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Hydrogen generation via hydrolysis of Mg2Si

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DOI: 10.1016/j.jallcom.2018.08.122

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 Journal of Alloys and Compounds 770 (2019) 108e115

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Hydrogen generation via hydrolysis of Mg2Si

Z.H. Tan a, L.Z. Ouyang a, b, *, J.M. Huang a, J.W. Liu a, H. Wang a, H.Y. Shao c, **, M. Zhu a
a
School of Materials Science and Engineering, Guangdong Provincial Key Laboratory of Advanced Energy Storage Materials, South China University of
Technology, Guangzhou, 510641, People's Republic of China
b
China-Australia Joint Laboratory for Energy & Environmental Materials, Key Laboratory of Fuel Cell Technology of Guangdong Province, Guangzhou,
510641, People's Republic of China
c
Joint Key Laboratory of the Ministry of Education, Institute of Applied Physics and Materials Engineering (IAPME), University of Macau, Macau SAR,
People's Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: A convenient, high-density and low-cost hydrogen supply technology is essential to hydrogen energy
Received 21 May 2018 system by providing hydrogen to fuel cell component. Magnesium silicide (Mg2Si) can be a good hy-
Received in revised form drolysis candidate due to its low cost and ability of releasing hydrogen gas during hydrolysis process.
14 August 2018
However, previous studies have demonstrated that Mg2Si could easily produce large amount of silanes
Accepted 16 August 2018
Available online 17 August 2018
during hydrolysis reaction, which may cause serious problem of explosive danger when in contact with
air. Here it is the first time that Mg2Si was used for generation of hydrogen by a simple and convenient
one-step hydrolysis reaction. In this study, hydrolysis kinetics and mechanisms of Mg2Si in NH4Cl and
Keywords:
Hydrogen generation
NH4F solutions were investigated. The silanes could be almost completely turned into hydrogen by
Magnesium silicide introduction of fluorine ion during the hydrolysis reaction of Mg2Si, leading to very low silanes content in
Hydrolysis the produced hydrogen. The kinetic studies indicated that when the concentration of the NH4F solution
Activation energy increased to 13.0%, the hydrogen generation rate and the reaction yield were improved significantly and
reached the best performance, producing 466 mL g
1 H2 in 10 min and 616 mL g
1 H2 in 30 min at 25  C.
The activation energy was calculated to be 37.3 ± 0.8 kJ mol
1. Furthermore, the hydrogen yield and the
hydrolysis rate of Mg2Si can be further improved by high-energy ball milling. After ball milling for 2 and
5 h, the hydrogen generation yield in 30 min increased to 698 and 771 mL g
1, respectively, and the
activation energy was decreased to 23.9 ± 0.6 kJ mol
1 and 12.9 ± 0.1 kJ mol
1, respectively. The results
revealed that NH4F can be a promising reagent for promoting the hydrolysis of Mg2Si for onsite hydrogen
supply.
© 2018 Published by Elsevier B.V.

1. Introduction by lack of convenient hydrogen production, storage technologies

In the context of climate change and energy economy conver-
sion, the transition from fossil fuels to renewable energy has
become a consensus of people. Hydrogen is thought to be a
promising energy carrier, especially for renewable power, due to its
cleanness, high energy density and regenerative properties. How-
ever, worldwide utilization of hydrogen energy is greatly hampered
* Corresponding author. School of Materials Science and Engineering, Guangdong
Provincial Key Laboratory of Advanced Energy Storage Materials, South China
University of Technology, Guangzhou, 510641, People's Republic of
China.meouyang@scut.edu.cn
** Corresponding author. Joint Key Laboratory of the Ministry of Education,
Institute of Applied Physics and Materials Engineering (IAPME), University of
Macau, Macau SAR, People’s Republic of China.
and infrastructures. Regarding hydrogen production, there are
various options including electrolysis of water [1], photolysis of
water [2,3], gasification of heavy oil, coal or biomass, and steam
reforming of hydrocarbons [4,5]. However, those methods all have a
lot of disadvantages, such as low efficiency, high price and high
energy consumption [6]. Recently hydrogen generation through
hydrolysis reactions has attracted increasing attention because of
its safety, low cost and possible recyclability of the hydrolysis
products [7,8]. In certain hydrolysis reactions, a quick hydrogen
release may take place soon after the contact between reactants
even under mild conditions, which makes the real-time hydrogen
production possible via hydrolysis reactions [9]. So far, studies have
been performed on the materials including ammonia borane
[10e12], alloys [13e16], metal hydrides [17e19], sodium borohy-
dride [20,21] etc. to generate hydrogen. Among these chemicals,

