Sustainable Horizons 9 (2024) 100079

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Sustainable Horizons
journal homepage: www.elsevier.com/locate/horiz

Critical Reviews

Hydrogen from waste metals: Recent progress, production techniques,

purification, challenges, and applications
Mohammad Ali Abdelkareem a, b, c, *, Mohamad Ayoub a, b, Rami Issa Al Najada a, Abdul
Hai Alami a, b, A.G. Olabi a, b
a
Sustainable and Renewable Energy Engineering Deptartment, University of Sharjah, Sharjah 27272, United Arab Emirates
b
Sustainable Energy & Power Systems Research Centre, RISE, University of Sharjah, Sharjah 27272, United Arab Emirates
c
Chemical Engineering Department, Minia University, Elminia, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, hydrogen production from metals, specifically metal waste (scrap metal), is discussed based on a
Hydrogen literature review of recently published research. Hydrogen production from scrap aluminum, magnesium and
Waste metal zinc is broken down into details, providing context on their overall processes, and advantages and disadvantages.
Hydrogen production
Moreover, conventional hydrogen production methods are presented, to provide a baseline for comparison. It
Hydrogen applications
Hydrogen purification
was shown that hydrogen production from metal waste had a 70 % hydrogen yield from magnesium due to its
high specific energy density, which gives magnesium an edge in hydrogen production within the context of scrap
metal. Additonally, aluminum-based alloy powders showed a hydrogen yield of ~98 %, whereas zinc-based
hydrogen production showed relatively low conversion rates bordering ~20 %. Furthermore, purification
techniques that enhance the quality of the produced hydrogen, such as pressure swing adsorption, cryogenic
distillation and novel membrane-based, which have shown performnace enhancements compared to their pre­
decessors, are discussed. Finally, economic, technical and social limitations that hinder the progression of
hydrogen production from metal waste, as well as the applications and future perspectives, which include on-
board hydrogen production and combustion, fuel cells and the chemical industry, are showcased.

1. Introduction
The scarcity of fossil fuel has been felt on a global scale, which
directed an imminent search for alternatives, to attenuate corresponding
effects on industries and sectors that are heavily dependent on it (Zheng
et al., 2022). A sparked interest in renewable energy technologies has
been propelling the development of the renewable energy sector for
decades and has achieved tangible results in terms of the global
renewable energy installed capacity (Allam et al., 2022). This also led to
an optimization of renewable energy operation to remedy conventional
intermittency-related issues. For instance, according to the International
Energy Agency (IEA) (International Energy & Agency, 2022) and as seen
from Fig. 1, photovoltaic (PV), wind, hydro, and bio energy installed
capacities have increased drastically in the short period between 2019
and 2021. Where it is shown to have exceeded installment expectations
in 2021, almost skimming 300 GW, with the highest shares between PV
and wind at 150 GW and 100 GW, respectively.
On the other hand, the increase in capacity of various renewable
energy installations (Md Khairi et al., 2022) and intermittency proper­
ties, need a parallel increase and development of energy storage systems
that can accommodate corresponding demands (Alami, 2020c). There
are various energy storage systems that have been utilized in renewable
energy installations, which are categorized into mechanical, thermal,
chemical, electrical, and electrochemical. Table 1 summarizes these
energy storage technologies and showcases their advantages and
disadvantages.
Based on Table 1 chemical energy storage through a hydrogen me­
dium is a competitive candidate within the wide arsenal of energy
storage technologies. Moreover, with the rapid transition towards a
green economy, it would only make sense to further peruse and improve
this technology. Which is why hydrogen has been on the rise recently,
given its high energy density, relatively low cost (depending on the
mean of production), and versatile storage technologies. Most of the
hydrogen production is done via steam methane reforming, a technique
where hydrocarbons are reacted with steam to produce hydrogen, which
is counteractive in the context of global warming attenuation, due to the

* Corresponding author.
E-mail address: mabdulkareem@sharjah.ac.ae (M.A. Abdelkareem).

https://doi.org/10.1016/j.horiz.2023.100079
Received 9 September 2023; Received in revised form 13 October 2023; Accepted 23 October 2023
Available online 31 December 2023
2772-7378/© 2023 The Author(s). Published by Elsevier B.V. on behalf of Southern University of Science and Technology. This is an open access article under the
CC BY license (http://creativecommons.org/licenses/by/4.0/).
M.A. Abdelkareem et al.
undesirable emissions that accompany this process. However, this is
compensated due to the low cost of the produced hydrogen. Moreover,
electrolysis, where water is split into hydrogen and oxygen by passing an
electric current through it (preferably from a renewable source), has
been on the rise, and is a great source for high quality oxygen production
(Aljaghoub et al., 2023). On the contrary, its progression is hindered due
to commercialization and scaling up-related complications. Although
electrolysis-produced hydrogen is free of emissions and undesirable
byproducts, the cost of the produced hydrogen from this technique
impedes its commercialization. Fig. 2. lists conventional hydrogen
production techniques. Due to the limitations that have held back the
progression of conventional hydrogen production methods, alternative
means had to be explored.
Hydrogen production from metal combines advantages from its
predecessor processes, such as low cost and emission-free hydrogen
production, with an ease of scalability according to the targeted appli­
cation. The process of hydrogen production from metal involves reacting
different metals with water at different external conditions to achieve a
forward reaction that would produce hydrogen. One of the drawbacks of
this method of hydrogen production is that some of the abundant metals
that would be suitable for this type of process require stringent external
energy inputs to reach a certain reaction activation temperature. On the
other hand, utilizing scrap metal, instead of pristine raw metal, which is
better utilized in other applications and industries, reduces the cost and
the energy input of the overall hydrogen production process.
This work aims to highlight the importance of repurposing scrap
metal and utilizing it in hydrogen production. The current literature falls
short on reporting on the novelty and opportunity of hydrogen pro­
duction from scrap metal, a what could be wasted resource. Various
conventional hydrogen production techniques are summarized to
showcase their current limitations and areas where they lack superior­
ity. It is revealed that there is a wide spectrum of scrap metal that can be
utilized for hydrogen production, as well as secondary techniques that
can maximize the potential of this method of hydrogen production such
as ball-milling. Moreover, this work sheds light on hydrogen purification
techniques, limitations, applications, and future prospects of hydrogen
production from scrap metal.
2. Conventional hydrogen production means
2.1. Steam methane reforming
Steam methane reforming (SMR) is known as the process of reacting
natural gas or methane with water vapor to produce syngas. Generally,
the syngas components are carbon monoxide and hydrogen gas (Xu
et al., 2018b). In addition, the reaction takes place at high temperatures
of around 700–1000 ◦ C (Martino et al., 2021). The process includes an
initial step of reacting methane (a hydrocarbon) with steam to produce
syngas, followed by a secondary water gas shift reaction to produce
Fig. 1. Installed renewable energy systems’ capacity - visual representation adapted from (International Energy & Agency, 2022).
2
Sustainable Horizons 9 (2024) 100079
extra hydrogen. The SMR reactions are shown in Eqs. (1–3) (Ji and
Wang, 2021a). The byproduct of the water gas shift reaction is carbon
dioxide, which can be extracted by technologies such as pressure swing
adsorption (PSA) (Shi et al., 2018), cryogenic distillation and
membrane-based carbon capture.
CH4 + H2 O → CO + 3H2 (1)
CO + H2 O →CO2 + H2 (2)
Total Reaction : CH4 + 2H2 O→CO2 + 4H2 (3)
SMR is currently one of the most developed and cost-effective
hydrogen production methods available (El-Emam and Özcan, 2019).
Moreover, SMR is an endothermic reaction, which means the process
requires external energy input to occur. While the operating tempera­
tures of SMR are workable and are used in the industry, working with
lower temperatures would harbor a convenient operation and a faster
and smoother startup.
2.2. Dry methane reforming
Dry methane reforming is a chemical process that involves reacting
methane with carbon dioxide to produce hydrogen and carbon monox­
ide (Szima and Cormos, 2019). This process is not as common as steam
methane reforming, as it is used in the context of applications that de­
mand carbon monoxide -rich syngas (Wang and Economides, 2009).
Moreover, given the stability of both methane and carbon dioxide with
high dissociation energies, the dry methane process is considered to be
extremely endothermic. A conventional dry methane process requires
high temperatures reaching 730 ◦ C at atmospheric pressure. It is worthy
to note that the ratio between methane and carbon dioxide heavily in­
fluences the production of the corresponding hydrogen and carbon
monoxide, where an ideal ratio of 1 is usually desired (Li et al., 2021).
2.3. Water electrolysis
Electrolysis is a rising hydrogen production technology in terms of
research and development, however it did not claim the same industrial
success as SMR due to its cost, and dependence on the variable output of
renewable energy sources. Electrolysis requires a supply of direct elec­
tric current feed from a renewable energy source to an electrolyzer to
separate water molecules into hydrogen and oxygen. Water electrolysis
is a viable choice for small hydrogen production applications, as elec­
trolysis is more scalable than SMR. Operating conditions and electrolysis
systems differ based on the electrolyzer type. Common electrolyzers
include proton exchange membranes (PEM) (Burton et al., 2021),
alkaline electrolysis (AEL) (Brauns and Turek, 2020), and anion ex­
change membranes (AEM) (Li and Baek, 2021). PEM and AEL are the
most widely available types of electrolyzers.. According to Pinsky et al.
M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

(2020), the Gibbs free energy required to operate an electrolyzer in
standard temperature and pressure is 237.1 kJ/mol. Compared to other
hydrogen production methods, electrolysis can be very efficient, with
working efficiencies between 67 and 84 % for PEM electrolyzers (Ji and
Wang, 2021b). However, electrolysis is still susceptible to the drawback
of their respective energy sources, such as the limited capacity factor of
solar and wind resources, high capital costs, and the physical limitations
that accompany electrolyzers in general.
2.4. Biological hydrogen production
Hydrogen that is produced or obtained from biological means is
known as biohydrogen. The interest in research in biohydrogen pro­
duction has increased drastically, which is explained by the promise of
biohydrogen being one of the most environmentally friendly means of
hydrogen production, as well as the potential to be highly cost effective
(Chandrasekhar et al., 2020; Mona et al., 2020; Tian et al., 2019). The
three most studied methods of biohydrogen production reported in
literature are biophotolysis, fermentation, and the usage of microbial
electrolysis cells (MECs).
Biophotolysis, such as shown in Fig. 3, is categorized into two types:
Direct (DbP) and indirect biophotolysis (iDbP). In DbP, the organisms
can produce hydrogen directly from water provided sunlight. Some of
the well-studied organisms that can perform direct biophotolysis include
cyanobacteria and green algae (Ghiasian, 2019; Javed et al., 2022;
Pathy et al., 2022). On the other hand, iDbP utilizes a multi-step process
to produce biohydrogen. In the initial step, the organism, which can be
microalgae or cyanobacteria for instance, uses photosynthesis to pro­
duce organic compounds and oxygen molecules. Afterwards, organic
materials are broken down into hydrogen and carbon dioxide, and some
soluble metabolites (Ferraren-De Cagalitan and Abundo, 2021; Kossal­
bayev et al., 2020).
Fermentation, which is another technique for bio-based hydrogen
production, also has two methods of operation: photofermentation and
dark fermentation. There are also reports in literature of the usage of
combined photo-and-dark fermentation (Cai et al., 2019; Das and
Basak, 2022). Both types rely on the fermentation of an organic sub­
strate, which could be acquired from biomass or waste resources.
However, dark fermentation does not rely on light energy, which gives it
several advantages over light dependent biohydrogen production. Mi­
crobial electrolysis cells work vaguely like water electrolyzers, but
instead of oxidizing water at the anode, MECs oxidize organic com­
pounds (Rousseau et al., 2020).
Although biological hydrogen production seems to resolve numerous

Table 1
Energy storage technologies comparison.
Energy Storage Mechanism Advantages Disadvantages Cost Reference

Mechanical Pumped Cost Effective Expensive ~242 $/kWh (Alami, 2020d; Berrada and Loudiyi, 2016;
Hydro High round-trip efficiency Time-consuming to get it Bowen et al., 2021)
(~81 %) operating
Long life time ~60 years Requires a site with water
elevation
Compressed Fast response time Requires underground/ or ~126$/kWh (Alami et al., 2022b; Alami, 2020a, 2022;
Air High efficiency ~50 % aboveground reservoirs Bowen et al., 2021)
High energy Density
Flywheel Low maintenance (over Safety hazard (high ~11,500 $/kWh (Alami, 2020b, 2022; Bowen et al., 2021)
100,000 full depth discharge) rotation speeds)
Fast response time Preferred to be operated in
a vacuum environment
Buoyancy Easily Scalable Relatively low energy 45.17 $/kWh (investment (Alami et al., 2023)
Low footprint output (unless scaled up) cost)
Rapid energy discharge Requires high water depths
Can be coupled with pre-
existing wind-energy systems
Thermal Sensible Heat Simplest heat storage system Significant heat (Energy ~20$/kWh (Alami, 2020e; Ann Cruickshank and
Versatility of storage mediums loss) to ambient Baldwin, 2016; Tetteh et al., 2021; Wang
High energy density for a environment et al., 2016)
small range of temperature
variation
Latent Heat High energy storage in a Corrosiveness ~12–50 $/kWh (Alami, 2020e; Belyakov, 2019; Elfeky
narrow temperature range Supercooling (reducing et al., 2022; Ramos et al., 2022)
High storage density storage capacity)
Undesired solidification
Instability
Chemical Hydrogen Very high energy density Transportation of Compressed Gas hydrogen (Reuß et al., 2021), (Zivar et al., 2021), (
~8.8 MJ/kg compressed gas hydrogen storage (Underground) (~2 Parks et al., 2020; Wulf et al., 2018)
Negligible environmental tanks $/kg)
impact Safety hazards
99 % energy conversion
efficiency
Electrochemical Batteries Power quality sensitive loads Loss of charge over time ~200 $/kWh (Breeze, 2018; Šimić et al., 2021; Wesley
Not suitable for long term Cole et al., 2021)
usage
Flow Scalability Low energy density ~140$/kWh (Abdelkareem et al., 2023; Arabkoohsar,
Batteries No effect for deep discharge Low charge and discharge 2021;Liu et al., 2022; Šimić et al., 2021;
cycles rates Williamson et al., 2011)
Low self discharge
Low cost compared to
conventional batteries
Fuel Cells High energy efficiency Need for expensive ~8000–15,000 $/kWh (Coralli et al., 2019; Godula-Jopek and
Low pollutant emissions catalysts (Capital Cost) Westenberger, 2022; Khezri et al., 2022)
Low noise levels Catalyst degradation
Scalability Electrolyte poisoning
Low power density

