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Kinetics study on the generation of hydrogen from an aluminum/water

system using synthesized aluminum hydroxides

Article  in  International Journal of Energy Research · December 2017

DOI: 10.1002/er.3955

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Received: 27 July 2017 Revised: 6 November 2017 Accepted: 7 November 2017
DOI: 10.1002/er.3955

RESEARCH ARTICLE

Kinetics study on the generation of hydrogen from an

aluminum/water system using synthesized aluminum
hydroxides

Yu‐Chieh Wen | Wei‐Min Huang | Hong‐Wen Wang

Department of Chemistry, Chung Yuan

Christian University, Zhongli 320, Taiwan,
R.O.C.
Correspondence
Hong‐Wen Wang, Department of
Chemistry, Chung Yuan Christian
University, Zhongli, 320, Taiwan, R.O.C.
Email: hongwen@cycu.edu.tw
Funding information
Ministry of Science and Technology, Tai-
wan, R.O.C., Grant/Award Number:
MOST 105‐2119‐M‐033‐003
Summary
Kinetics study on the generation of hydrogen from an Al/water system is per-
formed. The reaction is affected by 3 major factors such as the concentration
of hydroxyl ions (pH values), catalysts, and temperature. However, these fac-
tors are interacted and sometimes difficult to separate. This study demon-
strates how these factors affect the generation of hydrogen in an Al/water
system. Aluminum hydroxide, Al(OH)3 (bayerite phase), synthesized using a
chemical solution method, is proved to be a very effective catalyst for the
reaction of Al and water. Approximately 95% yield (1300 mL) of hydrogen
is produced from 1 g Al in 10 mL water using 3 g Al(OH)3 catalyst at room
temperature within 1 minute. The generation rate of hydrogen is accelerated
due to the catalyst Al(OH)3 and the exothermic heat. In this report, a ball‐
mixing process, the ratio of Al:Al(OH)3:H2O, and the reacting temperatures
are investigated to clarify the effect of catalyst Al(OH)3. The synthesized
Al(OH)3 catalyst is found to reduce the activation energy of Al/water reaction
from 158 kJ/mol to 73.3 to 76.9 kJ/mol. The roles of hydroxyl ions (ie, pH
values), temperature, and catalyst on this phenomenal reaction are explained
using a kinetics study and the concept of Fick first law. The 3 factors all
improve the flux of hydroxyl ions through the passive Al2O3 layer; therefore,
the generation of hydrogen is enhanced.

KEYWORDS
Al(OH)3, ball‐mixing, hydrogen generation

1 | INTRODUCTION because of a dense Al2O3 passive layer on the surface of

Hydrogen is considered to be a clean energy due to its
lightweight, high energy density, and zero pollution.1 Alu-
minum (Al) metals, abundant in earth, has low density,
high capacity, and excellent activity to water and is an
ideal material for the generation of hydrogen.2-5 Since
the direct reaction of metal Al with pure water is difficult
Yu‐Chieh Wen and Wei‐Min Huang contributed equally.
the metal, which is about 3 to 6 nm in thickness,6 differ-
ent methods7-10 were adopted to facilitate the generation
reaction of hydrogen. For example, NaOH solution7 was
commonly used to react with metal Al powders and pro-
duced hydrogen. A solution with pH ≥ 13 was required
to achieve a rapid hydrogen generation. Alloying Al with
Ga, Li, Sn, etc8,9 or mechanically milling metal Al with
salt compounds10 could also render the metal Al powders
continuously react with water. Metal oxides such as γ‐

