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A Review of Unique Aluminum−Water Based Hydrogen Production

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Andre Bolt,* Ibrahim Dincer,* and Martin Agelin-Chaab*

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ABSTRACT: This comprehensive review paper compares the different methods developed experimentally to produce hydrogen by
reacting aluminum and water. The alumina oxide layer which forms on the exterior surface of aluminum inhibits the reaction from
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taking place. Therefore, this paper presents a variety of techniques used to eliminate the oxide layer so that the reaction can
continuously take place. The review paper aims to evaluate these techniques by comparing the hydrogen yield and maximum
hydrogen production rate. On the basis of the analyses conducted, it was identified that the addition of hydroxide promoters, such as
NaOH and KOH, is highly beneficial. This was also evident in the various studies where yields greater than 99% are achieved.
Additionally, it is determined that the addition of NaCl or KCl to ball-milled samples of aluminum can be extremely advantageous
when examining the maximum hydrogen production rate. For instance, an experimental sample composed of 2% NaCl was able to
achieve a maximum hydrogen production rate of 1140 mL/min. Furthermore, numerous other studies are discussed by considering
their specific advantages and disadvantages.

1. INTRODUCTION considered to be water splitting techniques. Water splitting

As hydrogen production strategies and technologies continue
to be studied further, the potential to grow a viable hydrogen
economy through its implementation as an energy carrier is a
greater possibility. Hydrogen as an energy carrier holds
substantial benefit in its molecular energy density as well as
its ability to be environmentally benign during its combustion
process. This is evident in liquid hydrogen’s high heating value
(HHV) of 141.9 J/kg, which is substantially large compared to
those of other liquid fuel sources, such as liquefied petroleum
gas (LPG) and liquefied natural gas (LNG), which have HHV
values of 48.8 and 50.0 J/kg, respectively.1 Furthermore, if a
stoichiometric reaction takes place between hydrogen gas (H2)
and half a mole of oxygen gas (1/2 O2), the reaction will
produce a single mole of water (H2O) with energy.2 Unlike
other fuel sources that produce greenhouse gases during the
combustion process, hydrogen does not.
Although hydrogen as an energy carrier can be seen as
environmentally benign given that the only physical byproduct
of its combustion is water, which has a low global warming
potential (GWP) of zero, hydrogen’s production process may
not be benign. For instance, fossil-fuel-based methods to
produce hydrogen such as steam reforming, partial oxidation,
and autothermal reforming can be considered nonrenewable.3,4
These methods can be considered counterproductive given
that a primary benefit of using hydrogen as an energy carrier is
its ability to produce harmless emissions during its combustion
process.
A viable alternative is implementing hydrogen production
techniques that use more sustainable resources such as water
and do not produce harmful emissions. For instance, the
earth’s surface is covered by approximately 71% water.5
Hydrogen production strategies that use water are often
techniques separate the hydrogen and oxygen molecule to
produce hydrogen gas. Prominent water splitting techniques
include electrolysis and thermolysis.3 Of the water splitting
techniques listed, electrolysis is considered to show substantial
promise, given its efficiency and the extent to which it has been
studied. As an alternative method, water splitting can also be
achieved by using aluminum to separate the water molecule
through chemical reactions.6 Aluminum can be considered to
be more advantageous than other metal options because of it
being the most abundant metal found within the earth’s crust,
accounting for 8.1% in the form of bauxite and cryolite,7 and
also the cheapest metal on earth given its approximate cost of
$1506.90 (United States dollars) per ton.8
However, it should be noted that the primary barrier within
this chemical reaction is the oxide layer, which forms on the
exterior surface of aluminum after it comes into contact with
moisture. As a result, researchers have developed numerous
technologies and systems that can mitigate the formation of
the oxide layer so that hydrogen can be produced effectively.
In this paper, various hydrogen production strategies that
were studied and implemented by different researchers will be
presented. After this, a performance analysis comparison will
be conducted to identify which technologies/systems show the
most potential. Using the provided information from each of
Received: November 1, 2020
Revised: December 5, 2020
Published: January 7, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c03674

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Figure 1. Various stages of the aluminum−water chemical reaction, with the addition of sodium hydroxide.

the various studies, we will also study the system’s environ-

mental impact.

2. ALUMINUM−WATER HYDROGEN PRODUCTION

TECHNIQUES
In this section, several aluminum−water hydrogen production
techniques that are commonly used will be introduced. These
techniques include, but are not limited to, the following: (i)
the addition of hydroxide promoters, (ii) the use of oxide and Figure 2. Aluminum−water chemical reaction 1: 2Al + 3H2O →
salt promoters, either used separately or in conjunction with Al2O3 + 3H2.
each other, (iii) pretreating aluminum through various
techniques (e.g., ball milling), and (iv) the use of molten
aluminum alloys. Lastly, this section will explore the
importance of having an inert environment for the reaction
to place in.
2.1. Hydroxide Promoters. A commonly used technique
to mitigate the formation of the oxide layer is through the
introduction of a hydroxide promoter to the process.
Commonly used hydroxide promoters are NaOH and KOH. Figure 3. Aluminum−water chemical reaction 2: 2Al + 4H2O →
Upon addition of NaOH to water, it dissociates into OH and 2AlO(OH)2 + 3H2.
Na ions, OH− and Na+, respectively. After Al is added to the
aqueous solution, the aluminum oxide layer on the exterior
surface of the aluminum particle is quickly eroded through its
reaction with the ions. The presence of the dissociated ions
allows the reaction to continuously take place so that H2 is
produced. The chemical reaction is highly exothermic,
therefore causing a portion of the water within the reaction
vessel to sometimes vaporize. This process has been
summarized in the following pictorial representation, as
shown in Figure 1.
According to the United States Department of Energy Figure 4. Aluminum−water chemical reaction 3: 2Al + 6H2O →
(USDOE), there are three main aluminum−water chemical 2Al(OH)3 + 3H2.
reactions. Each reaction is differentiated based on the amount
of H2O molecules added to the reaction stage. Whether it be 3,
4, or 6 mol of H2O that is added, all reactions will produce 3 The introduction of NaOH to the reaction process to inhibit
mol of H2. Figures 2−4 depict the three aluminum−water the formation of the oxide layer can be represented by the
chemical reactions, with the corresponding products. The following three reactions:6
byproducts produced from the chemical reactions depend on 2Al + 2NaOH + 6H 2O → 2NaAl(OH)4 + 3H 2 (1)
the mole ratio of the reactants as well as the temperature the
reaction is conducted at. 2Al + 2NaOH + 2H 2O → Na 2Al 2O4 + 3H 2 (2)