3
M.A. Abdelkareem et al.
Fig. 2. Hydrogen production means.
Fig. 3. Direct biophotolysis process representation.
issues regarding the production of clean, carbon-neutral hydrogen, the
technology still has several shortcomings. A common drawback is the
low hydrogen yield and conversion efficiencies in many biohydrogen
production setups (Jayachandran et al., 2022; Ramprakash et al., 2022).
A summary and a comparison between different conventional hydrogen
produciton techniques in terms of advantages and disadvantages is
presented in Table 2.
3. Hydrogen generation from waste
3.1. Hydrogen production from plant-based waste biomass and municipal
solid waste
Waste in all of its forms is a burden in terms of space and disposal.
Moreover, landfill carbon footprints and emissions are issues that should
be addressed (Carvalho et al., 2019; Tansel, 2023; Zhou et al., 2022).
Mashentsev et al. (Mashentsev et al., 2021), reported that over young
landfill bodies in the city of Moscow the concentration of methane in the
Table 2
Hydrogen production means summary - advantages and disadvantages.
Method of Process
Production
Steam Methane Steam reaction with methane – Produces hydrogen and
Reforming carbon monoxide
Water gas shift – Produces carbon dioxide and
hydrogen
Dry Methane Reacting methane with carbon dioxide to produce
Reforming hydrogen and carbon monoxide
Water Electrolysis Water molecules are split into hydrogen and oxygen
Biological Microorganisms convert water directly into hydrogen
and oxygen when exposed to sunlight
Sustainable Horizons 9 (2024) 100079
soil was between 8 and 16 ppm, which led to a considerable amount of
methane emissions reaching the city. A study by Rosa and Mazzotti
(2022), evaluated the potential of hydrogen usage for bioenergy with
carbon capture and storage (BECCS) in Europe. It was concluded that the
proposed BECCS supply chain structure would generate 12.5 MT of
hydrogen per year. Interestingly, this is more than Europe’s entire
hydrogen demand, as it was reported that the total usage is around 10
MT H2.
Bundhoo (2019), estimated the potential of biological hydrogen
production using dark fermentation on a global scale. Out of the many
crop residues studied, such as sugarcane tops, rice straw, husk, soybean
straw, it was determined that the highest potential yield is achievable by
dark fermentation of rice straw, which would produce 58,002 Mm3/year
of biohydrogen. Additional stages of the process, such as a pre-treatment
step and implementing an anaerobic digestion process (Assis and Gon­
çalves, 2022; Cremonez et al., 2021), would be better in terms of eco­
nomic feasibility, as well as the hydrogen production volume and energy
potential.
Around 2 BT of municipal solid waste (MSW) was introduced to the
environment in 2016, according to Kaza et al. (2018). Moreover,
research shows that the numerous trace gases that are emitted from
municipal solid waste landfills are known to be toxic (Duan et al., 2021).
Therefore, efforts in utilizing MSW as a feedstock for hydrogen pro­
duction are increasing. Zheng et al. (2018), studied a drop tube reactor
(DTR) to produce hydrogen and syngas using municipal solid waste
gasification by reusing carbon dioxide. It was reported that under
CO2/steam ratio of 2.5, the carbon dioxide conversion efficiency is
slightly above 50 %, and a maximum hydrogen molar yield of 18.82
mol/kg of municipal solid waste. It was also indicated that a higher
CO2/steam ratio in the range of 0.5 to 2.5 correlates to a higher
hydrogen molar yield. Salkuyeh et al. (2018), conducted a
techno-economic analysis and a life cycle assessment (LCA) on hydrogen
production from various biomass gasification methods. It was shown
that entrained flow gasification was 11 % more thermally efficient than
fluidized bed gasification. Moreover, the LCA indicated that greenhouse
Advantages Disadvantages
Mature Hydrogen production technology Endothermic reaction - requires working at very
Cost-effective high temperatures.
Undesirable Emissionss
Used in the context of applications that The stability of both methane and carbon dioxide
demand carbon monoxide -rich syngas with high dissociation energies
The dry methane process is considered to be
extremely endothermic
Emission-free hydrogen production Limited capacity factor of solar and wind
resources
High capital costs
Physical limitations that accompany
electrolyzers
Production of clean, carbon-neutral hydrogen Low hydrogen yield
Low conversion efficiencies
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M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

gas emissions are indeed possible byproducts in all studied such as Magnesium (Mg) and Aluminum (Al), which require external
biomass-based selections. Studies have also been made on utilizing palm inputs that provide what is known as the reaction activation energy, to
oil mill effluent (POME) to produce clean hydrogen gas (Hossain et al., trigger the metal-water reaction, which is governed by the formula
2022; Kadier et al., 2022; Khongkliang et al., 2019). shown in Eq. (4) Furthermore, the third category harbors metals such as
iron (Fe), zinc (Zn) and titanium (Ti) that exclusively react with water
vapor at a very high temperature, that follow the reaction stated in Eq.
3.2. Hydrogen production from wastewater
(5).
As more freshwater resources around the globe get polluted, the need n
Metal + nH2O →Metaln+ + n(OH)− + H2 (4)
for wastewater treatment is drastically increased. This issue, paired with 2
existing global warming concerns, makes hydrogen production via
Where n is the valence state of the metal.
wastewater treatment a potential candidate for clean waste-to-energy
projects (Qadir et al., 2020; Senfter et al., 2021; Sharmila et al., nMetal + mH2 O→Mn Om + mH2 (5)
2020). Researchers have spent valuable time in achieving innovative
These reactions occur through a series of steps. First, the water
results to purify wastewater and utilize waste to produce hydrogen gas
molecule diffuses through solution medium that creates a contact be­
(Park et al., 2023). Islam et al. (2021), compared several hydrogen
tween water and the metal species. The water molecule is then adsorbed
production processes using wastewater. Five technologies of wastewater
onto the metal surface, where the reaction occurs at the metal (solid)/
hydrogen production were compared: photofermentation, photo­
water (liquid interface), to produce metal oxide and hydrogen, which
catalysis, dark fermentation, microbial photo electrochemical processes
subsequently diffuses into the solution. This begs a question on the
and microbial electrolysis cells (MECs). It was indicated that MECs
possibility of using metals, especially metal waste sourced from different
provide a favorable solution to wastewater treatment, due to their
industries, to produce high grade hydrogen for energy production pur­
relatively high H2 production yield, which is around 3.6 to 7.9 L/L/d
poses, such as shown in the flowchart in Fig. 4. Moreover, how does
and the possibility of removing 80 % of the chemical oxygen demand
hydrogen production from metal wastes compare to other forms of
from influent streams.
hydrogen production from different waste feedstocks. Table 3 Shows a
Additionally, a study conducted by Aydin et al. (2021), reviewed
comparison between different hydrogen production methods from
several hydrogen production technologies from wastewater treatment.
various waste sources. Yavor et al. (2015), evaluated the reactivity of
The study includes similar technologies listed in (Islam et al., 2021), in
several metal powders in water. The study concluded that magnesium
addition to other processes such as reverse electrodialysis and super­
and aluminum yielded the most amounts of hydrogen gas in comparison
critical water gasification (Higa et al., 2019; Yan et al., 2020). Electro­
with other studied metals at 200 ◦ C, with 921 cm3/g and 1145 cm3/g for
dialysis utilizes an ion exchange membrane to separate the ions under
magnesium and aluminum, respectively. The study also found that some
potential electric difference (Al-Amshawee et al., 2020). In some cases,
metals do not respond effectively to temperature increments, such as
it was reported that syngas produced by supercritical water gasification
iron and nickel. Fig. 5. shows the hydrogen yield from different metals at
of wastewater is 55 % hydrogen (Ibrahim and Akilli, 2019; Gong et al.,
different temperatures, data adapted from Xu and Liu (2019a), Yavor
2019). Although supercritical water gasification and electrodialysis are
et al. (2015).
arguably great alternatives, they are accompanied with their respective
Research has been conducted on different metals for clean hydrogen
disadvantages, such as purity and scalability issues, as well as the
production. Buryakovskaya et al. (2019), studied the hydrogen pro­
maturity of the technologies involved, as most electrodialysis technol­
duction capability of magnesium and some of magnesium-based mate­
ogies are still under research and development (Aydin et al., 2021).
rials, when added to aqueous solutions of aluminum and magnesium
chloride. The experiment was studied at low temperatures of − 40 ◦ C to
4. Hydrogen production from metal waste
0 ◦ C. It appears that the aluminum chloride solution performed better
than its counterpart magnesium chloride, with hydrogen yields of 850
Hydrogen generation from metal can be subdivided into 3 categories.
mL and 622 mL for aluminum chloride and magnesium chloride,
The first category being metals that inherently react with water (under
respectively. Furthermore, the effect of temperature, AlCl3 concentra­
ambient conditions), such as Lithium (Li), sodium (Na), potassium (K),
tion, and mechanochemical treatment, were investigated. All three
rubidium (Rb), cesium (Cs) and francium (Fr). The second being metals

Fig. 4. Hydrogen production from waste metal flowchart.

