Supporting Information

 Wiley-VCH 2015
69451 Weinheim, Germany

Hydrogen Storage Materials: Room-Temperature Wet-Chemistry

Approach toward Mixed-Metal Borohydrides**
Tomasz Jaroń,* Piotr A. Orłowski, Wojciech Wegner, Karol J. Fijałkowski, Piotr J. Leszczyński,
and Wojciech Grochala*

anie_201408456_sm_miscellaneous_information.pdf
TABLE OF CONTENTS

1. Experimental Section

1.1. General Remarks

1.2. Mechanochemical Synthesis

1.2.1. Reference samples of Li[Zn2(BH4)5], samples D_Li2.5, D_Li3

1.2.2. Na[Zn(BH4)3], sample D_Na3

1.2.3. [(C6H5)4P][Zn(BH4)3] ‒ mechanochemical synthesis (joint steps I and II in the scheme 1 from the
article)

1.2.4. [(C6H5)4P][Zn2(BH4)5] ‒ mechanochemical synthesis (steps I and II in the scheme 1 from the article)

1.3. Wet synthesis

1.3.1. M[Al{OC(CF3)3}4], M = Li, Na, K

1.3.2. KAlH4

1.3.3 [(n-C4H9)4N][Zn(BH4)3]

1.3.4. Li[Zn2(BH4)5] and M[Zn(BH4)3], M=Na, K (step III in the scheme 1 from the article)

Table S1. Summary of the most important samples; [Al(ORF)4] – [Al{OC(CF3)3}4], [BArF4] – [B{3,5-
(CF3)2C6H3}4].

1.4. Analytical methods and data processing

1.4.1. Fourier Transform Infrared spectroscopy (FTIR)

1.4.2. Powder X–ray diffraction (PXD)

1.4.3. X–ray diffraction analysis

1.4.4. Solution and refinement of the crystal structure of [(C6H5)4P][Zn2(BH4)5]

1.4.5. Thermal decomposition (TGA/DSC) and evolved gases analysis (EGA)

2. Supporting Results

2.1. Crystal structure of [(C6H5)4P][Zn2(BH4)5]

Supporting References

1. Experimental Section

1.1. General Remarks

All manipulations were performed in an inert gas (Ar) atmosphere ‒ in the Schlenk-type
glassware or in a Labmaster DP glovebox from MBraun (<1 ppm O2, <1 ppm H2O), the latter was
also used for storage of the reagents and products. Fine chemicals (>95%), usually from Sigma-
Aldrich were used. Dichloromethane (DCM) was either dried with P4O10 and distilled prior to use, or

S1
bought in an anhydrous form (Sigma-Aldrich), as the other solvents which were used in minor
amounts (benzene, hexane, tetrahydrofuran (THF)).

1.2. Mechanochemical Synthesis

Reagents were weighted, mixed and placed in a stainless steel disc bowl sealed under Ar.
Testchem laboratory vibrational mill (LMW-S) was used for milling, with the nominal frequency of
1400 rpm, Fig. S1. The mechanochemical reactions were done in 5 min periods altered with several
minutes rest to avoid overheating and thermal decomposition of the products. The disc bowls were
cooled slightly with liquid nitrogen to maintain the room temperature.

Figure S1. Testchem laboratory vibrational mill, LMW-S (left-hand picture) and heavy stainless steel
disc bowls (right-hand picture) used for mechanochemical synthesis.

1.2.1. Reference samples of Li[Zn2(BH4)5], samples D_Li2.5, D_Li3

Anhydrous ZnCl2, and LiBH4 were mixed in ca. 1:2.5 (sample D_Li2.5) or 1:3 (D_Li3)
molar ratio and milled for 45 min or 75 min, respectively.

1.2.2. Na[Zn(BH4)3], sample D_Na3

Anhydrous ZnCl2, and NaBH4 were mixed in ca. 1:3.1 molar ratio (10 mol% excess of
NaBH4) and milled for 75 min.

