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Title: TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

Abstract

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO₂ nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O₂ (oxidizing), Ar (inert), and H₂ (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO₂ nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO₂ nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H₂-annealed nanotubes than with the Ar- and O₂-annealed nanotube samples. This enhanced photocatalytic response of the H₂-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such asmore » Ti3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [2];  [1]
  1. Northeastern Univ., Boston, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1221760
Report Number(s):
BNL-108391-2015-JA
Journal ID: ISSN 0734-2101; JVTAD6; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Vacuum Science and Technology A
Additional Journal Information:
Journal Volume: 33; Journal Issue: 2; Journal ID: ISSN 0734-2101
Publisher:
American Vacuum Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanotubes; crystal structure; x-ray absorption spectroscopy; absorption spectra; catalysis

Citation Formats

Liu, Jing, Hosseinpour, Pegah M., Luo, Si, Heiman, Don, Menon, Latika, Arena, Dario A., and Lewis, Laura H. TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure. United States: N. p., 2014. Web. doi:10.1116/1.4902350.
Liu, Jing, Hosseinpour, Pegah M., Luo, Si, Heiman, Don, Menon, Latika, Arena, Dario A., & Lewis, Laura H. TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure. United States. https://doi.org/10.1116/1.4902350
Liu, Jing, Hosseinpour, Pegah M., Luo, Si, Heiman, Don, Menon, Latika, Arena, Dario A., and Lewis, Laura H. Wed . "TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure". United States. https://doi.org/10.1116/1.4902350. https://www.osti.gov/servlets/purl/1221760.
@article{osti_1221760,
title = {TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure},
author = {Liu, Jing and Hosseinpour, Pegah M. and Luo, Si and Heiman, Don and Menon, Latika and Arena, Dario A. and Lewis, Laura H.},
abstractNote = {To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO₂ nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O₂ (oxidizing), Ar (inert), and H₂ (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO₂ nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO₂ nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H₂-annealed nanotubes than with the Ar- and O₂-annealed nanotube samples. This enhanced photocatalytic response of the H₂-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.},
doi = {10.1116/1.4902350},
journal = {Journal of Vacuum Science and Technology A},
number = 2,
volume = 33,
place = {United States},
year = {Wed Nov 19 00:00:00 EST 2014},
month = {Wed Nov 19 00:00:00 EST 2014}
}

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Works referenced in this record:

A Review of Photocatalysis using Self-organized TiO 2 Nanotubes and Other Ordered Oxide Nanostructures
journal, September 2012


Self-Organized TiO2 Nanotube Layers as Highly Efficient Photocatalysts
journal, February 2007


Water-Photolysis Properties of Micron-Length Highly-Ordered Titania Nanotube-Arrays
journal, July 2005

  • Varghese, Oomman K.; Paulose, Maggie; Shankar, Karthik
  • Journal of Nanoscience and Nanotechnology, Vol. 5, Issue 7
  • DOI: 10.1166/jnn.2005.195

A room-temperature TiO2-nanotube hydrogen sensor able to self-clean photoactively from environmental contamination
journal, February 2004

  • Mor, Gopal K.; Carvalho, Maria A.; Varghese, Ooman K.
  • Journal of Materials Research, Vol. 19, Issue 2
  • DOI: 10.1557/jmr.2004.19.2.628

A Titania Nanotube-Array Room-Temperature Sensor for Selective Detection of Hydrogen at Low Concentrations
journal, September 2004

  • Varghese, Oomman K.; Mor, Gopal K.; Grimes, Craig A.
  • Journal of Nanoscience and Nanotechnology, Vol. 4, Issue 7
  • DOI: 10.1166/jnn.2004.092

Unprecedented ultra-high hydrogen gas sensitivity in undoped titania nanotubes
journal, December 2005


Highly-ordered TiO 2 nanotube arrays up to 220 µm in length: use in water photoelectrolysis and dye-sensitized solar cells
journal, January 2007


Use of Highly-Ordered TiO 2 Nanotube Arrays in Dye-Sensitized Solar Cells
journal, February 2006

  • Mor, Gopal K.; Shankar, Karthik; Paulose, Maggie
  • Nano Letters, Vol. 6, Issue 2
  • DOI: 10.1021/nl052099j

Formation of ‘single walled’ TiO2 nanotubes with significantly enhanced electronic properties for higher efficiency dye-sensitized solar cells
journal, January 2013

  • Mirabolghasemi, Hamed; Liu, Ning; Lee, Kiyoung
  • Chemical Communications, Vol. 49, Issue 20
  • DOI: 10.1039/c3cc38793c

Photoelectrochemical and water photoelectrolysis properties of ordered TiO2 nanotubes fabricated by Ti anodization in fluoride-free HCl electrolytes
journal, January 2008