Int J Energy Res. 2017;1–10. wileyonlinelibrary.com/journal/er Copyright © 2017 John Wiley & Sons, Ltd. 1
2 WEN ET
Al2O3,11 CaO,12 TiO2,13 aluminum hydroxides Al(OH)3,14
and sodium carbonate Na2CO315 were also proved to be
effective to promote the generation of hydrogen from
Al/water system. An efficient Al/water system was used
for a novel electricity and heat cogeneration system
recently.16 This facile reaction system can also be used
to deal with the waste Al problem.17 However, the reac-
tion of aluminum with aqueous alkaline can lead to an
environmental pollution, and the easy passivation of
metallic Al is also a concern. The cost and waste of
alloying materials such as Ga and Li are also critical issues
for the practical implementation of this process. Never-
theless, the rapid generation of hydrogen using Al/water
system at around 50°C to 100°C has great potential in
the application as a hydrogen generator for the fuel cells
for the bikes, motorcycles, and even cars. The reclaims
of Al metals from the reaction waste, Al(OH)3, can be
done by a low temperature (<100°C) chemically reduc-
tion method in ionic liquids, making Al/water an excel-
lent system for the clean energy.18
Deng et al19-23 have demonstrated the mechanism and
influence factors for the generation of hydrogen from an
Al/water system. They proposed that hydroxide and
oxides could dissociate water molecules and promote the
hydration of the passive oxide film on the surface of Al
particles.22 Analyses showed that the hydroxyl ions disso-
ciated from H2O molecules on the catalysts' surface are
easy to hydrate the oxide layer of Al particle and promote
the hydrogen generation.22 Their recent kinetics study23
on Al‐water reaction promoted by an ultrasonically pre-
pared Al(OH)3 suspension concluded that the contact
between Al and Al(OH)3 particles and the reaction heat
are 2 key factors that control the progress of the reaction.
Indeed, in our previous studies,24-26 a rapid generation of
hydrogen can be realized by using synthesized Al(OH)3
nanosized powders. Al(OH)3 is considered to be one of
the most powerful catalysts for the generation of hydro-
gen from an Al/water system in low cost. However,
hydrogen can also be generated rapidly from simply
mixing Al powder and water at a temperature of 45°C or
above24 without any catalysts in a solution of pH = 7, as
well as at room temperature in a solution with pH ≥ 13.
Here, we present a different approach in this study to
explain these interacted factors affecting the reaction of
Al and water.
The generation of hydrogen from an Al/water system
can be described in 3 stages: (1) an incubation period,
where the dense oxide was hydrated, (2) a rapid reaction
period, where the metallic Al directly reacted with water,
and (3) a saturation period, where the by‐product Al(OH)3
thickened and Al core was getting small. It was proposed
that the 2 reactants formed intermediate AlOOH accord-
ing to the following reaction (1) when Al(OH)3 was used
AL.
as a catalyst. The regenerated Al2O3 in the reaction (2) is
a loose layer and cannot protect metallic Al from
water.20,24
Al2 O3 þ AlðOHÞ3 →3AlOOH (1)
2Al þ 6AlOOH→4Al2 O3 þ 3H2 (2)
The proposed reaction mechanism explained the role
of Al(OH)3 and the breaking of a dense layer of Al2O3.
However, how the hydroxyl ions and temperature and
the reaction kinetics affect the generation of hydrogen
was not well explained. Furthermore, these reactions
implied the diminishing of Al(OH)3 and the existence of
by‐product Al2O3. However, this is not the case. The final
products of Al/water reaction are always Al(OH)3 and
hydrogen, and the loose Al2O3 by‐product is hardly
detected.
In this study, an optimum combination of Al:Al(OH)3:
H2O was revealed. The effect of temperature and ball‐
mixing process for the Al/Al(OH)3 powders on the gener-
ation rate of hydrogen was evaluated. The influences of
catalyst and temperature were investigated using 2 differ-
ent experimental setups, as will be explained soon in the
following section. Activation energies of Al/water system
for the generation of hydrogen with and without the cata-
lyst Al(OH)3 were calculated using a conventional kinet-
ics method and a steady‐state diffusion model using the