https://doi.org/10.1016/j.jallcom.2018.08.122
0925-8388/© 2018 Published by Elsevier B.V.
 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115
Mg and its compounds are very promising materials for hydrogen
generation because Mg can be as a safe, environmental friendly and
compact source of hydrogen. These merits make Mg-based mate-
rials very competent as hydrogen supply source for fuel cell
particularly mobile applications. Besides, the electrochemical per-
formances [22e27] for energy storage applications of hydrogen
storage alloys as hydride battery electrodes [28e31] have also been
intensively investigated.
Magnesium silicide (Mg2Si), the only intermetallic in the MgeSi
binary system, has been widely used as semiconductor, thermo-
electric and lithium-ion battery electrode materials [32e35]. Be-
sides, Mg2Si is also used to produce silanes industrially by reacting
with ammonium chloride or bromide in liquid ammonia [36,37].
However, it is worth noting that the products of these reactions are
usually series of silanes and small amount of hydrogen. Similarly,
Nandi et al. also obtained such gas mixture when they put Mg2Si in
hydrochloric acid at 23  C [38]. Moreover, since the silanes are very
sensitive to water, with the increasing percentage of water in
aqueous solution, the yield of hydrogen increases [38,39]. These
results indicate that Mg2Si may be a potential candidate material
for hydrogen generation. However, it remains some key problems,
especially the safety concern of explosive silanes when in contact
with air. Such problems lead to failure in meeting the requirements
for its commercial applications. Therefore, it is critical to eliminate
silanes or transform them into hydrogen during hydrolysis process
of Mg2Si. Fortunately, silanes may be easily and completely absor-
bed by alkaline solutions [40] with the formation of metasilicate
and hydrogen. Thus, it is possible to remove silane gas by absorp-
tion into alkaline solutions. Moreover, if the content of silanes in
hydrogen is too high, the potential explosive danger is inevitable
when the gas mixture is exposed to air. Therefore, exploring new
strategies to improve the purity of hydrogen, inhibit the generation
of silanes, and developing an efficient, safe and economical
hydrogen-producing method is highly desirable.
Herein, we reported a new method for hydrogen generation of
Mg2Si using NH4F as the reactive agent through hydrolysis. As far as
we know, there is no report about using a one-step method to
produce hydrogen using Mg2Si as the reducing agent. Ammonium
salts were chosen as hydrolysis medium because they have been
reported to be promising reagent for promoting the hydrolysis ki-
netics [41e43]. Besides, fluorine ion was introduced into hydrolysis
due to its high chemical affinity to silicon ion, which may break the
Si-H bond and form H2 and SiF2
6 [44] in aqueous solution. In this
paper, in order to prevent the generation of silanes and try to
transform the explosive silanes into hydrogen, we introduced NH4F
to the aqueous solution for hydrolysis reaction of Mg2Si. We
investigated the kinetic properties and activation energy of the
hydrolysis reactions between Mg2Si and NH4F solutions and we
also used high-energy ball milling technique to enhance the reac-
tion kinetics. Meanwhile, to reveal the reaction process and
mechanism, we also investigated NH4Cl as reactive agent for
comparison.
2. Experimental
Mg2Si with a purity of 99.5% was purchased from Aladdin.
