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Theoretical insights into the surface physics and chemistry of redox-active oxides

Nature Reviews Materials volume 5, pages 460–475 (2020)Cite this article

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An Author Correction to this article was published on 15 June 2020

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Abstract

Redox-active oxides find use in many applications, including catalysts, photovoltaic devices, self-cleaning glasses, chemical sensors and electronic components. Their utility derives from their unique ability to access multiple metal-charge states within a finite energy window. However, this property also confounds our ability to study reducible oxides, because it leads to structural, compositional and electronic complexities that elude simplistic models of materials structure and function. Oxygen vacancies play a critical role in shaping the functional properties of such oxides; most notably, they lead to mobile-charge imbalances that impact surface processes at substantial distances from the originating defect. Atomistic simulations are inherently equipped to illuminate these phenomena at a fundamental level; however, reducible oxides pose great challenges, owing to the high level of electron correlation needed to correctly describe them. Understanding how defects form, couple, propagate, agglomerate or repel each other and influence the surface properties of reducible oxides is only now coming into the grasp of modern theory and simulation capabilities. This knowledge is also key to discovering and controlling emergent materials properties with tunable multifunctionalities at the nanometre scale and beyond.

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Fig. 1: Defects in TiO2.
Fig. 2: Polaronic states created by a surface oxygen vacancy on rutile TiO2 (110) and anatase TiO2 (101).
Fig. 3: Surface structure and typical defects on rutile TiO2 (110).
Fig. 4: Dependence of the reaction barriers at metal catalysts on the availability of charge carriers at the surface of redox-active oxides.
Fig. 5: Surface acid/base properties are important for understanding the reactive dissociation of molecules on redox-active oxide surfaces.
Fig. 6: Simulation of polaron mobility to and from a hydroxylated anatase TiO2 (101) surface in contact with liquid water.

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Acknowledgements

This manuscript was written with support of all three authors from U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Work by R.R. and V.-A.G. was performed at Pacific Northwest National Laboratory (PNNL), which is a multiprogramme laboratory operated for the DOE by the Battelle Memorial Institute under contract no. DE-AC05-76RL01830. A.S. was supported under award DE-SC0007347.

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  1. Basic & Applied Molecular Foundations Group, Physical & Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, USA

    Roger Rousseau & Vassiliki-Alexandra Glezakou

  2. Princeton University, Princeton, NJ, USA

    Annabella Selloni

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Rousseau, R., Glezakou, VA. & Selloni, A. Theoretical insights into the surface physics and chemistry of redox-active oxides. Nat Rev Mater 5, 460–475 (2020). https://doi.org/10.1038/s41578-020-0198-9

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