Reducing the irreducible: Dispersed metal atoms facilitate reduction of irreducible oxides.

23 September 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


heterogeneous catalysis
density functional theory
catalyst reducibility
single atom catalyst

Supplementary materials

Supporting Information for "Reducing the irreducible: Dispersed metal atoms facilitate reduction of irreducible oxides."
Details on constraint-induced gap states, technical details for the linear-response DFT+U implementation in GPAW, effects of varying U on TM adsorption energies, projected density of states plots, and analysis between the correlations.


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