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Title: Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride

Abstract

A complex hydride (LaMg2NiH7) composed of La3+, two Mg2+, [NiH4]4– with a covalently bonded hydrogen, and three H was formed from an intermetallic LaMg2Ni via an intermediate phase (LaMg2NiH4.6) composed of La, Mg, NiH2, NiH3 units, and H atoms at tetrahedral sites. The NiH2 and NiH3 units in LaMg2NiH4.6 were reported as precursors for [NiH4]4– in LaMg2NiH7 [Miwa et al. J. Phys. Chem. C 2016, 120, 5926–5931]. To further understand the hydrogen states in the precursors (the NiH2 and NiH3 units) and H atoms at the tetrahedral sites in the intermediate phase, LaMg2NiH4.6, we observed the hydrogen vibrations in LaMg2NiH4.6 and LaMg2NiH7 by using inelastic neutron scattering. A comparison of the hydrogen vibrations of the NiH2 and NiH3 units with that of [NiH4]4– shows that the librational modes of the NiH2 and NiH3 units were nonexistent; librational modes are characteristic modes for complex anions, such as [NiH4]4–. Furthermore, the hydrogen vibrations for the H atoms in the tetrahedral sites showed a narrower wavenumber range than that for H and a wider range than that for typical interstitial hydrogen. The results indicated the presence of intermediate hydrogen states before the formation of [NiH4]4– and H.

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [4]
  1. Tohoku Univ., Sendai (Japan). Inst. for Materials Research
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Neutron Sciences Directorate
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Neutron Sciences Directorate
  4. Tohoku Univ., Sendai (Japan). Inst. for Materials Research; Tohoku Univ., Sendai (Japan). WPI-Advanced Inst. for Materials Research
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Laboratory Directed Research and Development (LDRD) Program; Japan Society for the Promotion of Science (JSPS)
OSTI Identifier:
1422532
Grant/Contract Number:  
AC05-00OR22725; 16K06766; 25220911
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 2; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Inelastic neutron scattering; complex hydride; hydrogen state

Citation Formats

Sato, Toyoto, Ramirez-Cuesta, Anibal J., Daemen, Luke L., Cheng, Yongqiang, and Orimo, Shin-ichi. Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b02834.
Sato, Toyoto, Ramirez-Cuesta, Anibal J., Daemen, Luke L., Cheng, Yongqiang, & Orimo, Shin-ichi. Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride. United States. https://doi.org/10.1021/acs.inorgchem.7b02834
Sato, Toyoto, Ramirez-Cuesta, Anibal J., Daemen, Luke L., Cheng, Yongqiang, and Orimo, Shin-ichi. Tue . "Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride". United States. https://doi.org/10.1021/acs.inorgchem.7b02834. https://www.osti.gov/servlets/purl/1422532.
@article{osti_1422532,
title = {Evidence of Intermediate Hydrogen States in the Formation of a Complex Hydride},
author = {Sato, Toyoto and Ramirez-Cuesta, Anibal J. and Daemen, Luke L. and Cheng, Yongqiang and Orimo, Shin-ichi},
abstractNote = {A complex hydride (LaMg2NiH7) composed of La3+, two Mg2+, [NiH4]4– with a covalently bonded hydrogen, and three H– was formed from an intermetallic LaMg2Ni via an intermediate phase (LaMg2NiH4.6) composed of La, Mg, NiH2, NiH3 units, and H atoms at tetrahedral sites. The NiH2 and NiH3 units in LaMg2NiH4.6 were reported as precursors for [NiH4]4– in LaMg2NiH7 [Miwa et al. J. Phys. Chem. C 2016, 120, 5926–5931]. To further understand the hydrogen states in the precursors (the NiH2 and NiH3 units) and H atoms at the tetrahedral sites in the intermediate phase, LaMg2NiH4.6, we observed the hydrogen vibrations in LaMg2NiH4.6 and LaMg2NiH7 by using inelastic neutron scattering. A comparison of the hydrogen vibrations of the NiH2 and NiH3 units with that of [NiH4]4– shows that the librational modes of the NiH2 and NiH3 units were nonexistent; librational modes are characteristic modes for complex anions, such as [NiH4]4–. Furthermore, the hydrogen vibrations for the H atoms in the tetrahedral sites showed a narrower wavenumber range than that for H– and a wider range than that for typical interstitial hydrogen. The results indicated the presence of intermediate hydrogen states before the formation of [NiH4]4– and H–.},
doi = {10.1021/acs.inorgchem.7b02834},
journal = {Inorganic Chemistry},
number = 2,
volume = 57,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Crystal structures of (a) LaMg2NiH7 and (b) LaMg2NiH4.6. Gray, orange, green, blue, and cyan circles and cyan tetrahedra indicate La, Mg, Ni, H (Hcov.), and H (Htet.) atoms and the tetrahedral sites of H (Htet.), respectively. The local atomic structures around Ni ([NiH4]4−, NiH1.9, and NiH3.3) and Hmore » (H and Htet.) are illustrated on the right.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.