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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 metalhydrogen
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 signicant difference in making them cost-effective.
2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Metal hydrides; Synthesis
1. Introduction
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 synthesized 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 hydrogen 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 MgH2 O
system that a hydride can be synthesized by an exothermic reaction 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.
0360-3199/$ - see front matter 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.09.032
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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.
2.
3.
4.
5.
6.
7.
8.
9.
Li + B + H2 O
Li + B + Mg(OH)2
Na + B + H2 O
4 Li + H2 O
2 Mg + Mg(OH)2
2 Mg + H2 O
Na + Al + H2 O
Li + Al + H2 O at 225 bar
Be + H2 O at 375 bar
319
282
297
494
397
392
344
365
167
3. Experimental work
Several experiments were conducted to test the thermodynamic predictions in the MgH2 O system. This system is
important for hydrogen storage for automobile use because
MgH2 may be used in oil-based slurry for lling the tanks [2].
In four different experiments, the formation of MgH2 from water 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 experiments 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 150400 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 reections for MgH2 and good
development of the MgO reections which show the validity 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
dissociation temperature is lowered due to vacuum and water 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 nal 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
4. Discussion
Since the purpose of this work was to establish that hydrides
can be synthesized from a reaction between water or a hydroxide, no attempt is made here to study the kinetics which will
depend on temperature and particle size. It appears that the reaction would be sufciently 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 hydrogen, 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
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