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M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

Table 3
Hydrogen production from different waste sources.
Method of Input Details Advantages Disadvantages and Ref
waste hydrogen improvements
production

Biomass: plant- Plant residue examples: Biomass can be utilized by biological Large pool of choices of Not easily scalable, low (Bundhoo, 2019; Rosa
based, wheat straw, sugarcane means such as fermentation/ inputs, has the potential to hydrogen yield in volume, and Mazzotti, 2022;
municipal tops, corn straw biophotolysis, or other biomass be cost effective gasification requires high Salkuyeh et al., 2018)
solid waste Municipal solid waste treatment means such as gasification temperature and pressure
rejected by civilians and and pyrolysis
industries
Plastic Waste Plastic Waste in Hydrogen can be produced by Shown to reduce cost and High temperature and (Al-Qadri et al., 2022;
environment, such as gasification alone or paired with CO2 emissions, great to pressure for gasification, Jeong et al., 2020;
polypropylene and existing SMR projects, pyrolysis and reduce plastic pollution in efficiencies could be Lazzarotto et al., 2020;
polyethylene, or HDPE plasma, or catalytic reforming the environment improved, high influence Weiland et al., 2021;
from catalysts Aminu et al., 2022)
Wastewater Wastewater from Utilizing biological methods such as Can be inexpensive, No technologies ready for (Aydin et al., 2021;
industries or polluted photofermentation, MECs, dark feedstock in abundance, industry, numerous Qyyum et al., 2022;
freshwater fermentation contributes to clean water parameters affecting Sharmila et al., 2020)
bodies performance such as
temperature, nutrients, pH
Metals Waste resource: Through chemical hydrogen Low cost, environmentally Control of reaction and (Ratnakar et al., 2021;
recycled scrap production, by reacting with water or positive, wide range of activity, metal may require Xu and Liu, 2019a)
acidic/basic solutions, hydrolysis of potential inputs, good treatment, various efficiency
metals and metal oxides hydrogen volume yield results

abundance of magnesium, like several other metals in this context, al­

Fig. 5. Total yield of hydrogen gas for a selection of metals at different
temperatures.
experiments enhanced the evolution of hydrogen production. Higher
temperatures and aluminum chloride concentrations, and ball-milled
magnesium metals produced additional hydrogen in a more efficient
manner. It is worthy to mention that the mechanochemical addition of
nickel to the magnesium sample enhanced the evolution rate of
hydrogen, to produce a maximum of 120 ml/(min⋅gMg). In the following
sections, hydrogen production from magnesium, aluminum, zinc and
other kinds of metals that have been found in literature are discussed.
4.1. Hydrogen from magnesium metal
Magnesium is highly reactive on its own. When magnesium is
exposed to water, a reaction is initiated, and hydrogen and magnesium
hydroxide are formed abiding by the following reaction formula:
(Kantürk Figen and Coşkuner Filiz, 2015):
Mg(s) + 2H2 O(l)→Mg(OH)2 (s) + H2 (g)
The high specific energy density of magnesium (Shah et al., 2021)
gives it a great potential in hydrogen production. Moreover, the
lows for cheaper production of hydrogen, with fast reaction rates and
minimal environmental impact. Compared to other metals such as
aluminum, the passivating layer manifested in the form of magnesium
oxide, is way thinner than that of aluminum, which corresponds to the
reduction in the activation barrier. However, the corrosion rate of
magnesium in ambient conditions does pose a challenge in related
processes. Several studies have shown interest in using magnesium and
its alloys to produce hydrogen gas. Al Bacha et al. (2021), ball milled
magnesium powder with nickel and graphite in an argon atmosphere,
which was used as the primary reaction reagent. Different compositions
of the solution that reacts with the powder were tested, as well as the
effect of temperature on the reaction. Lowering the pH of the hydrolysis
solution decreased the activation energy of the reaction. In addition, the
reactions tested were all completed in less than 5 min, except for the
solution at 0 ◦ C. Buryakovskaya et al. (2022), ball milled a
magnesium-aluminum scrap powder as a reagent. The powders were
tested with no additives, with KCl, and with Wood’s alloy. The powder
with the Wood’s alloy had the highest percentage of hydrogen yield,
which was around 73.5 %, while the powder with no additives was
slightly lower, harboring a hydrogen yield close to 70.6 %. It was
concluded that the particles’ shape and defects in its crystal lattice can
alter the kinetics of the hydrogen production reaction.
In addition to sole magnesium, alloys of magnesium metal could be
used for this reaction. Al bacha et al. (2019), implemented the usage of
WE43 magnesium alloy for the production of hydrogen by hydrolysis.
The effect of ball milling time with carbon and nickel was studied.
Pre-milling of the alloy was deemed vital for the activation of the
powder. Compared to Ni, carbon provided better reaction performance.
The timing order of the additives also affected the reaction. The mixture
created by adding Ni and C each at a stage has the best hydrolysis po­
tential, reaching its maximum yield in around 9 min.
Altering the ball milling technique has also dictated a change in the
hydrolysis performance. Milling under argon atmosphere has contrib­
uted to a better hydrolysis performance compared to milling under H2
atmosphere. In addition, the milling device has significantly changed the
time of material preparation. The Fritsch Pulverisette 6 (P6) ball mill
took one-tenth of the time of the Australian Uni-Ball-II (UB) to prepare a
sample that contained the same specific amount of MgH2 Al Bacha et al.
(6) (2019).
Xiao et al. (2019), studied the hydrolysis of different Mg-based metal
alloys in seawater and methanol. Alloys were prepared using

