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:
-
- Department of Chemistry, Imperial College London, London, UK
- Department of Materials, Imperial College London, London, UK, Department of Materials Science and Engineering
- Department of Chemistry, Imperial College London, London, UK, The Grantham Institute
- Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, USA
- 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}
}
https://doi.org/10.1039/C9SC00693A
Web of Science
Figures / Tables:

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