Issue 12, 2023

Universal properties of metal-supported oxide films from linear scaling relationships: elucidation of mechanistic origins of strong metal–support interactions

Abstract

The properties of ultrathin (1–2 monolayer) (hydroxy)oxide films on transition metal substrates have been extensively studied as models of the celebrated Strong Metal–Support Interaction (SMSI) and related phenomena. However, results from these analyses have been largely system specific, and limited insights into the general principles that govern film/substrate interactions exist. Here, using Density Functional Theory (DFT) calculations, we analyze the stability of ZnOxHy films on transition metal surfaces and show that the formation energies of these films are related to the binding energies of isolated Zn and O atoms via linear scaling relationships (SRs). Such relationships have previously been identified for adsorbates on metal surfaces and have been rationalized in terms of bond order conservation (BOC) principles. However, for thin (hydroxy)oxide films, SRs are not governed by standard BOC relationships, and a generalized bonding model is required to explain the slopes of these SRs. We introduce such a model for the ZnOxHy films and confirm that it also describes the behavior of reducible transition metal oxide films, such as TiOxHy, on metal substrates. We demonstrate how the SRs may be combined with grand canonical phase diagrams to predict film stability under conditions relevant to heterogeneous catalytic reactions, and we apply these insights to estimate which transition metals are likely to exhibit SMSI behavior under realistic environmental conditions. Finally, we discuss how SMSI overlayer formation for irreducible oxides, such as ZnO, is linked to hydroxylation and is mechanistically distinct from the overlayer formation for reducible oxides such as TiO2.

Graphical abstract: Universal properties of metal-supported oxide films from linear scaling relationships: elucidation of mechanistic origins of strong metal–support interactions

Supplementary files

Article information

Article type
Edge Article
Submitted
05 Dec 2022
Accepted
31 Jan 2023
First published
04 Feb 2023
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., 2023,14, 3206-3214

Universal properties of metal-supported oxide films from linear scaling relationships: elucidation of mechanistic origins of strong metal–support interactions

K. J. Sawant, Z. Zeng and J. P. Greeley, Chem. Sci., 2023, 14, 3206 DOI: 10.1039/D2SC06656D

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.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements