Journal Pre-proof

Hydrogen storage capability of porous silicon powder fabricated from Al–Si alloy

Honghao Li, Ilizel Retita, Junjie Huang, S.L.I. Chan

PII: S0254-0584(21)01188-3
DOI: https://doi.org/10.1016/j.matchemphys.2021.125405
Reference: MAC 125405

To appear in: Materials Chemistry and Physics

Received Date: 13 October 2021

Revised Date: 29 October 2021
Accepted Date: 1 November 2021

Please cite this article as: H. Li, I. Retita, J. Huang, S.L.I. Chan, Hydrogen storage capability of porous
silicon powder fabricated from Al–Si alloy, Materials Chemistry and Physics (2021), doi: https://
doi.org/10.1016/j.matchemphys.2021.125405.

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 CRediT author statement

Honghao Li: Methodology, Investigation, Formal analysis, Writing - Original Draft, Visualization
Ilizel Retita: Validation, Conceptualization, Writing - Original Draft, Writing - Review & Editing
Junjie Huang: Resources, Methodology
S.L.I. Chan: Supervision, Writing - Review & Editing

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Hydrogen storage capability of porous silicon powder from Al-Si alloy
Hydrogen Storage Capacity As-received powder Single-etched pSi Double-etched pSi
As-received
Single-etched with nickel
Single-etched
Double-etched with nickel
Double-etched
Pressure (Mpa)

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Large increase in specific surface area Nickel catalyst spillover effect
of pSi samples after etching

r
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m2/g Double Hydrogen

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Single etched
250

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etched 218.8 Surface Area
Hydrogen Content (wt%) 200 179.5 (more binding sites)

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0.9
Physisorption
0.8 150

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0.7 Hydrogen sorption

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100
0.6 As capacity Chemisorption
0.5 50 received
0.4 0.9
0
0.3
0.2
0.1 CONCLUSION: Double-etching and Ni blending increased the hydrogen storage
0 uptake of fabricated porous silicon (pSi) powder. The results provide a strong
Absorption Retained Usable Hydrogen
(wt%) H2(wt%) Capacity Retained/Absorbed evidence on the potential of pSi from Al-Si alloy to be an effective solid-state
(wt%) hydrogen ratio
storage material for hydrogen.

Honghao et al.
 Hydrogen storage capability of porous silicon powder fabricated
from Al-Si alloy

Honghao Li1, Ilizel Retita1, Junjie Huang2 and S.L.I. Chan1,3*

1
School of Materials Science & Engineering, University of New South Wales,
Sydney, New South Wales 2052, Australia
2
College of Chemistry & Chemical Engineering, Shaoxing University, Shaoxing,
312000, China

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3
Department of Chemical and Materials Engineering, National Central University,

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Taoyuan 320, Taiwan (R.O.C.)

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Abstract
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Porous silicon powder has been fabricated from an Al-Si alloy by etching in strong acids, and its
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hydrogen storage capacity has been studied. Double acid etching in the fabrication and nickel
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blending have been proposed to further enhance the hydrogen storage capacity of the etched
powder. The etching effectively removed the aluminum from the Al-Si alloy to form a porous Si
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structure, with a large increase in surface area. After charging under a hydrogen pressure of 3.7
MPa at 150 ℃, the hydrogen uptake of double-etched and Ni-blend porous silicon samples was
0.81 wt%, which was >13 times higher than that of the as-received Al-Si alloy (0.06 wt%). The
percentage of retained hydrogen after desorption was also largely decreased. The results of this
study provide strong evidence on the potential of using porous silicon powder from Al-Si alloy as
a cost-effective solid-state storage material for hydrogen.