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Figure 5. Aluminum−gallium phase diagram.19
2Al + 6NaOH + x H 2O → Na6Al 2O6 + x H 2O + 3H 2
(3)
It should be noted that the chemical reactions shown in eqs 1
and 2 use the least NaOH. Therefore, these reactions can be
considered more favorable from a research and sustainability
perspective in regards to material procurement and minimizing
the amount of energy needed for the reaction to take place. It
should also be noted that the aqueous solution formed by
adding NaOH to water is highly corrosive.6 This can be
considered to be a major drawback in regards to selecting a
reaction vessel. The corrosiveness of the solution eliminates
several metal options as the material used as the reaction
vessels.
2.2. Oxide and Salt Promoters. The addition of oxide
and salt promoters can be highly beneficial in inhibiting the
formation of the aluminum oxide layer, by either working
separately or in tandem with each other. Inorganic salts such as
NaCl and KCl are commonly used salt promoters, capable of
rupturing Al2O3 layer through pitting corrosion.9,10 The
cavities created within Al2O3 allow for the aluminum−water
reaction to continue unimpeded so that hydrogen can be
continuously produced.11,12 The use of salt promoters to
facilitate the reaction is very dependent on temperature;
therefore, initial temperature conditions must be satisfied
before the reaction can effectively take place.6 This can be
viewed as a drawback if the appropriate temperature conditions
cannot be satisfied.
Typically, if oxide promoters are used to facilitate an
aluminum−water chemical reaction, Al2O3 is selected, which
can be grounded into a powder and then mixed with pure
aluminum. This powder mixture can then be added to water
for hydrogen generation. This was proven to be an effective
method of hydrogen production for water having a pH level
between 4 and 9, with a water temperature between 10 and 90
°C.13−15 In a US patent, Chaklader et al.14,15 compared an
pubs.acs.org/EF Review
aluminum compound that had a 20 wt % composition of Al2O3
to pure aluminum and measured its ability to produce
hydrogen. As expected, the sample containing a 20 wt %
composition of Al2O3 produced significantly more hydrogen
than pure aluminum. Aluminum oxide exists mainly in the
following four forms:6 alpha-alumina (α-Al2O3), gamma-
alumina (γ-Al2O3), bayerite (Al(OH)3), and boehmite (AlO-
(OH)). Among the four aluminum oxide powders listed, α-
Al2O3 has the greatest ability to produce hydrogen. However,
in a study conducted by Deng et al.16 γ-Al2O3 was used to
produce hydrogen. The conducted study found that γ-Al2O3
was able to react with water at a standard temperature and
pressure continuously. Additional studies were also conducted
at water temperatures that exceeded 40 °C. The chemical
reaction used by Deng et al.16 is a multiple-stage process, as
shown in the following equations:16
Al 2O3 + H 2O → 2AlOOH (4)
2Al + 6AlOOH → 4Al 2O3 + 3H 2 (5)
In eq 4, Al2O3 is converted to AlOOH after it becomes fully
hydrated. After this, the AlOOH layer surrounding the
aluminum particle reacts to form hydrogen bubbles.
To maximize the reaction yield, different methods to reduce
the oxide layer can be used in conjunction with others. The
positive attributes of using oxides and salt promoters
individually have been expressed. However, Anand et al.17
studied the effect of combining these techniques. In their
study, they combined salt and oxides at 20 °C and determined
that the ideal salt and oxide promoter available were NaCl and
CaO, respectively. In the conducted experiments, they varied
the amount of CaO added in each trial from 0% to 20% for five
trials. The results showed that the ideal amount of CaO should
be between 0.5% and 4%, and also a 1:1 ratio between Al and
NaCl is optimal for the designed system. Under these
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Table 1. Comparison of Aluminum−Water Hydrogen Production Using Hydroxide Promoters Studies

researchers study methodology results and significant findings
Porciúncula et al.20 production of the study compares how effectively hydrogen can be produced increasing the starting temperature of the solution produced
hydrogen In from the addition of NaOH and KOH as hydroxide promoters; better results in regards to the yield percentage in the trials
the reaction variation in the study includes a change in molar concentration conducted. for instance, most tests conducted over 315 K
between alu- from 1 to 3 mol/L; the solution temperature fluctuated from 295 produced a yield of over 90.00%. with the only exception
minum and to 345 K; the aluminum samples used consisted of foil and being 1 test which had a 1 mm thick aluminum plate, and 1
water in the aluminum plates that vary in thickness mol/L of NaOH concentration. the study was able to
presence of display trials where NaOH and KOH were able to produce
NaOH and hydrogen yields greater than 99%, when used as a reaction
KOH promoter.
Ma et al.21 controlled hy- the study examines how to enhance hydrogen production rates and smaller aluminum particles produced the highest maximum
drogen gener- hydrogen yields with the addition of NaOH and Na2SnO3 at hydrogen production rate and the highest yield percentage.
ation by reac- different ratios to the production process; variations within the for instance, 16 μm aluminum powder had a maximum
tion of alumi- study included the type of water medium (deionized, tap, and production rate of 2100 mL/min, and a yield of 100%.
num/sodium sea), NaOH powder mass (0.2−1.2 g), and aluminum particle furthermore, the 2:1 ratio of NaOH to Na2SnO3 produced
hydroxide/so- size (278−16 μm) the best hydrogen yield, and production rate compared to
dium stannate ratios, 1:1 and 1:2.
solid mixture
with water
́
Martinez et al.22 recycling of alu- the study used recycled aluminum as an alternative to primary (i) based on the results presented, the NaOH concentration
minum to aluminum; this should have a positive effect on the environment and the volume of H2 produced are closely correlated. This
produce green given that the aluminum has already been extracted and refined is evident in the trial having a mole ratio of 1.10 between Al
energy to a large extent; the study only used NaOH at various mole and NaOH and producing 755 mL of H2 gas after 3 h, as
ratios between 1.10 and 3.00; researchers then compared the opposed to the trial that used a ratio of 3.00 producing 1379
volume of hydrogen produced by using these various mL H2. (ii) the volumes of 755 and 1379 mL of H2 also
concentrations; furthermore, the amount of hydrogen produced correlate with 2.27 and 4.14 Wh of electricity produced.
after 1, 2, and 3 h was recorded; the study also provided an
estimate of the amount of energy that can be obtained from the
reactions’ hydrogen produced; a Kipp generator was the primary
apparatus used throughout the experiments
Hiraki et al.23 hydrogen pro- in this study, researchers used NaOH as the reaction promoter; researchers were clearly able to establish the relationship
duction from ́ et al., researchers used
similar to the work conducted by Martinez between the yield (degree of reaction), length of time of the
waste alumi- waste aluminum as a method to make the process more experiment, and the starting temperature of the process; the
num at differ- ecologically sustainable; the aluminum used was recycled from a aqueous solution with a starting temperature of 333 K
ent tempera- domestic setting and then was grounded into a powdered particle reacted the quickest and was able to achieve a full yield
tures, with between 180 and 425 μm; of the 5 different experiment trials
LCA conducted, researchers primarily varied the starting temperature
of the aqueous solution between 291.2 and 333.2 K; however,
researchers did not vary the concentration of the NaOH; it
remained constant throughout the trials at 500 mol/m3; the
study also focused on the effect temperature has on yield and
performed an analysis on surface reaction rate (ks)
Bolt et al.24 experimental (i) in this study researchers present an experimental study to (i) most notably, this study was able to establish that when
study and hy- produce hydrogen from an aluminum−water chemical reaction, using seawater in tandem with NaOH as the promoter, a
drogen pro- facilitated by NaOH; the study used several variations including reasonable yield of 58.8% can still be achieved. (ii) the
duction proc- changes in water temperature (40 to 70 °C), aluminum sample study confirmed that higher water temperatures were better
ess with alu- mass, water volume, water type (tap, distilled, and artificial sea), able to facilitate the reaction taking place when comparing
minum and and NaOH mass. (ii) during each trial, researchers were able to trials conducted at 40−70 °C. (iii) also, in the trials where
water collect raw data from the flow meter and gas sensor to later the NaOH mass was increased and decreased by 50%, the
identify the yield and hydrogen production rate trials that increased the mass were able to achieve a high
yield of 97.15% and 95.44%
Ho and Huang25 enhancement of (i) in this study, researchers used waste aluminum in the form of (i) in the first study where researchers investigated the impact
hydrogen cans and alkaline deionized water to generate hydrogen. (ii) in of ball milling at different time lengths and using water at
generation one of the studies, researchers attempted to identify the impact of temperatures between 50 and 70 °C; the samples that were
using waste ball milling 3 aluminum samples for 20 h and another 3 samples milled for 20 h produced hydrogen at a higher generation
aluminum for 5 h; to add another dimension to the study, the temperature rate compared to samples that were milled for 5 h; also, it
cans hydroly- of the alkaline deionized water used in the trials was 50, 60, and was observed that an increase in water temperature
sis in low al- 70 °C. (iii) following this, researchers conducted a test where increases the hydrogen generation rate as well. (ii) in the
kaline deion- they used 7 different samples; in each trial, the NaOH following study where the NaOH concentration was held
ized water concentration was 0.25 M; the first 3 trials only used Al and constant at 0.25 M, researchers found that the tests with Bi,
water between 50 and 70 °C; the final 3 trials had a constant Ni, and Ni/Bi additives were able to achieve the highest
water temperature of 70 °C; 1 of the final 3 samples contained possible yield of 1350 mL; also, the trial that contained no
Bi, the other Ni, and the last sample Ni/Bi. (iv) following this, additives and used water at 70 °C was able to achieve a full
researchers also conducted a study to identify how changing the yield; also, the trials that used a high NaOH concentration
NaOH concentration would impact the results; in this study, 4 were able to achieve a greater yield and hydrogen
different NaOH concentrations (1, 0.75, 0.5, and 0.25 M) in 50 production rate; although, it should also be noted that trials
°C water for each trial; also, 2 different types of Al samples; which had a concentration of 0.5 M and used Al powder
powder and can were used; in total, 8 trials were completed were able to achieve a full yield of 1350 mL of hydrogen
Soler et al.26 aluminum and researchers conducted a study in which 0.1 g of aluminum foil was by using Ca(OH)2, with an initial solution pH of 12.6,
aluminum al- compressed into a spherical ball and then added to an alkaline researchers were able to achieve a hydrogen production rate
loys as sour- solution containing either KOH or NaOH for preliminary tests; of 146 cm3/min, with a yield percentage of 76% after a
ces of hydro- after this researchers also conducted a test with Ca(OH)2 to duration of 100 min; however, according to presented
gen for fuel determine whether it was a suitable option for a hydroxide figures published by researchers, NaOH and KOH were
cell applica- solution able to achieve a maximum hydrogen production rate of
tions about 3200 and 2900 cm3/min, respectively; these tests
were performed at about 350 K and with a concentration of
5.3 mol/L

