Structural evolution of titanium dioxide during reduction in high-pressure hydrogen
Abstract
The excellent photocatalytic properties of titanium oxide (TiO2) under ultraviolet light have long motivated the search for doping strategies capable of extending its photoactivity to the visible part of the spectrum. One approach is high-pressure and high-temperature hydrogenation, which results in reduced ‘black TiO2’ nanoparticles with a crystalline core and a disordered shell that absorbs visible light. Here we elucidate the formation mechanism and structural features of black TiO2 using first-principles-validated reactive force field molecular dynamics simulations of anatase TiO2 surfaces and nanoparticles at high temperature and under high hydrogen pressures. Simulations reveal that surface oxygen vacancies created upon reaction of H2 with surface oxygen atoms diffuse towards the bulk material but encounter a high barrier for subsurface migration on {001} facets of the nanoparticles, which initiates surface disordering. Besides confirming that the hydrogenated amorphous shell has a key role in the photoactivity of black TiO2, our results provide insight into the properties of the disordered surface layers that are observed on regular anatase nanocrystals under photocatalytic water-splitting conditions.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1543760
- Grant/Contract Number:
- AC02-05CH11231; SC0007347
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Materials
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 10; Journal ID: ISSN 1476-1122
- Publisher:
- Springer Nature - Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Materials Science; Physics
Citation Formats
Selcuk, Sencer, Zhao, Xunhua, and Selloni, Annabella. Structural evolution of titanium dioxide during reduction in high-pressure hydrogen. United States: N. p., 2018.
Web. doi:10.1038/s41563-018-0135-0.
Selcuk, Sencer, Zhao, Xunhua, & Selloni, Annabella. Structural evolution of titanium dioxide during reduction in high-pressure hydrogen. United States. https://doi.org/10.1038/s41563-018-0135-0
Selcuk, Sencer, Zhao, Xunhua, and Selloni, Annabella. Mon .
"Structural evolution of titanium dioxide during reduction in high-pressure hydrogen". United States. https://doi.org/10.1038/s41563-018-0135-0. https://www.osti.gov/servlets/purl/1543760.
@article{osti_1543760,
title = {Structural evolution of titanium dioxide during reduction in high-pressure hydrogen},
author = {Selcuk, Sencer and Zhao, Xunhua and Selloni, Annabella},
abstractNote = {The excellent photocatalytic properties of titanium oxide (TiO2) under ultraviolet light have long motivated the search for doping strategies capable of extending its photoactivity to the visible part of the spectrum. One approach is high-pressure and high-temperature hydrogenation, which results in reduced ‘black TiO2’ nanoparticles with a crystalline core and a disordered shell that absorbs visible light. Here we elucidate the formation mechanism and structural features of black TiO2 using first-principles-validated reactive force field molecular dynamics simulations of anatase TiO2 surfaces and nanoparticles at high temperature and under high hydrogen pressures. Simulations reveal that surface oxygen vacancies created upon reaction of H2 with surface oxygen atoms diffuse towards the bulk material but encounter a high barrier for subsurface migration on {001} facets of the nanoparticles, which initiates surface disordering. Besides confirming that the hydrogenated amorphous shell has a key role in the photoactivity of black TiO2, our results provide insight into the properties of the disordered surface layers that are observed on regular anatase nanocrystals under photocatalytic water-splitting conditions.},
doi = {10.1038/s41563-018-0135-0},
journal = {Nature Materials},
number = 10,
volume = 17,
place = {United States},
year = {Mon Jul 16 00:00:00 EDT 2018},
month = {Mon Jul 16 00:00:00 EDT 2018}
}
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Works referenced in this record:
Steps on anatase TiO2(101)
journal, July 2006
- Gong, Xue-Qing; Selloni, Annabella; Batzill, Matthias
- Nature Materials, Vol. 5, Issue 8
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals
journal, January 2011
- Chen, X.; Liu, L.; Yu, P. Y.