6
M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

magnesium ball-milled with different low melting point metals: Zn, Sn, worthy to note that aluminum water reaction results in net zero
Bi, and In. Mg-10 %In alloy with the highest hydrogen generation rate of greenhouse gas emissions, as well as posing little to no safety hazards in
7.4 mL/g/s and the highest hydrogen conversion rate of 93 % at 30 ◦ C in the context of storage and transportation. In addition, the aluminum-
saline water, exhibits the greatest hydrolysis performance among all the water reaction is exothermic, and the aluminum hydroxide can be
samples. As with methanol, the Mg-10 %In alloy reacts faster in meth­ converted to Al2O3, to which metallic aluminum can be extracted (Liu
anol than water, due to the methanol having higher proton activity. The et al., 2015). The reaction can also take place in seawater and deionized
possibility of using dioctyl sebacate as a coating agent to prevent the water (du Preez and Bessarabov, 2021). However, a challenge is present
activated powder from deactivation was also investigated. It was when aluminum is to be reacted with water, as pre-treatment of the
concluded that the dioctyl sebacate is efficient at preventing the powder metal must be done to eliminate the oxide layer on its surface. Numerous
from oxidizing. researchers have proposed and successfully tested multiple methods to
It can be seen that the magnesium performance in hydrolysis re­ treat aluminum for hydrogen production. Common methods that were
actions indicates that it can be efficiently utilized for clean, low envi­ present in literature include mechanical treatment by ball milling
ronmental impact hydrogen production. A summary of the studied (Davies et al., 2022b), amalgamation (Setiani et al., 2018), submersion
literature in that regard is provided in Table 4. in acidic or alkaline media (Xu et al., 2018a; Yang et al., 2018). Amal­
gamation is usually unfavorable due to the usage of harmful substances..
4.2. Hydrogen from aluminum metal A more conventional method of aluminum activation that showed great
potential was the activation by creating a gallium-indium eutectic
Similar to magnesium, aluminum has the ability to readily react with (Meroueh et al., 2020; Nizovskii et al., 2020; Slocum et al., 2020). du
water. However, due to the aluminum oxide passivation layer deposited Preez and Bessarabov (du Preez and Bessarabov, 2021) compared mul­
on its surface. The possible reactions of aluminum and water are as seen tiple aluminum activation technologies, in terms of electrical efficiency
in the following equations (Godart et al., 2019): and challenges. Another prominent challenge is the recycling of the
formed aluminum hydroxide byproduct. Ongoing research focuses
2Al + 6H2 O →3H2 + 2Al(OH)3 + Q1 (7) heavily on attenuating these challenges to make up for a more efficient
hydrogen production process from aluminum.
2Al + 4H2 O →3H2 + 2AlOOH + Q2 (8) Wang et al. (2021), used gas atomization to prepare an Al-Bi-Zn
composite powder in order to produce hydrogen through hydrolysis.
2Al + 3H2 O →3H2 + Al2 O3 + Q3 (9) The three metals were used from raw high purity (99.9 %) sources and
The high availability of aluminum in the Earth’s crust and in recy­ melted through an induction melting furnace. Then, the powder was
clable materials, as well as its light weight, hands it a great advantage atomized by a high-pressure argon flow, which was recorded to be
when choosing an input metal for the hydrolysis reaction. Moreover, the around 5–8 MPa. According to the findings, Al-12Bi-7 Zn (wt%) powder
high energy density of aluminum corresponds to large amounts of converted at a yield of 98 % with balanced hydrogen production in 280
hydrogen production with minimal aluminum consumption. It is also min at 50 ◦ C. Similar studies had success with hydrolysis with materials
prepared using gas atomization (Chen et al., 2018; Liu et al., 2017).
Table 4
Table 5 summarizes the widely used aluminum activation methods for
Magnesium based hydrogen production. usage in the hydrolysis reaction.
With the high usage of aluminum metal in many industries, many
Study Methods and Findings
Materials
researchers have taken this advantage to utilize waste aluminum to
produce hydrogen through the Al-water reactions (Küp Aylikci et al.,
Al Bacha (al Bacha Ball milling Mg, Ni, - Tested different solution
2021; Yang et al., 2019). Küp Aylikci et al. (2021), used waste aluminum
et al., 2021) and graphite in argon compositions
atmosphere; varied - Lower pH decreased beverage cans and culinary foil to produce hydrogen through an elec­
hydrolysis solution activation energy trolysis system. The waste aluminum was then compared to the results of
pH - Reactions completed in < 5 using pure Al. Waste aluminum resources were pretreated from con­
Different mins (except 0 ◦ C)
taminants and coating materials. Among these sets of parameters were
temperatures tested
Buryakovskaya ( Ball milled Mg-Al - Tested with no additives, KCl,
tested, the 5 V potential with 2 N NaOH solution produced 750 cm3
Buryakovskaya et al., scrap powder and Wood’s alloy hydrogen using 2 g of leftover aluminum can pieces provided the best
2022) - Wood’s alloy yielded highest combination of settings.
H2% (73.5 %) Chen et al. (2018) also utilized waste aluminum to produce
- No additives yielded ~70.6 %
hydrogen, where the effects of temperature, water addition and the re­
H2
- Particle shape/defects affect action aqueous solution were tested. Moreover, the waste gathered
kinetics included a variety of resources, which were beverage cans, door frames,
Al Bacha et al. (al Bacha Used WE43 Mg alloy - Studied ball milling time with wheel hubs and battery cases. The metals were prepared using gas at­
et al., 2019) for hydrolysis. C and Ni omization, with the addition of Bi and Sn. Out of the different waste
Pre-milling vital for - C showed better performance
activation than Ni
studied, door frames converted the most amount of aluminum to
Timing order of - Best yield achieved with hydrogen (93.40 %).
additives affected staged C and Ni Lim et al. (2021) studied the production of hydrogen from powdered
reaction - Max yield in around 9 mins aluminum waste cans. The cans were shredded to a powder using a
Xiao et al. (Xiao et al., Studied hydrolysis of - Prepared alloys with low
medicine blender. Then, the final powder was prepared by ball milling.
2019) Mg-based alloys melting point metals
(Zn, Sn, Bi, In) in - Mg-10 %In alloy had highest The aluminum can powder (3 % Sn–3 % Mg) produced the maximum
seawater and H2 generation rate (7.4 mL/g/ hydrogen volume, which was 660 mL from 0.5 g in 660 s. The product
methanol s) hydrogen could later be used in a methanation process. Yang et al.
- Mg-10 %In alloy had highest (2019), prepared an Al powder for hydrolysis through magnetically
H2 conversion rate (93 %) at
30 ◦ C in saline
grinding waste aluminum cans. One gram of the powder, which was
- Faster reaction in methanol grinded for 40 min, was able to generate slightly less than 1300 mL of
due to higher proton activity hydrogen gas in under 6 min. The hydrolysis is done through an alkaline
- Dioctyl sebacate efficient solution of NaOH, and the concentration of the NaOH was shown to
coating to prevent oxidation
influence the rate and performance of the hydrolysis reaction. The

