Hydrogen-Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions

Toyoto Sato; Luke L. Daemen; Yongqiang Cheng; Anibal J. Ramirez-Cuesta; Kazutaka Ikeda; Takuma Aoki; Toshiya Otomo; Shin ichi Orimo

doi:10.1002/cphc.201801082

Hydrogen-Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions

Toyoto Sato
, Luke L. Daemen
, Yongqiang Cheng
, Anibal J. Ramirez-Cuesta
, Kazutaka Ikeda
, Takuma Aoki
, Toshiya Otomo
, Shin ichi Orimo

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

The hydrogen-release reaction of a complex transition metal hydride, LaMg ₂ NiH ₇ , composed of La ³⁺ , 2×Mg ²⁺ , [NiH ₄ ] ⁴⁻ and 3×H ⁻ , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg ₂ NiH ₇ released hydrogen at approximately 567 K and decomposed into LaH ₂₋₃ and Mg ₂ Ni. Before the reaction, covalently bound hydrogen (H ^c ° ^v. ) in [NiH ₄ ] ⁴⁻ exhibited a larger atomic displacement than H ⁻ , although a weakening of the chemical bonds around [NiH ₄ ] ⁴⁻ and H ⁻ was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of H ^c ° ^v. that induces the hydrogen-release reaction rather than H ⁻ . As an isothermal reaction, LaMg ₂ NiH ₇ formed LaMg ₂ NiH _2.4 at 503 K in vacuum for 48 h, and LaMg ₂ NiH _2.4 reacted with hydrogen to reform LaMg ₂ NiH ₇ at 473 K under 1 MPa of H ₂ gas pressure for 10 h. These results revealed that LaMg ₂ NiH ₇ exhibited partially reversible hydrogen-release and uptake reactions.

Original language	English
Pages (from-to)	1392-1397
Number of pages	6
Journal	ChemPhysChem
Volume	20
Issue number	10
DOIs	https://doi.org/10.1002/cphc.201801082
State	Published - May 16 2019
Externally published	Yes

Funding

We are grateful for the technical support from Ms. H. Ohmiya and Ms. N. Warifune. This research was supported by MEXT/JSPS KAKENHI (16K06766, JP18H05513, JP18H05518). The PND experiment was approved by the Neutron Science Proposal Review Committee of J-PARC/MLF (Proposal No. 2017A0115). The INS experiment benefited from the use of the VISION beamline (IPTS-16527) at ORNL's Spallation Neutron Source, supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract No. DE-AC0500OR22725. Computational resources were made available through the VirtuES and ICE-MAN projects, funded by the Laboratory Directed Research and Development at ORNL.

Keywords

complex transition metal hydride
crystal structure
inelastic neutron scattering
neutron diffraction
vibration

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10.1002/cphc.201801082

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title = "Hydrogen-Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions",

abstract = " The hydrogen-release reaction of a complex transition metal hydride, LaMg 2 NiH 7 , composed of La 3+ , 2×Mg 2+ , [NiH 4 ] 4− and 3×H − , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg 2 NiH 7 released hydrogen at approximately 567 K and decomposed into LaH 2−3 and Mg 2 Ni. Before the reaction, covalently bound hydrogen (H c ° v. ) in [NiH 4 ] 4− exhibited a larger atomic displacement than H − , although a weakening of the chemical bonds around [NiH 4 ] 4− and H − was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of H c ° v. that induces the hydrogen-release reaction rather than H − . As an isothermal reaction, LaMg 2 NiH 7 formed LaMg 2 NiH 2.4 at 503 K in vacuum for 48 h, and LaMg 2 NiH 2.4 reacted with hydrogen to reform LaMg 2 NiH 7 at 473 K under 1 MPa of H 2 gas pressure for 10 h. These results revealed that LaMg 2 NiH 7 exhibited partially reversible hydrogen-release and uptake reactions.",

keywords = "complex transition metal hydride, crystal structure, inelastic neutron scattering, neutron diffraction, vibration",

author = "Toyoto Sato and Daemen, \{Luke L.\} and Yongqiang Cheng and Ramirez-Cuesta, \{Anibal J.\} and Kazutaka Ikeda and Takuma Aoki and Toshiya Otomo and Orimo, \{Shin ichi\}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2019",

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doi = "10.1002/cphc.201801082",

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AU - Sato, Toyoto

AU - Daemen, Luke L.

AU - Cheng, Yongqiang

AU - Ramirez-Cuesta, Anibal J.

AU - Ikeda, Kazutaka

AU - Aoki, Takuma

AU - Otomo, Toshiya

AU - Orimo, Shin ichi

PY - 2019/5/16

Y1 - 2019/5/16

N2 - The hydrogen-release reaction of a complex transition metal hydride, LaMg 2 NiH 7 , composed of La 3+ , 2×Mg 2+ , [NiH 4 ] 4− and 3×H − , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg 2 NiH 7 released hydrogen at approximately 567 K and decomposed into LaH 2−3 and Mg 2 Ni. Before the reaction, covalently bound hydrogen (H c ° v. ) in [NiH 4 ] 4− exhibited a larger atomic displacement than H − , although a weakening of the chemical bonds around [NiH 4 ] 4− and H − was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of H c ° v. that induces the hydrogen-release reaction rather than H − . As an isothermal reaction, LaMg 2 NiH 7 formed LaMg 2 NiH 2.4 at 503 K in vacuum for 48 h, and LaMg 2 NiH 2.4 reacted with hydrogen to reform LaMg 2 NiH 7 at 473 K under 1 MPa of H 2 gas pressure for 10 h. These results revealed that LaMg 2 NiH 7 exhibited partially reversible hydrogen-release and uptake reactions.

AB - The hydrogen-release reaction of a complex transition metal hydride, LaMg 2 NiH 7 , composed of La 3+ , 2×Mg 2+ , [NiH 4 ] 4− and 3×H − , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg 2 NiH 7 released hydrogen at approximately 567 K and decomposed into LaH 2−3 and Mg 2 Ni. Before the reaction, covalently bound hydrogen (H c ° v. ) in [NiH 4 ] 4− exhibited a larger atomic displacement than H − , although a weakening of the chemical bonds around [NiH 4 ] 4− and H − was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of H c ° v. that induces the hydrogen-release reaction rather than H − . As an isothermal reaction, LaMg 2 NiH 7 formed LaMg 2 NiH 2.4 at 503 K in vacuum for 48 h, and LaMg 2 NiH 2.4 reacted with hydrogen to reform LaMg 2 NiH 7 at 473 K under 1 MPa of H 2 gas pressure for 10 h. These results revealed that LaMg 2 NiH 7 exhibited partially reversible hydrogen-release and uptake reactions.

KW - complex transition metal hydride

KW - crystal structure

KW - inelastic neutron scattering

KW - neutron diffraction

KW - vibration

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Hydrogen-Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions

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