Ammonium chloride (NH4Cl, 96%), ammonium fluoride (NH4F, 96%)
and sodium hydroxide (NaOH, 96%) were bought from Shanghai
Titan Scientific Co. Ltd. Ball milling was performed in a planetary
mill using 250 mL stainless steel mixing jars and balls, at 400 rpm
under argon atmosphere with a ball-to-powder weight ratio of
40:1. All sample handling was performed in a glove box under Ar in
order to prevent the oxidation of the powder. The reactive me-
chanical grinding was performed by repeating milling (for 30 min)
and cooling (for 30 min) 3 or 9 times, resulting in a total milling
109
time of 2 or 5 h.
For hydrolysis reactions, in a typical experiment, 0.1 g of Mg2Si
was loaded in a 25 mL flask or PET bottle, and 20 mL different
concentration solution was added to start the reaction. The amount
of the released gas was measured by the mass of water drained
from gas washing bottles, which was weighed by a balance every
five seconds. For the hydrolysis of Mg2Si in NH4Cl solution, the gas
was passed through NaOH solution firstly in order to transform
silanes into hydrogen. Each measurement was repeated at least
twice to confirm the reliability. In order to obtain the activation
energy, the hydrolysis reactions of Mg2Si were performed at
various temperatures (5, 15, 25 and 35  C) in NH4F solution. The
hydrolysis products were passed through a drying cabinet at 80  C
and then were analyzed by a Mini Flex 600 X-ray diffractometer
(XRD) using Cu Ka radiation. The XRD patterns were recorded in a 2
theta range of 10e90 at a scanning rate of 0.05 s
1. The micro-
structures of the milled Mg2Si powder were characterized by a
scanning electron microscope (SEM) (Zeiss Supra-40, Germany). In
order to determine the gas composition, the produced gas was
directly passed though and analyzed by a mass spectrograph (MS,
QIC 20 gas analysis system).
3. Results and discussion
3.1. Hydrolysis of Mg2Si in NH4Cl and NH4F solutions
Based on the fact that the hydrolysis reaction of Mg2Si in NH4Cl
solution could release a mixture of hydrogen and silanes, we firstly
tested the hydrolysis performance of Mg2Si in NH4Cl solution. All
the produced gas was passed through NaOH solution to obtain H2.
The hydrogen generation curves for the hydrolysis of Mg2Si in
NH4Cl solution with different concentrations (4.5, 8.5, 15.7 and
27.1 wt%) are shown in Fig. 1(a). Evidently, all the curves show very
high hydrogen release rates in the first five minutes and then the
rates slow down with the hydrolysis reaction proceeding. Besides,
the increase in the concentration of NH4Cl solutions leads to a
significant improvement in the reaction rate and the hydrogen
yield. Fig. 1(b) shows the change of hydrogen yield of M2Si hydro-
lysis in the NH4Cl solutions with different concentrations. Gratify-
ingly, the reaction of Mg2Si with the 27.1 wt% NH4Cl solution shows
the best hydrolysis performance, producing 660 mL g
1 H2 in 5 min
and 738 mL g
1 H2 in 10 min. However, some white smoke with
small sparks appears when Mg2Si contacts with NH4Cl solution.
This is thought to be caused by the produced silanes which get
burned when exposed to air. In other words, the Mg2Si reacting
with NH4Cl solution does not produce hydrogen directly but
different types of silanes, which causes serious safety concern of
explosive danger when in contact with air. Therefore, we decided to
introduce fluorine ion into the hydrolysis process of Mg2Si. Namely,
using ammonium fluoride as the hydrolysis medium, we expect
that fluorine ion could effectively break the Si-H bond and form
SiF2