7
M.A. Abdelkareem et al.
Table 5
Different methods of aluminum activation for hydrogen production.
Method of Input Details
aluminum
activation
Ball milling Aluminum and other Ball milled alloys added metals through
preferred metals fracturing and rewelding into fine powders
Alkaline/acidic Aluminum and a solution A highly basic or acidic medium attacks the
medium of high pH, or low pH oxide layer on the surface of Al, providing a
solution fresh surface for reaction
Eutectic Ga-In Aluminum, Room Aluminum is immersed in the liquid metal and
temperature liquid metal then allowing it to diffuse through the
(RTLM) aluminum creating a eutectic reaction
Gas atomization Aluminum, gas atomizer A high-velocity gas, such as Ar, or air disrupts
the flow of liquid metal, creating a fine powder
utilization of waste aluminum resources has also influenced other re­
searchers to perform efficient hydrolysis reactions (Lim et al., 2020;
Yolcular et al., 2022).
In terms of the process’s impact on the environment, few researchers
have investigated the economic, social, and environmental variables of
using metal waste to produce hydrogen gas. Xu et al. (2019b) performed
a life cycle assessment (LCA) and a SWOT analysis of liquid metal
activated hydrogen production, from exploiting metal waste. The pro­
posed method of hydrogen generation bears 9 times more energy out­
put/input ratio than water electrolysis. In addition, the projected SWOT
analysis serves as a guide for researchers in the field for a more efficient
tackling to the issues. Sopha and Ma’mun (2021), studied the economic
and the environmental feasibility of using aluminum debris as fuel for a
power. Other researchers have implemented LCAs and economic studies
of their own (Alviani et al., 2021; Kumar and Muthukumar, 2020). Some
researchers’ efforts should be noted in studying the thermodynamics of
the Al-water reaction, as well as including its environmental impact (Bai
et al., 2022; Oruc and Dincer, 2021; Pini et al., 2020)
Furthermore, various researchers have studied the potential of
hydrogen production using a different form of waste, which is aluminum
dross (Kale et al., 2022; Meshram et al., 2019; Singh et al., 2019).
Aluminum dross is the mixture of metallic and non-metallic substances
which is formed on the surface of liquid Al in the process of its fusion.
Kale et al. (2022), showed that hydrogen can be produced from the
hydrolysis of black dross without the inclusion of a catalyst. Black dross
contains between 7 and 50 % metallic aluminum, compared to salt cake,
which possesses 3–5 % of its mass as metallic aluminum.
It appears that hydrogen production from waste aluminum sources is
a great alternative to existing hydrogen production resources. The high
availability, potential cost effectiveness and low environmental impact
gives aluminum superior advantages over other types of metal.
4.3. Hydrogen from zinc metal
Readily available zinc will not instantaneously react with water,
contrary to aluminum and magnesium. However, zinc reacts with steam
at high temperatures to produce hydrogen (Abu Hamed et al., 2008).
This reaction has allowed the exploration of the thermochemical split­
ting of water or utilizing the Zn/ZnO cycle to produce hydrogen gas
through solar thermal energy. The global end of life recycling rate for
zinc is 33 % (Meylan and Reck, 2017). The possible hydrogen produc­
tion from zinc could be a motive for many cities to invest in specialized
zinc recycling.
While not entirely a modern approach for hydrogen production.
Metal oxide reactions with steam at high temperatures can be used to
produce hydrogen gas by a two-step redox reaction process. In the first
phase, the metal oxide enters a reduction reaction at high temperatures
and produces oxygen gas. In the second phase, a low-temperature
oxidation reaction produces hydrogen gas. Early work in this reaction
8
Sustainable Horizons 9 (2024) 100079
Notes Reference
Highly dependent on the type of additives and (Davies et al., 2022a,
time of addition. 2022b; Ilyukhina et al.,
2017)
High pH can cause issues in the reaction, (Küp Aylikci et al., 2021;
equipment corrosion Xu et al., 2018a; Yang
et al., 2018)
Liquid metal is shown to be recoverable after (Meroueh et al., 2020;
the reaction has occurred. May not be the Nizovskii et al., 2020;
most economically effective Slocum et al., 2020)
High temperature requirements to melt the (Chen et al., 2018; Liu
required metals et al., 2017; Wang et al.,
2021)
was the utilization of the steam-iron process, to produce hydrogen from
coal (Yang et al., 2008). As effective as this process can be, it was not
able to compete sturdily with the steam-methane reforming (SMR)
method for hydrogen production, mainly for economic concerns (Ros­
trup-Nielsen and Rostrup-Nielsen, 2002).
Walking on virtually the same path as steam-iron process, many it­
erations utilizing the same principle have emerged, possibly from sus­
tainable and renewable approaches. Steinfeld (2002), studied the
reactions of zinc oxide to zinc and back to the oxide in the
above-mentioned redox reaction. Steinfield’s model includes solar
thermal energy input for the endothermic first step of the redox reaction,
with a proposed concentration ratio of 5000, and a working temperature
of 2300 kelvin. The second-law analysis done in this work informs a
maximum exergy conversion efficiency of 29 %.
A recent study on the zinc oxide redox reaction is done by Bhosale
(2021), where a thorough thermodynamic analysis on solar hydrogen
production using a thermochemical water splitting cycle based on the
reactions of Zinc oxide and zinc was conducted. It is argued that a
solar-to-fuel efficiency of 62.6 % can be reached by involving 50 % heat
recuperation (HR).
In terms of environmental impact, Safari and Dincer (2020) con­
ducted a comparative study on different thermochemical cycles for
hydrogen production. The study includes a comparison of efficiency,
environmental impact and cycle economics. The cycles mentioned in the
study include Zn/ZnO, which is a two-step, as well as three and four step
cycles, in addition to hybrid cycles. The work concludes that two step
cycles such as Zn/ZnO are recognized as an alternative for thermo­
chemical hydrogen production. Haltiwanger et al. (2010), did a cost and
policy analysis on the solar Zn/ZnO cycle to produce renewable
hydrogen. The economic feasibility of such technology to produce
hydrogen, as well as the policies required in order to accelerate the
technology taking place, were explored. It was determined that the
thermochemical cycle could become economically feasible within the
latter portion of the current century. More active investment prospects
will significantly enhance the opportunities of making the cycle a
competitive source of renewable hydrogen. Zinc can also be used as an
additive in ball milling in the process of activation of Al alloys for hy­
drolysis (Davies et al., 2022a).
4.4. Hydrogen from niche metals
Other metals have been reported to be useful in producing clean
hydrogen gas. However, in contrast to Al, Mg and Zn, the metals
mentioned in this section serve as an additive to other metals, usually to
create alloys that perform better in hydrolysis reactions.
Arun et al. (2020), studied the feasibility of synthesizing a catalyst
for bio-hydrogen production by using carbon-zinc battery waste. Kah­
veci and Kaya (2022) synthesized an Al-Cu alloy composed of pure
aluminum and waste copper from direct-current electric vehicle motor
M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

coils. The reaction takes place in a round-bottomed flask with an NaOH
solution. The metals were alloyed in an induction furnace. The alloyed
samples produced more hydrogen than pure Al in both 40 ◦ C and 60 ◦ C
testing conditions. However, at 80 ◦ C, pure Al performed better than the
Al-Cu alloys. This study generates more opportunities to recycled EVs
that are out of commission, which is vital as the EV industry is ever­
growing (Trends and Developments, 2022). The results of Kahveci and
Kaya indicate that Cu can improve hydrogen production performance.
Similar positive results were obtained by Wei et al. (2018).
generated electron to form hydrogen gas once again, however gas spe­
cies such as CO2, N2 and CH4 are blocked by the membrane material
(Kim et al., 2022). Zhang et al. (2022), successfully developed a super
activated carbon (AXE-21)-doped hydrogen purification adsorbent
Mg-MOF-74 which was utilized to treat CH4/H2, N2/H2, CO2/H2,
(CO2+CH4+N2)/H2, gas mixtures, which shows the versatility of the
scope of application within different gaseous conditions. Recent prog­
ress in membrane hydrogen separation applications is summarized in
Table 7.