  • Allam, Nageh K.; Shankar, Karthik; Grimes, Craig A.
  • Journal of Materials Chemistry, Vol. 18, Issue 20
  • DOI: 10.1039/b718580d

Reduced TiO2 nanotube arrays for photoelectrochemical water splitting
journal, January 2013

  • Kang, Qing; Cao, Junyu; Zhang, Yuanjian
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10689f

Smooth Anodic TiO2 Nanotubes
journal, November 2005

  • Macak, Jan M.; Tsuchiya, Hiroaki; Taveira, Luciano
  • Angewandte Chemie International Edition, Vol. 44, Issue 45
  • DOI: 10.1002/anie.200502781

High-Aspect-Ratio TiO 2 Nanotubes by Anodization of Titanium
journal, February 2005

  • Macák, Jan M.; Tsuchiya, Hiroaki; Schmuki, Patrik
  • Angewandte Chemie International Edition, Vol. 44, Issue 14
  • DOI: 10.1002/anie.200462459

250 µm long anodic TiO2 nanotubes with hexagonal self‐ordering
journal, November 2006

  • Albu, Sergiu P.; Ghicov, Andrei; Macak, Jan M.
  • physica status solidi (RRL) – Rapid Research Letters, Vol. 1, Issue 2
  • DOI: 10.1002/pssr.200600069

Enhancement and limits of the photoelectrochemical response from anodic TiO2 nanotubes
journal, December 2005

  • Beranek, R.; Tsuchiya, H.; Sugishima, T.
  • Applied Physics Letters, Vol. 87, Issue 24
  • DOI: 10.1063/1.2140085

Crystallization and high-temperature structural stability of titanium oxide nanotube arrays
journal, January 2003

  • Varghese, Oomman K.; Gong, Dawei; Paulose, Maggie
  • Journal of Materials Research, Vol. 18, Issue 1
  • DOI: 10.1557/JMR.2003.0022

Microstructure and Composition of TiO[sub 2] Nanotube Arrays Fabricated with HF and NH[sub 4]F Electrolytes and Their Evolution during Annealing
journal, January 2011

  • Hsu, Ming-Yi; Yang, Wei-Chun; Teng, Hsisheng
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3533388

Formation of Double‐Walled TiO2 Nanotubes and Robust Anatase Membranes
journal, October 2008

  • Albu, Sergiu P.; Ghicov, Andrei; Aldabergenova, Saule
  • Advanced Materials, Vol. 20, Issue 21
  • DOI: 10.1002/adma.200801189

Toward tailored functionality of titania nanotube arrays: Interpretation of the magnetic-structural correlations
journal, May 2013

  • Hosseinpour, Pegah M.; Panaitescu, Eugen; Heiman, Don
  • Journal of Materials Research, Vol. 28, Issue 10
  • DOI: 10.1557/jmr.2013.94

Morphology and structure of heat-treated titania nanotubes
journal, January 2013

  • Hosseinpour, Pegah M.; Panaitescu, Eugen; Lim, James
  • Nanomaterials and Energy, Vol. 2, Issue 1
  • DOI: 10.1680/nme.12.00021

Effects of structure of anodic TiO2 nanotube arrays on photocatalytic activity for the degradation of 2,3-dichlorophenol in aqueous solution
journal, March 2009


Characterization and Photocatalytic Activity of TiO2Nanotube Films Prepared by Anodization
journal, January 2013

  • Wang, Wen-Yu; Chen, Bo-Ruei
  • International Journal of Photoenergy, Vol. 2013
  • DOI: 10.1155/2013/348171

Preparation of Titania Nanotubes and Their Environmental Applications as Electrode
journal, April 2005

  • Quan, Xie; Yang, Shaogui; Ruan, Xiuli
  • Environmental Science & Technology, Vol. 39, Issue 10
  • DOI: 10.1021/es048684o

Effects of the Structure of TiO[sub 2] Nanotube Array on Ti Substrate on Its Photocatalytic Activity
journal, January 2006

  • Lai, Yuekun; Sun, Lan; Chen, Yicong
  • Journal of The Electrochemical Society, Vol. 153, Issue 7
  • DOI: 10.1149/1.2203112

Photocatalytic Properties of Size-Controlled Titania Nanotube Arrays
journal, January 2011

  • Hashishin, Takeshi; Misawa, Keisuke; Kojima, Kazuo
  • International Journal of Electrochemistry, Vol. 2011
  • DOI: 10.4061/2011/656939

The surface science of titanium dioxide
journal, January 2003


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
  • DOI: 10.1021/nl500710j

Effect of surface defects on biosensing properties of TiO2 nanotube arrays
journal, July 2011

  • Xiao, Peng; Zhang, Yunhuai; Cao, Guozhong
  • Sensors and Actuators B: Chemical, Vol. 155, Issue 1
  • DOI: 10.1016/j.snb.2010.11.041