6 in aqueous solution and H2 during the hydrolysis.
Hydrogen generation from the hydrolysis of Mg2Si in NH4F so-
lution was investigated in the presence of different concentrations.
Fig. 2(a) showed the H2 generation curves for Mg2Si in NH4F so-
lutions with various concentrations (7.0, 10.0, 13.0, 16.0 and 19.0 wt
%). We can see that the reactions of Mg2Si in 7.0 and 10.0% NH4F
solutions show poor hydrolysis performance. The hydrolysis yield is
relatively low and it generates only 53 and 49 mL g
1 in 10 min for
the 7.0 and 10.0% solution, respectively. Surprisingly, when the
concentration of NH4F is increased to 13.0%, the hydrogen gener-
ation rate and the reaction yield are improved significantly, pro-
ducing 466 mL g
1 in 10 min and 616 mL g
1 in 30 min. However,
additional increase in the concentration of NH4F reduces the
hydrogen yield. The hydrogen yield of M2Si hydrolysis in different
110 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115

Fig. 1. (a) Hydrogen generation curves and (b) hydrogen yield within 10 min, for the hydrolysis of Mg2Si in different concentration NH4Cl solutions at 25  C.

Fig. 2. (a) Hydrogen generation curves and (b) yield in 60 min, for the hydrolysis of Mg2Si in different concentration NH4F solutions at 25  C.

concentration NH4F solutions in 60 min is shown in Fig. 2(b). The
results indicate that the hydrolysis of Mg2Si in 13.0% NH4F solution
is the most appropriate system based on the resulting production
cost and yield, and therefore this concentration is employed in the
following experiments. Importantly, compared to the hydrolysis
reaction in NH4Cl solution, the process of Mg2Si in NH4F solution
showed no white smoke or sparks, indicating that the released gas
contains almost no silanes and it also demonstrates that the process
is safe even when it is exposed to air.
To reveal the hydrolysis reaction mechanism and to understand
the inhibition function of silanes production, the remaining prod-
ucts after the hydrolysis of Mg2Si in NH4F and NH4Cl solutions were
collected and analyzed. Fig. 3 shows XRD patterns of the byprod-
ucts of Mg2Si hydrolyzed in (a) 13.0% NH4F solution and (b) a series
of concentrations of NH4Cl solutions. As shown in Fig. 3(b), the
byproducts of Mg2Si hydrolysis in NH4Cl solution are composed of
Mg(NH4)Cl3$6H2O and unreacted Mg2Si. The diffraction peaks for
Mg(NH4)Cl3$6H2O is observed in the XRD curve of the byproducts
after hydrolysis reaction in NH4Cl solution because Mg2þ ions and
excess NH4Cl are easily to form a double salt Mg(NH4)Cl3$6H2O
when they co-exist in one solution [45], which may decrease the
passivated layer and thus improve the kinetics of Mg2Si hydrolysis.
However, all the peaks for compounds related to silicon are absent
in all the NH4Cl solutions with different concentrations. This may
be due to the high affinity of Si4
and Hþ ions, which may lead to
near-complete conversion of Si4
into silanes via hydrolysis. This is
similar to Yasakau group's result in which they reported that Mg2Si
can be hydrolyzed by water resulting in formation of different types
of silanes, in particular mono-silane and magnesium hydroxide
[46]. By contrast, the XRD peaks of the byproducts for Mg2Si hy-
drolysis in NH4F solution (as shown in Fig. 3(a)) are attributed to
(NH4)3SiF7, (NH4)2SiF6, (NH4)2MgF4 and unreacted Mg2Si.

Fig. 3. XRD patterns of the hydrolysis byproducts of Mg2Si with (a) 13.0 wt% NH4F and (b) NH4Cl solutions with different concentrations at 25  C.
 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115
Compared to the hydrolysis of Mg2Si in NH4Cl solution, it should be
noted that the (NH4)3SiF7 and (NH4)2SiF6 compounds appear after
the hydrolysis in NH4F solution, indicating that Si can combine with
fluorine to form SiF2