Fick first law. With these results, the role of catalyst, tem-
perature, and hydroxyl ions on the reaction of Al/water
system can be understood using the concept of diffusion
flux J for the hydroxyl ions.
2 | EXPERIMENTAL PROCEDURE
2.1 | Synthesis of Al(OH)3
A 0.175 mol NaOH was dissolved in 100 mL deionized
(D.I.) water, bathed with ice. The temperature of ice bath
water was kept under 5°C. Another 0.05 mol Al(NO3)3
was also dissolved in 50 mL D.I. water at 5°C. Al(NO3)3
solution was gradually dripped into the NaOH solution
with stirring. The reaction was kept stirring for 48 hours
in the ice bath. The final pH value of the ice bath solution
is 12. The white precipitates were separated centrifugally
and washed with D.I. water twice and kept it in a freezer
at −40°C for 8 hours. The synthesized Al(OH)3 powders
were dried using a freeze dryer before use.
2.2 | Generation of hydrogen
There are 2 methods to generate hydrogen in this study.
One is temperature‐controlled (TC, a slow generation
WEN ET AL.
rate), and the other is temperature‐uncontrolled (TUC, a
fast generation rate). For the TC method, the temperature
of reaction flask is kept constant using a circulating water
bath. For the TUC method, the temperature of reaction
flask is not under controlled, and the exothermic heat
from the reaction itself is taken as an advantage to the
generation process of hydrogen. Metallic Al powders with
a particle size of approximately 12 μm (Alfa Aesar, 325
mesh, 99.5% purity) were used for all experiments.
Figure 1 shows the experimental setup.
For experiments using the TUC way, the weight ratio
of Al:Al(OH)3:H2O that is 1:5:10 or 3:15:50 in grams was
used. The TUC method is aiming at a rapid generation
rate. To find out the minimum quantity of water required
for a rapid hydrogen generation, weight ratios in grams
such as 1:5:7, 1:5:10, and 1:5:15 for Al:Al(OH)3:H2O were
tested for reactions. The experiments were performed by
mixing the desired quantity of Al(OH)3 powders into the
D.I. water, and then the Al metallic powders were added.
The generated hydrogen was measured using water
replacement method, where a silicone tube was passing
through a cool water bath to a 2000 mL cylinders filled
with water. The cool water bath is used to minimize the
water vapor.
For experiments using the TC method, the weight
ratio of Al:Al(OH)3:H2O is 1:1:200 in grams, ie, a large
amount of water was used for a stable temperature.
The TC experiments were performed at 25°C ±
1°C、35°C ± 1°C、45°C ± 1°C、55°C ± 1°C using a cir-
culating water bath. The hydrogen generated was mea-
sured using a precision gas flow meter (±[0.3%
reading + 0.2% flow speed], Alicat Scientific, Inc). There-
fore, the reported hydrogen volume may have a deviation
of ±0.5%. The generated hydrogen was connected using a
silicone tube passing through a cool water bath to the gas
flow meter, which automatically recorded the output data
every second till the reaction reached 100% yield. 100%
yield of hydrogen from 1 g Al is 1360 mL at room temper-
ature by a theoretical calculation. Approximately 95%
yield of hydrogen is considered to be a state of saturation,
where the last bit of Al metal material resides in the core
of by‐product Al(OH)3, causing a further reaction
FIGURE 1 The experimental setup
[Colour figure can be viewed at
wileyonlinelibrary.com]
Reactor Water trap
3
difficult. The diagrams of generated hydrogen volume
(mL) vs time (min) were constructed, and the reaction
rate constants, k, are calculated. The “k” value was calcu-
lated using the data at the 50% yield of the reaction
divided by the time at a specific temperature. According
to the Arrhenius equation: k = ko·exp(−Ea/RT), the acti-
vation energy for the reaction can be calculated using
the slope of ln k vs 1/T, which was −Ea/R. The activation
energy is a direct consequence of a specific catalyst
imposed on the reaction of Al/water system. A solid‐state
diffusion model was also used to calculate the diffusion
coefficients and activation energies, as will be explained
in the final discussion.
2.3 | Ball‐mixing
The ball‐mixing process was performed for Al and
Al(OH)3 powders to evaluate its influence on the effect
of the catalyst. Five millimeters of Al2O3 ceramic balls
(600 g) were installed in a plastic bottle (polyethylene,
