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Title: Effect of oxygen deficiency on the excited state kinetics of WO 3 and implications for photocatalysis

Abstract

Oxygen vacancies are widely used to tune the light absorption of semiconducting metal oxides, but a photophysical framework describing the impact of such point defects on the dynamics of photogenerated charges, and ultimately on catalysis, is still missing. We herein use WO3 as a model material and investigate the impact of significantly different degrees of oxygen deficiency on its excited state kinetics. For highly oxygen-deficient films, photoelectron spectroscopy shows an over 2 eV broad distribution of oxygen vacancy states within the bandgap which gives rise to extended visible light absorption. We examine the nature of this distribution using first-principles defect calculations and find that defects aggregate to form clusters rather than isolated vacancy sites. Using transient absorption spectroscopy, we observe trapping of photogenerated holes within 200 fs after excitation at high degrees of oxygen deficiency, which increases their lifetime at the expense of oxidative driving force. This loss in driving force limits the use of metal oxides with significant degrees of sub-stoichiometry to photocatalytic reactions that require low oxidation power such as pollutant degradation, and highlights the need to fine-tune vacancy state distributions for specific target reactions.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3];  [1]; ORCiD logo [1];  [4]; ORCiD logo [5]; ORCiD logo [5];  [4]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry, Imperial College London, London, UK
  2. Department of Materials, Imperial College London, London, UK, Department of Materials Science and Engineering
  3. Department of Chemistry, Imperial College London, London, UK, The Grantham Institute
  4. Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, USA
  5. Department of Chemistry, University College London, London, UK
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1511761
Alternate Identifier(s):
OSTI ID: 1624974
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 22; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE; Chemistry

Citation Formats

Sachs, Michael, Park, Ji-Sang, Pastor, Ernest, Kafizas, Andreas, Wilson, Anna A., Francàs, Laia, Gul, Sheraz, Ling, Min, Blackman, Chris, Yano, Junko, Walsh, Aron, and Durrant, James R. Effect of oxygen deficiency on the excited state kinetics of WO 3 and implications for photocatalysis. United Kingdom: N. p., 2019. Web. doi:10.1039/C9SC00693A.
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Sachs, Michael, Park, Ji-Sang, Pastor, Ernest, Kafizas, Andreas, Wilson, Anna A., Francàs, Laia, Gul, Sheraz, Ling, Min, Blackman, Chris, Yano, Junko, Walsh, Aron, & Durrant, James R. Effect of oxygen deficiency on the excited state kinetics of WO 3 and implications for photocatalysis. United Kingdom. https://doi.org/10.1039/C9SC00693A
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Sachs, Michael, Park, Ji-Sang, Pastor, Ernest, Kafizas, Andreas, Wilson, Anna A., Francàs, Laia, Gul, Sheraz, Ling, Min, Blackman, Chris, Yano, Junko, Walsh, Aron, and Durrant, James R. Wed . "Effect of oxygen deficiency on the excited state kinetics of WO 3 and implications for photocatalysis". United Kingdom. https://doi.org/10.1039/C9SC00693A.
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@article{osti_1511761,
title = {Effect of oxygen deficiency on the excited state kinetics of WO 3 and implications for photocatalysis},
author = {Sachs, Michael and Park, Ji-Sang and Pastor, Ernest and Kafizas, Andreas and Wilson, Anna A. and Francàs, Laia and Gul, Sheraz and Ling, Min and Blackman, Chris and Yano, Junko and Walsh, Aron and Durrant, James R.},
abstractNote = {Oxygen vacancies are widely used to tune the light absorption of semiconducting metal oxides, but a photophysical framework describing the impact of such point defects on the dynamics of photogenerated charges, and ultimately on catalysis, is still missing. We herein use WO3 as a model material and investigate the impact of significantly different degrees of oxygen deficiency on its excited state kinetics. For highly oxygen-deficient films, photoelectron spectroscopy shows an over 2 eV broad distribution of oxygen vacancy states within the bandgap which gives rise to extended visible light absorption. We examine the nature of this distribution using first-principles defect calculations and find that defects aggregate to form clusters rather than isolated vacancy sites. Using transient absorption spectroscopy, we observe trapping of photogenerated holes within 200 fs after excitation at high degrees of oxygen deficiency, which increases their lifetime at the expense of oxidative driving force. This loss in driving force limits the use of metal oxides with significant degrees of sub-stoichiometry to photocatalytic reactions that require low oxidation power such as pollutant degradation, and highlights the need to fine-tune vacancy state distributions for specific target reactions.},
doi = {10.1039/C9SC00693A},
journal = {Chemical Science},
number = 22,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {6}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C9SC00693A
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Cited by: 11 works
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Figures / Tables:

Fig. 1 Fig. 1: (a) Optical properties of the m-WO3 and b-WO3 thin films. UV-NIR absorptance spectra, calculated as 100-transmittance-reflectance (full lines), and photoluminescence emission spectra of m-WO3 and b-WO3 upon 355 nm excitation (dashed lines). The inset shows a photograph of the two types of films side by side. (b) Incident-photon-to-currentmore » conversion efficiency (IPCE) spectra for water oxidation at 1.23 V vs. RHE for m-WO3 and b-WO3 thin films.« less
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Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Electrochemical reduction induced self-doping of Ti3+ for efficient water splitting performance on TiO2 based photoelectrodes
journal, January 2013

  • Zhang, Zhonghai; Hedhili, Mohamed Nejib; Zhu, Haibo
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 37
  • DOI: 10.1039/c3cp52759j

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

Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO 2
journal, September 2016

  • Sachs, Michael; Pastor, Ernest; Kafizas, Andreas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01501

Size-Dependent Optical Spectroscopy of a Homologous Series of CdSe Cluster Molecules
journal, March 2001

  • Soloviev, V. N.; Eichhöfer, A.; Fenske, D.
  • Journal of the American Chemical Society, Vol. 123, Issue 10
  • DOI: 10.1021/ja003598j

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

Projector augmented-wave method
journal, December 1994

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance
journal, January 2013

Electrochemical deposition and photoelectrochemistry of CuWO4, a promising photoanode for water oxidation
journal, January 2011

  • Yourey, Joseph E.; Bartlett, Bart M.
  • Journal of Materials Chemistry, Vol. 21, Issue 21
  • DOI: 10.1039/c1jm11259g

Photoelectrolysis and physical properties of the semiconducting electrode WO 2  
journal, May 1977

  • Butler, M. A.
  • Journal of Applied Physics, Vol. 48, Issue 5
  • DOI: 10.1063/1.323948

Water Oxidation and Electron Extraction Kinetics in Nanostructured Tungsten Trioxide Photoanodes
journal, October 2018

  • Corby, Sacha; Francàs, Laia; Selim, Shababa
  • Journal of the American Chemical Society, Vol. 140, Issue 47
  • DOI: 10.1021/jacs.8b08852

Infrared Light-Driven CO2 Overall Splitting at Room Temperature
journal, May 2018

Oxygen deficient ZnO 1−x nanosheets with high visible light photocatalytic activity
journal, January 2015

Charge carrier concentration dependence of ultrafast plasmonic relaxation in conducting metal oxide nanocrystals
journal, January 2017

  • Johns, Robert W.; Blemker, Michelle A.; Azzaro, Michael S.
  • Journal of Materials Chemistry C, Vol. 5, Issue 23
  • DOI: 10.1039/C7TC00600D

Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations
journal, January 2009

Coupling to light, and transport and dissipation of energy in silver nanowires
journal, January 2009

  • Staleva, Hristina; Skrabalak, Sara E.; Carey, Christopher R.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 28
  • DOI: 10.1039/b901105f

Optimizing the Activity of Nanoneedle Structured WO 3 Photoanodes for Solar Water Splitting: Direct Synthesis via Chemical Vapor Deposition
journal, March 2017

  • Kafizas, Andreas; Francàs, Laia; Sotelo-Vazquez, Carlos
  • The Journal of Physical Chemistry C, Vol. 121, Issue 11
  • DOI: 10.1021/acs.jpcc.7b00533

Photoelectrochemistry of Quantized WO 3 Colloids: Electron Storage, Electrochromic, and Photoelectrochromic Effects
journal, October 1993

  • Bedja, Idriss; Hotchandani, Surat; Kamat, Prashant V.
  • The Journal of Physical Chemistry, Vol. 97, Issue 42
  • DOI: 10.1021/j100144a027

Determination of the electron–phonon coupling constant in tungsten
journal, July 2014

  • Daraszewicz, Szymon L.; Giret, Yvelin; Tanimura, Hiroshi
  • Applied Physics Letters, Vol. 105, Issue 2
  • DOI: 10.1063/1.4890413

Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface
journal, February 2017

  • Pastor, Ernest; Le Formal, Florian; Mayer, Matthew T.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14280

Hydrogenated titania: synergy of surface modification and morphology improvement for enhanced photocatalytic activity
journal, January 2012