1.2.3. [(C6H5)4P][Zn(BH4)3] ‒ mechanochemical synthesis (joint steps I and II in the scheme 1 from
the article)

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 Anhydrous ZnCl2, [(C6H5)4P]BH4 and NaBH4 were mixed in ca. 1:1:2 molar ratio (with a 5
mol% excess of NaBH4) and milled for 30-45 min, Eq. S1:

ZnCl2 + [(C6H5)4P]BH4 + 2 NaBH4 → [(C6H5)4P][Zn(BH4)3] + 2 NaCl (S1).

[(C6H5)4P][Zn(BH4)3] was then extracted with dichloromethane and NaCl by-product was filtered
off. The product was then precipitated with hexane and filtered off; purity has been confirmed by
FTIR and PXD diffraction.[S1]

1.2.4. [(C6H5)4P][Zn2(BH4)5] ‒ mechanochemical synthesis (steps I and II in the scheme 1 from the
article)

[(C6H5)4P]Cl was mixed with the freshly prepared sample D_Li2.5 (in 5 mol% excess) and
milled for 30 min:

Li[Zn2(BH4)5] + 4 LiCl + [(C6H5)4P]Cl → [(C6H5)4P][Zn2(BH4)5] + 5 LiCl (S2).

[(C6H5)4P][Zn2(BH4)5] was then extracted with dichloromethane and LiCl by-product was removed
by filtration. The constitution and purity of the product was then confirmed by solving its structure
from powder X-ray diffraction data (see sections 1.4.4 and 2.1).

The attempt towards [(C6H5)4P][Zn2(BH4)5] in a one-pot mechanochemical reaction

(i.e. reaction (S1) with altered stoichiometry):

2 ZnCl2 + [(C6H5)4P]BH4 + 4 NaBH4 → [(C6H5)4P][Zn2(BH4)5] + 4 NaCl (S3),

resulted in a mixture of [(C6H5)4P][Zn2(BH4)5] and [(C6H5)4P][Zn(BH4)3]; the analogous reaction

with NaBH4 replaced by LiBH4 has not been tested.

1.3. Wet synthesis

1.3.1. M[Al{OC(CF3)3}4], M = Li, Na, K

The synthesis of these substances were performed according to the slightly modified synthetic
procedures described for Li[Al{OC(CF3)3}4].[S2,S3] The suspension of MAlH4 (LiAlH4 ‒ pure, from
Alfa-Aeser, used as obtained, NaAlH4 ‒ purified by dissolution in THF, filtration and evaporation of
solvent, KAlH4 ‒ prepared as described in the section 1.3.2) in toluene (hexane was occasionally
used instead) was cooled to ca. 0 oC and (CF3)3COH (http://www.fluorochem.co.uk, used without
purification) was slowly added with an excess easily allowing for the complete alcoholysis of Al‒H
bonds (150-200 %). The reaction mixture was then refluxed overnight, cooled, and the product was
precipitated with excess of hexane, filtered, washed with hexane and dried under vacuum. The purity
of the products has been evaluated by FTIR spectroscopy.

1.3.2. KAlH4
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 A modified procedure reported previously by Dilts and Ashby was used.[S4] To a suspension
of KH (with ca. 2 mol% excess) in diglyme (ca. 0.5‒1 ml per 1 mmol of KH) commercially
available LiAlH4 solution in tetrahydrofuran (2 mol dm‒3, Sigma-Aldrich) was added. The mixture
was then stirred for 2 h and filtered. The product was precipitated with excess of toluene and dried
under vacuum; yield: >75%.

