Synthesis of Defect Perovskites (He2–x⟂x)(CaZr)F6 by Inserting Helium into the Negative Thermal Expansion Material CaZrF6

Hester, Brett R.; dos Santos, António M.; Molaison, Jamie J.; Hancock, Justin C.; Wilkinson, Angus P.

doi:10.1021/jacs.7b07860

Synthesis of Defect Perovskites (He_2–x⟂_x)(CaZr)F₆ by Inserting Helium into the Negative Thermal Expansion Material CaZrF₆

Journal Article · Mon Sep 11 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b07860· OSTI ID:1399917

Hester, Brett R. ^[1]; dos Santos, António M. ^[2]; Molaison, Jamie J. ^[2]; Hancock, Justin C. ^[1]; ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Defect perovskites (He_2–x⟂_x)(CaZr)F₆ can be prepared by inserting helium into CaZrF₆ at high pressure. They can be recovered to ambient pressure at low temperature. There are no prior examples of perovskites with noble gases on the A-sites. The insertion of helium gas into CaZrF₆ both elastically stiffens the material and reduces the magnitude of its negative thermal expansion. It also suppresses the onset of structural disorder, which is seen on compression in other media. Measurements of the gas released on warming to room temperature and Rietveld analyses of neutron diffraction data at low temperature indicate that exposure to helium gas at 500 MPa leads to a stoichiometry close to (He₁⟂₁)(CaZr)F₆. Helium has a much higher solubility in CaZrF₆ than silica glass or crystobalite. An analogue with composition (H₂)₂(CaZr)F₆ would have a volumetric hydrogen storage capacity greater than current US DOE targets. We anticipate that other hybrid perovskites with small neutral molecules on the A-site can also be prepared and that they will display a rich structural chemistry.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1399917

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 139; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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