international journal of hydrogen energy 34 (2009) 3404–3409

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Catalytic effect of monoclinic WO3, hexagonal WO3 and

H0.23WO3 on the hydrogen sorption properties of Mg

Florent Tonusa, Valeria Fusterb, Guillermina Urretavizcayab, Facundo J. Castrob,

Jean-Louis Bobeta,*
a
CNRS, Université de Bordeaux, ICMCB, 87 avenue du Dr. A. Schweitzer, Pessac F-33608, France
b
Centro Atómico Bariloche (CNEA, CONICET), Instituto Balseiro (UNCUYO), Av. Bustillo 9500, San Carlos de Bariloche, Argentina

article info abstract

Article history: The H sorption properties of mixtures Mg þ WO3 (having various structures) and
Received 22 December 2008 Mg þ H0.23WO3 are reported. First, the higher conversion of Mg into MgH2 during reactive
Received in revised form mechanical grinding (under 1.1 MPa of H2) for higher WO3 content is due to the improve-
6 February 2009 ment of the milling efficiency. Then, it is shown that the hydrogen absorption properties
Accepted 9 February 2009 are almost independent of the crystal structure of the catalyst and that only the particles’
Available online 17 March 2009 size and the specific surface play a major role. Finally, for the desorption process, it appears
that the chemical composition and structure of the catalyst, together with the particle size
Keywords: and specific surface have an effect.
Hydrogen storage ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
Magnesium hydride reserved.
Kinetics
Mechanical alloying

1. Introduction devoted to magnesium. Magnesium offers a high gravimetric

capacity (7.6 wt.%) and a relatively good volumetric capacity
What we are emitting today and disposing in the atmosphere (110 g/L compared with 71 g/L for liquid H2). Nevertheless, it
will keep busy our next generation. The most serious envi- also exhibits high reaction temperatures and poor kinetics. To
ronmental problem today is the greenhouse global warming, overcome these drawbacks, Mg is usually mixed with several
caused mainly by CO2 accumulation in the atmosphere, additives and subjected to ball milling. From the thermody-
which cannot be stopped as long as carbon is present in any namic point of view it is assumed that the decrease of particle
form in the fuel used. This leaves us with hydrogen as the size can lead to a decrease of the sorption temperature.
only choice, as it is the only known carbon-free combustible Aguey-Zinsou et al. [3] demonstrated that 5 nm sized
material. magnesium can absorb and desorb hydrogen at temperatures
Hydrogen clearly appears as the ‘‘fuel for tomorrow’’, but as low as 80  C. Nevertheless, such experimental condition
the problem of mass production (C free) and storage has to be has not been reproduced so far, to the best of our knowledge.
solved. Considering the storage, metal hydrides offer a safe From the kinetics point of view, in recent studies [4–8] it has
and valuable solution from the volumetric capacity point of been shown that the addition of oxides (especially Cr2O3 and
view, although from the gravimetric capacity standpoint, Nb2O5) and the use of reactive atmospheres during milling is
some problems related to the low values achieved still a good way to improve the kinetic behaviour of magnesium.
remains [1,2]. For that reason, a lot of studies have been Although the mechanism of catalysis is not well understood at

* Corresponding author. Tel.: þ33 54000 2653; fax: þ33 54000 2761.
E-mail address: [email protected] (J.-L. Bobet).
0360-3199/$ – see front matter ª 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.02.030
 international journal of hydrogen energy 34 (2009) 3404–3409 3405

the present time, it is sometimes assumed that the use of an 100

oxide that presents various oxidation states (Cr3þ/Cr4þ for Mg + 50wt% WO3
Cr2O3 or Nb5þ/Nb4þ for Nb2O5) can enhance the catalytic effect
80
[9,10].

wt.% of β-MgH2 formed

In WO3, the tungsten can present various oxidation states
(W6þ/W5þ) and WO3 is also known to form some bronzes 60
(inserting some alkali or hydrogen in the structure) [11]. Mg +
10wt%Cr2O3[6]
Moreover, it exhibits a large variety of symmetries from
monoclinic to hexagonal depending on the elaboration process 40
and on the temperature [12–14]. The present paper deals with Mg + 10wt% WO3
the study of the effect of the structure of WO3 and the effect of
20
H0.23WO3, used as catalysts, on the sorption properties of
magnesium based mixtures. The relationship between struc-
ture and properties as well as the connection between micro- 0
structure and properties will be tentatively established. 0 2 4 6 8 10
milling time (hour)