6 rather than form Si-H bond. This strong ev-
idence confirms that the introduction of fluorine can destroy the Si-
H bond and inhibit the produce of silanes effectively. Therefore, the
introducing of NH4F can induce Mg2Si to release hydrogen with
high purity via hydrolysis reaction and this conclusion is also
consistent with the previous results.
Besides, based on the phase analysis mentioned above, the main
hydrolysis reaction of Mg2Si with NH4F solution can be expressed
as reaction formula (1). It should be noted that the produced NH3 is
mostly dissolved in the solution. Similarly, the reactions between
Mg2Si and NH4Cl solution can be inferred as reaction Equations (2)
and (3). Reaction (3) is the side reaction for generating silanes,
which should not be ignored considering the hydrolysis results
above. The produced Si2H2O3 in reaction (2) may be amorphous
after drying, making it difficult to be detected by XRD.
Mg2Si þ 14NH4F ¼ (NH4)2SiF6 þ 2(NH4)2MgF4 þ 4H2 þ 8NH3 (1)
2Mg2Si þ 12NH4Cl þ 27H2O ¼ 4Mg(NH4)
Cl3$6H2O þ 6H2 þ Si2H2O3 þ 12NH3 (2)
Mg2Si þ 6NH4Cl þ 12H2O ¼ 2Mg(NH4)Cl3$6H2O þ SiH4 þ 4 NH3(3)
3.2. Gas characterization
Through the introduction of NH4F in the hydrolysis of Mg2Si, the
formation of silanes could be suppressed effectively. In order to
further determine the specific composition of the produced gas and
quantify this effect, the mass spectrometer was used for qualitative
detection while a volume method was adopted for quantitative
analysis. The released gas from Mg2Si hydrolysis in 13.0% NH4F
solution was directly passed through a mass spectrometer. In Fig. 4,
the mass spectrum shows that H2 is the main component of the gas
released from hydrolysis reaction, and a small amount of NH3 is also
detected. This is due to the volatilization of NH3 dissolved in the
solution after the reaction. It should be pointed out that the silane
Fig. 4. Gas characterization of hydrolysis between Mg2Si and NH4F solution by MS.
111
signal is observed (the red line in Fig. 4) and a small amount of
silanes is produced during the incubation period, and then there is
a decrease in the monosilane signal during the reaction accelera-
tion period. That is to say, during the acceleration period of the
reaction, monosilane is inhibited. As the reaction rate reaches the
maximum, the proportion of hydrogen in the gas flow decreases,
and the monosilane signal begins to rise and get stabilized after-
wards. The gas characterization results demonstrate that a small
amount of monosilane is produced but highly suppressed in the
hydrolysis reaction between Mg2Si and NH4F. These is no obvious
presence evidence of Si2H6, Si3H8 and SiF4.
In order to quantitatively analyze the proportion of monosilane
in the gas, a volume change experiment was conducted using NaOH
solution to absorb the gas produced by the hydrolysis of Mg2Si with
NH4F and NH4Cl solutions, and the silane content in the gas was
calculated by measuring the volume change. The experimental
device is shown in Fig. 5. The experimental principle is that 1 mol of
monosilane reacts with NaOH solution to produce 4 mol of
hydrogen and the volume increases by a factor of 3 according to the
reaction equation shown in Fig. 5(a). The comparative experimental
solutions were chosen from the concentration with best perfor-
mance in this research-13.0% NH4F solution and 27.1% NH4Cl so-
lution. In the experiment, two 100 mL cylinders were used to
collect 91 mL gas released from Mg2Si hydrolysis in NH4F and NH4Cl
solutions by drainage method. At the same time, a set for blank test
with air was also conducted. Then 30 wt% NaOH solution was added
to the solution for absorption. After standing for a while, the vol-
ume change was recorded as shown in Table 1. From it, we can see
that the gas volume in the Mg2Si-NH4F group and the Mg2Si-NH4Cl
one increases by 1 and 4 mL, respectively, after 12 h absorption in
the NaOH solution. The volume of the blank group does not change.
The calculation shows that the proportion of the silane in the
Mg2Si-NH4Cl group gas is 1.47 vol%, while that of the Mg2Si-NH4F
group is only 0.37 vol%. The results show that the NH4F solution
could effectively inhibit the production of silanes during the
hydrogen production by hydrolysis of Mg2Si, and significantly
reduce the impurity content of gas silanes.
3.3. Ball milling
From reaction formula (1), 1 mol of Mg2Si could generate 4 mol
hydrogen (if considering the side reaction for generating silanes,
1 mol of silane could react with NaOH solution to produce 4 mol of
hydrogen, the ratio of H2 to Si is still 4/1). The theoretical hydrogen
generation capacity of Mg2Si is 1278 mL g
1 (10.4 wt% with no
water included in the calculation, 25  C). In contrast, the theoretical
hydrogen generation capacity of Mg is 1008 mL g
1 (8.2 wt%, 25  C),
which is much lower than that of Mg2Si-NH4F system, not to
mention the formation of passive Mg(OH)2 layer on the surface of
Mg which hinders the reaction. Therefore, Mg2Si has better
hydrogen generation potential than Mg.
Considering the theoretical value, although the hydrolysis per-
formance of Mg2Si shows great improvement in 13.0% NH4F solu-
tion, the hydrogen yield is still relatively low, only 48%. Hence, we
investigate the effect of high-energy ball milling on its hydrogen
production performance. The aim is to obtain highly refined and
reactive materials to ensure a full completion of the hydrolysis
reaction in NH4F aqueous solution. Fig. 6 presented XRD pattern of
the Mg2Si powders with different milling time. These is no obvious
difference of Mg2Si with milling, except the accentuation of the
peak broadening reflecting the decrease of the Mg2Si crystallite size
with the milling time. This is also confirmed by the SEM observa-
tions as shown in Fig. 7. From the low magnification images in Fig. 7
(d, e, f), it can be seen that the Mg2Si powder particles are aggre-
gated before ball milling. After ball milling, the morphology
112 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115

Fig. 5. The experimental device and process of volumetric method via NaOH solution absorption.