Keywords: Hydrogen storage, Porous materials, Catalyst, Chemical etching, Aluminum alloys
1. Introduction

Climate change is one of the biggest issues that scientists are investigating on [1].The use of
renewable energy sources such as solar energy [2], wind energy [3] and geothermal energy [4] can
address the issue of burning fossil fuel which is the main contributor for climate change. Hydrogen
energy is one of the renewable energy sources that has been the focus of intensive research but
hydrogen storage is still one of the major challenges in the realization of hydrogen economy [5].
There are existing technologies for storing hydrogen such as liquefaction [5] and high pressurized
tank [6]. However, these storage methods require very low temperature or high hydrogen pressure,
which increase the risk and cost in applying these methods to store hydrogen. Solid-state storage

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method is an exciting approach for hydrogen storage. Ideally, hydrogen storage materials can store

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hydrogen in a safe and effective manner by physisorption or chemisorption of hydrogen in the

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materials. The performance criteria of the hydrogen storage materials to be considered are usable
hydrogen storage capacity, hydrogenation/dehydrogenation temperatures, kinetics, and cost.
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Hydrogen storage using metal hydride has been studied for a long time and is a relatively
mature technology. However, metal hydrides are usually heavy, and some are very stable
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compounds and require high dehydrogenation temperature of more than 300 ºC [7, 8]. Metal-
organic frameworks (MOFs) are an example of solid-state porous material that can be used for
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hydrogen storage under a temperature range from -196 °C to 25 °C [9]. Unfortunately, hydrogen
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interactions with MOFs are relatively weak and this can affect its long-term storage capacity at
higher temperature [9]. Thus, a low-cost, porous hydrogen storage material that can be operated at
around room temperature would be highly sought-after.

Porous silicon (pSi) can be one of the candidates for highly efficient solid-state hydrogen
storage material [10, 11]. In a recent study, Boaks et al. used density function theory (DFT) to
simulate the behaviour of pSi during hydrogenation and the result showed that pSi has hydrogen
storage density of at least 1.36 wt% [12]. This material has also been exploited for other
applications. It can be used for light-emitting diodes (LED) and gas sensors because of its efficient
emission visible photoluminescence and large internal surface area [13, 14]. In addition, pSi is
currently used in biomedical applications due to its flexible and non-hazardous properties [15].
Another recent application is in biomonitoring for wearable devices where Davoodi et. al used 3D
printing to fabricate graphene-coated pSi materials which had high strain-recoverability and good
resistance to temperature and humidity [16]. In addition, pSi fabricated by hydrofluoric acid
electrochemical etching of silicon wafer was used in perovskite solar cell application [17]. It has
been reported that during fabrication of pSi thin film by electrochemical etching, a large amount
of hydrogen is generated and stored in the pSi nanostructures which showed that pSi can be
hydrogen reservoirs [18]. However, the electrochemical etching technique is expensive, hazardous
and the amount of pSi thin film fabricated is very limited [19]. Another method of pSi fabrication
was proposed by Bakar et al. [20] and Zhang et al. [21] to produce cost-effective pSi powder by
chemical etching of Al-Si alloy as effective catalyst for reduction of p-nitrophenol and for lithium
storage applications, respectively [20, 21]. Recently, Sun et al. also fabricated pSi from Al-Si alloy

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by ball milling and HCl etching for lithium ion battery anode material with high reversible capacity
[22].

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Thus, the present work fabricated pSi from Al-Si alloy, and to the knowledge of the authors, is
the first to study the hydrogen storage properties of the pSi material so produced. The hydrogen
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storage capacity of the pSi powder was further enhanced by double etching during fabrication and
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the addition of Ni catalyst before hydrogenation test.

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2. Methodology
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Al-Si powder with a eutectic composition of 12.5 wt% silicon and 87.5 wt% aluminum was
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used as the as-received powder to fabricate the pSi powder. Chemical etching was applied to
remove aluminum from the alloy powder, thus leaving a porous structure which is mainly Si. Single
etching was done in Samples A and C in which only hydrochloric acid (HCl) was used for etching,
while double etching was applied to Samples B and D which included single etching and secondary
etching using the nitric acid (HNO3) as a secondary etchant.