250 mL). One gram of Al powders and the desired quan-
tity of Al(OH)3 powders were added in the polyethylene
bottle for ball‐mixing 2 hours. The weights of Al(OH)3
for 1 g Al were 1, 3, 5 g. The mixed Al/Al(OH)3 powders
then were added into the reaction flask with 10 g D.I.
water inside for hydrogen generation. These results were
compared to those performed using the TUC method
shown above, where no ball‐mixing was performed and
Al(OH)3 was added in D.I. water first and then the reac-
tion started by adding the Al powders.
2.4 | Characterization
The morphology of synthesized Al(OH)3 was observed by
a field emission scanning electron microscope (JEOL
JSM‐7600F) equipped with an energy dispersive spectro-
scope (Oxford, 80 nm2). The crystalline phase of Al(OH)3
was analyzed using a PANalytical PW3040/60 X'Pert Pro
X‐ray diffractometer with a Cu target and Ni filter at a
scanning rate of 4°/min from 10° to 80° for 2θ. The sur-
face areas of synthesized Al(OH)3 were measured using
N2 adsorption‐desorption isotherms, which were obtained
Flow meter Computer
4 WEN ET
via an automated sorption analyzer, ASAP 2010
(Micrometric, Lincolnshire, UK). The samples were
outgassed at 350°C for 8 hours before characterization by
the Brunauer‐Emmet‐Teller method. Fourier transform
infrared (FTIR) spectrometry measurements were per-
formed with a JASCO FTIR 4200 Plus spectrophotometer.
3 | R E S U L T A N D DI S C U S S I O N
3.1 | Optimum condition for TUC method
The X‐ray powder diffraction crystal phase and scanning
electron microscope morphologies of synthesized Al(OH)3
powders were shown in Figures 2 and 3A, respectively. It
is clear that the synthesized Al(OH)3 powders were
bayerite phase.
The morphology shown in Figure 3A reveals the size
and shape of these bayerite crystals. Small plate‐like crys-
tals (50‐90 nm) were observed. The surface area of these
Al(OH)3 powders is 37.65 m2/g, which is higher than those
FIGURE 2 X‐ray powder diffraction for synthesized Al(OH)3 in
ice bath for 48 hours
FIGURE 3 Field emission scanning electron microscope for, A, synthesized Al(OH)3 in ice bath for 48 hours and, B, Al metallic powders
ball‐mixed with synthesized Al(OH)3 powders for 2 hours
AL.
of our previous studies.13,24-26 When these synthesized
Al(OH)3 powders were ball‐mixed with Al metallic pow-
ders, numerous tiny Al(OH)3 particles were stuck on the
surface of Al powders, as shown in Figure 3B. We will dis-
cuss the effect of ball‐mixing in Section 3.3. Figure 4 illus-
trates the FTIR spectrum for the synthesized Al(OH)3. The
absorptions at wave number around 3655 cm−1, 3548 cm
−1
, and 3465 cm−1 are the OH stretches from residual water
molecules. The 1384 cm−1 is associated with the NO2,
which may come from our precursor Al(NO3)3. The
766 cm−1 represents [AlO2]−, and the 518 cm−1 is the
Al─O bond. The 1024 cm−1 absorption might be associated
with the OH bond from AlOOH boehmite phase.27 The
boehmite phase was found occasionally during the synthe-
sis of Al(OH)3 but cannot be detected by X‐ray powder dif-
fraction due to its minor quantity.
A combination of 3:15:50 for Al:Al(OH)3:H2O in
grams as starting reactants was used for a consecutive 3
runs of hydrogen reaction for a TUC experiment. Fifteen
grams of catalyst Al(OH)3 were added in water at the first
run of reaction and no more additions for the following
runs. As shown in Figure 5A,B, the first run of reaction
took 50 seconds for incubation, and only 87% yield of
hydrogen (~3500 ml) was produced in approximately
150 seconds. Compare to those approximately 100% yield
of our previous studies,13,24-26 the first run shows a much
less yield of hydrogen, and so do the following second and
third runs. This is considered to be due to an incomplete
reaction resulted from a small amount of unreacted Al
powders sticking on the bottom of the flask, being covered
by an increasingly thick layer of by‐product Al(OH)3. For
the second and third run of consecutive batches of Al/
water into the original reaction solution, the hydrogen
generation reached saturation at around 80 seconds, with
only approximately 2 seconds incubation time, as shown
in Figure 5A. That is, the hydrogen generation took place
only 2 seconds after the Al/water was added into the
WEN ET AL. 5