Table 1 grinding. With the prolongation of milling time, this refinement

The volume changes of gas before and after absorption in NaOH solution. effect becomes more obvious. This result is also consistent with the
Statistics Mg2Si-NH4F Air (blank) Mg2Si-NH4Cl observation from XRD pattern in Fig. 6. However, after 2 h milling,
Initial volume (mL) 91 88 91
some tiny additional peaks attributed to MgO and Si phases appear.
Volume after 12 h absorption (mL) 92 88 95 This may be due to the leak of the steel jars, which allows Mg2Si to
Volume increase (mL) 1 0 4 react with the small amount of oxygen from air. Fortunately, the
Silane volume content 0.37% e 1.47% peak intensity does not increase obviously with further milling.
The hydrogen generation in 13.0% NH4F of hydrolysis reactions
for Mg2Si with different milling time was tested and Fig. 8 shows
the hydrogen generation curves and conversion yield in 30 min for
these hydrolysis reactions. As seen in Fig. 8, the ball milling treat-
ment has considerable improvement effect on the reactivity of
Mg2Si in NH4F solution. Compared to the original Mg2Si without
milling, after ball milling for 2 and 5 h, the hydrogen conversion
rate is increased from 48.1% (releasing 616 mL g
1 H2) to 54.6%
(698 mL g
1) and 60.3% (771 mL g
1) within 30 min, and from 50.6%
(647 mL g
1) to 59.6% (763 mL g
1) and 65.1% (833 mL g
1) within
60 min, respectively. The results show that as the milling time in-
creases, the hydrogen generation yield and the rate are further
increased. The major reason to this enhancement seems to be the
decreased size of the Mg2Si particles which leads to a rise in the
kinetics of hydrolysis reaction and in the conversion yield. How-
ever, with the prolongation of the milling time, the induction
period is prolonged at the initial stage of the hydrolysis reaction.
This may be due to the formation of an oxidized protective layer on
the surface of the particles as the ball milling progresses and
especially, more and more SiO2-X in the outer layer could be con-
verted to SiO2. [47].
Fig. 6. XRD pattern of the Mg2Si samples as a function of milling time. Here, we also studied the effect of initial temperature (5, 15, 25
and 35  C) on the hydrolysis of milled and unmilled Mg2Si in 13%
NH4F solution, and the hydrogen evolution curves are shown in
observation shows that the blocks become more sphere-like one, Fig. 9. From it, we may see obviously that when the initial tem-
and the particle size is significantly reduced. The average size of perature of the solution increases, the reaction rate and the
unmilled Mg2Si was measured to be 11.4 mm, and after ball milling hydrogen yield of the Mg2Si with NH4F increase. Even at low
for 2 and 5 h, the size value decreased to 2.7 and 1.9 mm, respec- temperatures, the ball milled Mg2Si still exhibits good hydrogen
tively. From the images in Fig. 7 (a, b, c), the surface morphology of production kinetics. At 5  C, the Mg2Si samples milled for 2 and 5 h
the individual particles can be observed clearly by high magnifi- produce 633 mL g
1 (49.5%) and 660 mL g
1 (51.6%) H2 in 13% NH4F
cation. It can be seen that before ball milling, the surface of the solution within 60 min, respectively. When the temperature goes to
massive particles is smooth and lamellar, and there are a few fine 35  C, the hydrogen production performance of Mg2Si in NH4F so-
particles attached to the massive ones and existing as a single block. lution is superior. The unmilled Mg2Si could release 714 mL g
1
After ball milling, the original massive particles become fine (55.8%) H2 in 60 min, and after ball milling for 2 and 5 h, the yield
spherical ones, and the particles are dispersed independently. This increases to 852 mL g
1 (66.6%) and 936 mL g
1 (73.2%),
means that the original massive particles are impacted by the high- respectively.
energy ball milling and they are completely broken after the As we known, the relationship between temperature and rate of
 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115