5. Purification of hydrogen from waste 6. Environmental aspects

Hydrogen production from waste feedstock is lucrative in terms of
utilizing what could be a wasted hydrogen-rich source and extending the
benefits of industrial processes to yield higher returns. However, this
mean of hydrogen production dictates a requirement of a purification
step to allow its usage in power production applications such as in fuel
cells. When it comes to hydrogen production from metal waste, con­
taminants from the aqueous solution and the source metal potentially
hinder the quality of the hydrogen produced. Which is why it is essential
to consider the various purification technologies that can be applied to
ensure a level of purity that suits the stringent power generation re­
quirements. Hydrogen purification can be subdivided into physical and
chemical-based hydrogen purification. Physical based hydrogen purifi­
cation includes adsorption-based techniques such as pressure swing
adsorption, cryogenic temperature purification such as cryogenic
distillation and membrane-based gas separation.
Techniques such as pressure swing adsorption (PSA), which rely on
hydrogen adsorption and a high-hydrogen selectivity material to obtain
hydrogen with high purities (~99.999 %), with the disadvantage of high
hydrogen loss (~20 %), due to the pressure drop that accompanies the
hydrogen desorption step. Moreover, cryogenic distillation is used to
obtain a relatively lower-purity hydrogen, based on the partial
condensation of a gas mixture (containing hydrogen) at low tempera­
tures and high pressures (Bernardo et al., 2020). The merits and draw­
backs of both methods are summarized in Table 6.
The usage of membranes in PSA results in a better performance by
utilizing the available pressure to enrich the H2 to be fed to the PSA, to
minimize both the system size and cost (Allevi and Collodi, 2017), which
means that development in membrane technologies will facilitate better
stand-alone membrane and hybrid applications. Recent progress in
hydrogen purification includes the development of various adsorbents
and gas separators that include carbon molecular sieve membranes
(CMSMs), metal organic framework (MOF)-based adsorbents ionic
liquids-based, and palladium membranes (Olabi et al., 2023). Moreover,
metal waste or metals in general can be intensively utilized to obtain the
membrane separators themselves rather than just being a hydrogen
generation feedstock. Metals pose as a good candidate to fabricate gas
(hydrogen) membrane separators. Once hydrogen comes in contact with
a metal-based membrane, it decomposes into a proton and an electron.
The proton then permeates through the metal and recombines with the
The environmental impact of hydrogen generation is mostly related
to its mean of production. Gray and blue hydrogen suffer from the
production of carbon dioxide. However, the addition of carbon capture
systems (CCS) in the latter that may help attenuate this effect. Producing
carbon dioxide as a byproduct of hydrogen generation acts as a coun­
teractive factor that hinders the sole purpose of transitioning into a
hydrogen-based economy. However, very few studies have looked into
the environmental impact of hydrogen itself. Hydrogen can be consid­
ered as an indirect greenhouse gas; it is said that 0.2 to 10 % of mo­
lecular hydrogen is leaked through its production and transportation
phases (van Ruijven et al., 2011). Given the low effect on the earth’s
gravitational pull-on hydrogen gas, its ascension to earth’s lower at­
mosphere levels is quite easy. Once hydrogen reaches the stratosphere, it
reacts rapidly with hydroxyl radicals, which are compounds that are
stable in dilute gas phases and decay very quickly in a condensed state
and reduces their concentration. The reduced concentration of these
hydroxyl radicals hinders the rate of the oxidation of different green­
house gasses, such as methane and carbon monoxide, which in turn
increases the greenhouse effect (Yue et al., 2021).
Moreover, in comparison to other power generation means such as
fossil fuel and synthetic fossil fuel, hydrogen generation, especially
green hydrogen, bears a minimalistic effect on the environment. With
most emissions (CO2, CO, SO2 and NOX) being related to fossil fuel and
synthetic fossil fuel as well as vapor production which directly con­
tributes to the greenhouse effect and global warming (Baykara, 2018).
7. Barriers and limitations
There are limitations that govern the current hydrogen production
from metals or metal waste in particular, which can be perceived as
economical and financial, technical and social. From an economic point
of view, obtaining the raw materials (metals) for this type of hydrogen
production is costly. According to (Cushman-Roisin and Cremonini,
2021) a kg of aluminum requires a 210 MJ of energy input, with a
carbon footprint of 12 kgCO2/kg and a water usage that ranges from 495
to 1490 L/kg. Additionally, recycling aluminum comes at a high but
relatively lower energy requirement in comparison to producing pristine
aluminum at 26.7 MJ/kg and a carbon footprint of 2.1 kgCO2/kg, which
is where utilizing metal waste for “cheap” hydrogen production comes

Table 6
PSA and cryogenic distillation comparison.
Technique Advantages Disadvantages Reference

Pressure Swing Integrating in plants: Ability to remove
Adsorption impurities to any level ppm
Produces high purity hydrogen
Recovery range of H2 80–90 %
Cryogenic Allows for the production of liquid
Distillation (Separated) CO2 that is ready for
transportation
Suitable for high CO2 concentrations
No need for chemical reagents or additives
Suitable for >50 % CO2 concentration
removal (vol)
short cycle times bring high switch losses. (Allevi and Collodi, 2017;
At low pressures, PSA may add impurities to the gas components and these Kwon et al., 2011)
components may hinder the CO2 adsorption and the purification efficiency
PSA has low-cost effectiveness for CO2 recovery from flue gasses.
High energy requirement for regeneration, high operating cost and high (Alcántara-Avila et al., 2014)
possibility of process
High energy consumption due to the high temperature difference
requirement between the inlet and outlet of the working fluid

9
M.A. Abdelkareem et al. Sustainable Horizons 9 (2024) 100079

Table 7
Membrane technologies for hydrogen purification (separation).
Membrane Details Permeability mol m- Selectivity Flow Pressure Temperature Reference
2 s-1 Pa-1 Rate

Palladium Pd plated Al2O3 0.5 L/ – (Lim et al., 2022)

min
10 h plating Ideal: 325 100 kPa (difference
between permeate H2 and
retentate N2)
5 h plating Ideal: 75 500 kPa (difference
between permeate H2 and
retentate N2)
Pd-Ti3C2TX (Pd- 2.66 E-7 242 (H2/CO2) 60 mL/ – 25 ◦ C (Wang et al., 2022)
MXene) min
TiO2/Pd 4.16 E-4 mol s-1 m-2 Complete hydrogen ~250 400 ∘C∘ C (Sanz-Villanueva
Pa-0.5 @400 ∘C selectivity for H2 feed - Nml/min et al., 2022)
1000 h
CMSM BATPPP-6FDA 2622.4 Barrer H2/N2 524.48 Pyrolyzed at (Hou et al., 2022)
800 ∘C∘ C
H2/CH4 1248.76
H2/CO2 7.51
FeCoNi 3.3 E-8 mol m-2 pa-1 s- Ideal H2/CO2 11.4 (He et al., 2022)
1
oxyhydroxide
nanosheets
MOF MOF-801-Mxene 22,000 GPU H2/CO2 26.6 (Li et al., 2022)

into play. Moreover, as mentioned in a previous section, utilizing metal
waste or waste in general dictates a requirement of purifying the output
hydrogen, where methods such as pressure swing and cryogenic distil­
lation as well as membrane-based purification are accompanied with a
high capital cost. Finally, due to the formation of a passivating layer on
top of the conventional metals used for hydrogen production, innovative
additions on metals that would help surpass the formation of this
passivating layer and incorporating them with conventional metals
within a single alloy requires a high investment in pre-treating this metal
waste.
From a technical point of view, there are factors that bear limitations
on the overall process of producing hydrogen from metal waste, such as
the rapid and rather uncontrollable reaction of alkali metals when
exposed to water, which poses extra control requirements on on-board
hydrogen generation, as well as the volume expansion that happens at
the metal/liquid(water) interface.
Socially, it becomes clear that normalizing certain aspects into the
daily lives of general public is quite essential for the commercialization
of hydrogen production from metal waste, as mentioned earlier, recy­
cling certain metals is way cheaper than producing pristine
counterparts. Moreover, pushing for the implementation of domestic
hydrogen-based power production systems will play a crucial part in the
future of any hydrogen-based economy. A summary of the technical,
economic, and social limitations is presented in Fig. 6.
8. Applications and future perspectives
Hydrogen is one of the most increasingly engaging topics in recent
literature with a diverse collection of applications that include power
generation through on-board vehicular systems, high quality fuel
(aerospace applications), underwater vehicles, small scale mobile de­
vices power production, etc. Moreover, projected futuristic applications
include the utilization of on-board hydrogen generation in various
sectors.
8.1. On-Board hydrogen production (for combustion applications)
According to a report published by the United States department of
energy an on-board aluminum/water reaction system to produce
hydrogen for built-in fuel cell vehicular applications includes a fresh

Fig. 6. Hydrogen production from metal waste limitations.

