A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface

Zhang, Zhen; Yates Jr., John T.

doi:10.1016/j.susc.2016.04.015

Title: A new form of chemisorbed photo- and electro-active atomic H species on the TiO₂(110) surface

Abstract

Hydrogen adsorption on TiO₂ is of importance in chemical and photochemical reduction processes. Using several surface science methods, we clearly distinguish two kinds of H species on the surface of rutile TiO₂(110)-1 × 1. In contrast with the well-studied bridge-bonded OH species (α-H) originating from H₂O dissociation on the surface oxygen vacancy site on TiO₂(110), atomic H adsorption on the TiO₂(110) (denoted as β-H) exhibits special high sensitivity to the electronic excitation of the TiO₂(110) by either electrons or UV photons. The formation of molecular H₂ gas by photoexcitation of β-H/TiO₂(110) surfaces has been observed, which may shed light on the basic understanding of the processes of photocatalytic H₂ production by splitting water.

Authors:

Zhang, Zhen ^[1]; Yates Jr., John T. ^[1]

University of Virginia, Charlottesville, VA (United States)

Publication Date:: Sat Apr 30 00:00:00 EDT 2016

Research Org.:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1534355

Alternate Identifier(s):: OSTI ID: 1359913

Grant/Contract Number:: SC0002365; FG02-O9ER16080

Resource Type:: Accepted Manuscript

Journal Name:: Surface Science

Additional Journal Information:: Journal Volume: 652; Journal Issue: C; Journal ID: ISSN 0039-6028

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electron stimulated desorption; TiO2(110); H2O; atomic H

Citation Formats


                    Zhang, Zhen, and Yates Jr., John T. A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface.  United States: N. p., 2016. 
Web.  doi:10.1016/j.susc.2016.04.015.

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                    Zhang, Zhen, & Yates Jr., John T. A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface.  United States.  https://doi.org/10.1016/j.susc.2016.04.015

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                    Zhang, Zhen, and Yates Jr., John T. Sat .  
"A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface".  United States.  https://doi.org/10.1016/j.susc.2016.04.015.  https://www.osti.gov/servlets/purl/1534355.

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@article{osti_1534355,

  title        = {A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface},

  author       = {Zhang, Zhen and Yates Jr., John T.},

  abstractNote = {Hydrogen adsorption on TiO2 is of importance in chemical and photochemical reduction processes. Using several surface science methods, we clearly distinguish two kinds of H species on the surface of rutile TiO2(110)-1 × 1. In contrast with the well-studied bridge-bonded OH species (α-H) originating from H2O dissociation on the surface oxygen vacancy site on TiO2(110), atomic H adsorption on the TiO2(110) (denoted as β-H) exhibits special high sensitivity to the electronic excitation of the TiO2(110) by either electrons or UV photons. The formation of molecular H2 gas by photoexcitation of β-H/TiO2(110) surfaces has been observed, which may shed light on the basic understanding of the processes of photocatalytic H2 production by splitting water.},

  doi          = {10.1016/j.susc.2016.04.015},

  journal      = {Surface Science},

  number       = C,

  volume       = 652,

  place        = {United States},

  year         = {Sat Apr 30 00:00:00 EDT 2016},

  month        = {Sat Apr 30 00:00:00 EDT 2016}

}

Copy to clipboard

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https://doi.org/10.1016/j.susc.2016.04.015

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Title: A new form of chemisorbed photo- and electro-active atomic H species on the TiO2(110) surface

Abstract

Citation Formats

Electron-stimulated desorption: Principles and applications journal, January 1991

Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals journal, January 2011

Hydrogen Loading of Oxide Powder Particles: A Transmission IR Study for the Case of Zinc Oxide journal, November 2010

Electrochemical Photolysis of Water at a Semiconductor Electrode journal, July 1972

Defect-Electron Spreading on the TiO 2 (110) Semiconductor Surface by Water Adsorption journal, February 2013

Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature journal, November 2013

Direct Observation of Surface-Mediated Electron−Hole Pair Recombination in TiO 2 (110) journal, February 2010

