Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides

Journal article

Zhang, X., Liu, T., Zhu, L., Guan, J., Lu, Y., Keal, T. W., Buckeridge, J., Catlow, R. and Sokol, A. A. (2023). Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides. Angewandte Chemie International Edition. e202308411. https://doi.org/10.1002/anie.202308411
AuthorsZhang, X., Liu, T., Zhu, L., Guan, J., Lu, Y., Keal, T. W., Buckeridge, J., Catlow, R. and Sokol, A. A.
Abstract

Determining the absolute band edge positions in solid
materials is crucial for optimising their performance in wide-ranging applications including photocatalysis and electronic devices. However, obtaining absolute energies is challenging, as seen in CeO2, where experimental measurements show substantial discrepancies in the ionisation potential (IP). Here, we have combined several theoretical approaches, from classical electrostatics to quantum mechanics, to elucidate the bulk and surface contributions to the IP of metal oxides. We have determined a theoretical bulk contribution to the IP of stoichiometric CeO2 of only 5.38 eV, while surface orientation results in intrinsic IP variations from 4.2 eV to 8.2 eV. Highly tuneable IPs were also found in TiO2, ZrO2, and HfO2, in which surface polarisation plays a pivotal role in long-range energy level shifting. Our analysis, in addition to rationalising the observed range of experimental results, provides a firm basis for future interpretations of experimental and computational studies of oxide band structures.

KeywordsGeneral Chemistry; Catalysis; Metal oxides; Surface chemistry; QM/MM; Ionization potential; Ceria
Year2023
JournalAngewandte Chemie International Edition
Journal citatione202308411
PublisherWiley
ISSN1433-7851
1521-3773
Digital Object Identifier (DOI)https://doi.org/10.1002/anie.202308411
Publication dates
Online28 Jul 2023
Publication process dates
Accepted28 Jul 2023
Deposited22 Aug 2023
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Buckeridge et al. Reply:
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