High Pressure Synthesis of Pr <sub>2</sub> O <sub>5</sub> – A Unique Lanthanoid(IV) Oxide Peroxide
Reacting praseodymium(IV) oxide with oxygen at 27 GPa in a diamond anvil cell yielded the oxide peroxide Pr<sub>2</sub> <sup>IV</sup>(O<sub>2</sub>)O<sub>3</sub>, which was characterized by single crystal X-ray diffraction on multi-grain samples, Raman spectroscopy and quantum theoretical calculations at various pressure points. The presence of tetravalent praseodymium ions is supported by electronic structure calculations, showing a band gap of ca. 1.2 eV, which is consistent with the anticipated chemical model of an ionic solid. Pr<sub>2</sub>(O<sub>2</sub>)O<sub>3</sub> thus far represents the most oxygen rich phase of any binary compound of a lanthanoid and oxygen and is the first example of a peroxide anion next to Pr<sup>4+</sup>. Additionally, these results demonstrate that instead of oxidizing the praseodymium ions past their +IV oxidation state, oxygen undergoes a comproportionation to form peroxide anions. Direct oxidation of the oxide anions by Pr<sup>4+</sup>-ions was ruled out by a control experiment in argon instead of oxygen, where no oxidation of oxide ions was observed.
Authors
- Vitali B. Prakapenka (ORCID: https://orcid.org/0000-0001-9270-2330)
- Timofey Fedotenko (ORCID: https://orcid.org/0000-0002-4602-2059)
- Mohamed Mézouar (ORCID: https://orcid.org/0000-0001-5336-544X)
- Nico Giordano (ORCID: https://orcid.org/0000-0001-9518-1251)
- Mohammad Amirabbasi (ORCID: https://orcid.org/0000-0003-1457-8949)
- Mathias S. Wickleder (ORCID: https://orcid.org/0000-0002-8864-4227)
- Stella Chariton (ORCID: https://orcid.org/0000-0001-5522-0498)
- Björn Wehinger (ORCID: https://orcid.org/0000-0002-7089-595X)
- Elena A. Bykova (ORCID: https://orcid.org/0000-0001-8652-024X)
- Maxim Bykov (ORCID: https://orcid.org/0000-0003-0248-1728)
- Niko T. Flosbach (ORCID: https://orcid.org/0000-0003-0778-762X)
- Marcus Ekholm (ORCID: https://orcid.org/0000-0002-7563-1494)
- Igor A. Abrikosov (ORCID: https://orcid.org/0000-0001-7551-4717)
- Pascal L. Jurzick (ORCID: https://orcid.org/0009-0006-3044-3955)
- Lukas Brüning (ORCID: https://orcid.org/0000-0002-3119-4464)
Institutions
- Linköping University (SE)
- Goethe University Frankfurt (DE)
- University of Cologne (DE)
- Deutsches Elektronen-Synchrotron DESY (DE)
- European Synchrotron Radiation Facility (FR)
- Technische Universität Darmstadt (DE)
- University of Chicago (US)
- Physical Sciences (United States) (US)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-02-03
- DOI
- https://doi.org/10.1002/anie.202422929
- Citations
- 3
- Primary Topic
- Crystal Structures and Properties
- Type
- article
- Field-Weighted Citation Impact
- 1.28
Funders
- National Science Foundation
- U.S. Department of Energy
- University of Chicago
- Swedish e-Science Research Centre
- European Commission
- Deutsche Forschungsgemeinschaft
- European Synchrotron Radiation Facility
- National Science Council
- Linköpings Universitet
- Knut och Alice Wallenbergs Stiftelse
- Vetenskapsrådet
- China Scholarship Council
- Office of Science
- Deutsches Elektronen-Synchrotron
- National Supercomputer Centre, Linköpings Universitet
- Argonne National Laboratory