experimental conditions, the hydrogen generation rate was 2.3. Aluminum Pretreatment. Aluminum pretreatment
0.001 g H2/s.17 techniques targeting hydrogen production are commonly used
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Figure 6. Hydroxide promoter studies (maximum achievable production rate).
Figure 7. Hydroxide promoter studies (achieved hydrogen yield).
in conjunction with other methods. For instance, the use of
aluminum powder is a highly favorable technique used to
increase the surface area of aluminum particles exposed to
water during the reactions. To effectively pretreat/activate
aluminum, it can be ball-milled while being submerged in
water and then implemented in a rapid heating and cooling
process. This form of aluminum treatment was conducted by
Watanabe et al.,18 in which 5 g of aluminum particles was used
to generate hydrogen over 50 h. The results of the experiment
showed that aluminum after metal activation was significantly
more effective compared to hydrogen production without
aluminum activation.18 Although aluminum pretreatment has
the potential to drastically improve the amount of hydrogen
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generated from the process, it can be considered to be an
energy-intensive process, given that it can require ball milling,
rapid heating, and rapid cooling.
2.4. Molten Aluminum Alloys. Through the use of
molten aluminum alloys containing other elements such as
gallium, lithium, or others, the formation of the oxide layer can
be mitigated. In this molten state, aluminum alloys have do not
have an oxide layer that inhibits the reactions from taking
place. On its own, aluminum has a relatively high melting point
of about 660 °C. However, aluminum’s melting point can be
considerably decreased when converted into an aluminum
alloy. Figure 5 illustrates this behavior and shows how
aluminum and gallium alloys change phase with temperature.
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Table 2. Comparison of Aluminum−Water Hydrogen Production Using Oxide Promoters Studies
researchers study methodology
Chaklader and hydrogen genera- (i) in the patent, researchers presented their findings on
Chandra28 tion from water the hydrogen generation from the water splitting
split reaction reaction; they conducted numerous tests which varied
the γ-alumina weight percentage and process temper-
ature (30−70 °C). (ii) the study aimed to identify the
ideal pH by adjusting the water pH between 1.5 and
12. (iii) a variety of catalysts were tested to identify
which catalyst option was most effective; the tested
catalysts include SiO2, CaCO3,Ca(OH)2, china clay,
ball clay, and Al2O3 0.2 μm
Deng et al.16 physicochemical (i) this study aimed to achieve a continuous Al−water
mechanism for hydrogen reaction, through the use of Al2O3 modified
the continuous powder. (ii) researchers explained the theory behind
reaction of γ- the process with a schematic representation of the
Al2O3 modified process; the process was separated into 2 stagesan
aluminum pow- induction stage and another stage in which AlOOH
der with water film growth occurs and H2 bubbles are formed; during
the induction stage, Al2O3 and water react with each
other to produce AlOOH; afterward, during the
following stage, the AlOOH previously formed reacts
with 2 mol of Al; two products are produced4Al2O3
and 3H2; as a result of Al2O3 being produced, the
process can be repeated. (iii) the test conducted varied
the water temperature between RT and 70 °C
Irankhah et al.29 hydrogen genera- (i) in this study, researchers conducted a variety of
tion by using studies that used activated aluminum and reacted it
activated alumi- with water under various tested conditions. (ii) in the
num/water reac- first test, 3 different samples were compared (Al foil +
tion 1 wt % NaCl, Al powder + 1 wt % NaCl, and Al powder
without ball milling). (iii) following this the impact of
using NaCl at different weight compositions was tested
to identify the impact of changing the amount of NaCl
added; the weight compositions of NaCl used were
0.5%, 1%, and 2%. (iv) after this, the type of salt added
as an activator was changed to determine which
performed the best; the salts investigated included KCl,
NaCl, and BaCl2. (v) after this, a more simple test was
conducted, where only the water temperature was
varied; in this portion of the study only 3 temperatures
were considered65, 75, and 80 °C. (vi) overall this
study was extremely comprehensive and detailed;
numerous other metrics related to the effect of ball
millings, such as milling time and speed, were
investigated; additionally, the effect of air exposure and
the impact of using an alkaline aqueous solution rather
than regular water would have on the process was also
evaluated
Wang et al.30 preparation and (i) in this study researchers conducted mainly 3 different
hydrolysis of types of tests, where they varied the element
aluminum-based composition of each different aluminum-based com-
composites for posite sample. (ii) in the first test, researchers used a
hydrogen pro- combination of Al and CaO composites; each test
duction in pure varied the mass percentage of the CaO; the CaO mass
water percentages in the 4 tests were 3%, 5%, 7%, and 9%.
(iii) in the following test, researchers investigated the
effect of adding NaCl to the Al and CaO composite
samples; all samples kept the CaO mass % constant at
9%, except for the first which used 0 as a reference; the
NaCl mass % was varied between 3% and 9%. (iv) the
study was done twiceonce with water at 25 °C and
the other with water at 60 °C. (v) lastly, rather than
just using pure Al within the composite samples, the
last study used various Al alloys; each alloy used was
composed of different elements (In, Sn, and Ga) at
different mass %; all tests except for the 1st and 5th test
of 7 kept the mass % of CaO and NaCl constant at 9%;
the 1st and 5th tests had 0% CaO and 0% NaCl; also,
this study was completed twiceonce at 25 and 60 °C
Roseband13 composition and in the patent presented the invention pertained to the
methods for hy- equipment, method, and compositions used to generate
drogen genera- hydrogen; the impact of water medium type, aluminum
tion particle size, experiment temperature, and activator
composition weight % was investigated
Troczynski and compositions and in this study, inventors patented their methods used,
Edith11 methods for chemical compositions, and their experimental system
generating hy- for hydrogen production; the study performs a
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results with key findings
(i) the findings from the numerous experiments were reported; a
positive linear relationship between γ-alumina content and the
hydrogen production rate within 1 h was established. (ii) also, the
highest water temperature of 70 °C and pH of 12 were determined to
be the best option to facilitate the reaction taking place, given the
amount of hydrogen gas produced. (iii) the effectiveness of the
catalyst was evaluated based on the hydrogen yield after 1 h, the
maximum production rate as well as the time it takes to reach the
maximum hydrogen produced; it was noted that the ball reacted the
best in regards to the hydrogen released after 1 h, given its yield of
201 mL; however, the Ca(OH)2 catalyst has the highest hydrogen
production rate and the lowest time to release a full hydrogen yield of
25 mL/min and 1 min
as expected, the test where the experiments were performed at RT
performed the worst, whereas the 50 °C test performed the best
(i) in the first test, the sample that used Al powder with NaCl did
perform the best, producing drastically more hydrogen. (ii) for the
second test, it was established that the sample that had the most NaCl
(sample containing 2% NaCl) performed the best; this was evident in
this sample achieving the highest maximum hydrogen production rate,
highest average hydrogen production rate, and producing the most
hydrogen cumulatively; the achieved values were 1140, 518.4, and
1593 mL/min total; these values were drastically better compared to
the sample that used 0.5% NaCl, which produced 42 mL/min as its
maximum hydrogen production rate, 35.4 mL/min as its average
hydrogen production rate, and 614 mL as its cumulative amount of
hydrogen produced. (iii) in the following test which varied the salt
type, all samples performed better in a particular category; the sample
that contained KCl had the highest maximum hydrogen production
rate 856.8 mL/min, whereas NaCl had the lowest maximum hydrogen
production rate at 304.8 mL/min; however, NaCl did produce the
most hydrogen cumulatively at 1641 mL, whereas BaCl2 performed
the worst, only producing 1168 mL; it should also be noted that
BaCl2 did have the highest average hydrogen production rate at 229.2
mL/min. (iv) in the next test which varied the water temperature, the
trial that used the highest water temperature performed the best on all
categories related to hydrogen production and yield
(i) based on the results of the first test, the increase of CaO in the
composite sample does have a positive impact on the hydrogen yield;
this is evident in the 3% CaO sample having a yield of 0.78%
compared to the 9% CaO sample having a yield of 8.89%. (ii) in the
second test, the hydrogen yield percentages at 60 °C were
significantly higher than its 25 °C test, which used the sample test
conditions; the addition of NaCl to the composite sample also proved
to have a very positive effect on hydrogen production; for instance, in
the sample that had 3% NaCl the yield was 18.8% when the water
temperature was 60 °C; however, when the mass % was increased to
9% for NaCl, the achieved yield was 53.35%. (iii) in the third study,
the increase in water temperature also had a positive impact on the
hydrogen yield; this is evident in the fact that the hydrogen yield for
all tests conducted at 60 °C was higher than 25 °C. (iv) by comparing
the yield produced from each sample when the water temperature was
60 °C, the researchers were able to establish which sample performed
the best; it was determined that the last sample (Al:Ga:In:Sn =
96:1:1: 2) performed the best, given its yield of 95.84%; the fifth test
with the same alloy composition, but without CaO and NaCl, had a
yield of only 14.71%; this proved again that the presence of CaO and
NaCl is highly beneficial
the patent was able to establish that if the water temperature is used in a
range between 74 and 50 °C, 74 °C water will be able to produce the
highest hydrogen production rate and yield; also if the activator
weight composition has fluctuated between 2.5% and 10%, the sample
that produced the best yields was 10%; it was also established that all
the water mediums did perform very similar; however, pure water
performed better between 0.5 and 4 s
results generated by the inventors proved NaCl and KCl to both be an
effective inorganic salt catalyst; given the 55 °C starting temperature
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Table 2. continued
researchers study methodology results with key findings
drogen from comparison between different inorganic salt catalysts to for the inorganic salt compound, having a 1 to 1 ratio between salt
water display how effective it can contribute toward hydrogen and aluminum was ideal
generation, within an aluminum−water chemical
reaction; prior to the aluminum being added to the
water, the water was heated to 55 °C and inorganic salt
was added
Razavi-Tousi and effect of addition in this study, the researchers used various aluminum it was identified that the milling time greatly impacted the volume of the
Szpunar31 of water-soluble powder samples that were activated by using the ball hydrogen generated, where the aluminum sample that was milled the
salts on the hy- milling process, at various periods (15 min, 30 min, 1 h, longest (19 h) had the greatest amount of hydrogen generated; if only
drogen genera- 2 h, 4 h, 7 h, 11 h, 19 h); the study measured hydrogen NaCl was used, the higher weight composition of 0.75 performed
tion of alumi- generation by adding the various aluminum samples of better than the weight composition of 0.25, producing over 1200 mL
num in reaction hot water; the hot water in which the aluminum compared to less than 800 mL of hydrogen produced; furthermore,
with hot water powder was added to contained different weight researchers compared the KCl and NaCl each with a weight
compositions (0.25, 0.5, 0.75) of NaCl and KCl to composition of 0.5; it was identified that the KCl performed better
identify the impact of adding different salt promoters to than the NaCl across all of the milling times
the process at varying concentrations