1.3.3 [(n-C4H9)4N][Zn(BH4)3]

A modified preparation method reported by Saidov et al. has been used.[S1] Anhydrous THF
was added to the sample D_Na3 (ca. 40 ml per 10 mmol of Zn); the suspension was then stirred for
ca. 15 min, filtered and the solvent has been removed under vacuum at room temperature. The crude
solid product was then extracted with benzene, the remaining NaBH4 has been filtered off, and the
solvent has been removed under vacuum at room temperature resulting in purified
Na[Zn(BH4)3]·xTHF. This intermediate product has been used for the following reactions without
characterization. To 1.57 g of Na[Zn(BH4)3]·xTHF dissolved in ca. 45 ml of benzene 1.75 g of [(n-
C4H9)4N]BH4 has been added and the mixture was vigorously shaken for 5 min. The lower oily layer
was separated, washed with benzene (3 x ca. 15 ml), and dried in vacuum to give a viscous oil which
crystallized when stored at ‒35 oC. This compound has been used for the further reactions without a
thorough characterization.

1.3.4. Li[Zn2(BH4)5] and M[Zn(BH4)3], M=Na, K (step III in the scheme 1 from the article)

To a suspension or solution of M[Al{OC(CF3)3}4], M = Li, Na, K, or Na[B{3,5-

(CF3)2C6H3}4] in dichloromethane a solution of organic zinc borohydride in the same solvent was
added and the mixture was stirred for ca. 60 min. [(n-C4H9)4N][Zn(BH4)3], [(C6H5)4P][Zn(BH4)3]
and [(C6H5)4P][Zn2(BH4)5] have been used as the zinc-containing precursors. Typically ca. 50 ml of
DCM per 1 mmol of M[Al{OC(CF3)3}4] and Na[B{3,5-(CF3)2C6H3}4] salts was used, while much
better solubility of zinc compounds allows for their dissolution in only ca. 10 ml of DCM per 1
mmol. The suspension was then allowed to settle and the precipitate was filtered off, washed several
times with the fresh portions of DCM and dried under vacuum; typical yield: 95 – 99%. The purity
of borohydrides prepared using this method was monitored by FTIR spectroscopy, PXD, and
TGA/DSC coupled with EGA. The samples prepared according to this method are collected in Table
S1.

Table S1. Summary of the most important samples; [Al(ORF)4] – [Al{OC(CF3)3}4], [BArF4] – [B{3,5-
(CF3)2C6H3}4].

Phase analysis from

Symbol Reagent 1 Reagent 2 Remarks
PXD [wt%]
reaction in Li[Zn2(BH4)5] 89.0
W_LiA [(n-C4H9)4N][Zn(BH4)3] Li[Al(ORF)4] dichloromethane according LiBH4 10.1
to 1.3.4 LiCl 0.9

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 Li[Zn2(BH4)5] 87.0
W_LiB [(C6H5)4P][Zn(BH4)3] Li[Al(ORF)4] LiBH4 6.6
LiCl 6.5
Li[Zn2(BH4)5] 99.8
W_LiC* [(C6H5)4P][Zn2(BH4)5] Li[Al(ORF)4]
LiCl 0.2

Na[Zn(BH4)3] 92.4
W_NaA [(n-C4H9)4N][Zn(BH4)3] Na[BArF4]
NaBH4 7.6
Na[Zn(BH4)3] 64.4
W_NaB [(C6H5)4P][Zn(BH4)3] Na[BArF4] NaBH4 32.3
NaCl 3.3
K[Zn(BH4)3] 93.6
W_KA [(n-C4H9)4N][Zn(BH4)3] K[Al(ORF)4]
KBH4 6.4
Li[Zn2(BH4)5] 52.9
LiCl 43.8
D_Li2.5* ZnCl2 2.5 LiBH4
ZnCl2 3.4
mechanochemical LiBH4 - traces
synthesis according to 1.2.1 Li[Zn2(BH4)5] 50.0
LiCl 42.6
D_Li3 ZnCl2 3 LiBH4
LiBH4 7.1
ZnCl2 0.7
Na[Zn(BH4)3] 56.0
mechanochemical
D_Na3 ZnCl2 3 NaBH4 NaCl 43.4
synthesis according to 1.2.2
NaBH4 0.6
* - samples described in details in the article.