Fig. 2 – Wt.% of b-MgH2 formed as a function of reactive

2. Experimental details mechanical grinding for different amounts of monoclinic
WO3.
In the present paper we report the results obtained for
Mg þ additive mixtures synthesized by milling in a planetary
ball miller (Fritsch P5) with a fixed rotation speed of 250 rpm. PW 1710 diffractometer with Cu-Ka radiation (l ¼ 0.15405 nm).
The vial (stainless steel) containing both powder (8 g) and balls The FULLPROF software (Version Mar 03, LLB Juan Rodriguez-
(17 stainless steel balls of 10 mm of diameter) was filled with Carvajal) was used to determine the weight percentage of Mg
hydrogen up to 1.1 MPa. Milling was done during 15 min then and MgH2. In order to take into account the crystallite size
rested for 5 min and milled again for 15 min. After that, the (and then the difference of crystallinity of each phase), the
vial was recharged with hydrogen (P ¼ 1.1 MPa). peak shape was described by a Thompson-Cox-Hastings
High purity (more than 99.9%) Mg supply from Strem pseudo-Voigt function. Finally, according to the small differ-
Chemicals (93-2438) was used. Two different crystallographic ence in absorption coefficients (mMg ¼ 6.83  103 mm1 and
varieties of WO3 and a H bronze have been employed: (i) mMgH2 ¼ 5.49  103 mm1), no correction for it has been per-
monoclinic WO3 supplied by Strem Chemicals (74-3105) or by formed. According to the large difference between the
Aldrich (204781); (ii) hexagonal WO3 obtained following the absorption coefficient of Mg and WO3 (a factor 102), the last
method of Solonin et al. [15], and (iii) tetragonal H0.23WO3 one is not taken into consideration for the relative wt.%
obtained after ball milling of monoclinic WO3 for 10 h in determination.
a Fritsch P5 miller under 1.1 MPa of H2 [16,17]. All the SEM images were obtained with a JEOL JSM 840 instrument
handlings of the Mg þ additive mixtures were done within operating at an accelerating voltage of 20 kV. The Energy-
a glove box under purified argon atmosphere to avoid oxida- Dispersive X-ray (EDX) analysis was performed with a Noran
tion processes. The milling energy was kept constant and spectrometer (Voyager 4 system) coupled with the SEM. Size
some powder was removed from the vial after different measurements in liquid (ethanol) media were performed
milling times in order to perform XRD analysis. using a Malvern Mastersizer hydro 2000S analyzer. The
The structural changes of the powders were analyzed by X- sample (20 mg) was dispersed in ethanol using an ultrasonic
ray diffraction (10 s per 2q step equal to 0.02 ) using a Philips
100
Mg
Mg + 10wt% H0.23 WO3 tetra
β-MgH2
Al (sample holder)
80
wt.% of β-MgH2 formed

8000
10 h

60
Intensity (a.u.)

6000 5h

4000 2h 40
Mg + 10wt% WO3 hexa

2000
20 Mg + 10wt% WO3 monoclinic
1h
0
0
20 30 40 50 60 70 0 2 4 6 8 10
2θ (°) Milling time (hour)

Fig. 1 – X-ray diffraction patterns for the mixture Mg D 10% Fig. 3 – Wt.% of b-MgH2 formed as a function of reactive
monoclinic WO3 ball milled under hydrogen for different mechanical grinding for different additives (monoclinic
milling times (1, 2, 5 and 10 h). WO3, hexagonal WO3, and tetragonal H0.23WO3).
3406 international journal of hydrogen energy 34 (2009) 3404–3409

50% WO3 m 300°C

25% WO3 m 300°C
100

10% WO3 m 200°C

Fraction of H abs (%)

80 10% WO3 m 300°C

60
50% WO3 m 200°C
40
25% WO3 m 200°C

20

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
Time (s)

Fig. 4 – Relative fraction of H absorbed as a function of time at two different temperatures (200 and 300 8C) for Mg D x% mWO3
(stands for monoclinic) with x [ 10, 25 and 50.

