International Journal of Hydrogen Energy 32 (2007) 2501 – 2503

www.elsevier.com/locate/ijhydene

Synthesis of metal hydride from water

Surendra K. Saxena ∗ , Vadym Drozd, Andriy Durygin
Center for the Study of Matter at Extreme Conditions, College of Engineering, Florida International University, VH-140, University Park, Miami, FL 33199, USA

Received 1 September 2006; received in revised form 18 September 2006; accepted 18 September 2006
Available online 8 December 2006

Abstract
A number of hydrides are considered good candidates for hydrogen storage material for various applications in particular for automobile
use. A metal hydride is synthesized through the reaction of a metal with hydrogen which is formed on industrial scale either by the electrolysis
of water, by heating coke with steam in the water gas shift reaction or using hydrocarbons with steam. This study demonstrates that under
certain conditions, it is possible to synthesize a metal hydride by the reaction of a metal with water or with a hydroxide. Such a synthesis
route dispenses with the need for separately forming hydrogen by an expensive process and then to synthesize a hydride by metal–hydrogen
reaction. If adopted in many of the hydrogen storage projects which plan to use a hydride for producing hydrogen through a chemical reaction
or by a reversible dissociation for automobile use, this method could make a significant difference in making them cost-effective.
䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Metal hydrides; Synthesis

1. Introduction vehicular use. Such projects will benefit immensely if MgH2

A binary metal hydride is usually prepared from a reaction
between metal and hydrogen. Presence of oxygen in any form is
considered detrimental to the synthesis and all water is avoided.
In this study, we have shown that a hydride can be synthe-
sized directly by a reaction between a metal and water or a
water-bearing solid. Normal method of synthesizing a hydride
is by reacting it with hydrogen, which requires that hydrogen
be formed from an expensive process such as the electrolytic
method or from fossil fuel.
Many metals when brought in contact with water form hy-
drogen and cases of any hydride formation are rarely recorded
[1]. We have shown both by thermodynamic calculations for a
number of reactions and by experimenting with the Mg–H2 O
system that a hydride can be synthesized by an exothermic re-
action if a suitable adjustment is made in the amount of the
reactants.
The hydrides are important solids as hydrogen storage
materials. There is currently a DOE supported project from
Safe Hydrogen LLC [2] who use MgH2 slurry and water for
∗ Corresponding author.
E-mail address: saxenas@fiu.edu (S.K. Saxena).
and other hydrides can be synthesized in a cost-effective way.
The reaction studied here produces oxide or hydroxide along
with the hydride. The total cost of winning the metal back
must be compared with the cost of separately producing the
hydrogen. The Safe Hydrogen LLC is working on a process
for reduction of hydroxide to metal which they believe will be
cost-effective [2].
2. Hydride forming reaction
To illustrate this process, the following reactions are consid-
ered: 2M+H2 O=MH2 +MO, and 2M+M(OH)2 =MH2 +2MO,
where M could be a divalent cation such as Mg. Several other
reactions using different metals are listed in Table 1. Thermo-
dynamically both the sets of reactions proceed forward at room
temperature (kinetics permitting). The availability of thermo-
dynamic data restricts the list to the following but others could
be added as more data becomes available: binary NaH, LiH,
MgH2 and ternary LiAlH4 , NaAlH4 , LiBH4 and NaBH4 . Ther-
modynamic calculations showing the formation of these com-
pounds are summarized in Table 1. The calculations have been
performed using the FACTSAGE databases (mostly JANAF
tables). The mixture of water and the solids must be carefully

0360-3199/$ - see front matter 䉷 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.09.032
2502 S.K. Saxena et al. / International Journal of Hydrogen Energy 32 (2007) 2501 – 2503