up to 90°C again due to the exothermic reaction of the

second batch Al. The warm temperature (50°C) greatly
assisted the reaction of the second and third run and
shortened the incubation time for hydrogen generation.
The third run was almost an identical process to that of
the second run; no further enhancement of hydrogen gen-
eration rate could be observed. Just for a comparison, we
also performed 3 consecutive runs starting from room tem-
perature. When the second and third batches of Al/water
were added after the temperature of first run is cooled to
room temperature, then the 2 runs will be very similar to
that of the first run (not shown). They all took 150 seconds
to complete the hydrogen generation. It is then confirmed
that the effect of warm temperature approximately 50°C
FIGURE 4 Fourier transform infrared of synthesized Al(OH)3
significantly decreases the incubation time, ie, the hydra-
tion of oxide layer is enhanced by the warm temperature.
To search an optimum condition for Al:Al(OH)3:H2O,
the combination of 1:5:7, 1:5:10, and 1:5:15 was per-
formed. As shown in Figure 6, a small amount of reactant
(1 g Al) reacted more completely than those of 3 g Al. The
combination of 1:5:10 exhibits the best generation rate
and reaches approximately 95% yield around 60 seconds.
For 1:5:7, the quantity of water is too little to wet through-
out all the Al and Al(OH)3 powders effectively, and the
solution becomes highly viscous. For 1:5:15, the quantity
of water is too much to reach a high temperature quickly.
Although it eventually saturated and produced approxi-
mately 95% yield of hydrogen, it took 80 seconds, which
is 20 seconds longer than that of 1:5:10. It is then con-
firmed that 1:5:10 is one of the best combinations for a
rapid generation of hydrogen from our Al/water system.

3.2 | The effect of starting temperature

A higher starting temperature of Al/water system is help-
ful to the generation of hydrogen, as well known from

FIGURE 5 A, Hydrogen generation of 3 consecutive batches of Al

and water system. No additional catalyst was added for the second
and third batches of Al/water. B, The temperature change for the
reaction shown in A. Three grams of Al powders were used for each
run

reaction flask. The second batch of Al/water (3 g/50 mL)