1.4. Analytical methods and data processing

1.4.1. Fourier Transform Infrared spectroscopy (FTIR)

FTIR spectra of all solid products were measured using Vertex 80v FT–IR spectrometer
(Bruker). Anhydrous KBr was used as a pellet material (200 mg per pellet of 12 mm diameter).

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1.4.2. Powder X–ray diffraction (PXD)

PXD patterns of solids (sealed under argon inside 0.3, 0.5 or 1 mm quartz capillaries) were
measured using Bruker D8 Discover diffractometer (parallel beam; the CuKα1 and CuKα2 radiation
intensity ratio of ca. 2:1).

1.4.3. X–ray diffraction analysis

The following software was used: Crystal Sleuth[S5] – preliminary data analysis; Mercury,
VESTA[S6] – structure visualization, simulation of powder patterns; Jana2006[S7] – Rietveld
refinement, phase analysis. During the Rietveld refinement the restraints have been applied to the H–
B–H angles and B–H distances in BH4 groups of zinc borohydrides: 109.47o (with a standard
uncertainty, s.u.=0.01o) and 1.12 Å (s.u.=0.01 Å), respectively. Atomic displacement parameters
(ADP) of H were fixed as 1.5 ADP of adjacent B atom (riding model). The background for structure
refinement was described by 30–36 Legendre polynomials; pseudo-Voigt peak shape function was
used. Anisotropic particle broadening correction (direction 1 3 1) was necessary for the refinement of
Li[Zn2(BH4)5] prepared in wet synthesis; Li[Zn2(BH4)5] synthesized mechanochemically showed no
anisotropic broadening.

1.4.4. Solution and refinement of the crystal structure of [(C6H5)4P][Zn2(BH4)5]

The as-milled sample showed diffraction peaks from LiCl and from unknown phase(s). The
latter has been indexed using X-Cell program (Materials Studio package from Accelrys)[S8] in
monoclinic unit cell of the volume corresponding to Z=4; systematic absences indicated C2/c space
group. The structure has been solved in real space using FOX[S9] without using antibump restraints.
Rietveld refinement has been performed in Jana2006 with the number of parameters
restrained due to complexity of the unit cell (37 independent atoms) and strong overlapping of
diffraction peaks: geometry of the aromatic rings has been kept plane with all respective angles close
to 120o (with 0.01 standard uncertainty, s.u.); C‒H distances were set as 0.95 Å (s.u.=0.01);
geometry of BH4 groups was kept tetrahedral with B‒H distances fixed close to 1.12 Å (s.u.=0.01);
atomic displacement parameters (ADP) of all hydrogen atoms were restrained according to riding
model as 1.2*ADP of the adjacent heavier atom; ADP of the carbon atoms has been equalized. Also
the bidentate bonding of BH4 groups towards Zn has been restrained (equidistant chosen H atoms
with s.u.=0.01). The background for structure refinement was described by 36 Legendre
polynomials; pseudo-Voigt peak shape function was used.

1.4.5. Thermal decomposition (TGA/DSC) and evolved gases analysis (EGA)

Thermal decomposition of the samples placed inside Al2O3 crucibles was investigated with a
combined thermogravimeter (TGA) and differential scanning calorimeter (DSC) from Netzsch –

S6
STA 409 PG, at a constant Ar (99.9999%) flow of 70 ml/min, and at 5 K min-1 heating rate. The
evolved gases were analyzed with a quadruple mass spectrometer (MS) QMS 403 C (Pfeiffer
Vacuum), connected to the TGA/DSC device by quartz capillary preheated to 200 oC to avoid
condensation of low-boiling volatiles. Range of M/Z from 0 to 100 was studied.

2. Supporting Results

S7
Figure S2. Powder X-ray Diffraction (PXD) measured and refined for the sample W_LiA.

