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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]
  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.
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
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.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C9SC00693A

Citation Metrics:
Cited by: 11 works
Citation information provided by
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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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