was added after the first run was saturated (~180 s), where
the temperature was still high. The exothermic reaction of
first run heated the reaction flask up to 90°C, as the tem-
perature rising during the reaction was shown in Figure 5 FIGURE 6 Different weight ratio of Al:Al(OH)3:H2O used for
B. The temperature was dropped to approximately 50°C hydrogen generation using the temperature‐uncontrolled way. The
due to the addition of 50 mL room‐temperature water optimum condition is 1:5:10, where the water content is neither too
for the second run. However, the temperature soon rose much nor too little. One gram of Al powder was used for each run
6 WEN ET
literature19 and data above. How about a lower starting
temperature than room temperature? By instinct, a slow
reaction is expected. As shown in Figure 7, using the com-
bination of 1:5:10 for hydrogen generation, a lower
starting temperature 5°C and 15°C was compared to those
of other starting temperatures such as 25°C, 35°C, and
50°C. Temperatures of 5°C and 15°C resulted in a longer
incubation time, 260 seconds and 80 seconds, respectively.
It reacted rapidly once it got warm due to the exothermic
heat and eventually reached approximately 95% yield of
hydrogen within 40 seconds. The starting temperature
50°C produced hydrogen almost immediately (~3 s) right
after the Al powders were added into Al(OH)3/water mix-
ture solution. That is, there is almost no incubation time
for the starting temperature 50°C. However, to reach
approximately 95% yield of hydrogen, it still took around
approximately 40 seconds. Figure 7 indicates when an
Al/water system starts at a lower temperature, it may
need a longer incubation time but still produce approxi-
mately 95% yield of hydrogen within 40 seconds once
the incubation period ends.
3.3 | Effect of ball‐mixing
In this section, mixing Al and Al(OH)3 was performed
first before adding into the water for hydrogen generation.
The morphology of mixed Al(OH)3/Al powders was
shown in Figure 3B. Generation of hydrogen was con-
ducted using the TUC way with combinations of 1:1:10,
1:3:10 and 1:5:10 for Al:Al(OH)3:H2O. As shown in
Figure 8, it is clear that when the amount of catalyst
Al(OH)3 is reduced, the hydrogen generation rate
decreases significantly due to longer incubation time as
FIGURE 7 For the 1:5:10 system using temperature‐uncontrolled
way, an approximately 95% yield of hydrogen was obtained around
60 seconds after the reaction starts at different temperatures. 5°C
and 15°C showed significant delays of hydrogen generation, but they
still completed the reaction in 60 seconds. One gram of Al powder
was used for each run
AL.
FIGURE 8 Generation of hydrogen using the temperature‐
uncontrolled way: The ratio of Al:Al(OH)3 has been varied from
1:1 to 1:5. Water is kept at 10 mL for all cases. One gram of Al
powder was used for each run
well as a slower reaction rate in the second period. Suffi-
cient quantity of catalyst plays an important role in this
reaction. It is considered that the numerous active sites
of the hexagonal crystal structure of bayerite for hydroxyl
ions dissociation from water molecules are the key criteria
for a rapid generation of hydrogen, as depicted in our pre-
vious report.26 Sufficient quantity of Al(OH)3 is required
for an efficient catalysis process. Ball‐mixing of Al and
Al(OH)3 forced both powders to an intimate contact and
shortened the distance for the diffusion of hydroxyl ions,
therefore facilitated the hydrogen generation. The combi-
nation 1:1:10 was a slow reaction, as shown in Figure 8.
The ball‐mixing step can only slightly help but not much
due to the insufficient quantity of Al(OH)3.
3.4 | Activation energy
As shown in Figure 9, the hydrogen generation of Al:
Al(OH)3:H2O (1:1:200) system was recorded at different
temperatures. The generation rate for the first 50% yield
was used to calculate the rate constant k and construct
the diagram of ln k vs 1/T, where a slope was obtained
and the activation energy calculated. The activation ener-
gies for the reaction of aluminum and D.I. water without
any catalysts were calculated to be 164.85 ± 51.10 kJ/mol.
For synthesized Al(OH)3 in water (no soaking time before
adding Al powder), Al(OH)3 soaking in water for 1 hour
(soaking 1 h before adding Al powder), and mixed with
Al powders, the same Al/water reaction experiments were
performed. Their ln k vs 1/T diagrams are shown in
Figure 10A‐C. The calculated activation energies and
deviation are shown in Table 1. It is clear when synthe-
sized Al(OH)3 catalyst was soaking in water for 1 hour,
the activation energy is the lowest. The hydrogen genera-
tion is the most rapid. This means that Al(OH)3 in water
required some time to dissociate the hydroxyl ions or
WEN ET AL. 7

FIGURE 9 Hydrogen generation using the temperature‐

controlled way with catalyst at different temperatures. One gram
of Al powder was used for each run

establish a higher concentration of hydroxyl ions around

the powders. It is these hydroxyl ions very important for
the hydrogen generation of Al/water reaction.
The literature shows that the activation energies for
the Al/water reaction are 64.2 to 88.7 kJ/mol,28 24 to
80 kJ/mol,29 and 73 ± 6 kJ/mol,30 respectively, depending
on their experimental conditions. In our study, when the
synthesized Al(OH)3 powders were filtered and washed
with D.I. water twice or more after the ice bath, the resid-
ual OH− ions resulted in a pH value of <10 in the
Al(OH)3/H2O solution. The activation energy obtained
was then as high as 76.9 kJ/mol. However, when the syn-
thesized Al(OH)3 powders were washed only once and
not completely free from hydroxyl ions, the residual OH
−
ions resulted in a solution of pH ≈ 12 when the Al(OH)3
was added into D.I. water, causing a more rapid reaction
than those of pH ≤ 10. The activation energy, in this case,
is as low as 33.25 kJ/mol,26 which could be partially con-
tributed from the residual hydroxyl ions. Lower activation
energy resulted from a higher rate constants k at high pH
values was not discussed in the literature. The knowledge
of activation energies provides a better insight to the effect
of catalyst Al(OH)3 for the Al/water system. That is, the
addition of catalyst reduced the activation energy and FIGURE 10 Kinetic study on, A, the synthesized Al(OH)3 in
enhanced the generation of hydrogen. We may argue that water, B, the synthesized Al(OH)3 soaking in water for 1 hour,
the active sites of bayerite crystals provide many ideal and, C, synthesized Al(OH)3 milled with Al powders
locations for the dissociation of water molecules and the
attraction of many hydroxyl ions near the surface of Al Figure 7, the duration of incubation at different tempera-
particles, as depicted in Figure 11. However, the role of tures could be assumed to be the migration time for the
catalyst, temperature, and concentration of hydroxyl ions dominated diffusion species, hydroxyl ions, to hydrate
on this reaction is not well distinguished. the passive layer. The incubation time for temperatures
Let us calculate activation energy in a different 5°C to 50°C shown in Figure 7 was tabulated in Table 2.
approach using the Fick first law. Assumed the thickness The migration velocity ν (m/s) of hydroxyl ions then can
of passive layer Al2O3 on the surface of Al particles to be be calculated, as shown in Table 2, if the distance x for
approximately 6 nm,6 as shown in Figure 11. From data of the passive oxide layer to be 6 nm. A homogeneous flux
8 WEN ET AL.

