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Title: Structure and Formation Mechanism of Black TiO2 Nanoparticles

Abstract

The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti3+ surface species that are the key to the enhancedmore » photocatalytic activity of black TiO2.« less

Authors:
 [1];  [2];  [3];  [3];  [2];  [3];  [2];  [2];  [2];  [2];  [4]
+ Show Author Affiliations
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineeringvv; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1324061
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; black TiO₂; core−shell structure; nanoparticles; nonstoichiometry; reduced band-gap; TEM characterization

Citation Formats

Tian, Mengkun, Mahjouri-Samani, Masoud, Eres, Gyula, Sachan, Ritesh, Yoon, Mina, Chisholm, Matthew F., Wang, Kai, Puretzky, Alexander A., Rouleau, Christopher M., Geohegan, David B., and Duscher, Gerd. Structure and Formation Mechanism of Black TiO2 Nanoparticles. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b04712.
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Tian, Mengkun, Mahjouri-Samani, Masoud, Eres, Gyula, Sachan, Ritesh, Yoon, Mina, Chisholm, Matthew F., Wang, Kai, Puretzky, Alexander A., Rouleau, Christopher M., Geohegan, David B., & Duscher, Gerd. Structure and Formation Mechanism of Black TiO2 Nanoparticles. United States. https://doi.org/10.1021/acsnano.5b04712
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Tian, Mengkun, Mahjouri-Samani, Masoud, Eres, Gyula, Sachan, Ritesh, Yoon, Mina, Chisholm, Matthew F., Wang, Kai, Puretzky, Alexander A., Rouleau, Christopher M., Geohegan, David B., and Duscher, Gerd. Tue . "Structure and Formation Mechanism of Black TiO2 Nanoparticles". United States. https://doi.org/10.1021/acsnano.5b04712. https://www.osti.gov/servlets/purl/1324061.
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@article{osti_1324061,
title = {Structure and Formation Mechanism of Black TiO2 Nanoparticles},
author = {Tian, Mengkun and Mahjouri-Samani, Masoud and Eres, Gyula and Sachan, Ritesh and Yoon, Mina and Chisholm, Matthew F. and Wang, Kai and Puretzky, Alexander A. and Rouleau, Christopher M. and Geohegan, David B. and Duscher, Gerd},
abstractNote = {The remarkable properties of black TiO2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO2 nanoparticles consists of a disordered Ti2O3 shell. The measurements show a transition region that connects the disordered Ti2O3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitial atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti2O3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti2O3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO2 for preserving and stabilizing Ti3+ surface species that are the key to the enhanced photocatalytic activity of black TiO2.},
doi = {10.1021/acsnano.5b04712},
journal = {ACS Nano},
number = 10,
volume = 9,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2015},
month = {Tue Oct 27 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acsnano.5b04712
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Works referenced in this record:

Titanium Dioxide Nanomaterials:  Synthesis, Properties, Modifications, and Applications
journal, July 2007

  • Chen, Xiaobo; Mao, Samuel S.
  • Chemical Reviews, Vol. 107, Issue 7
  • DOI: 10.1021/cr0500535

Quantum size effect in TiO2 nanoparticles: does it exist?
journal, August 2000

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

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
  • DOI: 10.1021/ja3012676

Characterization of Oxygen Vacancy Associates within Hydrogenated TiO 2 : A Positron Annihilation Study
journal, October 2012

  • Jiang, Xudong; Zhang, Yupeng; Jiang, Jing
  • The Journal of Physical Chemistry C, Vol. 116, Issue 42
  • DOI: 10.1021/jp307573c

The effect of valence state and site geometry on Ti L3,2 and O K electron energy-loss spectra of TixOy phases
journal, April 2007

  • Stoyanov, E.; Langenhorst, F.; Steinle-Neumann, G.
  • American Mineralogist, Vol. 92, Issue 4
  • DOI: 10.2138/am.2007.2344

Core level electron energy-loss spectra of minerals: pre-edge fine structures at the oxygen K -edge
journal, August 1998

  • van Aken, P. A.; Liebscher, B.; Styrsa, V. J.
  • Physics and Chemistry of Minerals, Vol. 25, Issue 7
  • DOI: 10.1007/s002690050140

