Halide substitution in magnesium borohydride

Satoshi Hino; Jon Erling Fonneløp; Marta Corno; Olena Zavorotynska; Alessandro Damin; Bo Richter; Marcello Baricco; Torben R. Jensen; Magnus H. Sørby; Bjørn C. Hauback

doi:10.1021/jp303123q

Halide substitution in magnesium borohydride

Satoshi Hino, Jon Erling Fonneløp, Marta Corno, Olena Zavorotynska, Alessandro Damin, Bo Richter, Marcello Baricco, Torben R. Jensen, Magnus H. Sørby, Bjørn C. Hauback

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

Abstract

The synthesis of halide-substituted Mg(BH ₄) ₂ by ball-milling, and characterization with respect to thermodynamics and crystal structure, has been addressed. The ball-milled mixture of Mg(BH ₄) ₂ and MgX ₂ (X = Cl, Br) has been investigated by in situ/ex situ synchrotron powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), and infrared and Raman spectroscopy. High resolution SR-PXD patterns reveal that the unit cell volume of β-Mg(BH ₄) ₂ in milled and annealed mixtures of Mg(BH ₄) ₂ with MgCl ₂/MgBr ₂ is smaller than that of pure β-Mg(BH ₄) ₂. This is due to substitution of BH ₄ ^- by Cl ^-/Br ^- ions which have ionic radii smaller than that of BH ₄ ^-. For comparison, ab initio calculations were run to simulate Cl substitution in α-Mg(BH ₄) ₂. The α-polymorph was used rather than the β-polymorph because the size of the unit cell was more manageable. Electronic energy data and thermodynamic considerations confirm the miscibility of MgCl ₂ and Mg(BH ₄) ₂, both in α- and β-polymorphs.

Original language	English
Pages (from-to)	12482-12488
Number of pages	7
Journal	Journal of Physical Chemistry C
Volume	116
Issue number	23
DOIs	https://doi.org/10.1021/jp303123q
Publication status	Published - 14 Jun 2012
Externally published	Yes

Access to Document

10.1021/jp303123q

Cite this

@article{3ea418ffece646dd85b1ea863c0c7be4,

title = "Halide substitution in magnesium borohydride",

abstract = "The synthesis of halide-substituted Mg(BH 4) 2 by ball-milling, and characterization with respect to thermodynamics and crystal structure, has been addressed. The ball-milled mixture of Mg(BH 4) 2 and MgX 2 (X = Cl, Br) has been investigated by in situ/ex situ synchrotron powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), and infrared and Raman spectroscopy. High resolution SR-PXD patterns reveal that the unit cell volume of β-Mg(BH 4) 2 in milled and annealed mixtures of Mg(BH 4) 2 with MgCl 2/MgBr 2 is smaller than that of pure β-Mg(BH 4) 2. This is due to substitution of BH 4 - by Cl -/Br - ions which have ionic radii smaller than that of BH 4 -. For comparison, ab initio calculations were run to simulate Cl substitution in α-Mg(BH 4) 2. The α-polymorph was used rather than the β-polymorph because the size of the unit cell was more manageable. Electronic energy data and thermodynamic considerations confirm the miscibility of MgCl 2 and Mg(BH 4) 2, both in α- and β-polymorphs.",

author = "Satoshi Hino and Fonnel{\o}p, {Jon Erling} and Marta Corno and Olena Zavorotynska and Alessandro Damin and Bo Richter and Marcello Baricco and Jensen, {Torben R.} and S{\o}rby, {Magnus H.} and Hauback, {Bj{\o}rn C.}",

year = "2012",

month = jun,

day = "14",

doi = "10.1021/jp303123q",

language = "English",

volume = "116",

pages = "12482--12488",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Halide substitution in magnesium borohydride

AU - Hino, Satoshi

AU - Fonneløp, Jon Erling

AU - Corno, Marta

AU - Zavorotynska, Olena

AU - Damin, Alessandro

AU - Richter, Bo

AU - Baricco, Marcello

AU - Jensen, Torben R.

AU - Sørby, Magnus H.

AU - Hauback, Bjørn C.

PY - 2012/6/14

Y1 - 2012/6/14

N2 - The synthesis of halide-substituted Mg(BH 4) 2 by ball-milling, and characterization with respect to thermodynamics and crystal structure, has been addressed. The ball-milled mixture of Mg(BH 4) 2 and MgX 2 (X = Cl, Br) has been investigated by in situ/ex situ synchrotron powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), and infrared and Raman spectroscopy. High resolution SR-PXD patterns reveal that the unit cell volume of β-Mg(BH 4) 2 in milled and annealed mixtures of Mg(BH 4) 2 with MgCl 2/MgBr 2 is smaller than that of pure β-Mg(BH 4) 2. This is due to substitution of BH 4 - by Cl -/Br - ions which have ionic radii smaller than that of BH 4 -. For comparison, ab initio calculations were run to simulate Cl substitution in α-Mg(BH 4) 2. The α-polymorph was used rather than the β-polymorph because the size of the unit cell was more manageable. Electronic energy data and thermodynamic considerations confirm the miscibility of MgCl 2 and Mg(BH 4) 2, both in α- and β-polymorphs.

AB - The synthesis of halide-substituted Mg(BH 4) 2 by ball-milling, and characterization with respect to thermodynamics and crystal structure, has been addressed. The ball-milled mixture of Mg(BH 4) 2 and MgX 2 (X = Cl, Br) has been investigated by in situ/ex situ synchrotron powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), and infrared and Raman spectroscopy. High resolution SR-PXD patterns reveal that the unit cell volume of β-Mg(BH 4) 2 in milled and annealed mixtures of Mg(BH 4) 2 with MgCl 2/MgBr 2 is smaller than that of pure β-Mg(BH 4) 2. This is due to substitution of BH 4 - by Cl -/Br - ions which have ionic radii smaller than that of BH 4 -. For comparison, ab initio calculations were run to simulate Cl substitution in α-Mg(BH 4) 2. The α-polymorph was used rather than the β-polymorph because the size of the unit cell was more manageable. Electronic energy data and thermodynamic considerations confirm the miscibility of MgCl 2 and Mg(BH 4) 2, both in α- and β-polymorphs.

UR - http://www.scopus.com/inward/record.url?scp=84862285783&partnerID=8YFLogxK

U2 - 10.1021/jp303123q

DO - 10.1021/jp303123q

M3 - Article

SN - 1932-7447

VL - 116

SP - 12482

EP - 12488

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 23

ER -

Halide substitution in magnesium borohydride

Abstract

Access to Document

Other files and links

Fingerprint

Cite this