device (47 kHz, 125 W, 30 min). Surface area measurements that the formation of MgH2 during milling depends on the
were performed using a Quantachrome Autosorb 1 milling conditions (temperature [20] and ball/powder weight
equipment. ratio [21]). The XRD patterns obtained after different milling
The mixture Mg þ WO3 was introduced in a volumetric time are presented in Fig. 1. After 1 h of milling, the Bragg
apparatus (Hera) and was evacuated for 2 h at room temper- peaks of tetragonal b-MgH2 (JCPDS card no. 12-0697) start to
ature under primary vacuum. The first absorption was done at appear on the XRD pattern. As expected, increasing the
300  C under 1 MPa. As the mixture consists of both Mg and milling time leads to an increase of the Bragg peaks intensity
MgH2, we wait for the complete absorption (between 2 and 8 h) of MgH2 and to a decrease of the Bragg peaks intensity of Mg.
before recording the first desorption at 330  C and 0.03 MPa. The Moreover, it has to be pointed out that the crystallinity of the
following absorption–desorption cycles were done at 300  C – MgH2 formed during milling is lower than that of the initial
1 MPa and 330  C – 0.03 MPa, respectively. The results presented magnesium. This is in agreement with previous results [19,20].
in this paper correspond to the third cycle (second and third are After 5 h of milling, a very small amount of orthorhombic g-
similar). After these first 3 cycles, the absorption and desorption MgH2 (JCPDS card no. 35-1184) is also formed, but according to
were performed at lower temperatures (250 and 200  C for the very small intensity of the Bragg peaks, it has not been
absorption, and 300 and 280  C for desorption) at the same taken into account in the calculation of the relative amount of
pressure (1 MPa and 0.03 MPa, respectively). MgH2 formed. Moreover, the amount of g-MgH2 does not
increase as milling proceeds, and it does not play a significant
role during sorption (it disappears after the first cycle).
3. Results and discussion Rietveld refinements allow-us to determine the relative
amount of MgH2 formed as a function of milling time (Figs. 2
3.1. Conversion of Mg into MgH2 during reactive ball and 3). As already mentioned, no correction was performed
milling due to the difference between the absorption coefficients of
Mg and MgH2 due to their close similarity. Nevertheless, the
It has already been shown that ball milling under a reactive calculated hydride amount should be considered carefully,
media could lead to the formation of nitrides [18], oxides or taking into account an accuracy of at most 95%, mainly
hydrides [19]. In the case of magnesium, it has been reported because WO3 and g-MgH2 were not taken into account in the

H0.23WO3tetra 300°C WO3 hexa 300°C WO3 monoC 300°C

3
Wt% H abs

WO3 monoC 200°C

1 H0.23WO3 tetra 200°C

WO3 hexa 200°C

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
Time (s)

Fig. 5 – Wt. % of H absorbed as a function of time at two different temperatures (200 and 300 8C) for Mg D 50 wt.% of different
additives (monoclinic WO3, hexagonal WO3, and tetragonal H0.23WO3).
 international journal of hydrogen energy 34 (2009) 3404–3409 3407

Particle Size Distribution by (i) a higher H2/Mg ratio, as the total amount of magnesium
10 decreases and the H2 pressure is constant, (ii) a higher milling
WO3 monoclinic efficiency; as more WO3 is added, more fresh surface is
9
created, and as the amount of H2 is also more important, this
8 leads to an increase of the conversion rate.
In Fig. 3, the effect of different additives is examined.
7 Almost the same results were obtained with the addition of
H0.23 WO3 tetragonal
(milled monoC) monoclinic or hexagonal WO3. This result is surprising
Volume (%)

