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.
Bibliographical noteFunding Information:
J. R. D. and M. S. acknowledge support from ERC AdG Intersolar (291482) and the Imperial College President's PhD Scholarship scheme. E. P. acknowledges the Engineering and Physical Sciences Research Council (EPSRC) for DTP funding. A. K. thanks Imperial College for a Junior Research Fellowship, the EPSRC for a Capital Award Emphasising Support for Early Career Researchers and the Royal Society for an Equipment Grant (RSG\R1\180434). L. F. thanks the EU for a Marie Curie fellowship (658270). J. Y. is supported by the Director, Office of Science, Office of Basic Energy Sciences (OBES), Division of Chemical Sciences, Geosciences, and Biosciences (CSGB) of the Department of Energy (DOE). The XAS work was done at BL 7-3 at the Stanford Synchrotron Radiation Lightsource. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. J.-S. P. thanks the Royal Society for a Shooter International Fellowship. A. W. and J.-S. P. are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1).
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