Topotactic Reduction-Induced Stabilization of β-La<sub>2</sub>Mo<sub>2</sub>O<sub>8.68</sub> Phase: Structure, Static Oxygen Disorder, and Electrical Properties
La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> is acknowledged as an exceptional oxide ion conductor. It undergoes a reversible phase transition around 580 °C from the nonconductive low-temperature monoclinic α-La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> phase to the highly conductive high-temperature cubic β-La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> phase. In addition, La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> demonstrates complex chemistry under reducing conditions. This study reports, for the first time, the stabilization at ambient temperature of a novel cubic phase through a topotactic reduction of α-La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> employing CaH<sub>2</sub>. This phase contains approximately ∼3 atom % oxygen vacancies relative to the nominal composition (La<sub>2</sub>Mo<sub>2</sub>O<sub>8.68(1)</sub>). The cubic symmetry is associated with a static distribution of these vacancies, in contrast to the dynamic distribution observed in the high-temperature cubic β-La<sub>2</sub>Mo<sub>2</sub>O<sub>9</sub> phase reported previously. Additionally, the material exhibits mixed-ion-electronic conduction, which expands its potential use in applications requiring both ionic and electronic transport.
Authors
- Xiaojun Kuang (ORCID: https://orcid.org/0000-0003-2975-9355)
- Michael J. Pitcher (ORCID: https://orcid.org/0000-0003-2044-6774)
- Alberto J. Fernández‐Carrión (ORCID: https://orcid.org/0000-0001-8320-2828)
- Cécile Genevois (ORCID: https://orcid.org/0000-0003-2955-2688)
- Mathieu Allix (ORCID: https://orcid.org/0000-0001-9317-1316)
- Cheng Li (ORCID: https://orcid.org/0000-0002-6546-6413)
- Xueting Zhang (ORCID: https://orcid.org/0000-0002-2502-7790)
- Xiaoyan Yang (ORCID: https://orcid.org/0000-0003-2493-7079)
Institutions
- Université d'Orléans (FR)
- Oak Ridge National Laboratory (US)
- Centre National de la Recherche Scientifique (FR)
- Guilin University of Technology (CN)
- Instituto de Ciencia de Materiales de Sevilla (ES)
- Le Studium (FR)
- Services déconcentrés d'appui à la recherche Val de Loire (FR)
- Conditions Extrêmes et Matériaux Haute Température et Irradiation (FR)
- Universidad de Sevilla (ES)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-11-19
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c02151
- Citations
- 3
- Primary Topic
- Electronic and Structural Properties of Oxides
- Type
- article
- Field-Weighted Citation Impact
- 0.35
Funders
- Natural Science Foundation of Guangxi Zhuang Autonomous Region
- National Natural Science Foundation of China
- Studium Loire Valley-Institute for Advanced Studies
- Junta de Andalucía
- Basic Energy Sciences