Table 1
Formation reactions of hydrides at 300 K

No. Reactants Products H , kJ

1. Li + B + H2 O 0.5 LiBH4 + 0.5 LiBO2 −319

2. Li + B + Mg(OH)2 MgO + 0.5 LiBH4 + 0.5 LiBO2 −282
3. Na + B + H2 O 0.5 NaBO2 + 0.5 NaBH4 −297
4. 4 Li + H2 O 2 LiH + Li2 O −494
5. 2 Mg + Mg(OH)2 2 MgO + MgH2 −397
6. 2 Mg + H2 O MgO + MgH2 −392
7. Na + Al + H2 O 0.57 NaH + 0.36 NaAlH4 + 0.071NaAl9 O14 −344
8. Li + Al + H2 O at 225 bar 0.667 LiH + 0.333 LiAlH4 + 0.333 Al2 O3 −365
9. Be + H2 O at 375 bar 0.5 BeO + 0.5 BeH2 −167

weighed for the hydride formation; otherwise the reaction to

produce hydrogen sets in. It is possible to use hydroxide in-
stead of water (Table 1). In each case, the product is a mixture
of hydride and oxide, which must be separated from each other.
This can be achieved with density separation methods because
the hydrides are significantly lighter than the oxides. Data on
Li–H2 O (reaction 4, Table 1) have been reported by Klanchar
et al. [1] and others [3,4]. Klanchar et al. [1] used a ther-
moelectric calorimeter to study the lithium-water reaction and
reported the final product as consisting of a mixture of Li2 O
and LiH with small amounts of LiOH and H2 .

