A1 Journal article (refereed)
Reducing the Irreducible : Dispersed Metal Atoms Facilitate Reduction of Irreducible Oxides (2022)

Korpelin, V., Melander, M. M., & Honkala, K. (2022). Reducing the Irreducible : Dispersed Metal Atoms Facilitate Reduction of Irreducible Oxides. Journal of Physical Chemistry C, 126(2), 933-945. https://doi.org/10.1021/acs.jpcc.1c08979

JYU authors or editors

Korpelin, Ville
Melander, Marko
Honkala, Karoliina

Publication details

All authors or editors: Korpelin, Ville; Melander, Marko M.; Honkala, Karoliina

Journal or series: Journal of Physical Chemistry C

ISSN: 1932-7447

eISSN: 1932-7455

Publication year: 2022

Publication date: 10/01/2022

Volume: 126

Issue number: 2

Pages range: 933-945

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.jpcc.1c08979

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/79312

Web address of parallel published publication (pre-print): https://chemrxiv.org/engage/chemrxiv/article-details/614c375ab1d4a6c2ea917354

Abstract

Oxide reducibility is a central concept quantifying the role of the support in catalysis. While reducible oxides are often considered catalytically active, irreducible oxides are seen as inert supports. Enhancing the reducibility of irreducible oxides has, however, emerged as an effective way to increase their catalytic activity while retaining their inherent thermal stability. In this work, we focus on the prospect of using single metal atoms to increase the reducibility of a prototypical irreducible oxide, zirconia. Based on extensive self-consistent DFT+U calculations, we demonstrate that single metal atoms significantly improve and tune the surface reducibility of zirconia. Detailed analysis of the observed single atom induced reducibility allows us to attribute the enhanced reducibility to strong interactions between the metal atom and the electrons trapped in the vacancy and d–p orbital interactions between the metal atom and oxygen. This analysis enables transferring the obtained theoretical understanding to other irreducible oxides as well. The detailed understanding of how oxide reducibility can be tuned offers precise control over the catalytic properties of metal oxides.

Keywords: catalysis; oxidation-reduction reaction; oxides; zirconium dioxide; metals; adsorption; surface chemistry