6
because the hexagonal structure is less compact and should
5 offer some hydrogen trap sites which should play a role during
milling. On the other side, the use of the bronze H0.23WO3
4 leads to a significant improvement of the conversion degree.
We assumed, and it will be justified in the second part, that
3
the difference on the specific surface of the additives (3 m2/g
2 for monoclinic WO3 and 20 m2/g for the bronze) is the origin of
WO3 hexagonal
the distinct conversion rates of Mg into MgH2 during milling.
1 It is finally worth pointing out that the catalysts remain in
their initial crystal structure during milling and that no
0
0.01 0.1 1 10 100 1000 chemical change (H content in the bronze) has been observed.
Particle Size (µm)
3.2. Hydriding and dehydriding properties
Fig. 6 – Particle size distribution of monoclinic WO3,
hexagonal WO3 and tetragonal H0.23WO3 (obtained by
In a first step, the influence of the WO3 content was studied.
milling monoclinic WO3).
The goal was to verify that the use of a large quantity of WO3
(useful to be able to check the evolution of WO3 structure
during milling and subsequent hydruration) produces the
refinement, and also due to the possible disappearance of Mg same effect on the sorption properties (except the maximum
reflections due to reduction of crystallite size. The following capacity) than a small quantity. As clearly seen in Fig. 4, no
general trends are observed in the curves (Figs. 2 and 3): (i) significant difference can be found in the kinetic behaviour
during the first hour of milling only a small quantity of MgH2 is when varying the amount of monoclinic WO3 from 10 to
formed; (ii) from 1 to 5 h the formation of MgH2 is rather rapid 50 wt.%. This is in good agreement with previous results (but
and two thirds of the initial Mg is transformed into MgH2; (iii) with lower catalyst content) [7–10]. It is worth pointing out
from 5 to 10 h, the remaining Mg is transformed into MgH2 but that 10 wt.% of WO3 represents only 1.15 molar % and 50 wt.%
in some cases a complete transformation is not reached after only 9.49 molar %. It can be rather surprising that an increase
10 h. The reported behaviour is similar to the one observed for in the amount of WO3 during milling improves the trans-
Mg þ Cr2O3 mixtures in the same milling conditions [6]. By formation of Mg into MgH2, whereas it does not have any
optimizing the milling conditions (increasing the ball to appreciable effect on the sorption properties of the milled
powder weight ratio [21] or the milling temperature [20]) it material. But both facts are not contradictory as, the use of
should be easy to reach the full transformation in a few hours. different amounts of additives has an impact on the milling
The effects of different amounts of monoclinic WO3 are efficiency (i.e. by adding more brittle component in the
presented in Fig. 2. An increase in the WO3 content leads to powder mixture), but it does not have any effect on the kinetic
a higher conversion rate (e.g. almost 80% of the Mg is trans- properties of the milled material. It is therefore worth
formed after 5 h). Such improved conversion can be explained concluding that the higher transformation rate during milling

Fig. 7 – SEM (backscattered electrons) images of Mg D WO3 monoclinic (left) and Mg D H0.23WO3 tetragonal (right). Both
mixtures were ball milled for 5 h.
3408 international journal of hydrogen energy 34 (2009) 3404–3409

Mg+H0.23 WO3 tetra 300°C small particles (around 0.8 mm) exist compared with mono-
3 Mg+WO3 monoC HSS 300°C
clinic WO3. The BET measurements confirm the granulo-
metric measurements as the specific surface of the bronze
was 20 m2/g and that of the monoclinic and hexagonal WO3
only 3 and 3.6 m2/g, respectively. Moreover, the SEM obser-
2
Wt% H abs