  • Zheng, Zhaoke; Huang, Baibiao; Lu, Jibao
  • Chemical Communications, Vol. 48, Issue 46
  • DOI: 10.1039/c2cc32220j

Hydrogen-Treated TiO 2 Nanowire Arrays for Photoelectrochemical Water Splitting
journal, July 2011

  • Wang, Gongming; Wang, Hanyu; Ling, Yichuan
  • Nano Letters, Vol. 11, Issue 7
  • DOI: 10.1021/nl201766h

Charge Carrier Dynamics on Mesoporous WO 3 during Water Splitting
journal, July 2011

  • Pesci, Federico M.; Cowan, Alexander J.; Alexander, Bruce D.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 15
  • DOI: 10.1021/jz200839n

Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes
journal, January 2013

  • Barroso, Monica; Pendlebury, Stephanie R.; Cowan, Alexander J.
  • Chemical Science, Vol. 4, Issue 7
  • DOI: 10.1039/c3sc50496d

Efficient photocatalytic hydrogen evolution over hydrogenated ZnO nanorod arrays
journal, January 2012

  • Lu, Xihong; Wang, Gongming; Xie, Shilei
  • Chemical Communications, Vol. 48, Issue 62
  • DOI: 10.1039/c2cc31773g

Correlation of Optical Properties, Electronic Structure, and Photocatalytic Activity in Nanostructured Tungsten Oxide
journal, April 2017

  • Ling, Min; Blackman, Christopher S.; Palgrave, Robert G.
  • Advanced Materials Interfaces, Vol. 4, Issue 18
  • DOI: 10.1002/admi.201700064

Quantitative Study of Charge Carrier Dynamics in Well-Defined WO 3 Nanowires and Nanosheets: Insight into the Crystal Facet Effect in Photocatalysis
journal, June 2018

  • Lin, Rui; Wan, Jiawei; Xiong, Yu
  • Journal of the American Chemical Society, Vol. 140, Issue 29
  • DOI: 10.1021/jacs.8b05293

Black titanium dioxide (TiO 2 ) nanomaterials
journal, January 2015

  • Chen, Xiaobo; Liu, Lei; Huang, Fuqiang
  • Chemical Society Reviews, Vol. 44, Issue 7
  • DOI: 10.1039/C4CS00330F

Efficient Suppression of Electron–Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO 2 Nanowires for Photoelectrochemical Water Splitting
journal, November 2013

  • Pesci, Federico M.; Wang, Gongming; Klug, David R.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp4099914

A full-sunlight-driven photocatalyst with super long-persistent energy storage ability
journal, August 2013

  • Li, Jie; Liu, Yuan; Zhu, Zhijian
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02409

Hydrogenated black ZnO nanoparticles with enhanced photocatalytic performance
journal, January 2014

  • Xia, Ting; Wallenmeyer, Petra; Anderson, Alicia
  • RSC Adv., Vol. 4, Issue 78
  • DOI: 10.1039/C4RA04826A

Safe and facile hydrogenation of commercial Degussa P25 at room temperature with enhanced photocatalytic activity
journal, January 2014

  • Lu, Haiqiang; Zhao, Binbin; Pan, Ruili
  • RSC Adv., Vol. 4, Issue 3
  • DOI: 10.1039/C3RA44493G

Ultrafast Dynamics of Defect-Assisted Electron–Hole Recombination in Monolayer MoS 2
journal, December 2014

  • Wang, Haining; Zhang, Changjian; Rana, Farhan
  • Nano Letters, Vol. 15, Issue 1
  • DOI: 10.1021/nl503636c

Long-lived charge separated states in nanostructured semiconductor photoelectrodes for the production of solar fuels
journal, January 2013

  • Cowan, Alexander J.; Durrant, James R.
  • Chem. Soc. Rev., Vol. 42, Issue 6
  • DOI: 10.1039/C2CS35305A

Oxygen deficient α-Fe 2 O 3 photoelectrodes: a balance between enhanced electrical properties and trap-mediated losses
journal, January 2015

  • Forster, Mark; Potter, Richard J.; Ling, Yichuan
  • Chemical Science, Vol. 6, Issue 7
  • DOI: 10.1039/C5SC00423C

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

Time-Resolved Spectroscopic Investigation of Charge Trapping in Carbon Nitrides Photocatalysts for Hydrogen Generation
journal, March 2017

  • Godin, Robert; Wang, Yiou; Zwijnenburg, Martijn A.
  • Journal of the American Chemical Society, Vol. 139, Issue 14
  • DOI: 10.1021/jacs.7b01547