Figure 8. Oxide promoter studies (maximum achievable production rate).

2.5. Inert Environment. An inert environment can be
highly beneficial for hydrogen production, especially when the
source of its production is through a chemical reaction. For
instance, aluminum is a metal that is capable of oxidizing
within its environment. Therefore, researchers often use gases
such as N2, Ar, or He which are inert and chemically stable.
Molecules are considered chemically stable if the constituent
atoms share a pair of electrons, and their valence shell becomes
full as a result, or if they are considered to be a noble gas.
3. SYSTEM PERFORMANCE COMPARISON
In this section, the various studies that use techniques such as
the implementation of hydroxide promoters, oxide and salt
promoters, molten aluminum, and aluminum pretreatment to
produce hydrogen are presented. Afterward, these studies are
compared by using the achieved hydrogen yields and the
maximum hydrogen production rates.
3.1. Hydroxide Promoters. Section 3.1 outlines hydrogen
production studies that incorporate the use of NaOH and
KOH primarily. These hydroxide promoter studies have been
summarized in Table 1.
1030
To further evaluate the performance of the process used by
researchers, the authors compared the achieved hydrogen yield
and the maximum hydrogen production rate achieved, among
the various studies. Figure 6 compares studies that disclose the
maximum hydrogen production rate when using hydroxide
promoters to facilitate the reaction, and Figure 7 compares the
achieved hydrogen yield when using hydroxide promoters.
Among the studies conducted, the study by Ma et al.21
performed drastically better compared to the other studies
when examining the maximum hydrogen production rate. This
was attributed to the aluminum pretreatment techniques used
in the study. In addition to using a hydroxide promoter,
researchers also used aluminum powder (the size of 16 μm).
By use of extrafine powder, the total surface area of aluminum
exposed during the process can be increased so that more
aluminum powder can react during the process.
Based on the achieved hydrogen yield, the use of hydroxide
promoters is an excellent method to improve the effectiveness
of the reaction. Four of the eight results presented depict a
100% yield or a near 100% hydrogen yield. The studies
conducted by Porciúncula et al.20 performed considerably well,
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Figure 9. Oxide promoter studies (achieved hydrogen yield).
producing a hydrogen yield of 99.91% and 99.96% when using
NaOH and KOH, respectively. The studies that used
Ca(OH)2 did not perform well, having a hydrogen yield of
approximately 76% and 12.5%.25 Based on the literature review
conducted, NaOH and KOH when used in a high
concentration (>2 mol/L) are excellent options as a promoter
compared to Ca(OH)2. It should also be noted that chlorine
hydroxide has also been used in the past as a hydroxide
promoter;27 however, the use of chlorine hydroxide is not
typically seen in many studies.
3.2. Oxide and Salt Promoters. In this subsection, the
benefits of oxide and salt promoters will be investigated, and a
comparison between studies that use salt and oxide promoters
will be performed. Table 2 presents several studies that use salt
and oxide promoters.
After the conducted literature review on oxide and salt
promoters, a comparison of studies was completed to identify
how effective each study was at producing hydrogen. The
studies used parameters such as hydrogen yield and the
maximum hydrogen production rate as shown in Figures 8 and
9, respectively.
The results listed for oxide and salt promoters studies were
relatively limited; therefore, results shown within Figures 8 and
9 are primarily from studies conducted by Chakladar and
Chandra,28 Irankhah et al.,29 Wang et al.,30 and Razavi-Tousi
and Szpunar.31
On the basis of the results shown in Figure 8, it is apparent
that the study conducted by Irankhah et al.29 which used 2%
NaCl performed the best. This study made it abundantly clear
that the increase of NaCl positively impacts the hydrogen
production rate when comparing the results of using 0.5%
NaCl. Also, based on the studies conducted by Chakladar and
Chandra,28 different oxide promoters were used; it was
identified that the test sample, Al with alpha bond, performed
better than any of the boehmite combinations.
In the studies presented by Razavi-Tousi and Szpunar,31
samples containing Al and KCl were milled for 19 and 7 h.
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Review
Both samples performed the same and were able to achieve a
100% hydrogen yield. The 100% hydrogen yield is not only
attributed to the addition of the salt but also attributed to the
pretreatment process the samples underwent. However, the
studies conducted by Wang et al.30 used a combination of CaO
as the oxide and NaCl as salt promoters. The sample
containing 9% CaO and 3% NaCl had a yield of 18.8%,
whereas the sample containing 9% CaO and 9% NaCl had a
yield of 53.35%. On the basis of this, it can be deduced that if
the oxide concentration is held constant, the increase in NaCl
will positively impact the achieved hydrogen yield.
3.3. Aluminum Pretreatment. In this subsection,
aluminum pretreatment processes are investigated, and the
studies used to generate hydrogen from the aluminum−water
chemical reaction are compared. Table 3 summarizes the
various studies evaluated.
Figures 10 and 11 compare the maximum hydrogen
production rate and hydrogen yields from various aluminum
pretreatment technique studies, respectively.
As seen in Figure 10, the studies conducted by Liu et al.39
performed exceptionally well. Their study used Al, which was
ball milled with CaH2 to facilitate the production of H2.CaH2
aids in opening Al grains, so that hydroxide ions can contribute
to their corrosion.
As seen in Figure 11, the study performed by Dupiano et
al.36 where the researchers used an Al−Bi2O3 composite
sample in 80 °C water produced the best yield. In this study,
Dupiano et al.36 referred to the Al−Bi2O3 sample as the finest
particles among all the samples used and that its sample was
the most reactive. It should also be noted that, among all the
samples tested by Dupiano et al.,36 Al−Bi2O3 had the fastest
average hydrogen production rate of 164.2 mL/min and the
shortest reaction time of 34 min.
3.4. Molten Aluminum Alloys. In this subsection, several
studies that use molten aluminum and molten aluminum alloys
to generate hydrogen are presented. The studies reviewed have
been summarized in Table 4.
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Table 3. Comparison of Aluminum−Water Hydrogen Production Using Aluminum Pretreatment Studies
researchers study methodology
Razavi-Tousi and role of ball milling (i) as seen in many other studies, researchers have used the
Szpunar32 of aluminum ball milling process as a pretreatment technique when
powders in pro- developing aluminum powder samples; in this study,
motion of alu- researchers used the volume of hydrogen that was able to be
minum−water generated to evaluate the effectiveness of the process. (ii)
reaction to gen- however, in this study researchers not only compared the
erate hydrogen various times the aluminum sample was milled for (2, 4, 7,
11, and 19 h), but they also used other parameters as well;
researchers compared the results of using aluminum samples
that were milled for 19 h to samples that had been annealed
for various time periods (1 min, 40 min, and 3 h); also,
researchers examined the impact using samples that were
milled 7 h and aged for various times (2.5 days, 8 days, 16
days, and more for other studies) would have on the total
hydrogen able to be generated
Razavi-Tousi and effect of structural (i) in this study researchers aimed to identify the impact of
Szpunar33 evolution of ball milling aluminum used in the hydrogen production
aluminum pow- process; to do this, researchers compared the amount of
der during ball hydrogen generated from aluminum that was ball milled. (ii)
milling on hy- in total 5 different milling times were compared7, 4, 11,
drogen genera- 18, and 2 h; researchers also compared the aluminum
tion in alumi- particle size with milling size. (iii) the aluminum sample
num−water re- used was also subjected to close microscopic study as well
action
Yavor et al.34 enhanced hydro- (i) in this study researchers aimed to generate hydrogen using
gen generation nano- and micro-sized aluminum particles; the particles used
from alumi- within the study were spherical in shape; researchers also
num−water re- performed a parametric study between 20 and 200 °C to
actions identify how the starting temperatures of the powder impact
the reaction. (ii) the experimental setup primarily consisted
of a reactor, bubbler condenser, flowmeters, and valves; the
reactor contained an ultrasonic rod to create agitation and
facilitate the reaction; the bubbler condenser subsystem used
within the experiment consisted of a container of water
Rosenband and application of ac- (i) the study used 3 different Al powder samples, denoted by