TABLE 1 The activation energy of Al/water reaction with and without the catalyst using the conventional kinetics study method

Activation energy, Ea (kJ/mol)

Synthesized Al(OH)3 soaked in water for 1 h 56.59 ± 13.04
Synthesized Al(OH)3 mixed with Al 58.25 ± 19.92
Synthesized Al(OH)3 in water 73.45 ± 17.70
Without catalyst Al(OH)3 164.85 ± 51.10

The deviation was calculated based on the error of the linear slope.

and Co is the concentration of hydroxyl ions at the surface

FIGURE 11 The concept of hydroxyl ion concentration gradient
in the passive layer Al2O3
“J” of hydroxyl ions through a plane is given by the prod-
uct of the volume concentration “Co” of the ions at the
plane and the average migration or drift velocity “ν”:
J ¼ Co ⋅ν
Furthermore, according to the Fick first law for diffu-
sion,
dC
J ¼ −D (4)
dx
The diffusion coefficient D could be obtained from the
combination of Equations 3 and 4. J is the diffusion flux,
of the Al2O3 passive layer. In fact, by equaling Equations 3
and 4, the concentration term Co can be removed from
both sides of the equal sign. The D value obtained here in
Table 2, 1.2 × 10−17 m2/s at 50°C, was much larger than
those reported value, 2.0 × 10−21 m2/s,6 which was also
obtained at 50°C without any catalysts and potential bias.
However, if we assumed the thickness of very front of the
passive layer to be 0.1 nm, the D value was calculated to
be 3.3 × 10−21 m2/s, which was at the same magnitude
of order as the reported value.6 The distance x, thickness
of hydrated oxide layer, is assigned arbitrarily but must
be reasonable and less than approximately 6 nm. If the
hydrated distance x was assigned to be 1 nm, the diffusion
coefficients D would be 100 times larger than those of
0.1 nm shown in Table 3. It is believed that the hydration
of whole oxide layer was accelerated immediately after
the very front layer approximately 0.1 nm being hydrated
and the temperature was raised due to exothermic heat.
(3) The diffusion coefficient D was then dramatically
increased afterward due to the raised temperature and
the critical chemical reaction (1) took place.
Since D = Do × exp (−Qa/RT), the Qa can be calcu-
lated from the slope of the plot log D vs 1/T. In this
way, we have obtained a value of 72.35 ± 12.99 kJ/mol,
well located within those obtained using the conventional
kinetics approach (Table 1) and the reported values.28-30 It

TABLE 2 Calculated migration velocity and diffusion coefficient for hydroxyl ions at various temperatures, assume the passive layer
thickness = 6 nm

Temperature, °C 5 15 25 35 50
Incubation, s (pH = 10) 260 80 20 14 3
−11 −11 −10 −10
Migration velocity, m/s 2.31 × 10 7.50 × 10 3.00 × 10 4.28 × 10 2 × 10−9
Diffusion coef., m2/s 1.38 × 10−19 4.50 × 10−19 1.80 × 10−18 2.57 × 10−18 1.2 × 10−17

TABLE 3 Calculated migration velocity and diffusion coefficient for hydroxyl ions at various temperatures, assume the very front of passive
layer thickness = 0.1 nm