- Science, Vol. 331, Issue 6018
Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co-Catalyst
journal, October 2014
- Liu, Ning; Schneider, Christopher; Freitag, Detlef
- Angewandte Chemie International Edition, Vol. 53, Issue 51
Black TiO 2 Nanotubes: Cocatalyst-Free Open-Circuit Hydrogen Generation
journal, May 2014
- Liu, Ning; Schneider, Christopher; Freitag, Detlef
- Nano Letters, Vol. 14, Issue 6
Prediction of TiO 2 Nanoparticle Phase and Shape Transitions Controlled by Surface Chemistry
journal, July 2005
- Barnard, A. S.; Curtiss, L. A.
- Nano Letters, Vol. 5, Issue 7
Effect of Nature and Location of Defects on Bandgap Narrowing in Black TiO 2 Nanoparticles
journal, April 2012
- Naldoni, Alberto; Allieta, Mattia; Santangelo, Saveria
- Journal of the American Chemical Society, Vol. 134, Issue 18
(Sub)Surface Mobility of Oxygen Vacancies at the Anatase (101) Surface
journal, September 2012
- Scheiber, Philipp; Fidler, Martin; Dulub, Olga
- Physical Review Letters, Vol. 109, Issue 13
Reactive Potentials for Advanced Atomistic Simulations
journal, July 2013
- Liang, Tao; Shin, Yun Kyung; Cheng, Yu-Ting
- Annual Review of Materials Research, Vol. 43, Issue 1
The ReaxFF reactive force-field: development, applications and future directions
journal, March 2016
- Senftle, Thomas P.; Hong, Sungwook; Islam, Md Mahbubul
- npj Computational Materials, Vol. 2, Issue 1
Evidence for Crystal-Face-Dependent TiO 2 Photocatalysis from Single-Molecule Imaging and Kinetic Analysis
journal, May 2011
- Tachikawa, Takashi; Yamashita, Soichiro; Majima, Tetsuro
- Journal of the American Chemical Society, Vol. 133, Issue 18
Self-Doped Ti 3+ Enhanced Photocatalyst for Hydrogen Production under Visible Light
journal, September 2010
- Zuo, Fan; Wang, Le; Wu, Tao
- Journal of the American Chemical Society, Vol. 132, Issue 34
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Development of a ReaxFF Reactive Force Field for Titanium Dioxide/Water Systems
journal, June 2013
- Kim, Sung-Yup; Kumar, Nitin; Persson, Petter
- Langmuir, Vol. 29, Issue 25
Titanium Dioxide Crystals with Tailored Facets
journal, May 2014
- Liu, Gang; Yang, Hua Gui; Pan, Jian
- Chemical Reviews, Vol. 114, Issue 19
A Liouville-operator derived measure-preserving integrator for molecular dynamics simulations in the isothermal–isobaric ensemble
journal, April 2006
- Tuckerman, Mark E.; Alejandre, José; López-Rendón, Roberto
- Journal of Physics A: Mathematical and General, Vol. 39, Issue 19
Introduction: Titanium Dioxide (TiO 2 ) Nanomaterials
journal, May 2014
- Chen, Xiaobo; Selloni, Annabella
- Chemical Reviews, Vol. 114, Issue 19
Water on Titanium Dioxide Surface: A Revisiting by Reactive Molecular Dynamics Simulations
journal, December 2014
- Huang, Liangliang; Gubbins, Keith E.; Li, Licheng
- Langmuir, Vol. 30, Issue 49
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces
journal, June 2016
- Selcuk, Sencer; Selloni, Annabella
- Nature Materials, Vol. 15, Issue 10
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
ReaxFF: A Reactive Force Field for Hydrocarbons
journal, October 2001
- van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois
- The Journal of Physical Chemistry A, Vol. 105, Issue 41
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Computational and Photoelectrochemical Study of Hydrogenated Bismuth Vanadate
journal, May 2013
- Wang, Gongming; Ling, Yichuan; Lu, Xihong
- The Journal of Physical Chemistry C, Vol. 117, Issue 21
TiO2 photocatalysis and related surface phenomena
journal, December 2008
- Fujishima, A.; Zhang, X.; Tryk, D.