Characterization of hydrogen species on metal-oxide surfaces by electron-stimulated desorption: TiO2 and SrTiO3 journal, December 1980

Interaction of Molecular Oxygen with the Vacuum-Annealed TiO 2 (110) Surface: Molecular and Dissociative Channels journal, June 1999

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results journal, May 1995

A surface science perspective on TiO2 photocatalysis journal, June 2011

An HREELS and TPD study of water on TiO2(110): the extent of molecular versus dissociative adsorption journal, June 1996

Oxygen Vacancies as Active Sites for Water Dissociation on Rutile TiO 2 ( 110 ) journal, December 2001

Probing electrons in TiO2 polaronic trap states by IR-absorption: Evidence for the existence of hydrogenic states journal, January 2014

Comment on “Imaging of the Hydrogen Subsurface Site in RutileTiO2” journal, March 2010

Enevoldsenet al.Reply: journal, March 2010

Calculations of reneutralization effects in ESDIAD journal, April 1986

Diffusion versus Desorption: Complex Behavior of H Atoms on an Oxide Surface journal, February 2008

Hydrogen in oxide semiconductors journal, May 2012

Interaction of water, oxygen, and hydrogen with TiO 2 (110) surfaces having different defect densities journal, July 1992

Surface Science Studies of the Photoactivation of TiO 2 New Photochemical Processes journal, October 2006

Observation of Photocatalytic Dissociation of Water on Terminal Ti Sites of TiO 2 (110)-1 × 1 Surface journal, June 2012

Photocatalytic Reduction of CO 2 on TiO 2 and Other Semiconductors journal, June 2013

The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania journal, June 2008

Hydrogen Spillover. Facts and Fiction journal, February 2012

Hydrogen Bonding Controls the Dynamics of Catechol Adsorbed on a TiO2(110) Surface journal, May 2010

Intrinsic Diffusion of Hydrogen on Rutile TiO 2 (110) journal, July 2008

Composition, structure, and stability of the rutile TiO 2 ( 110 ) surface: Oxygen depletion, hydroxylation, hydrogen migration, and water adsorption journal, March 2009

Hydrogen reactivity on highly-hydroxylated TiO2(110) surfaces prepared viacarboxylic acid adsorption and photolysis journal, January 2012

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity journal, April 2012

Hydrogen Adatoms on TiO 2 ( 110 ) − ( 1 × 1 ) Characterized by Scanning Tunneling Microscopy and Electron Stimulated Desorption journal, March 2000

Formation and Splitting of Paired Hydroxyl Groups on Reduced TiO 2 ( 110 ) journal, February 2006

Hydrogenation and Disorder in Engineered Black TiO 2 journal, August 2013

Molecular Hydrogen Formation from Photocatalysis of Methanol on TiO 2 (110) journal, May 2013

Spectroscopic Detection of Hydrogen Atom Spillover from Au Nanoparticles Supported on TiO 2 : Use of Conduction Band Electrons journal, January 2007

The surface science of titanium dioxide journal, January 2003

Tracking the motion of chemisorbed molecules on their adsorption sites journal, January 1998

Imaging Water Dissociation on TiO 2 (110): Evidence for Inequivalent Geminate OH Groups journal, November 2006

Ion Desorption by Core-Hole Auger Decay journal, April 1978

Imaging of the Hydrogen Subsurface Site in Rutile TiO 2 journal, April 2009

Elastic and inelastic processes in the interaction of 1–10 eV ions with solids: ion transport through surface layers journal, August 1997

n-Type doping of TiO2 with atomic hydrogen-observation of the production of conduction band electrons by infrared spectroscopy journal, February 2007

Direct visualization of defect-mediated dissociation of water on TiO2(110) journal, February 2006

Title: A new form of chemisorbed photo- and electro-active atomic H species on the TiO₂(110) surface

Electron-stimulated desorption: Principles and applications
journal, January 1991

Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals
journal, January 2011

Hydrogen Loading of Oxide Powder Particles: A Transmission IR Study for the Case of Zinc Oxide
journal, November 2010

Electrochemical Photolysis of Water at a Semiconductor Electrode
journal, July 1972