Fig. 7. SEM images of the Mg2Si samples with different milling time. High magnification: (a) before milling, (b) ball milled for 2 h, (c) ball milled for 5 h; low magnification: (d)
before milling, (e) ball milled for 2 h, (f) ball milled for 5 h.
Fig. 8. Hydrogen generation curves in 13.0% NH4F solution and conversion yield in
30 min for the hydrolysis of the Mg2Si as a function of the milling time.
hydrogen generation can generally be expressed by the Arrhenius
equation:
ln k ¼ ln A
Ea=RT
where k is the reaction rate, Ea is the activation energy (kJ$mol
1), R
113
is the gas constant (8.314 J (mol K)
1), and T is the temperature (K).
Thus, Ea for Mg2Si hydrolysis may be deduced from Equation (4).
Fig. 10 presents an Arrhenius plot for Mg2Si hydrolysis in 13.0%
NH4F solution. The goodness of fit r value is close to 0.99, indicating
that the Arrhenius equation is appropriate for describing the hy-
drolysis reactions. From the slope of the fitted line, Ea for Mg2Si
hydrolysis in 13.0% NH4F solution is calculated to be
37.3 ± 0.8 kJ mol
1. With the increase of the milling time for the
Mg2Si, the activation energies decrease to 23.9 ± 0.6 kJ mol
1 for
2 h and 12.9 ± 0.1 kJ mol
1 for 5 h. This means the increase of
milling time could lower the Ea for the Mg2Si hydrolysis. A lower
activation energy value generally indicates higher reactivity. This is
consistent with the results that the hydrolysis performances of the
Mg2Si samples are improved with the longer milling time.
4. Conclusions
The effect of NH4Cl and NH4F on the kinetics and reaction
mechanisms of Mg2Si hydrolysis was comprehensively investigated
in this paper. The hydrolysis reaction of Mg2Si with 27.1 wt% NH4Cl
solution showed favorable hydrolysis properties, producing
660 mL g
1 H2 in 5 min and 738 mL g
1 H2 in 10 min. However,
Mg2Si could not produce hydrogen safely in NH4Cl solution
considering the potential explosive danger from the high silane
content in the released gas mixture, which limits its applications
(4) for hydrogen supply to fuel cell. However, during the study of Mg2Si
with NH4F, it showed that silanes could be almost entirely turned
into hydrogen by introduction of fluorine ion during the hydrolysis.
114 Z.H. Tan et al. / Journal of Alloys and Compounds 770 (2019) 108e115
Fig. 9. Hydrogen generation curves of the hydrolysis of Mg2Si (a) without milling, (b) milling for 2 h, and (c) milling for 5 h in 13.0% NH4F solution at 5e35  C, and (d) the cor-
responding conversion yield within 60 min.
Fig. 10. Arrhenius plot for the activation energy calculation of Mg2Si hydrolysis in
NH4F solution.
Subsequently, nearly pure hydrogen could be safely obtained by
adding a simple alkaline wash step, which makes it possible for
Mg2Si used for hydrogen generation by convenient hydrolysis re-
action in NH4F solution. Besides, milling treatment showed
considerable improvement on the Mg2Si reactivity. Compared to
the unmilled Mg2Si, after ball milling for 2 and 5 h, the hydrogen
generation yield increased from 616 mL g
1 to 698 mL g
1 and
771 mL g
1 in 30 min, and the activation energy was decreased
from 37.3 ± 0.8 kJ mol
1 to 23.9 ± 0.6 kJ mol
1 and
12.9 ± 0.1 kJ mol
1, respectively. Meanwhile, the increase in reac-
tion temperature improved the total hydrogen yield and the hy-
drolysis rate. At 35  C, the unmilled Mg2Si could release 714 mL g
1
(55.8%) H2 in 60 min, and the yield increased to 852 mL g
1 (66.6%)
and 936 mL g
1 (73.2%) after milling for 2 and 5 h, respectively.
Acknowledgements
This work was supported by the Foundation for Innovative
Research Groups of the National Natural Science Foundation of
China (No. NSFC51621001), National Natural Science Foundation of
China Projects (Nos. 51431001 and 51771075) and International
Science & Technology Cooperation Program of China
(2015DFA51750). Author Ouyang also thanks Guangdong Province
Universities and Colleges Pearl River Scholar Funded Scheme
(2014). Shao acknowledges Macao Science and Technology Devel-
opment Fund (FDCT) for project of 118/2016/A3.
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