vations presented in Fig. 7 confirm this trend. On the mixture

Mg+WO3 monoC HSS 200°C Mg þ H0.23WO3, the bronze appears homogeneously dispersed
with a small particle size, whereas for the mixture with
Mg+H0.23WO3 tetra 200°C
1 monoclinic WO3, some rather large particles are present
together with some small ones. Therefore, if we assume
a catalytic effect due to the surface, we can conclude that the
higher specific surface of the bronze is related with the better
0 sorption properties of this mixture.
0 50 100 150 200
To check the effect of the nature of the catalyst, we
Time (s)
prepared some monoclinic WO3 with a high specific surface.
Fig. 8 – Wt. % of H absorbed as a function of time at two To achieve this, the high specific surface H0.23WO3 was heated
different temperatures (200 and 300 8C) for different at 410  C under reduced pressure (0.05 MPa Ar) for 1 day.
additives with similar specific surfaces: Mg D 50% HSS During this treatment, the bronze transformed to monoclinic
monoclinic WO3 (HSS: high specific surface) and Mg D 50% WO3 with similar specific surface (18 m2/g compared with
H0.23WO3. 20 m2/g for the initial H0.23WO3). In Fig. 8 the absorption
behaviour of the mixtures Mg þ WO3 and Mg þ H0.23WO3 with
nearly the same specific surface is presented. Hydriding
does not necessarily lead to any significant change of the kinetics is rather similar for both mixtures, confirming that
subsequent sorption properties. From Fig. 4, we can also say there is not a substantial difference based on the nature of the
that 90% of the full capacity is reached after about 3 min at additives. Instead, the important aspects in this system seem
300  C and about 60% after 6 min at 200  C. At 200  C, 80% of to be the specific surface and the particle size of the additive.
the full capacity is reached after 15 min but the full absorption In Fig. 9, the desorption kinetics are presented. At 300  C it
is rather long to be obtained (i.e. almost 1 day). takes little more than 3 min to achieve full desorption for
In Fig. 5, the effect of the different additives is compared. Mg þ H0.23WO3, and it takes more than 10 min for Mg þ low
The studied mixtures consist of Mg þ 50 wt.% additive specific surface monoclinic WO3. As previously mentioned for
(monoclinic WO3, hexagonal WO3 and tetragonal H0.23WO3) the absorption at low temperature (i.e. 200  C), the full
ball milled for 5 h under hydrogen. Irrespective of the desorption at 280  C is difficult to achieve, and takes a few
temperature, the mixture containing H0.23WO3 exhibits better hours. On Fig. 9, the desorption behaviour of Mg þ WO3
sorption kinetics than the one containing hexagonal WO3, monoclinic HSS (High Specific Surface) is also presented. As
which is in turn better than the one with monoclinic WO3. As a difference with the absorption process, the kinetic obtained
shown in Fig. 6, the average particle sizes of hexagonal and in this case is not close to the one with H0.23WO3 having
monoclinic WO3 are 22.5 and 19.3 mm respectively, and it is almost the same specific surface. After 100 s, the relative
only 3.7 mm for H0.23WO3. Then, the approximate number of amounts of hydrogen desorbed are 36, 44 and 65% for WO3
catalyst particles per magnesium particles (assuming spher- monoclinic, WO3 monoclinic HSS and H0.23WO3 tetragonal,
ical and homogeneous particles) is 1.3 and 2.1 for hexagonal respectively. After 150 s, it is respectively 53, 66 and 86%. The
and monoclinic WO3 respectively and it is about 290 for the difference between the first two values of both sets (i.e. 36 /
tetragonal H0.23WO3. Nevertheless, it is also worth pointing 44 and 53 / 66) is due to the distinct specific surfaces, and the
out that in the case of hexagonal WO3, a higher number of difference between the last two values (i.e. 44 / 65 and 66 /

3 WO3 monoC 300°C

Wt% H des

H0.23WO3 tetra 300°C

1
WO3 monoC HSS 300°C

0
0 100 200 300 400 500 600
Time (s)

Fig. 9 – Wt. % of H desorbed as a function of time at 300 8C for different additives: Mg D 50% low specific surface monoclinic
WO3, Mg D 50% HSS monoclinic WO3, and Mg D 50% H0.23WO3.
 international journal of hydrogen energy 34 (2009) 3404–3409 3409

