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Adsorption of water at the SrO surface of ruthenates

Abstract

Although perovskite oxides hold promise in applications ranging from solid oxide fuel cells to catalysts, their surface chemistry is poorly understood at the molecular level. Here we follow the formation of the first monolayer of water at the (001) surfaces of Srn+1RunO3n+1 (n = 1, 2) using low-temperature scanning tunnelling microscopy, X-ray photoelectron spectroscopy, and density functional theory. These layered perovskites cleave between neighbouring SrO planes, yielding almost ideal, rocksalt-like surfaces. An adsorbed monomer dissociates and forms a pair of hydroxide ions. The OH stemming from the original molecule stays trapped at Sr–Sr bridge positions, circling the surface OH with a measured activation energy of 187 ± 10 meV. At higher coverage, dimers of dissociated water assemble into one-dimensional chains and form a percolating network where water adsorbs molecularly in the gaps. Our work shows the limitations of applying surface chemistry concepts derived for binary rocksalt oxides to perovskites.

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Figure 1: Water adsorption at cleaved strontium ruthenate single crystals.
Figure 2: Dissociated water forming a ‘dynamic ion pair’.
Figure 3: Formation of H2O chains.
Figure 4: Full monolayer of water.
Figure 5: Interaction of water with O vacancies.

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Acknowledgements

This work has been supported by the ERC Advanced Grant ‘OxideSurfaces’ and by the Austrian Science Fund (FWF, Project F45). The Tulane team (D.F., J.P. and Z.M.) acknowledge support by the NSF under grant DMR-1205469. The Vienna Scientific Cluster is gratefully acknowledged for providing computing time. The authors thank B. Yildiz for useful discussions.

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Contributions

D.H., B.S. and M.S. performed the STM experiments and data analysis. D.H., J.Pavelec and G.S.P. performed the XPS measurements. W.M.-S., F.M. and J.R. performed the DFT calculations. D.F., J.Peng and Z.M. grew the sample. U.D. directed and supervised the project. B.S., D.H., F.M., M.S., G.S.P. and U.D. wrote the manuscript.

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Correspondence to Ulrike Diebold.

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The authors declare no competing financial interests.

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Halwidl, D., Stöger, B., Mayr-Schmölzer, W. et al. Adsorption of water at the SrO surface of ruthenates. Nature Mater 15, 450–455 (2016). https://doi.org/10.1038/nmat4512

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