Effect of oxygen-deficiency on electrical transport properties of tungsten trioxide crystals
journal, June 1970

A quantitative assessment of the competition between water and anion oxidation at WO3 photoanodes in acidic aqueous electrolytes
journal, January 2012

  • Mi, Qixi; Zhanaidarova, Almagul; Brunschwig, Bruce S.
  • Energy & Environmental Science, Vol. 5, Issue 2
  • DOI: 10.1039/c2ee02929d

Semiconductor-based Photocatalytic Hydrogen Generation
journal, November 2010

  • Chen, Xiaobo; Shen, Shaohua; Guo, Liejin
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr1001645

H-Doped Black Titania with Very High Solar Absorption and Excellent Photocatalysis Enhanced by Localized Surface Plasmon Resonance
journal, May 2013

  • Wang, Zhou; Yang, Chongyin; Lin, Tianquan
  • Advanced Functional Materials, Vol. 23, Issue 43
  • DOI: 10.1002/adfm.201300486

EXPGUI , a graphical user interface for GSAS
journal, April 2001

Nanostructure-based WO3 photoanodes for photoelectrochemical water splitting
journal, January 2012

  • Liu, Xien; Wang, Fengying; Wang, Qing
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 22
  • DOI: 10.1039/c2cp40976c

Role of oxygen vacancies in crystalline WO 3
journal, January 2016

  • Wang, Wennie; Janotti, Anderson; Van de Walle, Chris G.
  • Journal of Materials Chemistry C, Vol. 4, Issue 27
  • DOI: 10.1039/C6TC01643J

Effect of pH on the Anodic Behavior of Tungsten
journal, January 2002

  • Anik, M.; Osseo-Asare, K.
  • Journal of The Electrochemical Society, Vol. 149, Issue 6
  • DOI: 10.1149/1.1471544

Semiconducting materials for photoelectrochemical energy conversion
journal, January 2016

Ultrafast Charge Carrier Recombination and Trapping in Hematite Photoanodes under Applied Bias
journal, July 2014

  • Pendlebury, Stephanie R.; Wang, Xiuli; Le Formal, Florian
  • Journal of the American Chemical Society, Vol. 136, Issue 28
  • DOI: 10.1021/ja504473e

Femtosecond room-temperature measurement of the electron-phonon coupling constant γ in metallic superconductors
journal, April 1990

Size-Dependent Ultrafast Charge Carrier Dynamics of WO 3 for Photoelectrochemical Cells
journal, June 2016

  • Regan, Kevin P.; Koenigsmann, Christopher; Sheehan, Stafford W.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 27
  • DOI: 10.1021/acs.jpcc.6b04390

Opportunities and challenges in science and technology of WO3 for electrochromic and related applications
journal, February 2008

Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst
journal, December 2014

  • Lassalle-Kaiser, Benedikt; Merki, Daniel; Vrubel, Heron
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja510328m

Polaron and phonon properties in proton intercalated amorphous tungsten oxide thin films
journal, December 2008

An electrochemical method to enhance the performance of metal oxides for photoelectrochemical water oxidation
journal, January 2016

  • Wang, Gongming; Yang, Yi; Ling, Yichuan
  • Journal of Materials Chemistry A, Vol. 4, Issue 8
  • DOI: 10.1039/C5TA10477G

Electronic and Structural Properties of WO 3 : A Systematic Hybrid DFT Study
journal, April 2011

  • Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
  • The Journal of Physical Chemistry C, Vol. 115, Issue 16
  • DOI: 10.1021/jp201057m

Hydrogen-treated WO3 nanoflakes show enhanced photostability
journal, January 2012

  • Wang, Gongming; Ling, Yichuan; Wang, Hanyu
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee03158b

Optical properties of nanocrystalline WO 3 and WO 3-x thin films prepared by DC magnetron sputtering
journal, June 2014

  • Johansson, Malin B.; Zietz, Burkhard; Niklasson, Gunnar A.
  • Journal of Applied Physics, Vol. 115, Issue 21
  • DOI: 10.1063/1.4880162

Electrochromic properties of WO3 nanowire films and mechanism responsible for the near infrared absorption
journal, June 2007

  • Chen, Huanjun; Xu, Ningsheng; Deng, Shaozhi
  • Journal of Applied Physics, Vol. 101, Issue 11
  • DOI: 10.1063/1.2732534

Optical properties and electronic structure of amorphous Ge and Si
journal, January 1968

A Highly Efficient Photocatalyst-Hydrogenated Black TiO 2 for the Photocatalytic Splitting of Water
journal, November 2012

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