Direct Imaging of Reconstructed Atoms on TiO2 (110) Surfaces
journal, October 2008

The surface science of titanium dioxide
journal, January 2003

Reconstruction of TiO2(110) surface: STM study with atomic-scale resolution
journal, June 1994

Dynamic Visualization of a Metal-Oxide-Surface/Gas-Phase Reaction: Time-Resolved Observation by Scanning Tunneling Microscopy at 800 K
journal, January 1996

Reactive re-oxidation of reduced TiO 2 (110) surfaces demonstrated by high temperature STM movies
journal, January 1999

Topotactic Reduction Yielding Black Titanium Oxide Nanostructures as Metallic Electronic Conductors
journal, June 2012

Transferable potentials for the Ti–O system
journal, January 1997

  • Roux, Herman le; Glasser, Leslie
  • Journal of Materials Chemistry, Vol. 7, Issue 5
  • DOI: 10.1039/a607575d

Resistivity and Magnetic Order in Ti2O3
journal, February 1968

  • Van Zandt, L. L.; Honig, J. M.; Goodenough, J. B.
  • Journal of Applied Physics, Vol. 39, Issue 2
  • DOI: 10.1063/1.2163536

Polarization anisotropy of X-ray atomic factors and `forbidden' resonant reflections
journal, August 2005

  • Dmitrienko, Vladimir E.; Ishida, Kohtaro; Kirfel, Armin
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 61, Issue 5
  • DOI: 10.1107/S0108767305018209

Defect Chemistry of Titanium Dioxide. Application of Defect Engineering in Processing of TiO 2 -Based Photocatalysts
journal, March 2008

  • Nowotny, M. K.; Sheppard, L. R.; Bak, T.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 14
  • DOI: 10.1021/jp077275m

Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications
journal, January 2013

  • Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi
  • Nanoscale, Vol. 5, Issue 9
  • DOI: 10.1039/c3nr00476g
    Sort by:
    [ × clear filter / sort ]

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    Highly Conductive Cable-Like Bicomponent Titania Photoanode Approaching Limitation of Electron and Hole Collection
    journal, July 2018

    • Tian, Zhangliu; Wang, Dong; Bu, Kejun
    • Advanced Functional Materials, Vol. 28, Issue 36
    • DOI: 10.1002/adfm.201803328

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    journal, November 2019

    • Tian, Chen-Xi; Cui, Shi-Cong; Liu, Xiang-Yu
    • Research on Chemical Intermediates, Vol. 46, Issue 1
    • DOI: 10.1007/s11164-019-04028-3

    Apparatus-dependent sol-gel synthesis of TiO 2 nanoparticles for dye-sensitized solar cells
    journal, December 2019

    Recent progress in characterization of the core–shell structure of black titania
    journal, March 2019

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    • Journal of Materials Research, Vol. 34, Issue 07
    • DOI: 10.1557/jmr.2019.46

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    journal, February 2020

    • Lim, Joohyun; Kim, Se‐Ho; Aymerich Armengol, Raquel
    • Angewandte Chemie, Vol. 132, Issue 14
    • DOI: 10.1002/ange.201915709

    Enhancing formaldehyde oxidation on iridium catalysts using hydrogenated TiO 2 supports
    journal, January 2018

    • Chan, Hang Cheong; Chen, Ting; Xie, Lifang
    • New Journal of Chemistry, Vol. 42, Issue 22
    • DOI: 10.1039/c8nj04472d

    Physico-chemical Characterization and Basic Research Principles of Advanced Drug Delivery Nanosystems
    book, January 2017

    Electron‐Beam‐Related Studies of Halide Perovskites: Challenges and Opportunities
    journal, February 2020

    • Ran, Junhui; Dyck, Ondrej; Wang, Xiaozheng
    • Advanced Energy Materials, Vol. 10, Issue 26
    • DOI: 10.1002/aenm.201903191

    Black N/H-TiO 2 Nanoplates with a Flower-Like Hierarchical Architecture for Photocatalytic Hydrogen Evolution
    journal, August 2016