- Surface Science Reports, Vol. 63, Issue 12
Hydrogen interaction with the anatase TiO2(101) surface
journal, January 2012
- Aschauer, Ulrich; Selloni, Annabella
- Physical Chemistry Chemical Physics, Vol. 14, Issue 48
Anatase TiO2 single crystals with a large percentage of reactive facets
journal, May 2008
- Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang
- Nature, Vol. 453, Issue 7195
Enhanced Photocatalytic CO 2 -Reduction Activity of Anatase TiO 2 by Coexposed {001} and {101} Facets
journal, June 2014
- Yu, Jiaguo; Low, Jingxiang; Xiao, Wei
- Journal of the American Chemical Society, Vol. 136, Issue 25
Electronic and optical properties of anatase
journal, March 2000
- Asahi, R.; Taga, Y.; Mannstadt, W.
- Physical Review B, Vol. 61, Issue 11
Mechanisms of Oriented Attachment of TiO 2 Nanocrystals in Vacuum and Humid Environments: Reactive Molecular Dynamics
journal, March 2014
- Raju, Muralikrishna; van Duin, Adri C. T.; Fichthorn, Kristen A.
- Nano Letters, Vol. 14, Issue 4
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990
- Vanderbilt, David
- Physical Review B, Vol. 41, Issue 11, p. 7892-7895
Titanium Dioxide in the Service of the Biomedical Revolution
journal, May 2014
- Rajh, Tijana; Dimitrijevic, Nada M.; Bissonnette, Marc
- Chemical Reviews, Vol. 114, Issue 19
Tracer diffusion and chemical diffusion of oxygen in acceptor doped SrTiO 3
journal, August 2000
- Claus, J.; Leonhardt, M.; Maier, J.
- Journal of Physics and Chemistry of Solids, Vol. 61, Issue 8
Black titanium dioxide (TiO 2 ) nanomaterials
journal, January 2015
- Chen, Xiaobo; Liu, Lei; Huang, Fuqiang
- Chemical Society Reviews, Vol. 44, Issue 7
Parallel reactive molecular dynamics: Numerical methods and algorithmic techniques
journal, April 2012
- Aktulga, H. M.; Fogarty, J. C.; Pandit, S. A.
- Parallel Computing, Vol. 38, Issue 4-5
The surface science of titanium dioxide
journal, January 2003
- Diebold, Ulrike
- Surface Science Reports, Vol. 48, Issue 5-8
Active Facets on Titanium(III)-Doped TiO2: An Effective Strategy to Improve the Visible-Light Photocatalytic Activity
journal, May 2012
- Zuo, Fan; Bozhilov, Krassimir; Dillon, Robert J.
- Angewandte Chemie International Edition, Vol. 51, Issue 25
Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985
- Car, R.; Parrinello, M.
- Physical Review Letters, Vol. 55, Issue 22
Theoretical Studies on Anatase and Less Common TiO 2 Phases: Bulk, Surfaces, and Nanomaterials
journal, May 2014
- De Angelis, Filippo; Di Valentin, Cristiana; Fantacci, Simona
- Chemical Reviews, Vol. 114, Issue 19
Reduced and n-Type Doped TiO 2 : Nature of Ti 3+ Species
journal, September 2009
- Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella
- The Journal of Physical Chemistry C, Vol. 113, Issue 48
Ordered Mesoporous Black TiO 2 as Highly Efficient Hydrogen Evolution Photocatalyst
journal, June 2014
- Zhou, Wei; Li, Wei; Wang, Jian-Qiang
- Journal of the American Chemical Society, Vol. 136, Issue 26
Composition, structure, and stability of as a function of oxygen pressure
journal, December 2001
- Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 65, Issue 3
Atomic Level In Situ Observation of Surface Amorphization in Anatase Nanocrystals During Light Irradiation in Water Vapor
journal, January 2013
- Zhang, Liuxian; Miller, Benjamin K.; Crozier, Peter A.