Gany35 tivated alumi- N1, N2, and N3; the average size of the aluminum powder
num powder for particles in each sample was 6.36, 9.25, and 32.64 μm. (ii)
the generation the study examined isothermal conditions, nonisothermal
of hydrogen conditions, and the impact of activators; the nonisothermal
from water test conditions used a water temperature of 50, 55, 62, and
74 °C; the sample used in these tests was N2; the study also
used 2.5 wt % of activator. (iii) next, the amount of activator
used was also varied to identify the optimal amount of
activator that should be added to the process; the activator
weight percentage compared was 2.5%, 5%, and 10%. (iv)
other parameters were also compared; however, the test in
which the type of water medium used also presented
interesting results
Dupiano et al.36 hydrogen produc- researchers attempted to generate hydrogen using a combi-
tion by reacting nation of 6 different composite samples; the Al−Al2O3 and
water with me- Al−MgO samples were prepared after 4 h of milling via a
chanically milled shaker; the other samplesAl−CuO, Al−MoO3, Al−Bi2O3,
composite alu- and Al−MO3were milled for 1, 0.5, 2.5, and 0.5 h,
minum−metal respectively; all 4 samples listed were milled by using
oxide powders planetary milling
Zhang et al.37 preparation and (i) rather than using a more conventional process such as
characterization milling to activate the aluminum, researchers used a
of activated alu- magnetic grinding technique from homemade technology;
minum powder researchers evaluated the process by comparing how much
by magnetic hydrogen was generated when the aluminum sample was
grinding method ground at various times (0, 10, 20, 30, 40, 50, and 60 min).
for hydrogen (ii) the study also compared the use of different aluminum
generation composites to identify the most effective option; to do this
researchers would compare pure aluminum to aluminum
composites containing 10 wt % of other elements (Cu, C,
Ni, Zn, Co, and Fe). (iii) the starting temperature of the
water also fluctuated between 273 and 333 K to identify the
impact temperature has on the reaction process. (iv) to
facilitate their experiments, researchers added NaOH as a
promoter, with a concentration of 0.4 mol/L
Yolcular and Kar- activation of Al (i) in this study, researchers milled aluminum with NaCl to
aoglu38 powder with produce experimental samples; each sample contained
NaCl-assisted different weight percentages of NaCl ranging from 5% to
milling for hy- 20%; each 1 g sample of aluminum used was placed in a 250
drogen genera- mL flask; the average diameter of the samples used was 90
tion μm. (ii) the study used aluminum samples that were milled
for various times (1, 4, and 12 h); the study aimed to
identify the impact which milling aluminum samples for
different times would have on hydrogen generation. (iii) the
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Review
results with key findings
(i) based on the results collected, milling aluminum was considered
to be a superior option compared to annealing for various time
periods; the sample that was milled for 19 h was able to generate
more hydrogen across most of the experimental times. (ii)
furthermore, it was noted that aluminum samples that were aged
for 2.5 days were able to generate more hydrogen across 7000 s
compared to samples aged for 8 and 16 days. (iii) contrary to the
other studies conducted, the aluminum sample that was milled
for the longest (19 h) did not produce the highest maximum
hydrogen generation rate, but rather the highest generation rate
was produced from the sample that was milled for 7 h. (iv)
researchers stated that the high hydrogen production rate after 7
h was attributed due to the presence of internal surfaces, whereas
the sample that was milled for 19 h only had the reaction take
place on the outer surface
the amount of hydrogen generated was the smallest when the
aluminum sample that was milled for 2 h was used; however, the
sample that was milled for 7 h performed the best
by decreasing the aluminum particle’s size and increasing the
aluminum particle temperature, researchers were able to identify
that it had a positive impact on the observed hydrogen yield; also,
researchers were able to determine that ultrasonic agitation from
the rod did have a positive impact on the observed hydrogen
yield
(i) based on the results collected, the trial at 74 °C produced the
most favorable results in regards to the extent of hydrogen
evolved; also, it was determined that the increase in activator
weight composition would have a positive impact on the extent of
hydrogen evolved. (ii) all of the studies presented produced a
very similar amount of hydrogen produced when varying the type
of water medium used
of all the samples used, Al−Bi2O3 performed the best overall; by
use of this sample, it was able to achieve a 100% hydrogen yield
as well as the highest average hydrogen production rate of 164.2
mL/min and the shortest total reaction time of 34 min; however,
Al−CuO performed the worst in regards to its hydrogen yield,
producing a yield of 67%; the Al−MgO3 average hydrogen
production rate was the lowest, only producing 3.1 mL/min; also,
Al−Al2O3 had the longest total reaction time, being 1292 min
(i) most notably, researchers found that grinding aluminum for 40
min was able to produce 1340 mL g−1 in under 6 min. (ii)
although higher starting temperatures are ideal in most chemical
reactions, since the particles in the reaction reach an excited state,
the best results were achieved at 323 K
(i) rather than examining the achieved yield percentage of
hydrogen, researchers investigated the hydrogen generation rate
among the various parametric studies. (ii) researchers identified
that the addition of 20% NaCl to the process was very beneficial,
as its addition was able to elevate the hydrogen generation rate to
1300 mL/min; researchers also identified that increasing the
initial milling time from 1 to 12 h was able to increase the
hydrogen generation rate from 500 to 1300 mL/min
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Table 3. continued
researchers study methodology results with key findings
study also varied the starting temperature of the water
between 30 and 70 °C
Liu et al.39 study of hydrogen in this study aluminum was ball milled with CaH2 as a method (i) researchers were able to establish that the addition of CaH2 as a
generation from to increase the metal activation; the CaH2 composites open hydride to the process is more effective than other hydrides; also,
the hydrolysis of aluminum grains, allowing hydroxide ions to corrode it was determined that the yield increases if aluminum is milled
a ball-milled aluminum easier; this in turn will add to the experiment’s for a longer time. (ii) researchers were able to achieve a hydrogen
aluminum/calci- ability to more readily produce hydrogen yield of 97.8% and had a generation rate of 2074.3 mL min−1 g−1;
um hydride the test sample used in this experiment was Al−10 mol % CaH2
composite39 mixture, and had undergone 15 h of milling prior
Luo et al.40 hydrogen genera- in this study researchers prepared aluminum that was ball (i) most notably, researchers found that Al with 13 wt % Ce was
tion from highly milled for various periods (1h, 5h, 8h, and 12 h); researchers able to produce a hydrogen yield of 92.42% at 1 h, whereas the
activated Al−Ce used Al−Ce composite material at various weight percen- other weight percentages above 13% produced a lower hydrogen
composite ma- tages for the Ce composite; researchers also used a variety of yield. (ii) it was also noted that the samples which were milled
terials in pure water mediums; these water mediums consisted of pure longer had a higher hydrogen yield; for instance, the aluminum
water water and water with NaCl and KCl added powder that was 13 wt % Ce, but milled for 12 h, had a yield of
93.15%. (iii) researchers did note that the addition of NaCl and
KCl to the process did produce more favorable results when Al−
5 wt % Ce was used; the achieved hydrogen yield of Al−5 wt %
Ce was 66.74%, whereas the addition of 10 wt % NaCl produced
92.50% and the addition of 10 wt % KCl produced a yield of
93.86%
Razavi-Tousi and effect of ball size (i) in this study, researchers prepared 4 different aluminum based on the different milling conditions, researchers were able to
Szpunar41 on steady state powder samples to study the impact of steady-state milling determine that high-energy impacts were preferred over low-
of aluminum time; each aluminum powder sample used was milled at a energy impacts; however, it was noted that the accumulation of a
powder and effi- speed of 200 rpm and was prepared with a charge ratio of lot of low-energy impacts can have a similar effect; however, the
ciency of im- 30; the aluminum powder particles used were separated into energy is often wasted
pacts during 4 vials; each vial contained a different combination of
milling different aluminum balls. (ii) the aluminum powder
particles’ structural evolution was studied after the samples
had been milled by using the average particle size, lattice
imperfections, and crystallographic orientation