Temperature, °C 5 15 25 35 50
Incubation, s (pH = 10) 260 80 20 14 3
−13 −12 −12 −12
Migration velocity, m/s 3.85 × 10 1.25 × 10 5.00 × 10 7.14 × 10 3.33 × 10−11
Diffusion coef., m2/s 3.85 × 10−23 1.25 × 10−22 5.00 × 10−22 7.14 × 10−22 3.33 × 10−21
WEN ET AL.
is then concluded that the diffusion flux J is the key for
the period of incubation. Low‐flux J results in a long incu-
bation period. High‐flux J ends the incubation period
quickly and starts the rapid reaction period; therefore,
the hydrogen is generated fast. An adequate diffusion flux
for a rapid generation of hydrogen could be achieved with
a high concentration of hydroxyl ions Co (high pH value)
or a high migration velocity (high temperature for diffu-
sion). This is why that generation of hydrogen will con-
duct quickly from Al/water system without any catalysts
at pH greater than 13 at room temperature or pH = 7 to
12 at temperatures over 45°C.
A rapid generation of hydrogen using Al(OH)3 catalyst
at pH = 10 at room temperature can be explained that the
local concentration of hydroxyl ions near the Al2O3 oxide
passive layer is high due to the attraction of the catalyst
particles, even the pH of the bulk solution is not high,
ie, ≤12. In this sense, many catalysts such as γ‐Al2O3
and TiO2 can be the role in one way or another. The ini-
tial solution with a pH value 12 will quickly build up a
high local concentration of hydroxyl ions near the cata-
lysts and close by the surface of the Al2O3 layer. Since
the local Co is high at the passive layer, the diffusion flux
is high. The concept of diffusion flux J can also explain the
effect of Al particle sizes. It was known that smaller sized
Al powders were favored for a rapid generation rate of
hydrogen in water.27 This is understandable that smaller
sized Al powders accumulate sufficient hydroxyl ions
and hydrate the oxide layer more quickly. When there
is no catalyst and pH value is also at neutral, high tem-
perature can still promote the generation of hydrogen.
This can be understood that the diffusion rate of
hydroxyl ions is high and so does the flux J. Therefore,
the role of temperature, hydroxyl ions of solution (pH),
and catalyst for the rapid generation of hydrogen from
an Al/water system is well explained using the concept
of diffusion flux.
4 | CONCLUSION
Kinetics study on the Al/water system is performed, and
the concept of diffusion flux has been recognized as a
good indicator for the affecting factors such as tempera-
ture, pH value, and catalysts. An Al:Al(OH)3:H2O system
(1:5:10 in grams) has been investigated for the generation
of hydrogen, and an approximately 95% yield of hydrogen
can be obtained within 1 minute. Less quantity of water
cannot speed up the reaction rate due to incomplete wet-
ting of the reactants. A larger amount of water will slow
down the reaction rate due to a lower temperature
obtained. Higher starting temperature greatly assists the
generation reaction. However, lower starting temperature
9
such as 5°C still can achieve a high yield of hydrogen
(~95%) with a longer incubation time (260 s). Ball‐mixing
with Al and Al(OH)3 is a feasible way to enhance the gen-
eration of hydrogen. Activation energy has been reduced
from 164.85 to 56.59 to 73.45 kJ/mol when the synthe-
sized catalyst Al(OH)3 was used. The role of the pH value,
temperature, and catalysts is well explained using the
concept of Fick first law for the diffusion of hydroxyl ions.
The activation energy of hydrogen generation derived
using the concept of diffusion is 72.35 ± 12.99 kJ/mol,
which agrees well with those of conventional method.
ACKNOWLEDGEMENTS
The authors are grateful for the support from Ministry of
Science and Technology, Taiwan, R.O.C. (MOST 105‐
2119‐M‐033‐003). We also appreciate the useful discussion
with Prof Hsin‐Tsung Chen in our department, who is
devoted his study in Computational Chemistry.
ORCID
Hong‐Wen Wang http://orcid.org/0000-0002-0855-9488
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How to cite this article: Wen Y‐C, Huang W‐M,
Wang H‐W. Kinetics study on the generation of
hydrogen from an aluminum/water system using
synthesized aluminum hydroxides. Int J Energy Res.
2017;1–10. https://doi.org/10.1002/er.3955