Issue 22, 2019

Effect of oxygen deficiency on the excited state kinetics of WO3 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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
08 feb 2019
Accepted
12 apr 2019
First published
09 mei 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 5667-5677

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

M. Sachs, J. Park, E. Pastor, A. Kafizas, A. A. Wilson, L. Francàs, S. Gul, M. Ling, C. Blackman, J. Yano, A. Walsh and J. R. Durrant, Chem. Sci., 2019, 10, 5667 DOI: 10.1039/C9SC00693A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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