10
M.A. Abdelkareem et al.
reactants container and byproducts separator, components to control
the generation of hydrogen, thermal management control systems and
loading/unloading fresh reactants and byproducts system, respectively,
such as shown in Fig. 7. it is said that 8 kg of aluminum is required with
the corresponding water amount to achieve a hydrogen production rate
of 1.6 g/s to accommodate a fuel cell with a power rating of 80 kW.
However, an issue arises when it comes to aluminum water hydrogen
generation. As the reaction occurs, a layer of inert Al2O3 forms on the
aluminum surface preventing any further reaction. Which is why
methods to overcome this layer formation have been investigated to
mitigate this effect in the on-board hydrogen generation systems. Mer­
oueh et al. (2020), proposed the deposition of a low-temperature
eutectic gallium indium alloy deposition on the surface of the
aluminum block which penetrates through the aluminum grain bound­
aries that act as de-passivators which have reportedly allowed for a 90 %
generation of the theoretical hydrogen generation. Moreover, adding
silicon to the aluminum eGaIn alloy reportedly increased the hydrogen
yield by a further 20 %.
Additionally, from an article published by the center for strategic and
international studies (CSIS), hydrogen has been leading international
projects in maritime transportation with 106 projects that aim for zero
emissions related to maritime transportation. The ease of retrofitting
hydrogen-based fuel cells within marine vessels will play a part in pro­
pelling the usage of hydrogen in such applications, along with the aid of
on-board hydrogen generation. The article also stated that hydrogen fuel
can potentially replace 43 % of the voyages between the US and China
(Center for Strategic and International Studies, 2022).
The National Aeronautics and Space Administration (NASA) (Hei­
ney, 2015) has been using hydrogen fuels for their aerospace applica­
tions for decades. Their previously used shuttle booster rockets
consumed 500,000 gallons of liquid hydrogen to use as a propellent.
However, with rising interests on resuming manned space missions,
hydrogen must be innovatively produced, stored and used. With the
potential of producing hydrogen on spot, through processes such as
metal-water reactions, and with the aid of raw low-weight metal ma­
terials, the usage of fuel cells for power applications in space is not far
Fig. 7. Applications of hydrogen production from waste metal.
11
Sustainable Horizons 9 (2024) 100079
from being a viable option, which will also play a large part in reducing
the cost and complexity of future missions due to recycling and pro­
ducing hydrogen in space.
8.2. Hydrogen fuel cells
Hydrogen fuel cells have the potential to be utilized in a vast variety
of applications including industrial applications (), transportation and
backup power generation (Olabi et al., 2022). For instance, fuel cell
forklifts are already operating in warehouses which aim to provide a
safer environment for the workers by utilizing a hydrogen fuel cell stack.
Some of the advantages include the fast charging through in-house
hydrogen tanks and the independence of toxic materials that are asso­
ciated with lead-acid batteries. It is stated that fuel-cell based forklifts
can operate 3-times longer than battery-based alternatives (Guide to
Safety of Hydrogen and Hydrogen Systems, 2017); Hydrogen and Fuel
Cell Applications - CHFCA, 2022). Moreover, hydrogen fuel cells have
been utilized in the transportation sector within cars, busses, trucks, and
planes and given that one of the greatest challenges that is present in the
transportation sector around the world is methods to decarbonized
transportation means to cope with climate change (Boldrin and Bran­
don, 2019). Transportation is responsible for 23 % of emissions and 92
% of the fuel consumed is directly related to hydrocarbon products (AR5
Climate Change, 2014: Mitigation of Climate Change — IPCC, n.d.). Which
is why the focus has shifted to finding different alternatives with high
regard to their efficiencies such as fuel cells. Additionally, fuel cells can
be used effectively in heat and power securing energy purposes in the
residential applications (Olabi et al., 2020).
8.3. Chemical industry
Hydrogen in considered to be one of the most important feedstocks
for the chemical industry, it is used for the manufacturing of ammonia
(fertilizers), methanol (Alcohols) and oil refining. Utilizing hydrogen
produced from waste-metal and reacting it with nitrogen which is
separated from ambient air through the Habber process, will allow for a
M.A. Abdelkareem et al.
cheap production of ammonia (The Royal Society, 2022). Furthermore,
hydrogen is utilized to produce methanol, which is the second highest
consumer of hydrogen, by supplying a stream of hydrogen feed to a
carbon containing feedstock such as natural gas, coal, biomass, and
carbon dioxide (Ausfelder and Bazzanella, 2016). Moreover, utilizing
hydrogen to obtain higher-grade petrol, which is free from sulfur com­
pounds, allows for further protection of essential car components such as
catalytic converters (Hydrogen, 2022).
9. Conclusion
In conclusion the production of hydrogen form metal is categorized
based on the reactivity of the metal used when exposed to water. Alkali
earth metals such as Li, Na, and K, require little to no external input in
order to react with water. Whereas metlas such as Mg and Al mandate
some energy input to attain the required reaction temperature. On the
other end of the spectrum, metals such as Fe and Zn, require stringent
high-temperature conditions, as well as high temperature steam inputs
for any measurable hydrogen generation. This method of hydrogen
production has opened the gateway for repurposing metal scrap to be
used in the rising hydrogen scene. Metal scrap can be favoured over
pristine raw metals, that would be better utilized in other applications,
due to notable overall hydrogen cost reductions, as well as a decrease in
the required energy input. Moreover, the yield and efficiency of
hydrogen production from scrap metals differ based on the reactivity
and passivating layers’ thicknesses that can be formed on the surface.
For example, magnesium and aluminum-based hydrogen production
yields 70 % and 98 %, respectively. Whereas zinc-based hydrogen pro­
duction exhibits a rather low hydrogen production at 20 %. Resultant
hydrogen production from such reactions requires further purification
techniques such as pressure swing adsorption, cryogenic distillation, as
well as membrane-based methods. These purification routes ensure the
quality of the produced hydrogen, with a lot of room for improvement
that has yet to be explored in terms of research and development.
Furthermore, the applications of hydrogen production from metal
waste/scrap metal extend to on-board scenarios, which includes planes
and maritime vessels. Moreover, fuel cell power generation, as well as
the chemical industry can benefit from advancements made in the field
of hydrogen production from waste metal. Finally, contrary to conven­
tional hydrogen production techniques, hydrogen production from
waste metal harbours lower overall costs, positive environmental im­
pacts, as well as a favourable hydrogen production yield.
CRediT authorship contribution statement
Mohammad Ali Abdelkareem: Conceptualization, Writing – orig­
inal draft, Writing – review & editing. Mohamad Ayoub: Writing –
original draft, Writing – review & editing. Rami Issa Al Najada: Writing
– original draft, Writing – review & editing. Abdul Hai Alami:
Conceptualization, Writing – original draft, Writing – review & editing.
A.G. Olabi: Supervision, Writing – original draft, Writing – review &
editing.
Declaration of Competing Interest
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.
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Mohammad Abdelkareem got his PhD from Japan in 2008. Right now, he is professor in
sustainable and renewable energy engineering department, university of Sharjah, UAE. He
is working on the development of the different renewable energy resources, thermofluids,
and electrochemical devices that can be used in wastewater treatment and water desali­
nation. Moreover, he is working on the development of the electrodes for the different
electrochemical energy conversion/storage devices, such as direct methanol fuel cells,
direct urea fuel cells, microbial fuel cells, and supercapacitors. Professor Mohammad
published more than 300 manuscripts in ISI indexed journals.