Figure 10. Aluminum pretreatment studies (maximum achievable production rate).

4. COST ANALYSIS COMPARISON
The cost to produce hydrogen through the aluminum−water
chemical reaction is heavily dependent on the cost of
aluminum and water since they are the two primary ingredients
for the reaction. Presently, aluminum is considered the
cheapest metal on earth by a considerable margin. Currently
aluminum is valued $0.80 USD/lb, considerably cheaper than
metals such as copper ($3.07 USD/lb), nickel ($6.88 USD/
lb), and others.47 The low cost of aluminum enables the
process to be completed at a cheap and low price.
1033
Furthermore, the cost and accessibility of water do vary
depending on the particular location. However, water can be
readily accessible in most developed countries.
Despite aluminum being very affordable, additives may be
required to facilitate the reaction such as catalyst and
promoters. If catalysts or promoters are used in the reaction
process such a NaOH of KOH, their cost should be taken into
consideration for the entire process. Presently, NaOH is sold
for $13.95 USD per 500 g with a minimum purity of 96%, and
KOH is sold for $16.95 USD per 500 g with a minimum purity
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Figure 11. Aluminum pretreatment studies (achieved hydrogen yield).
of 85%.48,49 Given that NaOH and KOH are both capable of
producing similar results with regards to hydrogen yield, as
shown in section 3, it stands to reason that NaOH is the more
suitable option from an economic perspective given that it is
cheaper at a higher purity. Also, the price of aluminum that was
activated/prepared through the ball milling process can be
taken into consideration. Alternatively, a ball mill or another
milling device can also be purchased.
Figure 12 compares the cost of various hydrogen production
techniques. The aluminum−water hydrogen production
technique shown in Figure 12 uses the Hall−Heroult
electrolytic process, which is 24% efficient. Although the
process costs approximately $21.00/kg of hydrogen produced,
the United States Department of Energy (USDOE) hopes to
reduce the cost of the hydrogen produced between $2.00 and
$3.00.6 The cost to produce hydrogen through alternative
methods was extracted from a 2019 comparison by Kayfeci et
al.50
Compared to the other methods listed, water splitting
through the aluminum−water chemical reaction is still being
investigated by researchers to identify an optimal method to
produce hydrogen through this method. As seen in Figure 12,
more refined techniques of hydrogen production can be
drastically cheaper.
5. POTENTIAL ENVIRONMENTAL IMPACT AND
SCALABILITY
Presently, aluminum is the third most abundant element found
within the earth’s crust, accounting for 8.1% of its composition.
Only oxygen and silicon contribute more toward the earth’s
crust, accounting for 46.6% and 27.7%, respectively, therefore
also making aluminum the most abundant metal on earth.51
Water is also a very abundant resource. Presently, the earth’s
surface is covered by 71% water, of which 96.5% is ocean
water.5 If this process were to be scaled up, or done on a large-
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Review
scale operation, sea or ocean water should be used ideally due
to its abundance. Bolt et al.24,52 conducted several studies in
which researchers tested the viability of using ocean/seawater
to produce hydrogen gas from the aluminum−water chemical
reaction. Researchers were able to achieve a maximum yield of
58.8%. They were also able to artificially replicate ocean water
using water-soluble sea salt, primarily consisting of sulfate and
chlorine, sodium, and magnesium ions. Also, the maximum
hydrogen production rate achieved from their process was
17.98 mL/s. Additionally, Lu et al.53 conducted another study
to identify the feasibility of using seawater to artificially
generate hydrogen. The water used from various hydrogen
production processes can also be compared, as seen in Figure
13.
Figure 13 compares the water consumed from various
hydrogen production processes. It should be noted that in
Figure 13 steam methane reforming, proton exchange
membrane electrolysis, and solid oxide electrolysis are using
deionized water. Tap water was considered in the analysis of
coal gasification and biomass reforming, whereas softened
water was considered in the analysis of biomass gasification
and dark fermentation. The water consumed from the chemical
reactions presented earlier in eqs 1 and 2 was used as an
estimate to determine how much water is consumed from
aluminum−water chemical reactions. Based on the data
presented in Figure 13, aluminum−water chemical reactions
consume drastically less water compared to biomass gas-
ification and are even comparable to techniques such as proton
exchange membrane electrolysis and solid oxide electrolysis.
However, this analysis only took into consideration the water
directly consumed within the chemical reaction.
Elitzur et al.55 conducted an unconventional study where
urine was used instead of water to produced hydrogen. In this
study, Elitzur et al.54 fluctuated the urine temperature from 25
to 60 °C and recorded how hydrogen production rate and
yield were impacted over time. The study was able to produce
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Table 4. Comparison of Aluminum−Water Hydrogen Production Using Molten Alloys Studies