    TiO2 hollow spheres with surface-rich Ti3+ under Pd-catalyzed hydrogenation for improved visible-light photocatalysis
    journal, February 2019

    Increasing the optical response of TiO 2 and extending it into the visible region through surface activation with highly stable Cu 5 clusters
    journal, January 2019

    • Pilar de Lara-Castells, María; Hauser, Andreas W.; Ramallo-López, José M.
    • Journal of Materials Chemistry A, Vol. 7, Issue 13
    • DOI: 10.1039/c9ta00994a

    Defects Engineering in Photocatalytic Water Splitting Materials
    journal, October 2019

    Different Reactivity of Rutile and Anatase TiO 2 Nanoparticles: Synthesis and Surface States of Nanoparticles of Mixed‐Valence Magnéli Oxides
    journal, September 2009

    • Baktash, Elham; Capitolis, Jérôme; Tinat, Lionel
    • Chemistry – A European Journal, Vol. 25, Issue 47
    • DOI: 10.1002/chem.201901592

    Magnetic Conductive Outer Layer in Oxygen‐Deficient TiO 2 Single Crystals
    journal, April 2019

    • Zhang, Zhaoting; Yan, Hong; Ren, Lixia
    • physica status solidi (RRL) – Rapid Research Letters, Vol. 13, Issue 8
    • DOI: 10.1002/pssr.201900160

    Progress in Black Titania: A New Material for Advanced Photocatalysis
    journal, June 2016

    • Liu, Xiangye; Zhu, Guilian; Wang, Xin
    • Advanced Energy Materials, Vol. 6, Issue 17
    • DOI: 10.1002/aenm.201600452

    Black Titania with Nanoscale Helicity
    journal, August 2019

    • Nguyen, Thanh‐Dinh; Li, Jessica; Lizundia, Erlantz
    • Advanced Functional Materials, Vol. 29, Issue 40
    • DOI: 10.1002/adfm.201904639

    Femtosecond laser-induced transformations in ultra-low expansion glass: Microstructure and local density variations by vibrational spectroscopy
    journal, June 2018

    • Efthimiopoulos, I.; Palles, D.; Richter, S.
    • Journal of Applied Physics, Vol. 123, Issue 23
    • DOI: 10.1063/1.5030687

    Low pressure bottom-up synthesis of metal@oxide and oxide nanoparticles: control of structure and functional properties
    journal, January 2018

    Novel Black BiVO 4 /TiO 2− x Photoanode with Enhanced Photon Absorption and Charge Separation for Efficient and Stable Solar Water Splitting
    journal, June 2019

    • Tian, Zhangliu; Zhang, Pengfei; Qin, Peng
    • Advanced Energy Materials, Vol. 9, Issue 27
    • DOI: 10.1002/aenm.201901287

    Atomic‐Scale Mapping of Impurities in Partially Reduced Hollow TiO 2 Nanowires
    journal, February 2020

    • Lim, Joohyun; Kim, Se‐Ho; Aymerich Armengol, Raquel
    • Angewandte Chemie International Edition, Vol. 59, Issue 14
    • DOI: 10.1002/anie.201915709

    Mini Review of TiO 2 -Based Multifunctional Nanocomposites for Near-Infrared Light-Responsive Phototherapy
    journal, June 2018

    • Wang, Meifang; Hou, Zhiyao; Al Kheraif, Abdulaziz A.
    • Advanced Healthcare Materials, Vol. 7, Issue 20
    • DOI: 10.1002/adhm.201800351

    Tuning the Electronic Conductivity in Hydrothermally Grown Rutile TiO2 Nanowires: Effect of Heat Treatment in Different Environments
    journal, September 2017

    • Folger, Alena; Kalb, Julian; Schmidt-Mende, Lukas
    • Nanomaterials, Vol. 7, Issue 10
    • DOI: 10.3390/nano7100289

    Tuning the Electronic Conductivity in Hydrothermally Grown Rutile TiO2 Nanowires: Effect of Heat Treatment in Different Environments
    journal, September 2017

    • Folger, Alena; Kalb, Julian; Schmidt-Mende, Lukas
    • Nanomaterials, Vol. 7, Issue 10
    • DOI: 10.3390/nano7100289
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