Defect-Electron Spreading on the TiO ₂ (110) Semiconductor Surface by Water Adsorption
journal, February 2013

Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature
journal, November 2013

Direct Observation of Surface-Mediated Electron−Hole Pair Recombination in TiO ₂ (110)
journal, February 2010

Characterization of hydrogen species on metal-oxide surfaces by electron-stimulated desorption: TiO2 and SrTiO3
journal, December 1980

Interaction of Molecular Oxygen with the Vacuum-Annealed TiO ₂ (110) Surface: Molecular and Dissociative Channels
journal, June 1999

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results
journal, May 1995

A surface science perspective on TiO2 photocatalysis
journal, June 2011

An HREELS and TPD study of water on TiO2(110): the extent of molecular versus dissociative adsorption
journal, June 1996

Oxygen Vacancies as Active Sites for Water Dissociation on Rutile ${TiO}_{2} (110)$
journal, December 2001

Probing electrons in TiO2 polaronic trap states by IR-absorption: Evidence for the existence of hydrogenic states
journal, January 2014

Comment on “Imaging of the Hydrogen Subsurface Site in RutileTiO2”
journal, March 2010

Enevoldsenet al.Reply:
journal, March 2010

Calculations of reneutralization effects in ESDIAD
journal, April 1986

Diffusion versus Desorption: Complex Behavior of H Atoms on an Oxide Surface
journal, February 2008

Hydrogen in oxide semiconductors
journal, May 2012

Interaction of water, oxygen, and hydrogen with TiO ₂ (110) surfaces having different defect densities
journal, July 1992

Surface Science Studies of the Photoactivation of TiO ₂ New Photochemical Processes
journal, October 2006

Observation of Photocatalytic Dissociation of Water on Terminal Ti Sites of TiO ₂ (110)-1 × 1 Surface
journal, June 2012

Photocatalytic Reduction of CO ₂ on TiO ₂ and Other Semiconductors
journal, June 2013

The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania
journal, June 2008

Hydrogen Spillover. Facts and Fiction
journal, February 2012

Hydrogen Bonding Controls the Dynamics of Catechol Adsorbed on a TiO2(110) Surface
journal, May 2010

Intrinsic Diffusion of Hydrogen on Rutile TiO ₂ (110)
journal, July 2008

Composition, structure, and stability of the rutile ${TiO}_{2} (110)$ surface: Oxygen depletion, hydroxylation, hydrogen migration, and water adsorption
journal, March 2009

Hydrogen reactivity on highly-hydroxylated TiO2(110) surfaces prepared viacarboxylic acid adsorption and photolysis
journal, January 2012

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity
journal, April 2012

Hydrogen Adatoms on ${TiO}_{2} (110) - (1 \times 1)$ Characterized by Scanning Tunneling Microscopy and Electron Stimulated Desorption
journal, March 2000

Formation and Splitting of Paired Hydroxyl Groups on Reduced ${TiO}_{2} (110)$
journal, February 2006

Hydrogenation and Disorder in Engineered Black ${TiO}_{2}$
journal, August 2013

Molecular Hydrogen Formation from Photocatalysis of Methanol on TiO ₂ (110)
journal, May 2013

Spectroscopic Detection of Hydrogen Atom Spillover from Au Nanoparticles Supported on TiO ₂ : Use of Conduction Band Electrons
journal, January 2007

The surface science of titanium dioxide
journal, January 2003

Tracking the motion of chemisorbed molecules on their adsorption sites
journal, January 1998

Imaging Water Dissociation on TiO ₂ (110): Evidence for Inequivalent Geminate OH Groups
journal, November 2006

Ion Desorption by Core-Hole Auger Decay
journal, April 1978

Imaging of the Hydrogen Subsurface Site in Rutile ${TiO}_{2}$
journal, April 2009

Elastic and inelastic processes in the interaction of 1–10 eV ions with solids: ion transport through surface layers
journal, August 1997

n-Type doping of TiO2 with atomic hydrogen-observation of the production of conduction band electrons by infrared spectroscopy
journal, February 2007

Direct visualization of defect-mediated dissociation of water on TiO2(110)
journal, February 2006