Figure S3. Powder X-ray Diffraction (PXD) measured and refined for the sample W_LiB.

S8
Figure S4. Powder X-ray Diffraction (PXD) measured and refined for the sample W_LiC.

Figure S5. Powder X-ray Diffraction (PXD) measured and refined for the sample W_NaA.

S9
Figure S6. Powder X-ray Diffraction (PXD) measured and refined for the sample W_NaB.

Figure S7. Powder X-ray Diffraction (PXD) measured and refined for the sample W_KA.

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Figure S8. Powder X-ray Diffraction (PXD) measured and refined for the sample D_Li2.5.

Figure S9. Powder X-ray Diffraction (PXD) measured and refined for the sample D_Li3.

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Figure S10. Powder X-ray Diffraction (PXD) measured and refined for the sample D_Na3.

Figure S11. FTIR spectra of the samples (a) W_LiC, (b) W_NaA, (c) W_KA.

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Figure S12. FTIR spectra of the samples (a) W_LiA, (b) W_LiB, (c) W_LiC.

Figure S13. FTIR spectra of the samples (a) W_NaB, (b) W_NaA, (c) NaBH4 (reference).

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Figure S14. FTIR spectra of the samples (a) W_LiC, (b) D_Li2.5; l – signals from organic impurities; X
– signals altered by inorganic impurities (e.g. LiBH4); * ‒ δ(H-O-H) band from moisture.

Figure S15. FTIR spectra of the samples (a) W_LiC, (b) D_Li3, (c) LiBH4 (reference); * ‒ δ(H-O-H) band
from moisture.

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Figure S16. Raw time-resolved MS spectra of the gases evolved during the thermal decomposition of
the sample D_Li2.5. Only the selected M/Z have been plotted.

Figure S17. Raw time-resolved MS spectra of the gases evolved during the thermal decomposition of
the sample W_LiC. Only the selected M/Z have been plotted.

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Figure S18. Raw time-resolved MS spectra of the gases evolved during the thermal decomposition of
the sample W_LiC plotted in the vicinity of the fastest decomposition step. The signals have been
groupped according to the most probable source: brown - H2, blue - B2H6, grey - higher boranes, red
- (CF3)3CO fragments, green - CH2Cl2.

Figure S19. Time-resolved MS spectra of the gases evolved during the thermal decomposition of the
sample W_LiC. The signals attributed to the evolved species have been added as following: H2
M/Z=2; B2H6 M/Z=10, 11, 12, 13, 22, 23, 24, 25, 26, 27; higher boranes M/Z=33, 35, 37, 43, 45, 46,
47, 48, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64; CH2Cl2 M/Z=49, 51, 84, 86; (CF3)3CO M/Z=50,
51, 69, 78, 97, 100. Some less intense signals from these substances were omitted due to a very high
background from Ar impurities (mainly the gases present in the air).

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2.1. Crystal structure of [(C6H5)4P][Zn2(BH4)5]

The crystal structure of [(C6H5)4P][Zn2(BH4)5] has been solved from PXD data as described
in the section 1.4.4, cf. Fig S20. This mixed-cation borohydride crystallizes in a space group C2/c,
with a=21.716(3) Å, b=13.073(2) Å, c= 13.911(2) Å, β=128.072(2)o, V=3108.7(8) Å3, and four
formula units in the unit cell, Z=4.

Figure S20. Powder X-ray Diffraction (PXD) measured and refined for raw, not purified
[(C6H5)4P][Zn2(BH4)5] as prepared in a mechanochemical reaction according to p. 1.2.4.

Figure S21. [(C6H5)4P]+ cation and adjacent [Zn2(BH4)5]– anion in the crystal structure of
[(C6H5)4P][Zn2(BH4)5]; white ― H, pink ― B, blue ― Zn, violet ― P, black ― C.

