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

Sato, Toyoto; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.; Cheng, Yongqiang; Orimo, Shin-ichi

doi:10.1021/acs.inorgchem.7b02834

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

Journal Article · Tue Dec 26 00:00:00 EST 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b02834· OSTI ID:1422532

^[1]; Ramirez-Cuesta, Anibal J. ^[2]; Daemen, Luke L. ^[3]; Cheng, Yongqiang ^[3]; Orimo, Shin-ichi ^[4]

Tohoku Univ., Sendai (Japan). Inst. for Materials Research
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Neutron Sciences Directorate
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division, Neutron Sciences Directorate
Tohoku Univ., Sendai (Japan). Inst. for Materials Research; Tohoku Univ., Sendai (Japan). WPI-Advanced Inst. for Materials Research

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 (LaMg₂NiH_4.6) composed of La, Mg, NiH₂, NiH₃ units, and H atoms at tetrahedral sites. The NiH₂ and NiH₃ units in LaMg₂NiH_4.6 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, LaMg₂NiH_4.6, we observed the hydrogen vibrations in LaMg₂NiH_4.6 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^–.

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

Sponsoring Organization:: 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)

Grant/Contract Number:: AC05-00OR22725; 16K06766; 25220911

OSTI ID:: 1422532

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 2; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M. European Journal of Inorganic Chemistry, Vol. 2019, Issue 8 https://doi.org/10.1002/ejic.201801076	journal	January 2019
Hydrogen‐Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions Sato, Toyoto; Daemen, Luke L.; Cheng, Yongqiang ChemPhysChem, Vol. 20, Issue 10 https://doi.org/10.1002/cphc.201801082	journal	January 2019

Figures / Tables (3)

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