Initially, the alloy was dispersed in deionized water with the weight ratio of 1 g alloy to 20 mL
deionized water at 25 °C (5 wt% dispersion) and the acid etchant as shown in Table 1 was added
under constant magnetic stirring. After etching, the sample was washed with ethanol and centrifuge
was used to separate the powder and the solution. Finally, the powder was collected and dried in
an oven at 60 ℃ for 3 hours.
 Table 1. Sample preparation parameters of pSi powder

Sample Description Etchant and Time of Catalyst

Concentration etching (h) Added Before
(Molarity, M) Hydrogenation
O As-received powder n/a n/a n/a
A Single-etched 6 M HCl 48 n/a
B Double-etched First etchant: 6 M HCl 48 n/a
Second etchant: 2 M 24
HNO3

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C Single-etched with 6 M HCl 48 Ni powder

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nickel
D Double-etched with
nickel -p
First etchant: 6 M HCl
Second etchant: 2M
48
24
Ni powder
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HNO3
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Pressure-Composition-Isotherm (PCI) test using Sievert’s apparatus was employed to

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determine the hydrogen storage capacities of the samples. Argon-purging and leakage test were
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done to ensure the whole testing system was clean and leak-free. Before the PCI tests, all pSi
powder samples were activated under vacuum at 150 ℃ for 3 hours to remove any possible oxide
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layer and moisture on the surface of the material. The hydrogen storage capacity of the samples
was then tested at 150 ℃ in a pressure range from 0 to 3.7 MPa, with 5 steps each for absorption
and desorption. Hydrogen charging and discharging required 20 mins per step to reach equilibrium,
so as to reveal the hydrogen absorption and desorption characteristics of the pSi samples.

To investigate the effect of nickel powder as a catalyst for hydrogen storage of the pSi powder,
Ni was added to samples C and D before PCI testing. The Ni powder used in this study had a
particle size of about 10μm and purity ≥ 99.5%. The powders were mixed in an agate mortar with
a ratio of 1 wt% Ni: 2 wt% pSi.

3. Results

Figure 1(a) presents the SEM image of the as-received Al-Si powder, and (b) and (c) present
the SEM images of single etched and double-etched pSi powders, respectively. The surface of the
as-received powder was largely smooth without any pores. The SEM results of both single and
double etched samples, together with the EDS analyses described later, reveal that the Al was
etched from the surface of the powders which produced pore channels with lamellar structures. The
single-etched sample retained a spherical shape after etching, and bigger holes in the particles
reveal deep etching occurred into the particles, as shown in Fig 1(b). It has fine lamellar structures
all throughout the sample. The double-etched sample was generally found to be smaller as
compared with the as-received and single-etched particles. It did not retain its spherical shape and
its lamellar branches were thicker with visibly lesser branches than the single-etched sample, since
the finer branches were destroyed after second etching.

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b)
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Figure 1. SEM images of (a) As-received powder (b) Single-etched pSi and (c)Double-etched pSi.

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It can be seen that pores were created by the etching in (b) and (c).

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SEM observation was supported by the BET results in Figure 2, in which the surface area of
the etched powders has significantly increased. The specific surface area of the single-etched pSi
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was 196 times higher than that of as-received powder. Moreover, the surface area of the double-
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etched sample was even enhanced further to 218.8 m2/g.

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250
218.8
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200 179.5
Specific Surface

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150
Area(m2/g)

100

50
0.9
0
As-received Single-etched Double-etched
powder pSi pSi

Figure 2. Surface area of As-received powder and As-etched samples as determined by BET
analysis, showing a large increase in specific surface area of pSi samples after etching.

The EDS results in Figure 3 reveal the relative amounts of Al and Si elements present in the
samples. The Al to Si ratio of the as-received powder (Figure 3a) shows that there was mainly Al
in initial sample. After etching, the EDS results of both single and double-etched samples reveal
that the Al was significantly removed from the powders, and it has the least Al peak ratio in the
double-etched sample.

