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Characterization of peroxo reaction intermediates in the water oxidation process on hematite surfaces

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Abstract

We use density functional theory-based calculations to study structural, electronic, and magnetic properties of two key reaction intermediates on a hematite, \(\alpha \)-Fe2O3, photoanode during the solar-driven water splitting reaction. Both intermediates contain an oxygen atom bonded to a surface iron atom. In one case, the adsorbed oxygen also forms a peroxo bond with a lattice oxygen from hematite; in the second case no such bond is formed. Both configurations are energetically equivalent and are related to the overpotential-determining step in the oxygen evolution reaction. The calculated reaction path for the breaking of the peroxo bond shows a barrier of about 0.86 eV for the transformation between the two intermediates. We explain this high barrier with the drastically different electronic and magnetic structure, which we also analyze using maximally localized Wannier functions. Photo-generated electron holes are shown to localize preferentially close to the reaction center at the surface in both configurations. In the case of the oxo species, this localization favors subsequent electron transfer steps during the oxygen evolution cycle. In the case of the peroxo configuration, this fact together with the high barrier for breaking the oxygen–oxygen bond indicates a possible loss mechanism due to hole trapping.

Calculated spin density at a hematite surface with peroxo intermediate

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Acknowledgements

L. Tchibota Poaty is greatful to the OFID Postgraduate Fellowship Programme at ICTP and to the ICTP-IAEA Sandwich Training Educational Programme under which this work has been performed.

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Authors and Affiliations

  1. The Abdus Salam International Centre for Theoretical Physics (ICTP), Strada Costiera 11, 34151, Trieste, Italy

    Lodvert Tchibota Poaty, Kanchan Ulman, Nicola Seriani & Ralph Gebauer

  2. Groupe de Simulations numériques en Magnétisme et Catalyse, Université Marien Ngouabi, Faculté des Sciences et Techniques, BP. 69, Brazzaville, Congo

    Lodvert Tchibota Poaty & Bernard M’Passi-Mabiala

  3. Unité de Recherche en Nanomatériaux et Nanotechnologies, Institut National de Recherche en Sciences Exactes et Naturelles (IRSEN), Brazzaville, Congo

    Bernard M’Passi-Mabiala

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  1. Lodvert Tchibota Poaty
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  2. Kanchan Ulman
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Correspondence to Ralph Gebauer.

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This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

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Poaty, L.T., Ulman, K., Seriani, N. et al. Characterization of peroxo reaction intermediates in the water oxidation process on hematite surfaces. J Mol Model 24, 284 (2018). https://doi.org/10.1007/s00894-018-3815-4

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