researchers study methodology results with key findings
Shmelev et al.42 hydrogen genera- in this study, an experimental system to react steam with (i) researchers recorded a variety of parameters relating to the
tion by the re- molten aluminum was developed; in the system, a syringe operating of the experimental setup, such as water injection time
action of mol- containing steam at 380−360 °C is injected into a reactor and steam flow rate. (ii) the observed parameters that were used to
ten aluminum containing melted aluminum at 1000 °C, suspended 20−22 evaluate the system include a comparison between steam flow rate
with water mm above the bottom surface of the reactor; the steam that and hydrogen evolution and a comparison between hydrogen
steam remained unreacted travels through the piping system with generation time and specific hydrogen flow rate. (iii) it was
the produced hydrogen and enters the condenser and dryer; observed that the maximum hydrogen flow rate was experienced
the condenser and dryer liquefy the steam so that the water within the first 20 s of the process starting and then it drastically
can be collected in the process; the remaining hydrogen gas decreased in the time that followed; this was due to the process
is measured by using a flowmeter, and a buret bubbling starting at an unreacted state; then most of the particles reacting
system afterward within the first seconds, causing the hydrogen flow rate
to spike; the drastic decrease in the hydrogen flow rate afterward
was due to the reaction nearing its completion. (iv) also, the
system performed better with a slower steam flow rate; a curve of
best fit would indicate a drastic increase in the hydrogen evolution
percentage, as the steam flow rate decreased
Wang et al.43 a review on hy- in this article, researchers conducted a review of hydrogen (i) the article verifies that aluminum−water chemical reactions are
drogen produc- production by using aluminum and aluminum alloys; the usually conducted in neutral and alkaline conditions. (ii) the article
tion using alu- review study was compartmentalized according to the also asserts that processes such as ball milling and metal doping
minum and current status of hydrogen production, background can be highly effective processes to optimize the reaction
aluminum al- information about the use of alloys to produce hydrogen,
loys and the limitations associated with commercialization
Lapham et al.44 the detection of (i) due to hydrogen’s solubility within molten aluminum, the research study revealed that the electrochemical sensors were an
hydrogen in researchers conducted a study to identify the various effective option in detecting hydrogen in molten aluminum; as a
molten alumi- techniques that can be used to detect hydrogen within result, a novel electrochemical sensor was also developed
num molten aluminum. (ii) this research holds great relevance
due to the fact that as aluminum decreases in temperature
hydrogen bubbles form within the aluminum, causing
porosity to occur; the pores that formed within an
aluminum sample can be considered detrimental in regards
to the structural integrity of a part going through the casting
process. (iii) the difficulty in detecting the hydrogen within
the molten aluminum pertains to the harshness of the
environment; aluminum has a very high melting temper-
ature, therefore making it difficult to use devices that are
considered to be invasive. (iv) the study compared a variety
of detection technologies such as electrochemical hydrogen
sensors and investigated the microscopic structure of
aluminum
Xu et al.45 liquid metal acti- the study provides an in-depth review of hydrogen production the study confirms the gallium is a suitable option to optimize the
vated alumi- through the use of aluminum alloys; the review briefly aluminum−water chemical reaction; also, room temperature liquid
num− water provides a comparison of different yields and hydrogen metal (RTLM) was considered to be an excellent option for
reaction for di- generation rates; however, a very large emphasis is placed on aluminum−water hydrogen production
rect hydrogen the theory of why aluminum alloys are an effective option
generation at for aluminum−water hydrogen production
RT
An et al.46 insight into the the study places a substantial emphasis on hydrogen the first sample produced the highest maximum hydrogen
indium-related production from aluminum alloys containing gallium, production rate of about 300 mL/min and a yield of ∼100%; the
morphology indium, and tin; the study briefly compares the hydrogen aluminum particles in sample 1 use only granular particles and are
transformation production rate or yield; however, the study places a higher composed of mostly indium particles
and application emphasis on the morphology of aluminum; five main
for hydrogen samples were compared in the study, where each sample
production of consisted of granular, wormlike, and irregular barlike alloy
Al-rich alloys particles, each having a different composition of aluminum,
gallium, indium, and tin

very high hydrogen production rates ranging from 150 to 700
mL/min, with yields of ∼90%. However, LiH was required as
an activator to carry out the reaction.
Additionally, the processes for aluminum and water
hydrogen production can also be enhanced through the use
of solar energy, as seen in a study conducted by Sheikhbahaei
et al.56 The experimental setup primarily consisted of water
recirculating pumps, trough solar collectors, a mixer, and a
reactor. The solar energy provided to the process produced
hydrogen through a photocatalytic water splitting and worked
as a supplement to the reactions so that hydrogen can be
produced at a more constant rate.
Presently a process that uses the aluminum−water chemical
reaction has not yet been commercialized for large-scale
applications. However, researchers have continued to study the
process extensively.
The use of recycled aluminum material can also have a
positive environmental impact. For instance, Martinez et al.22
1035
and Ho et al.25 used recycled aluminum cans. Also, Ho et al.57
and Swamy et al.58 converted aluminum foil into aluminum
powder to generate hydrogen. The aluminum cans used in the
experiment can easily be pretreated by using sulfuric acid.25
Using recycled material does not require additional metal
extraction, therefore mitigating pollution during its extraction
and refinement stages. Also, by use of recycled material, less
waste will be sent to a landfill; this mitigates the aluminum
disposal process and any cost associated with the aluminum
disposal. In another study conducted by Yolcular et al.,59 the
ability to produce hydrogen from waste aluminum powders
and alloy chips was evaluated. The study used commercial
aluminum (1050, 6013, and 7075) as the test samples. NaCl
was added as an activator for the chips and NaOH as a reaction
promoter. Waste aluminum powder derived from 7075
aluminum alloy did produce the highest hydrogen generation
rate at over 1600 mL/min, when the starting process
temperature was 70 °C was used.
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Figure 12. Hydrogen production cost comparison (data from refs 6 and 50).

Figure 13. Water consumed in various hydrogen production processes (data from ref 54).