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c)
Figure 3. EDS spectrum of a) As-received powder, b) Single-etched pSi, c) Double-etched pSi. It
can be seen that the amount of aluminum in the powder has mostly been removed after etching.
 The hydrogen storage properties of the pSi powder were determined by PCI tests at 150 ℃ and
the result curves obtained are given in Figure 4a. Figure 4b compares their absorption, retained
hydrogen after desorption, usable capacity, and hydrogen retained/hydrogen absorbed ratio. The
usable hydrogen storage capacity in this study is defined as the hydrogen that can be liberated at
150 ℃ during desorption, and the retained hydrogen within the material is not considered as
available capacity. Moreover, the hydrogen retained/hydrogen absorbed ratio was calculated by the
ratio of the retained hydrogen to the total hydrogen absorbed in the pSi.

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b)

Figure 4. PCI results of pSi powder samples at 150℃, showing amounts of hydrogen
absorbed, retained and usable hydrogen in each sample.
 Sample O has a hydrogen uptake of 0.06 wt% but 0.05 wt% of hydrogen was retained into the
material after desorption at 150 ℃, that is, about 83% of the hydrogen uptake (0.83 hydrogen
retained/hydrogen absorbed ratio) was not released. This shows that as-received powder has no
significant hydrogen storage capacity. After single etching, the hydrogen uptake of Sample A
increased to 0.2 wt% and its retained hydrogen was 0.11 wt%, which means that its releasable
hydrogen is only about half of its absorbed hydrogen. The hydrogen uptake of Sample B was
increased further to 0.32 wt% and it has a lower hydrogen retained/hydrogen absorbed ratio after
desorption than Sample A. The effect of Ni catalyst was evident in the PCI curves where it
significantly increased the hydrogen absorption of Samples C and D with 0.69 wt% and 0.81 wt%

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hydrogen uptake, respectively. Even though the retained hydrogen for samples C and D have
increased compared to samples without Ni, their hydrogen retained/hydrogen absorbed ratio

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remained at about a third of their absorption capacity. Sample D which was double-etched and with

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added Ni catalyst has the highest hydrogen absorption and usable capacity among all samples.
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4. Discussion
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For hydrogen storage application, the presence of Al in the powder is considered as dead weight
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because it does not react with hydrogen easily, given that hydrogenation of Al metal is only
possible at 10 GPa and 600 °C [23]. The presence of Al also prevents the hydrogen sorption of the
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silicon. Thus, single and double etching were introduced in this study to etch out Al and to create
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a porous Si structure, so as to facilitate hydrogen uptake of Si. EDS spectrum in Figure 3 reveals
the sample peak of Al which was drastically decreased after etching. The Al peak ratio is the lowest
in double-etched pSi samples, which proves that double etching is an effective method to remove
most of the Al in the as-received powder.

Chahine’s rule states that hydrogen uptake for solid state material is linearly dependent on
specific surface area, which means that higher specific surface will increase the hydrogen storage
capacity proportionally [24]. The PCI and BET results clearly show that Chahine’s principle is
applicable to porous silicon as well. In Figure 4, as-received Sample O has a negligible hydrogen
storage capacity, whereas Sample A result revealed a usable hydrogen storage capability of 0.09
wt%. This can be attributed to the removal of Al through etching, which then created a porous
structure with a significantly higher surface area (Figure 2) that can easily react to hydrogen. This
resulted in 3.3 times higher hydrogen uptake in Sample A, and its usable hydrogen storage capacity
was 9 times higher than Sample O. The retained hydrogen for Sample A was lower than that in
Sample O, in which it decreased from 83.3% to 55% only by single etching. The retained hydrogen
in the samples could be due to the formation of strong bonds between pSi powder and hydrogen
atom during absorption. These strong bonds may not break until a temperature higher than 150 ℃
is introduced into the system [25, 26]. Therefore, there are still a lot of improvements that can be
made to release the retained hydrogen after desorption, and to further increase its usable hydrogen
storage capacity.

