2009/1/15

Y1 - 2009/1/15

N2 - We report the results of a combined experimental and theoretical investigation of the reaction of molecular oxygen with a partially hydroxylated TiO 2(110) surface. The consecutive steps of both primary and secondary site-specific reactions have been tracked with high-resolution scanning tunneling microscopy (STM). We have directly imaged stable, adsorbed hydroperoxyl (HO 2) species, which is believed to be a key intermediate in many heterogeneous photochemical processes but generally metastable and "elusive" until now. We also found terminal hydroxyl groups, which are another critical but never previously directly observed intermediates. Conclusive evidence that O 2 reacts spontaneously with a single bridging OH group as an initial reaction step is provided. The experimental results are supported by density functional theory (DFT) calculations that have determined the energies and configurations of these species. Reported observations provide a base for a consistent description of the elementary reaction steps and offer molecular-level insight into the underlying reaction mechanisms. Tthe results are also expected to have important implications for various catalytic systems involving the interconversion of O 2 and H 2O.

AB - We report the results of a combined experimental and theoretical investigation of the reaction of molecular oxygen with a partially hydroxylated TiO 2(110) surface. The consecutive steps of both primary and secondary site-specific reactions have been tracked with high-resolution scanning tunneling microscopy (STM). We have directly imaged stable, adsorbed hydroperoxyl (HO 2) species, which is believed to be a key intermediate in many heterogeneous photochemical processes but generally metastable and "elusive" until now. We also found terminal hydroxyl groups, which are another critical but never previously directly observed intermediates. Conclusive evidence that O 2 reacts spontaneously with a single bridging OH group as an initial reaction step is provided. The experimental results are supported by density functional theory (DFT) calculations that have determined the energies and configurations of these species. Reported observations provide a base for a consistent description of the elementary reaction steps and offer molecular-level insight into the underlying reaction mechanisms. Tthe results are also expected to have important implications for various catalytic systems involving the interconversion of O 2 and H 2O.

UR - http://www.scopus.com/inward/record.url?scp=63249093834&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=63249093834&partnerID=8YFLogxK

U2 - 10.1021/jp807030n

DO - 10.1021/jp807030n

M3 - Article

VL - 113

SP - 666

EP - 671

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 2

ER -