Self-ordering electrochemistry: a review on growth and functionality of TiO2 nanotubes and other self-aligned MOx structures
journal, January 2009

  • Ghicov, Andrei; Schmuki, Patrik
  • Chemical Communications, Issue 20
  • DOI: 10.1039/b822726h

L 2 , 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2 + , Sc 3 + , and Ti 4 + in O h (octahedral) symmetry
journal, January 1990


2p X-ray absorption of titanium in minerals
journal, September 1992

  • de Groot, F. M. F.; Figueiredo, M. O.; Basto, M. J.
  • Physics and Chemistry of Minerals, Vol. 19, Issue 3
  • DOI: 10.1007/BF00202101

Chemical changes induced by sputtering in TiO2 and some selected titanates as observed by X-ray absorption spectroscopy
journal, June 1993


Electronic structure and growth of vanadium on TiO2(110)
journal, April 2000


An NEXAFS investigation of the reduction and reoxidation of TiO2(001)
journal, February 1998


Electronic structure of titania aerogels from soft x-ray absorption spectroscopy
journal, June 2004


Electron energy loss and X-ray absorption spectroscopy of rutile and anatase: a test of structural sensitivity
journal, January 1989


Amorphous to anatase transformation in atomic layer deposited titania thin films induced by hydrothermal treatment at 120 °C
journal, September 2008

  • Zhang, Zhaoming; Triani, Gerry; Fan, Liang-Jen
  • Journal of Materials Research, Vol. 23, Issue 9
  • DOI: 10.1557/jmr.2008.0297

TiO 2 -SnO 2 :F interfacial electronic structure investigated by soft x-ray absorption spectroscopy
journal, March 2012

  • Kronawitter, Coleman X.; Kapilashrami, Mukes; Bakke, Jonathan R.
  • Physical Review B, Vol. 85, Issue 12
  • DOI: 10.1103/PhysRevB.85.125109

Oxygen 1 s x-ray absorption of tetravalent titanium oxides: A comparison with single-particle calculations
journal, July 1993


Ti 3 + in the Surface of Titanium Dioxide: Generation, Properties and Photocatalytic Application
journal, January 2012

  • Xiong, Liang-Bin; Li, Jia-Lin; Yang, Bo
  • Journal of Nanomaterials, Vol. 2012
  • DOI: 10.1155/2012/831524

Vacant states of TiO2 with rutile structure and their reflection in different-type x-ray absorption spectra
journal, January 2002

  • Finkelstein, L. D.; Zabolotzky, E. I.; Korotin, M. A.
  • X-Ray Spectrometry, Vol. 31, Issue 6
  • DOI: 10.1002/xrs.596

Polaronic satellites in x-ray-absorption spectra
journal, June 1990


Electronic structure of TiO2 nanotube arrays from X-ray absorption near edge structure studies
journal, January 2009

  • Zhou, J. G.; Fang, H. T.; Maley, J. M.
  • Journal of Materials Chemistry, Vol. 19, Issue 37
  • DOI: 10.1039/b909225k

Ti and O K edges for titanium oxides by multiple scattering calculations: Comparison to XAS and EELS spectra
journal, April 1997


Remarkable role of annealing time on anatase phase titania nanotubes and its photoelectrochemical response
journal, February 2013


Annealing effects on the photoresponse of TiO 2 nanotubes
journal, March 2006

  • Ghicov, Andrei; Tsuchiya, Hiroaki; Macak, Jan M.
  • physica status solidi (a), Vol. 203, Issue 4
  • DOI: 10.1002/pssa.200622041

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

Annealing study of titanium oxide nanotube arrays
journal, November 2011


Investigation of Physicochemical Parameters That Influence Photocatalytic Degradation of Methyl Orange over TiO 2 Nanotubes
journal, October 2009

  • Smith, York R.; Kar, Archana; Subramanian, Vaidyanathan (Ravi)
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 23
  • DOI: 10.1021/ie801851p

Self-organized TiO 2 nanotubular arrays for photoelectrochemical hydrogen generation: effect of crystallization and defect structures
journal, May 2008


Electrochemical and photoelectrical properties of titania nanotube arrays annealed in different gases
journal, September 2008

  • Xiao, Peng; Liu, Dawei; Garcia, Betzaida Batalla
  • Sensors and Actuators B: Chemical, Vol. 134, Issue 2
  • DOI: 10.1016/j.snb.2008.05.005

Works referencing / citing this record:

Influence of electrochemical reduction of selfdoping on the low temperature crystallization and photocatalytic activities of TiO 2 nanotubes
journal, August 2019

  • Nair, Sinitha B.; K., Aijo john; Menon, Sumithra S.
  • Semiconductor Science and Technology, Vol. 34, Issue 9
  • DOI: 10.1088/1361-6641/ab3822