Double etching is introduced in this study to increase the hydrogen storage capacity by further
removal of Al and increasing the specific surface area of the etched powder. In Figure 1, SEM

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images shows that thicker branches were left after double etching, which implies that more Al was

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etched out, leaving behind the main Si branches and hence created a more porous structure with a

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further higher specific surface area. BET results in Figure 2 show that Double-etched pSi has 20%
more specific surface area than the Single-etched pSi. Consequently, Sample B has 1.6 times higher
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hydrogen uptake and 2.4 times higher usable hydrogen storage capacity than sample A. In addition,
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it shows that double etching can reduce the hydrogen retained/hydrogen absorbed ratio from 0.55
to 0.31, demonstrating that hydrogen in Sample B was easier to release than in Sample A. This can
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be attributed to the successful further removal of Al and higher specific surface area by double
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etching.
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The addition of Ni catalyst is another method used in this study to enhance both the hydrogen
storage uptake and usable hydrogen storage capacity of pSi powder. Samples C and D showed an
even higher hydrogen uptake, which was 3.5 and 2.5 times more as compared to Samples A and B
respectively. This can be due to the spillover effect of Ni, in which Ni helps to break down the
hydrogen gas into hydrogen atoms, making it easier for hydrogen to bond with pSi [27]. Moreover,
the hydrogen retained-hydrogen absorbed ratio results show that Ni catalyst helped in the effective
release of hydrogen and is evident in the single-etched samples. However, its effect to release
hydrogen in double-etched samples was not significant. This can be further investigated to
understand the role of Ni catalyst on double-etched pSi. Overall, Sample D showed the highest
hydrogen absorption among all samples, which was expected since it has a combined effect of
double etching and spillover effect of catalyst together.
 The pSi in this study has similar hydrogen uptake to single-walled carbon nanotube (SWNT)
and zirconium-based MOF (UiO-66) at certain hydrogenation conditions. Both carbon nanotube
and MOFs are considered to store hydrogen by physisorption [28] which require very high surface
area for hydrogenation of 780 m2/g for SWNT [29] and 1413 m2/g for UiO-66[30], but the surface
area of the pSi was much lower as shown in Figure 2. Furthermore, SWNT and UiO-66 both
achieve 0.8 wt% hydrogen absorption at 0.1 MPa and -196 ℃ [29] and at 10 MPa and 25 ℃ [30],
respectively, whereas the pSi powder has a major advantage because its hydrogenation conditions
are closer to ambient temperature and pressure which is more favourable for fuel cell applications.

Nevertheless, it should be noted that all PCI curves did not plateau even under 3.7 MPa of

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hydrogen pressure, suggesting that it can absorb more hydrogen when a higher pressure is applied.

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Hence, pSi powder has the potential to store a higher amount of hydrogen in higher pressures at

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temperature closer to ambient. Moreover, its fabrication process is easy and cost-effective.
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5. Summary and Conclusion
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In summary, pSi powder was fabricated from as-received Al-Si alloy by chemical etching.
Single and double etching were applied to remove Al and increase the specific surface area of the
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powder. The hydrogen storage uptake of the double-etched sample was 1.5 times more than the
uptake of the single-etched sample. Nickel powder was added as a catalyst to enhance the
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hydrogenation properties of the etched samples, which led to 3 times higher hydrogen sorption
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capacity due to its spillover effect. Thus, the combination of both double etching and Ni catalyst
increased the hydrogen storage capacity even further and resulted to the highest hydrogen uptake
among all powders studied. Also, its hydrogenation condition is closer to ambient than MOFs and
carbon nanotube. Thus, the present work clearly indicates that pSi powder fabricated from low-
cost Al-Si alloy has a considerable potential as a hydrogen storage material.

Acknowledgment

The authors wish to thank the UNSW Digital Grid Futures Institute under grant number PS62036
for the funding to support this project.