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Figure S22. Layers in the crystal structure of [(C6H5)4P][Zn2(BH4)5]; H atoms have been removed for
clarity; pink ― B, blue ― Zn, violet ― P, black ― C.

The crystal structure of [(C6H5)4P][Zn2(BH4)5] is composed of [(C6H5)4P]+ cations and

binuclear complex [Zn2(BH4)5]– anions, Fig. S21. The cations are altered with the anions and the
layers parallel to the (1 0 0) plane can be distinguished, Fig. S22. The shortest Zn – P distance in
[(C6H5)4P][Zn2(BH4)5] of 6.252(13) Å is significantly larger as compared to its analogue containing
mononuclear complex anions, [(C6H5)4P][Zn(BH4)3], of ca. 6.007(3) Å.[S1] The opposite relation is
observed for the minimal distance between the hydrogen atoms of cation and anion moieties: ca.
2.30(10) Å and ca. 2.58 Å for [(C6H5)4P][Zn2(BH4)5] and [(C6H5)4P][Zn(BH4)3], respectively. These
relations can be explained by better packing of smaller [Zn(BH4)3]– anions than the binuclear
[Zn2(BH4)5]– anions. While the coordination of zinc by borohydride groups in [(C6H5)4P][Zn2(BH4)5]
looks significantly distorted from ideal triangular geometry, the reliable refinement of the position
and orientation of BH4- groups would require neutron diffraction, like in the case of Li[Zn2(BH4)5],
where the [Zn2(BH4)5]– anions refined from PXD data showed significant distortion, while powder
neutron diffraction revealed their regular geometry.[S10,S11,S12]

The details of the crystal structure may be obtained from Cambridge Crystallographic Data
Centre, http://www.ccdc.cam.ac.uk, on quoting its CCDC number: 1015948.

Supporting References

[S1] B.I. Saidov, A.P. Borisov, V.D. Makhaev, A. S. Antsyshkina, N.S. Kedrova, N.N. Mal'tseva, Russ. J. Inorg.
Chem. 1990, 35, 626-632.
[S2] I. Krossing, Chem. Eur. J. 2001, 7, 490-502.
[S3] I. Krossing, A. Reisinger, Coord. Chem. Rev. 2006, 250, 2721-2744.
[S4] J. A. Dilts, E. C. Ashby, Inorg. Chem. 1972, 11, 1230-1236.
[S5] T. Laetsch, R. Downs, Abstracts from the 19th General Meeting of the International Mineralogical
Association, Kobe, Japan, 23-28 July 2006.
[S6] K. Momma, F. Izumi, J. Appl. Cryst. 2011, 44, 1272-1276.

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[S7] V. Petricek, M. Dusek, L. Palatinus, Jana2006. Structure Determination Software Programs. Institute of
Physics, Praha, Czech Republic, 2006; V. Petricek, M. Dusek, L. Palatinus, Z. Kristallogr., 2014, 229, 345-352.
[S8] M. Neumann, J. Appl. Cryst., 2006, 36, 356-365.
[S9] V. Favre–Nicolin, R. Černý, J. Appl. Cryst., 2002, 35, 734-743. See also: http://objcryst.sourceforge.net.
[S10] D. Ravnsbæk, Y. Filinchuk, Y. Cerenius, H. J. Jakobsen, F. Besenbacher, J. Skibsted, T. R. Jensen, Angew.
Chem. 2009, 121, 6787-6791; Angew. Chem. Int. Ed. 2009, 48, 6659-6663.
[S11] R. Černý, K. C. Kim, N. Penin, V. D'Anna, H. Hagemann, D. S. Sholl, J. Phys. Chem. C, 2014, 114, 19127-
19133.
[S12] D. B. Ravnsbæk, C. Frommen, D. Reed, Y. Filinchuk, M. Sørby, B. C. Hauback, H. J. Jakobsen, D. Book, F.
Besenbacher, J. Skibsted, T. R. Jensen, J. Alloys Compd., 2011, 509, S698-S704.

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