- Nano Letters, Vol. 13, Issue 2
Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2
journal, July 2018
- Lu, Yue; Yin, Wen-Jin; Peng, Kai-Lin
- Nature Communications, Vol. 9, Issue 1
Active Facets on Titanium(III)-Doped TiO2: An Effective Strategy to Improve the Visible-Light Photocatalytic Activity
journal, May 2012
- Zuo, Fan; Bozhilov, Krassimir; Dillon, Robert J.
- Angewandte Chemie, Vol. 124, Issue 25
Hydrogenated Anatase: Strong Photocatalytic Dihydrogen Evolution without the Use of a Co-Catalyst
journal, October 2014
- Liu, Ning; Schneider, Christopher; Freitag, Detlef
- Angewandte Chemie, Vol. 126, Issue 51
Photoelectrochemical Cells
journal, February 1980
- Nozik, A. J.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 295, Issue 1414
Works referencing / citing this record:
Controlled Surface Modification of ZnO Nanostructures with Amorphous TiO 2 for Photoelectrochemical Water Splitting
journal, June 2019
- Gasparotto, Alberto; Maccato, Chiara; Sada, Cinzia
- Advanced Sustainable Systems, Vol. 3, Issue 9
Dynamics of Photo‐Induced Surface Oxygen Vacancies in Metal‐Oxide Semiconductors Studied Under Ambient Conditions
journal, September 2019
- Glass, Daniel; Cortés, Emiliano; Ben‐Jaber, Sultan
- Advanced Science, Vol. 6, Issue 22
Enhancing Catalytic Activity of Titanium Oxide in Lithium–Sulfur Batteries by Band Engineering
journal, May 2019
- Wang, Yuankun; Zhang, Ruifang; Chen, Jie
- Advanced Energy Materials, Vol. 9, Issue 24
Recent Advances in the Use of Black TiO 2 for Production of Hydrogen and Other Solar Fuels
journal, February 2019
- Chatzitakis, Athanasios; Sartori, Sabrina
- ChemPhysChem, Vol. 20, Issue 10
Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts
journal, April 2019
- Lee, Byoung-Hoon; Park, Sunghak; Kim, Minho
- Nature Materials, Vol. 18, Issue 6
The transformation of anatase TiO 2 to TiSe 2 to form TiO 2 –TiSe 2 composites for Li + /Na + storage with improved capacities
journal, January 2019
- Li, Pengchao; Chen, Changmiao; Huang, Zhao
- CrystEngComm, Vol. 21, Issue 15
How insignificant modifications of photocatalysts can significantly change their photocatalytic activity
journal, January 2019
- Trochowski, Mateusz; Kobielusz, Marcin; Mróz, Krystian
- Journal of Materials Chemistry A, Vol. 7, Issue 43
Efficient preparation of TiO 2 nanoparticle models using interatomic potentials
journal, June 2019
- Macià Escatllar, Antoni; Morales-García, Ángel; Illas, Francesc
- The Journal of Chemical Physics, Vol. 150, Issue 21
Structure and reactivity of highly reduced titanium oxide surface layers on TiO 2 : A first-principles study
journal, November 2019
- Wen, Bo; Liu, Li-Min; Selloni, Annabella
- The Journal of Chemical Physics, Vol. 151, Issue 18
Transformation of oxide ceramic textiles from insulation to conduction at room temperature
journal, February 2020
- Yan, Jianhua; Zhang, Yuanyuan; Zhao, Yun
- Science Advances, Vol. 6, Issue 6