The hydrogen produced through the aluminum−water
chemical reactions can be used as a clean method to generate
hydrogen for the methanation process. This was further
investigated by Phung et al.,60 where an experimental setup
was developed to synthesize hydrogen then combined the
hydrogen produced with CO2 to produce natural gas. The
study evaluated the amount of hydrogen produced depending
1036
on the concentration NaOH added to the solution, the type of
water used, and the impact aluminum particle size has on
hydrogen production. However, the study was able to record
how the concentration of NaOH in the aqueous water solution
was able to impact the amount of CH4 produced. In this
portion of the study, the NaOH concentration ranged from 0.2
to 1.0 M. The peak CH4 produced after a 25 min experiment
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time was 334 ppm and attained at a concentration of 0.8 M,
whereas the lowest CH4 produced of 27 ppm was achieved at a
concentration of 0.2 M.
6. APPLICATIONS FOR ALUMINUM AND WATER’S
CHEMICAL REACTIONS BYPRODUCTS
The waste produced from the aluminum−water chemical
reaction can also be examined. For instance, based on the
aluminum−water chemical reactions presented, the known
products of the reaction besides H2 are as follows: Al2O3,
AlO(OH)2, and Al(OH)3, all of which can be used to generate
useful products. Furthermore, if NaOH were used as a
promoter to facilitate the reaction, different products from the
reaction will be formed. The addition of NaOH to the reaction
process could cause NaAl(OH)4, Na2Al2O4, and Na6Al2O6 to
form. The products formed are various versions of sodium
aluminate. Also, if KOH is used a the reaction promoter
instead, K[Al(OH)4] can be formed. Possible applications for
most products are listed and summarized in Table 5.
Table 5. Useful Applications for Aluminum Water
Reactions’ Byproducts
product produced useful applications
aluminum oxide filler in products (sunscreen and in
(Al2O3) cosmetic products such as blush, face
powder, lipstick, and eye shadow)
catalyst
gas purification
glass
abrasive
paint
composite fiber
body armor
abrasive protection
electrical insulation
medical devices
aluminum hydroxide pharmaceuticals
(Al(OH)3)
sodium aluminate paper industry
(NaAl(OH)4, concrete
Na2Al2O4, and
Na6Al2O6) water treatment
fire brick
potassium aluminate concrete
(K[Al(OH)4])
Although the chemical reactions between additional
aluminum and water are primarily geared toward clean
hydrogen production, a variety of useful byproducts can be
produced, especially if sodium hydroxide or potassium
hydroxide is added to the reactions as a catalyst. Based on
the examples presented in Table 5, there are many possible
applications for the byproducts produced. For instance,
aluminum oxide can be used as a filler in many skincare
products and is considered to be an ingredient in glass,
abrasives, and even paint, whereas byproducts such sodium
aluminate and potassium aluminate, which are formed from
the addition of a catalyst, can be used as an ingredient in
concrete.
7. FUTURE DIRECTIONS AND DEVELOPMENTS
This section outlines the proposed future directive to
successfully introduce hydrogen produced from the alumi-
pubs.acs.org/EF Review
num−water chemical reaction to commercialization. The main
steps of implementation are summarized in Figure 14.
All aluminum−water hydrogen production research starts
with the basic aluminum−water chemical reactions, after which
the reactions are modified to reduce or stop the formation of
the aluminum oxide layer which inhibits the reaction. Ideally,
the process used should incorporate recycled aluminum and
seawater. Using recycled aluminum provides the benefit of
eliminating the extraction and procurement stage of using
aluminum in the process. Also, seawater is extremely abundant
and would require less refinement. Afterward the process can
be refined to minimize cost and resources used. Once satisfied
with the process, it can be commercialized for more broad use.
Presently, numerous institutions and organizations are
working toward making hydrogen a preeminent fuel source
and are exploring the various capabilities of hydrogen as an
energy carrier. The Clean Energy Research Laboratory
(CERL), located in Oshawa, Canada, is a cutting-edge
laboratory aiming to produce the world’s first lab-scale version
of the Cu−Cl cycle to facilitate thermochemical water splitting
as well as investigate the feasibility of nuclear hydrogen
production.79 Researchers working within the facility are also
investigating numerous other hydrogen production techniques
ref including photolysis, electrolysis, and even hydrogen produc-
61, 62 tion through the aluminum−water chemical reaction.
The National Research Energy Laboratory of the USA has
also invested in numerous hydrogen-related projects related to
63
fuel cell manufacturing and analysis. Their goal is to
64
commercialize products produced within their laboratory.
65
Additionally, the facility has allocated resources toward
66
hydrogen delivery and storage technologies.80,81
67
The USDOE is also an institution working diligently to
68
create a low carbon economy and elevate clean sources of fuel
69
such as hydrogen. In a recent report published in July 2020,
70
the USDOE outlines the numerous applications for hydrogen,
71
whether as a fuel, for electricity production, or other
72
applications such as fertilizer or metal refinement.82 The
73
USDOE has published and compiled the findings of numerous
74 reports/papers on hydrogen production strategies ranging
75 from more common techniques such as electrolysis to less
conventional techniques such as aluminum−water chemical
76
77 reactions.6,82
78
8. CONCLUSIONS
In this paper, a comprehensive review of hydrogen production
strategies through aluminum−water chemical reactions was
conducted. The review examined techniques that can be used
to mitigate the formation of the oxide layer. These techniques
include using hydroxide promoters, oxide promoters, salt
promoters, activated aluminum, and molten aluminum/
aluminum alloys. Each subsection presented within section 3
compared studies conducted by various researchers, which
used the same technique to mitigate the formation of the oxide
layer. Comparisons were drawn by examining the maximum
hydrogen production rates and the achieved hydrogen yield.
In section 3.2 the studies were compared which used
hydroxide promoters as a means to reduce the formation of the
oxide layer. The use of hydroxide promoters was found to be a
highly beneficial method to reduce the oxide layer’s formation.
This is evident in the studies examined that were able to
achieve a yield of over 99%. The main commonality between
these studies was the implementation of hydroxide promoters,
NaOH, or KOH. However, some studies did not produce
1037 https://dx.doi.org/10.1021/acs.energyfuels.0c03674
Energy Fuels 2021, 35, 1024−1040
Energy & Fuels pubs.acs.org/EF Review

Figure 14. Path to future advancements in aluminum−water reaction hydrogen production.

favorable results in regards to the hydrogen yield. This is likely

due to selecting of less effective hydroxide promoters, such as
Ca(OH)2.
However, in section 3.2, the impact of adding oxide and/or
salt promoters to the hydrogen production process was
examined. The conducted review confirmed that the addition
of NaCl can be highly beneficial in increasing the hydrogen
production rate. Studies identified that Al composites
containing 2% NaCl achieved a drastically higher maximum
hydrogen production rate of 1140 mL/min, whereas the
samples containing 0.5% NaCl was able to achieve a hydrogen
production rate of 42 mL/min. Additional studies also
confirmed that a full hydrogen yield can be obtained when
the salt promoter, KCl was added with aluminum and ball
milled for either 19 or 7 h. By ball milling the aluminum
samples, those conducting experiments can pretreat the
aluminum samples and increase the samples’ ability to perform
better.
■ AUTHOR INFORMATION
Corresponding Authors
Andre Bolt − Faculty of Engineering and Applied Science,
University of Ontario Institute of Technology, Oshawa,
Ontario L1H 7K4, Canada; orcid.org/0000-0002-2694-
6238; Email: Andre.Bolt@uoit.ca
Ibrahim Dincer − Faculty of Engineering and Applied Science,
University of Ontario Institute of Technology, Oshawa,
Ontario L1H 7K4, Canada; Email: Ibrahim.Dincer@
uoit.ca
Martin Agelin-Chaab − Faculty of Engineering and Applied
Science, University of Ontario Institute of Technology,
Oshawa, Ontario L1H 7K4, Canada; Email: Martin.Agelin-
Chaab@uoit.ca
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.0c03674
Notes
The authors declare no competing financial interest.

■
The pretreatment and preheating of aluminum samples were
also further investigated in sections 3.3 and 3.4. As expected,
pretreating and preheating of aluminum can be highly ACKNOWLEDGMENTS
beneficial and can easily be incorporated/combined with The authors acknowledge the financial support of the Natural
Sciences and Engineering Research Council of Canada.

■
other aluminum−water hydrogen production techniques. By
ball milling the aluminum sample, we can increase the surface
area of the aluminum exposed during the reaction process. NOMENCLATURE
Although aluminum−water hydrogen production can be Al = aluminum
highly beneficial due to its raw material cost and abundance, Al2O3 = aluminum oxide
the process is still considered expensive compared to the more Al(OH)3 = aluminum hydroxide
established methods of hydrogen production such as AlOOH = aluminum hydroxide oxide
electrolysis. Various institutions, including the USDOE, are BaCl2 = barium chloride
working toward reducing the cost of hydrogen production. Bi2O3 = bismuth(III) oxide
In addition to this, the potential byproducts produced from C = carbon
CaCO3 = calcium carbonate
the aluminum−water chemical reaction can be used for a
Ca(OH)2 = calcium hydroxide
multitude of purposes. Aluminum oxide in particular can be CaH2 = calcium hydride
used as a catalyst and in gas purification, glass, abrasive, or Ce = cesium
paint as well. Co = cobalt
Overall, hydrogen production through an aluminum−water Cu = copper
chemical reaction does show tremendous promise, given its Fe = iron
abundance, cost, and ability to achieve a high hydrogen yield. Ga = gallium
However, further research is still required to reduce the overall GWP = global warming potential
cost of the process and to determine the optimal production HHV = higher heating value
process. H2 = hydrogen gas
1038 https://dx.doi.org/10.1021/acs.energyfuels.0c03674
Energy Fuels 2021, 35, 1024−1040
Energy & Fuels
H2O = water
In = indium
ks = surface reaction rate
K[Al(OH)4] = potassium aluminate
KCl = potassium chloride
KOH = potassium hydroxide
LNG = liquefied natural gas
LPG = liquefied petroleum gas
MO3 = molybdenum trioxide
MgO = magnesium oxide
NaAl(OH)4, Na2Al2O4, and Na6Al2O6 = sodium aluminate
NaOH = sodium hydroxide
Na2SnO3 = sodium stannate
Ni = nickel
O2 = oxygen gas
RTLM = room temperature liquid metal
SiO2 = silicon oxide
Sn = tin
Zn = zinc
■
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