86) is due to the chemical composition of the catalyst and or to [4] Barkhordarian G, Klassen T, Bormann R. Effect of Nb2O5
the structure. The XRD analysis after the sorption process content on hydrogen reaction kinetics of Mg. J Alloys Compd
does not reveal any changes on the chemical composition or 2004;364:242–6.
[5] Dehouche Z, Klassen T, Oelerich W, Goyette J, Bose TK,
the crystal structure of the catalyst. Therefore, at the present
Schulz R. Cycling and thermal stability of nanostructured
time, we can conclude that the specific surface of the catalyst MgH2–Cr2O3 composite for hydrogen storage. J Alloys Compd
is the major factor to take into account considering hydrogen 2002;347:319–23.
absorption kinetics, but it is not the only factor for desorption. [6] Bobet J-L, Desmoulins-Krawiec S, Grigorova E, Cansell F,
For desorption, the chemical composition of the catalyst (WO3 Chevalier B. Addition of nanosized Cr2O3 to magnesium for
or H0.23WO3) as well as the structure (monoclinic and tetrag- improvement of the hydrogen sorption properties. J Alloys
onal) may also play an important role. Maybe the presence of Compd 2003;351(1–2):217–21.
[7] Barkhordarian G, Klassen T, Bormann R. Fast hydrogen
protons in the catalyst can help during the recombination
sorption kinetics of nanocrystalline Mg using Nb2O5 as
process, a step that has been considered as the rate limiting catalyst. Scripta Mater 2003;49:213–7.
step in the desorption [10]. [8] Dornheim M, Doppiu S, Barkhordarian G, Boesenberg U,
Klassen T, Gutfleisch O, et al. Hydrogen storage in
magnesium-based hydrides and hydride composites. Scripta
4. Conclusion Mater 2007;56:841–6.
[9] Barkhordarian G, Klassen T, Bormann R. Catalytic
mechanism of transition-metal compounds on Mg hydrogen
First, it is shown that a higher transformation of Mg into
sorption reaction. J Phys Chem B 2006;110(22):11020–4.
MgH2 during reactive milling could be obtained by adding [10] Barkhordarian G, Klassen T, Bormann R. Kinetic
more catalyst to the mixture. This is directly linked with investigation of the effect of milling time on the hydrogen
a higher milling efficiency. Then, this preliminary study also sorption reaction of magnesium catalyzed with different
allows-us to highlight the low influence of the nature of the Nb2O5 contents. J Alloys Compd 2006;407:249–55.
catalyst on the hydriding properties of Mg based mixtures. [11] Glemser O, Naumann C. Kristallisierte
Wolframblauverbindungen; Wasserstoffanaloga der
It can be assumed that if the additive is hexagonal WO3,
Wolframbronzen HxWO3. Z Anorg Allg Chem 1951;265(4–6):
monoclinic WO3 or H0.23WO3 all of them with similar 288–302.
particle size distribution and specific surface, then, there [12] Wells AF. Structural inorganic chemistry. 3rd ed. Clarendon
will be no significant differences on the hydrogen absorp- Press; 1962.
tion behaviour of the mixtures. The specific surface of the [13] Gerand B, Nowogrocki G, Guenot J, Figlarz M. Structural study
additive seems to be the important factor that should be of a new hexagonal form of tungsten trioxide. J Solid State
taken into account when looking for improvements in the Chem 1979;29:429–34.
[14] Han W, Hibino M, Kudo T. Synthesis of the hexagonal form of
kinetic absorption properties of magnesium based mate-
tungsten trioxide from peroxopolytungstate via ammonium
rials. Interestingly, this independence of the nature of the paratungstate decahydrate. Bull Chem Soc Jpn 1998;71:933–7.
catalyst (composition and or structure) has not been [15] Solonin YM, Khyzhun OY, Graivoronskaya EA.
observed during hydrogen desorption. In this case, both the Nonstoichiometric tungsten oxide based on hexagonal WO3.
microstructure (particle size and specific surface) and the Cryst Growth Des 2001;1:473–7.
nature of the catalyst (H0.23WO3, HSS monoclinic WO3 and [16] Urretavizcaya G, Tonus F, Gaudin E, Bobet J-L, Castro FJ.
Formation of tetragonal hydrogen tungsten bronze by
low specific surface monoclinic WO3) play a role during
reactive mechanical alloying. J Solid State Chem 2007;180:
hydrogen desorption.
2785–9.
[17] Castro F, Tonus F, Bobet J-L, Urretavizcaya G. Synthesis of
hydrogen tungsten bronzes HxWO3 by reactive mechanical
milling of hexagonal WO3. J Alloys Compd, submitted for
Acknowledgments
publication (JALCOM-D-08-02310).
[18] Sherif El-Eskandarany M. Solid state nitrization reaction of
Partial financial support from the SECYT-ECOS Cooperation amorphous tantalum aluminium nitride alloy powders: the
Program (A05-E04 Project) is gratefully acknowledged. role of amorphization by reactive ball milling. J Alloys Compd
1994;203:117–26.
[19] Bobet J-L, Akiba E, Nakamura Y, Darriet B. Study of Mg–M
references (M ¼ Co, Ni and Fe) mixture elaborated by reactive
mechanical alloying. Hydrogen sorption properties. Int J
Hydrogen Energy 2000;25:987–96.
[1] Züttel A. Materials for hydrogen storage. Materials Today [20] Huot J, Tremblay M-L, Schulz R. Synthesis of nanocrystalline
2003;6(9):24–33. hydrogen storage materials. J Alloys Compd 2003;356–357:
[2] Schlapbach L, Züttel A. Hydrogen-storage materials for 603–7.
mobile applications. Nature 2001;414:353–8. [21] Bobet J-L, Chevalier B, Song MY, Darriet B. Improvements of
[3] Aguey-Zinsou K-F, Ares-Fernández J-R. Synthesis of colloidal hydrogen storage properties of Mg-based mixtures
magnesium: a near room temperature store for hydrogen. elaborated by reactive mechanical milling. J Alloys Compd
Chem Mater 2008;20:376–8. 2003;356–357:570–4.