Structure, Magnetism, and the Interaction of Water with Ti-Doped Fe3O4 Surfaces

Kelsey A. Stoerzinger, Carolyn I. Pearce, Timothy C. Droubay, Vaithiyalingam Shutthanandan, Zhi Liu, Elke Arenholz, Kevin M. Rosso

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The functionality of magnetite, Fe3O4, for catalysis and spintronics applications is dependent on the molar ratio of Fe2+ and Fe3+ and their distribution at the surface. In turn, this depends on a poorly understood interplay between crystallographic orientation, dopants, and the reactive adsorption of atmospheric species such as water. Here, (100)-, (110)-, and (111)-oriented films of titano-magnetite, Fe(3-x)TixO4, were grown by pulsed laser deposition and their composition, valence distribution, magnetism, and interaction with water were studied by ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and X-ray magnetic circular dichroism. Although the bulk compositions match the desired stoichiometry, the surfaces were found to be enriched in Ti4+, especially the top 1 nm. The highest surface energy (110) film was the most reduced, tied to local Ti enrichment, and a corresponding decreased magnetic moment. AP-XPS showed that incorporation of x = 0.25 Ti dramatically lowered the propensity to form hydroxyl species at a given relative humidity, and also that hydroxylation is relatively invariant with orientation. In contrast, the affinity for water is similar across orientations, regardless of Ti incorporation, suggesting that relative humidity controls its uptake. The findings may help demystify the interactions that lead to specific distributions of Fe2+ and Fe3+ at magnetite surfaces, toward design of more deliberately active catalysts and magnetic devices.

Original languageEnglish (US)
Pages (from-to)13872-13879
Number of pages8
JournalLangmuir
Volume35
Issue number43
DOIs
StatePublished - Oct 29 2019
Externally publishedYes

Bibliographical note

Publisher Copyright:
Copyright © 2019 American Chemical Society.

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