This title appears in the Scientific Report :
2018
Please use the identifier:
http://dx.doi.org/10.1021/acs.inorgchem.8b00393 in citations.
(Nd/Pr) 2 NiO 4+δ : Reaction Intermediates and Redox Behavior Explored by in Situ Neutron Powder Diffraction during Electrochemical Oxygen Intercalation
(Nd/Pr) 2 NiO 4+δ : Reaction Intermediates and Redox Behavior Explored by in Situ Neutron Powder Diffraction during Electrochemical Oxygen Intercalation
Oxygen intercalation/deintercalation in Pr2NiO4+δ and Nd2NiO4+δ was followed by in situ by neutron powder diffraction during the electrochemical oxidation/reduction reaction, in a dedicated reaction cell at room temperature. Three phases were identified for both systems: orthorhombic RE2NiO4.23, obt...
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Personal Name(s): | Ceretti, Monica (Corresponding author) |
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Wahyudi, Olivia / André, Gilles / Meven, Martin / Villesuzanne, Antoine / Paulus, Werner | |
Contributing Institute: |
Heinz Maier-Leibnitz Zentrum; MLZ Streumethoden; JCNS-2 JCNS-FRM-II; JCNS-FRM-II |
Published in: | Inorganic chemistry, 57 (2018) 8, S. 4657 - 4666 |
Imprint: |
Washington, DC
American Chemical Society
2018
|
DOI: |
10.1021/acs.inorgchem.8b00393 |
PubMed ID: |
29620364 |
Document Type: |
Journal Article |
Research Program: |
FRM II / MLZ Jülich Centre for Neutron Research (JCNS) |
Subject (ZB): | |
Publikationsportal JuSER |
Oxygen intercalation/deintercalation in Pr2NiO4+δ and Nd2NiO4+δ was followed by in situ by neutron powder diffraction during the electrochemical oxidation/reduction reaction, in a dedicated reaction cell at room temperature. Three phases were identified for both systems: orthorhombic RE2NiO4.23, obtained by classical solid-state reaction, gets reduced in a 2-phase reaction step to a tetragonal intermediate phase RE2NiO4+δ with 0.07 ≤ δ ≤ 0.10, which again transforms on further reduction in a 2-phase reaction step towards the stoichiometric RE2NiO4.0. Electrochemical oxidation does not proceed fully reversibly for both cases: while the re-oxidation of Nd2NiO4+δ is limited to the tetragonal intermediate phase with δ = 0.10, the homologous Pr2NiO4+δ can be re-oxidized up to δ = 0.17, showing orthorhombic symmetry. For the tetragonal Pr2NiO4.12 phase, we were able to establish a complex anharmonic displacement behavior as analyzed by single crystal neutron diffraction and Maximum Entropy Analysis, in agreement with a low-T diffusion pathway for oxygen ions activated by lattice dynamics. |