Dopant Clusterization and Oxygen Coordination in Ta-Doped Bismuth Oxide: A Structural and Computational Insight into the Mechanism of Anion Conduction

Stefania Di Tommaso, Francesco Giannici, Antonino Martorana, Frédéric Labat, Alessandro Longo, Marianna Gambino

Risultato della ricerca: Article

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Abstract

Bi2O3 in its fluorite-like form can be obtained either at 730-824 °C, showing the highest oxide-ion conduction known so far, or by doping. We present a comprehensive appraisal of the local atomic structure of Ta-doped Bi2O3 investigating by X-ray absorption spectroscopy the aggregation motifs of Ta5+ and the interaction between dopants and oxygen vacancies. Using periodic density functional theory simulations, we show that the connection of Ta4O18 aggregates is energetically favorable. We find that the local coordination of Bi3+ and its electronic structure, as seen from the calculated density of states (DOS), are invariably determined by the Bi 6s2 lone pair in both doped and undoped Bi2O3. This does not depend on the long-range symmetry that is revealed by X-ray diffraction studies. From the similarity of the DOS of α-Bi2O3 and Ta-doped bismuth oxide, it is inferred that the force governing the local coordination of Bi is essentially the same in all forms of Bi2O3. As the local Bi environment, determined by X-ray absorption spectroscopy, is also found to be very similar in all investigated samples, regardless of the dopant concentration, the local mechanism of oxide ion diffusion is arguably similar in doped and undoped bismuth oxide.
Lingua originaleEnglish
pagine (da-a)26367-26373
Numero di pagine7
RivistaJOURNAL OF PHYSICAL CHEMISTRY. C
Volume119
Stato di pubblicazionePublished - 2015

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bismuth oxides
Bismuth
Anions
X ray absorption spectroscopy
Negative ions
Doping (additives)
Oxygen
anions
conduction
Oxides
absorption spectroscopy
oxygen
Ions
x rays
oxides
Fluorspar
fluorite
Oxygen vacancies
atomic structure
Electronic structure

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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title = "Dopant Clusterization and Oxygen Coordination in Ta-Doped Bismuth Oxide: A Structural and Computational Insight into the Mechanism of Anion Conduction",
abstract = "Bi2O3 in its fluorite-like form can be obtained either at 730-824 °C, showing the highest oxide-ion conduction known so far, or by doping. We present a comprehensive appraisal of the local atomic structure of Ta-doped Bi2O3 investigating by X-ray absorption spectroscopy the aggregation motifs of Ta5+ and the interaction between dopants and oxygen vacancies. Using periodic density functional theory simulations, we show that the connection of Ta4O18 aggregates is energetically favorable. We find that the local coordination of Bi3+ and its electronic structure, as seen from the calculated density of states (DOS), are invariably determined by the Bi 6s2 lone pair in both doped and undoped Bi2O3. This does not depend on the long-range symmetry that is revealed by X-ray diffraction studies. From the similarity of the DOS of α-Bi2O3 and Ta-doped bismuth oxide, it is inferred that the force governing the local coordination of Bi is essentially the same in all forms of Bi2O3. As the local Bi environment, determined by X-ray absorption spectroscopy, is also found to be very similar in all investigated samples, regardless of the dopant concentration, the local mechanism of oxide ion diffusion is arguably similar in doped and undoped bismuth oxide.",
author = "{Di Tommaso}, Stefania and Francesco Giannici and Antonino Martorana and Fr{\'e}d{\'e}ric Labat and Alessandro Longo and Marianna Gambino",
year = "2015",
language = "English",
volume = "119",
pages = "26367--26373",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",

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TY - JOUR

T1 - Dopant Clusterization and Oxygen Coordination in Ta-Doped Bismuth Oxide: A Structural and Computational Insight into the Mechanism of Anion Conduction

AU - Di Tommaso, Stefania

AU - Giannici, Francesco

AU - Martorana, Antonino

AU - Labat, Frédéric

AU - Longo, Alessandro

AU - Gambino, Marianna

PY - 2015

Y1 - 2015

N2 - Bi2O3 in its fluorite-like form can be obtained either at 730-824 °C, showing the highest oxide-ion conduction known so far, or by doping. We present a comprehensive appraisal of the local atomic structure of Ta-doped Bi2O3 investigating by X-ray absorption spectroscopy the aggregation motifs of Ta5+ and the interaction between dopants and oxygen vacancies. Using periodic density functional theory simulations, we show that the connection of Ta4O18 aggregates is energetically favorable. We find that the local coordination of Bi3+ and its electronic structure, as seen from the calculated density of states (DOS), are invariably determined by the Bi 6s2 lone pair in both doped and undoped Bi2O3. This does not depend on the long-range symmetry that is revealed by X-ray diffraction studies. From the similarity of the DOS of α-Bi2O3 and Ta-doped bismuth oxide, it is inferred that the force governing the local coordination of Bi is essentially the same in all forms of Bi2O3. As the local Bi environment, determined by X-ray absorption spectroscopy, is also found to be very similar in all investigated samples, regardless of the dopant concentration, the local mechanism of oxide ion diffusion is arguably similar in doped and undoped bismuth oxide.

AB - Bi2O3 in its fluorite-like form can be obtained either at 730-824 °C, showing the highest oxide-ion conduction known so far, or by doping. We present a comprehensive appraisal of the local atomic structure of Ta-doped Bi2O3 investigating by X-ray absorption spectroscopy the aggregation motifs of Ta5+ and the interaction between dopants and oxygen vacancies. Using periodic density functional theory simulations, we show that the connection of Ta4O18 aggregates is energetically favorable. We find that the local coordination of Bi3+ and its electronic structure, as seen from the calculated density of states (DOS), are invariably determined by the Bi 6s2 lone pair in both doped and undoped Bi2O3. This does not depend on the long-range symmetry that is revealed by X-ray diffraction studies. From the similarity of the DOS of α-Bi2O3 and Ta-doped bismuth oxide, it is inferred that the force governing the local coordination of Bi is essentially the same in all forms of Bi2O3. As the local Bi environment, determined by X-ray absorption spectroscopy, is also found to be very similar in all investigated samples, regardless of the dopant concentration, the local mechanism of oxide ion diffusion is arguably similar in doped and undoped bismuth oxide.

UR - http://hdl.handle.net/10447/192648

UR - http://pubs.acs.org/journal/jpccck

M3 - Article

VL - 119

SP - 26367

EP - 26373

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

ER -