References:

[1] U.Y. Ayikoe Tettey, L. Gustavsson, Energy savings and overheating risk of deep energy renovation of a
multi-storey residential building in a cold climate under climate change, Energy, 202 (2020) 117578.
[2] M.K.H. Rabaia, M.A. Abdelkareem, E.T. Sayed, K. Elsaid, K.-J. Chae, T. Wilberforce, A.G. Olabi,
Environmental impacts of solar energy systems: A review, Science of The Total Environment, 754 (2021)
141989.
[3] M. Mahmoud, M. Ramadan, A.-G. Olabi, K. Pullen, S. Naher, A review of mechanical energy storage
systems combined with wind and solar applications, Energy Conversion and Management, 210 (2020)
112670.
[4] A.G. Olabi, M. Mahmoud, B. Soudan, T. Wilberforce, M. Ramadan, Geothermal based hybrid energy
systems, toward eco-friendly energy approaches, Renewable Energy, 147 (2020) 2003-2012.
[5] H. Barthelemy, M. Weber, F. Barbier, Hydrogen storage: Recent improvements and industrial
perspectives, International Journal of Hydrogen Energy, 42 (2017) 7254-7262.
[6] J. Ogden, A.M. Jaffe, D. Scheitrum, Z. McDonald, M. Miller, Natural gas as a bridge to hydrogen
transportation fuel: Insights from the literature, Energy Policy, 115 (2018) 317-329.
[7] D. Fátay, Á. Révész, T. Spassov, Particle size and catalytic effect on the dehydriding of MgH2, Journal of
Alloys and Compounds, 399 (2005) 237-241.

of
[8] K.T. Møller, T.R. Jensen, E. Akiba, H.-w. Li, Hydrogen - A sustainable energy carrier, Progress in Natural
Science: Materials International, 27 (2017) 34-40.

ro
[9] M. Jafarzadehp, A.R. Abbasi, Application of Metal-Organic Frameworks (MOFs) for Hydrogen Storage,
Nanomaterials in Energy Devices, CRC Press, 2017, pp. 182-217.

-p
[10] Y. Honarpazhouh, F.R. Astaraei, H.R. Naderi, O. Tavakoli, Electrochemical hydrogen storage in Pd-
coated porous silicon/graphene oxide, International Journal of Hydrogen Energy, 41 (2016) 12175-12182.
re
[11] P. Kale, A.C. Gangal, R. Edla, P. Sharma, Investigation of hydrogen storage behavior of silicon
nanoparticles, International Journal of Hydrogen Energy, 37 (2012) 3741-3747.
lP

[12] M. Boaks, P.J. Schubert, Kinetics of hydrogen storage on catalytically-modified porous silicon, Journal
of Catalysis, 371 (2019) 81-87.
[13] B. Gelloz, Photoluminescence of Porous Silicon, in: L. Canham (Ed.) Handbook of Porous Silicon,
na

Springer International Publishing, Cham, 2014, pp. 307-320.

[14] B. Lawrence, N. Alagumanikumaran, N. Prithivikumaran, N. Jeyakumaran, V. Ramadas, B. Natarajan,
Effect of surface modification on the porous silicon infiltrated with biomolecules, Applied Surface Science,
ur

264 (2013) 767-771.

[15] P. Sharma, X. Sun, G. Parish, A. Keating, Optimising porous silicon electrical properties for thermal
Jo

sensing applications, Microporous and Mesoporous Materials, 312 (2021) 110767.

