Topotactic redox chemistry of NaFeAs in water and air and superconducting behavior with stoichiometry change.
We report experimental evidence that shows superconductivity in NaFeAs occurs when it is Na deficient. The oxidation of NaFeAs progresses differently in water and in air. In water the material oxidizes slowly and slightly retaining the original anti-PbFCl structure. In air NaFeAs oxidizes topotactically quickly and extensively transforming to the ThCr{sub 2}Si{sub 2} structure type. Water acts as a mild oxidizing agent on the FeAs layer by extracting electrons and Na{sup +} cations from the structure, while oxidation in air is more extensive and leads to change in structure type from NaFeAs to NaFe{sub 2}As{sub 2}. The superconducting transition temperature moves dramatically during the oxidation process. Exposed to water for an extended time period NaFeAs shows a substantial increase in T{sub c} up to 25 K with contraction of unit cell volume. NaFe{sub 2}As{sub 2}, the air oxidized product, shows T{sub c} of 12 K. We report detailed characterization of the redox chemistry and transformation of NaFeAs in water and air using single crystal and powder X-ray diffraction, magnetization studies, transmission electron microscopy, Moessbauer spectroscopy, pOH and elemental analysis.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC); NSF-NSEC; NSF-MRSEC; Keck Foundation; State of Illinois; Northwestern Univ.
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 984703
- Report Number(s):
- ANL/MSD/JA-66140; TRN: US201016%%1429
- Journal Information:
- Chem. Mater., Vol. 22, Issue 13 ; Jul. 13, 2010
- Country of Publication:
- United States
- Language:
- ENGLISH
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