3. Experimental work

Several experiments were conducted to test the thermo-

dynamic predictions in the Mg–H2 O system. This system is
important for hydrogen storage for automobile use because
MgH2 may be used in oil-based slurry for filling the tanks [2].
In four different experiments, the formation of MgH2 from wa-
ter proceeded via the reactions: Mg + 2H2 O = Mg(OH)2 + H2
and 2Mg + Mg(OH)2 = MgH2 + 2MgO. Therefore, only the
data on the hydroxide reaction with metal is presented. The ex-
periments were carried out in several different types of sealed
containers. A mixture of micron sized magnesium metal and
magnesium hydroxide was pressed into pellets. The pellets
were placed in a quartz tube which was evacuated and sealed.
The pellets were also put directly in a vacuum chamber. The
samples were heated in the temperature range of 150–400 ◦ C.
X-ray powder diffraction is done using Bruker GADDS/D8
X-ray system with Apex Smart CCD Detector and direct-drive
rotating anode. The MacSci rotating anode (Molybdenum) is
used with a 50 kV generator and 20 mA current. X-ray beam
size can vary from 50 to 300 m. The high intensity X-ray
beam results from the use of AXS optical device. The usual
collection time is 1800 s.
Fig. 1 shows the results obtained in vacuum heating. There
are two small but distinct reflections for MgH2 and good
development of the MgO reflections which show the valid-
ity of the thermodynamic reaction between the hydroxide
and metal. The temperature for the dissociation of brucite
to water and MgO is 263 ◦ C at 1 atm. It is likely that the
Fig. 1. X-ray results on a ball milled mixture of magnesium and brucite,
Mg(OH)2 (1:1 molar), which was pressed in a disc and heated in vacuum for
24 h: the diffraction at 150 ◦ C shows a small peak due to MgH2 at around
2 value of 12.8 and shoulder on the Mg peak at 16.5; this development is
more clearly established at 200 ◦ C.
dissociation temperature is lowered due to vacuum and wa-
ter is released to combine with the metal. However, since any
such water will be continuously removed, it is evident that
the metal reacted directly with the hydroxide. The patterns in
the evacuated and the vacuum heated samples at 200 ◦ C are
compared again at 200 ◦ C to validate this argument (Fig. 2).
While temperature may not be an important consideration in
manufacturing a hydride, a low temperature production will of
course be cost-effective. Fig. 2 show the X-ray diffraction of
a sample of 1:2 molar mixture of Mg(OH)2 and Mg. At low
temperatures there is a small recognizable shoulder peak of
MgH2 at 2 of 16.3◦ . The final result of this heating at 400 ◦ C
is a complete reaction of brucite and metal to form MgH2
and MgO.
 S.K. Saxena et al. / International Journal of Hydrogen Energy 32 (2007) 2501 – 2503
Fig. 2. Comparison of X-ray results on a ball milled mixture of magnesium
and brucite, Mg(OH)2 (2:1 molar). The diffraction from the sample heated
in vacuum at 200 ◦ C clearly shows the formation of MgH2 (small peak at 2
of 12.8 and the shoulder peak on the Mg peak at 16.3◦ ). The other results
are for a similar mixture, which was pressed in a disc and heated in a sealed
evacuated quartz tube for 24 h: the diffraction at 150 ◦ C shows a small peak
of MgH2 at around 2 value of 16.3◦ as a shoulder on the Mg peak; this
development continues with heating and finally results in a fully developed
pattern at 300 and 400 ◦ C. In the last heating practically all brucite and Mg
is consumed resulting in MgO and MgH2 . The MgH2 peak intensities are
half the intensity of the MgO peaks. A separately run mixture of 1:2 molar
mix of MgH2 and MgO confirmed that the MgH2 produced is half in moles
to that of MgO.
4. Discussion
Since the purpose of this work was to establish that hydrides
can be synthesized from a reaction between water or a hydrox-
ide, no attempt is made here to study the kinetics which will
depend on temperature and particle size. It appears that the re-
action would be sufficiently rapid above 300 ◦ C.
The oxides can be recycled to obtain the hydroxide. The
metals will have to be recovered at some cost which needs to be
taken into account for any application and must be compared
with the cost of producing the hydride from a metal and hydro-
gen, when the latter is produced separately by an electrolytic
reduction of water or from fossil fuel. McClaine et al. [2]
have demonstrated a successful use of MgH2 slurry and water
in producing hydrogen. In their process MgH2 is hydrolyzed
resulting in Mg(OH)2 and hydrogen. It has been shown here
2503
that we can obtain MgH2 from Mg(OH)2 , thus making their
process more economic by reducing the cost of making the
hydride from Mg and water.
Although we have used only the experimental information on
the Mg–H–O system, several other hydrides, as listed in Table 1
and others not listed due to lack of thermodynamic data, can
be synthesized by this method. Currently proposed methods
that involve the hydrogen production in the fuel tank by chemi-
cal reactions under study by DOE (Department of Energy, US)
supported researchers [5–7] are probably not cost-effective be-
cause of the need to remove the spent products and reduce the
oxide to metal. There is some development in searching for a
solution for recovering Mg from the hydroxide [2,8]. The study
here does not solve the basic problem of the cost associated
with the regeneration of the metal from the reaction products
but in absence of any viable solution to a reversible dissociation
of a hydride at ambient temperatures, the method suggested
here should bring down the cost associated with hydrogen pro-
duction in the fuel tank when using the chemical hydrides.
Acknowledgment
The authors’ work is supported through a grant from
National Science Foundation (DMR-0231291) and a grant
from Air Force (212600548).
References
[1] Klanchar M, Wintrode BD, Phillips JA. Lithium-water reaction chemistry
at elevated temperature. Energy and Fuels 1997;11(4):931–5.
[2] McClaine AW, Tullman S, Brown K. Chemical hydrogen slurry for
hydrogen production and storage. FY 2005 Progress report: DOE
hydrogen program.
[3] Phillips J, Bradford MC, Klanchar M. A calorimetric study of the
mechanism and thermodynamics of the lithium hydride-water reaction
at elevated temperatures. Energy and Fuels 1995;9(4):569–73.
[4] Bradford MC, Phillips J, Klanchar M. Novel high-temperature calvet-
type calorimeter for investigating metal-water reactions. Rev Sci Instrum
1995;66(1):171–5.
[5] U.S. Department of Energy. Advanced Reciprocating Engines Program.
Distributed Energy Resources.Washington, DC (www.eren.doe.gov/der).
[6] U.S. Department of Energy. Federal Energy Technology Center.
Distributed Generation—Securing America’s Future with Reliable,
Flexible Power. Morgantown, WV. October (www.fetc.doe.gov).
[7] Report of the Basic Energy Sciences Workshop on Hydrogen, Production,
Storages and use, May 13–15, 2003.
[8] FY 2005 Progress Report: DOE hydrogen program http://www.
hydrogen.energy.gov/annual_progress05.html.