[16] E. Davoodi, H. Montazerian, R. Haghniaz, A. Rashidi, S. Ahadian, A. Sheikhi, J. Chen, A. Khademhosseini,
A.S. Milani, M. Hoorfar, E. Toyserkani, 3D-Printed Ultra-Robust Surface-Doped Porous Silicone Sensors for
Wearable Biomonitoring, ACS Nano, 14 (2020) 1520-1532.
[17] K.A. Khalaph, Z.J. Shanan, F. Mustafa Al-Attar, A.N. Abd, A. Mashot Jafar, Fabrication and investigation
of hybrid Perovskite solar cells based on porous silicon, Materials Today: Proceedings, 20 (2020) 605-610.
[18] V. Lysenko, F. Bidault, S. Alekseev, V. Zaitsev, D. Barbier, C. Turpin, F. Geobaldo, P. Rivolo, E. Garrone,
Study of Porous Silicon Nanostructures as Hydrogen Reservoirs, The Journal of Physical Chemistry B, 109
(2005) 19711-19718.
[19] A. Loni, Porous Silicon Formation by Anodization, in: L. Canham (Ed.) Handbook of Porous Silicon,
Springer International Publishing, Cham, 2014, pp. 11-22.
[20] N.H.H. Abu Bakar, A. Ridzwan, W.L. Tan, M. Abu Bakar, N.A. Sabri, Facile preparation of porous silicon
from cost-wise silicon powder as effective catalyst for reduction of p-nitrophenol, Materials Chemistry and
Physics, 232 (2019) 387-392.
[21] X. Zhang, M. Huang, C. Yang, G. Dai, J. Huang, Fabrication of porous Si/nitrogen doped carbon
composite and its enhanced lithium storage capability, Materials Chemistry and Physics, 201 (2017) 302-
310.
[22] J. Sun, J. Li, B. Ban, J. Shi, Q. Wang, J. Chen, A simple method to fabricate size and porosity tunable Si
by Al–Si alloy as lithium ion battery anode material, Electrochimica Acta, 345 (2020) 136242.
[23] H. Saitoh, A. Machida, Y. Katayama, K. Aoki, Formation and decomposition of AlH3 in the aluminum-
hydrogen system, Applied Physics Letters, 93 (2008) 151918.
[24] D.P. Broom, C.J. Webb, G.S. Fanourgakis, G.E. Froudakis, P.N. Trikalitis, M. Hirscher, Concepts for
improving hydrogen storage in nanoporous materials, International Journal of Hydrogen Energy, 44 (2019)
7768-7779.
[25] V. Lysenko, J. Vitiello, B. Remaki, D. Barbier, V.J.A.S.S. Skryshevsky, Nanoscale morphology dependent
hydrogen coverage of meso-porous silicon, Applied Surface Science, 230 (2004) 425-430.
[26] P. Gupta, V. Colvin, S. George, Hydrogen desorption kinetics from monohydride and dihydride species
on silicon surfaces, Phys. Rev. B, 37 (1988) 8234.
[27] H. Nishihara, F. Ohtake, A. Castro-Muñiz, H. Itoi, M. Ito, Y. Hayasaka, J. Maruyama, J.N. Kondo, R.
Osuga, T. Kyotani, Enhanced hydrogen chemisorption and spillover on non-metallic nickel
subnanoclusters, Journal of Materials Chemistry A, 6 (2018) 12523-12531.
[28] S.-J. Park, S.-Y. Lee, Hydrogen storage behaviors of platinum-supported multi-walled carbon
nanotubes, International Journal of Hydrogen Energy, 35 (2010) 13048-13054.

of
[29] H. Takagi, H. Hatori, Y. Soneda, N. Yoshizawa, Y. Yamada, Adsorptive hydrogen storage in carbon and
porous materials, Materials Science and Engineering: B, 108 (2004) 143-147.

ro
[30] S.E. Bambalaza, H.W. Langmi, R. Mokaya, N.M. Musyoka, L.E. Khotseng, Experimental Demonstration
of Dynamic Temperature-Dependent Behavior of UiO-66 Metal–Organic Framework: Compaction of

-p
Hydroxylated and Dehydroxylated Forms of UiO-66 for High-Pressure Hydrogen Storage, ACS Applied
Materials & Interfaces, 12 (2020) 24883-24894.
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Highlights:

First study on porous silicon powder fabricated from Al-Si alloy powder for hydrogen storage.

Introduce a novel acid double etching method to increase its hydrogen storage capacity of Al-Si
alloy powder.

Both effects of Ni catalyst spillover effect and acid double etching on the porous silicon powder
have been studied.

This study provides strong evidence on the potential for low-cost porous silicon powder from Al-Si
alloy for hydrogen storage application.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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