DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Effect of oxygen deficiency on the excited state kinetics of WO3 and implications for photocatalysis

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/c9sc00693a · OSTI ID:1511761
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [4];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Imperial College, London (United Kingdom)
  2. Imperial College, London (United Kingdom); Yonsei Univ., Seoul (Korea, Republic of)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. College London (United Kingdom)

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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1511761
Alternate ID(s):
OSTI ID: 1624974
Journal Information:
Chemical Science, Vol. 10, Issue 22; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (62)

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
Black TiO 2 Nanotubes: Cocatalyst-Free Open-Circuit Hydrogen Generation journal May 2014
Evaluation of Surface State Mediated Charge Recombination in Anatase and Rutile TiO 2 journal September 2016
Size-Dependent Optical Spectroscopy of a Homologous Series of CdSe Cluster Molecules journal March 2001
Effect of Nature and Location of Defects on Bandgap Narrowing in Black TiO 2 Nanoparticles journal April 2012
Projector augmented-wave method journal December 1994
Hybrid functionals based on a screened Coulomb potential journal May 2003
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
Photoelectrolysis and physical properties of the semiconducting electrode WO 2 journal May 1977
Water Oxidation and Electron Extraction Kinetics in Nanostructured Tungsten Trioxide Photoanodes journal October 2018
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
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
Optimizing the Activity of Nanoneedle Structured WO 3 Photoanodes for Solar Water Splitting: Direct Synthesis via Chemical Vapor Deposition journal March 2017
Photoelectrochemistry of Quantized WO 3 Colloids: Electron Storage, Electrochromic, and Photoelectrochromic Effects journal October 1993
Determination of the electron–phonon coupling constant in tungsten journal July 2014
Spectroelectrochemical analysis of the mechanism of (photo)electrochemical hydrogen evolution at a catalytic interface journal February 2017
Hydrogenated titania: synergy of surface modification and morphology improvement for enhanced photocatalytic activity journal January 2012
Hydrogen-Treated TiO 2 Nanowire Arrays for Photoelectrochemical Water Splitting journal July 2011
Ultrafast charge carrier recombination and trapping in hematite photoanodes under applied bias text January 2014
Charge Carrier Dynamics on Mesoporous WO 3 during Water Splitting journal July 2011
Charge carrier trapping, recombination and transfer in hematite (α-Fe2O3) water splitting photoanodes journal January 2013
Efficient photocatalytic hydrogen evolution over hydrogenated ZnO nanorod arrays journal January 2012
Correlation of Optical Properties, Electronic Structure, and Photocatalytic Activity in Nanostructured Tungsten Oxide journal April 2017
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
Black titanium dioxide (TiO 2 ) nanomaterials journal January 2015
Efficient Suppression of Electron–Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO 2 Nanowires for Photoelectrochemical Water Splitting journal November 2013
A full-sunlight-driven photocatalyst with super long-persistent energy storage ability journal August 2013
Ultrafast Dynamics of Defect-Assisted Electron–Hole Recombination in Monolayer MoS 2 journal December 2014
Synproportionation Reaction for the Fabrication of Sn 2+ Self-Doped SnO 2-x Nanocrystals with Tunable Band Structure and Highly Efficient Visible Light Photocatalytic Activity journal November 2013
Long-lived charge separated states in nanostructured semiconductor photoelectrodes for the production of solar fuels journal January 2013
Oxygen deficient α-Fe 2 O 3 photoelectrodes: a balance between enhanced electrical properties and trap-mediated losses journal January 2015
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
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
Semiconductor-based Photocatalytic Hydrogen Generation journal November 2010
H-Doped Black Titania with Very High Solar Absorption and Excellent Photocatalysis Enhanced by Localized Surface Plasmon Resonance journal May 2013
EXPGUI , a graphical user interface for GSAS journal April 2001
Nanostructure-based WO3 photoanodes for photoelectrochemical water splitting journal January 2012
Iron-doping-enhanced photoelectrochemical water splitting performance of nanostructured WO 3 : a combined experimental and theoretical study journal January 2015
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Effect of pH on the Anodic Behavior of Tungsten journal January 2002
Semiconducting materials for photoelectrochemical energy conversion journal January 2016
Ultrafast Charge Carrier Recombination and Trapping in Hematite Photoanodes under Applied Bias journal July 2014
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
Opportunities and challenges in science and technology of WO3 for electrochromic and related applications journal February 2008
Growth mechanism of planar or nanorod structured tungsten oxide thin films deposited via aerosol assisted chemical vapour deposition (AACVD): Growth mechanism of planar or nanorod structured tungsten oxide thin films deposited via aerosol assisted chemical vapour deposition (AACVD) journal May 2015
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
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
Electronic and Structural Properties of WO 3 : A Systematic Hybrid DFT Study journal April 2011
Hydrogen-treated WO3 nanoflakes show enhanced photostability journal January 2012
Optical properties of nanocrystalline WO 3 and WO 3-x thin films prepared by DC magnetron sputtering journal June 2014
Electrochromic properties of WO3 nanowire films and mechanism responsible for the near infrared absorption journal June 2007
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

Cited By (2)

Quasi-degenerate states and their dynamics in oxygen deficient reducible metal oxides journal February 2020
Added value recyclability of glass fiber waste as photo-oxidation catalyst for toxic cytostatic micropollutants journal January 2020

Figures / Tables (5)


Similar Records

TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure
Journal Article · 2014 · Journal of Vacuum Science and Technology A · OSTI ID:1221760

TiO{sub 2} nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure
Journal Article · 2015 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:22392133

Creation and Ordering of Oxygen Vacancies at WO3-δ and Perovskite Interfaces
Journal Article · 2018 · ACS Applied Materials and Interfaces · OSTI ID:1455307

Related Subjects