Topotactic Reduction-Induced Stabilization of β-La2Mo2O8.68 Phase: Structure, Static Oxygen Disorder, and Electrical Properties

Xueting Zhang; Cecile Genevois; Cheng Li; Xiaoyan Yang; Michael J. Pitcher; Mathieu Allix; Xiaojun Kuang; Alberto J. Fernández-Carrión

doi:10.1021/acs.inorgchem.4c02151

Topotactic Reduction-Induced Stabilization of β-La₂Mo₂O_8.68 Phase: Structure, Static Oxygen Disorder, and Electrical Properties

Xueting Zhang, Cecile Genevois, Cheng Li, Xiaoyan Yang, Michael J. Pitcher, Mathieu Allix, Xiaojun Kuang, Alberto J. Fernández-Carrión

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

Abstract

La₂Mo₂O₉ is acknowledged as an exceptional oxide ion conductor. It undergoes a reversible phase transition around 580 °C from the nonconductive low-temperature monoclinic α-La₂Mo₂O₉ phase to the highly conductive high-temperature cubic β-La₂Mo₂O₉ phase. In addition, La₂Mo₂O₉ 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-La₂Mo₂O₉ employing CaH₂. This phase contains approximately ∼3 atom % oxygen vacancies relative to the nominal composition (La₂Mo₂O_8.68(1)). 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-La₂Mo₂O₉ phase reported previously. Additionally, the material exhibits mixed-ion-electronic conduction, which expands its potential use in applications requiring both ionic and electronic transport.

Original language	English
Pages (from-to)	22667-22676
Number of pages	10
Journal	Inorganic Chemistry
Volume	63
Issue number	48
DOIs	https://doi.org/10.1021/acs.inorgchem.4c02151
State	Published - Dec 2 2024

Funding

The authors thank the National Science Foundation of China (Nos. 21850410458, 22365011, 22090043) and the Guangxi Natural Science Foundation (Nos. 2019GXNSFGA245006, 2020GXNSFAA297050) for the financial support and the EMERGIA program from Junta de Andaluci\u0301a [No. 2022/00001043]. AJFC is extremely grateful to LE STUDIUM for the financial support. Use of the Advanced Photon Source at the Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to NOMAD on proposal number IPTS-28909. The project benefitted from the microscopy facilities of the Platform MACLE-CVL which was cofunded by the European Union and Centre-Val de Loire Region (FEDER). We thank Dr. Emmanuel Veron and Sandra Ory (CEMHTI laboratory) for the VT-XRD and DSC-TG data acquisition.

Funders	Funder number
STUDIUM
U.S. Department of Energy
VT-XRD
Office of Science
European Union and Centre-Val de Loire Region
European Regional Development Fund
Basic Energy Sciences	DE-AC02-06CH11357
Oak Ridge National Laboratory	IPTS-28909
National Natural Science Foundation of China	22365011, 21850410458, 22090043
Junta de Andalucía	2022/00001043
Natural Science Foundation of Guangxi Province	2019GXNSFGA245006, 2020GXNSFAA297050

Access to Document

10.1021/acs.inorgchem.4c02151

Cite this

@article{a1c52e244b8d4007bee7cb7f62bda552,

title = "Topotactic Reduction-Induced Stabilization of β-La2Mo2O8.68 Phase: Structure, Static Oxygen Disorder, and Electrical Properties",

abstract = "La2Mo2O9 is acknowledged as an exceptional oxide ion conductor. It undergoes a reversible phase transition around 580 °C from the nonconductive low-temperature monoclinic α-La2Mo2O9 phase to the highly conductive high-temperature cubic β-La2Mo2O9 phase. In addition, La2Mo2O9 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-La2Mo2O9 employing CaH2. This phase contains approximately ∼3 atom % oxygen vacancies relative to the nominal composition (La2Mo2O8.68(1)). 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-La2Mo2O9 phase reported previously. Additionally, the material exhibits mixed-ion-electronic conduction, which expands its potential use in applications requiring both ionic and electronic transport.",

author = "Xueting Zhang and Cecile Genevois and Cheng Li and Xiaoyan Yang and Pitcher, {Michael J.} and Mathieu Allix and Xiaojun Kuang and Fern{\'a}ndez-Carri{\'o}n, {Alberto J.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = dec,

day = "2",

doi = "10.1021/acs.inorgchem.4c02151",

language = "English",

volume = "63",

pages = "22667--22676",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "48",

}

TY - JOUR

T1 - Topotactic Reduction-Induced Stabilization of β-La2Mo2O8.68 Phase

T2 - Structure, Static Oxygen Disorder, and Electrical Properties

AU - Zhang, Xueting

AU - Genevois, Cecile

AU - Li, Cheng

AU - Yang, Xiaoyan

AU - Pitcher, Michael J.

AU - Allix, Mathieu

AU - Kuang, Xiaojun

AU - Fernández-Carrión, Alberto J.

PY - 2024/12/2

Y1 - 2024/12/2

N2 - La2Mo2O9 is acknowledged as an exceptional oxide ion conductor. It undergoes a reversible phase transition around 580 °C from the nonconductive low-temperature monoclinic α-La2Mo2O9 phase to the highly conductive high-temperature cubic β-La2Mo2O9 phase. In addition, La2Mo2O9 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-La2Mo2O9 employing CaH2. This phase contains approximately ∼3 atom % oxygen vacancies relative to the nominal composition (La2Mo2O8.68(1)). 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-La2Mo2O9 phase reported previously. Additionally, the material exhibits mixed-ion-electronic conduction, which expands its potential use in applications requiring both ionic and electronic transport.

AB - La2Mo2O9 is acknowledged as an exceptional oxide ion conductor. It undergoes a reversible phase transition around 580 °C from the nonconductive low-temperature monoclinic α-La2Mo2O9 phase to the highly conductive high-temperature cubic β-La2Mo2O9 phase. In addition, La2Mo2O9 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-La2Mo2O9 employing CaH2. This phase contains approximately ∼3 atom % oxygen vacancies relative to the nominal composition (La2Mo2O8.68(1)). 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-La2Mo2O9 phase reported previously. Additionally, the material exhibits mixed-ion-electronic conduction, which expands its potential use in applications requiring both ionic and electronic transport.

UR - http://www.scopus.com/inward/record.url?scp=85209764190&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.4c02151

DO - 10.1021/acs.inorgchem.4c02151

M3 - Article

AN - SCOPUS:85209764190

SN - 0020-1669

VL - 63

SP - 22667

EP - 22676

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 48

ER -

Topotactic Reduction-Induced Stabilization of β-La₂Mo₂O_8.68 Phase: Structure, Static Oxygen Disorder, and Electrical Properties

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this