chemengineering

Review
An Overview of Hydrogen Energy Generation
Gaydaa AlZohbi

Department of Mechanical Engineering, Prince Mohammad Bin Fahd University, Al Khobar P.O. Box 1664, Saudi
Arabia; [email protected] or [email protected]

Abstract: The global issue of climate change caused by humans and its inextricable linkage to our
present and future energy demand presents the biggest challenge facing our globe. Hydrogen has
been introduced as a new renewable energy resource. It is envisaged to be a crucial vector in the vast
low-carbon transition to mitigate climate change, minimize oil reliance, reinforce energy security,
solve the intermittency of renewable energy resources, and ameliorate energy performance in the
transportation sector by using it in energy storage, energy generation, and transport sectors. Many
technologies have been developed to generate hydrogen. The current paper presents a review of the
current and developing technologies to produce hydrogen from fossil fuels and alternative resources
like water and biomass. The results showed that reformation and gasification are the most mature and
used technologies. However, the weaknesses of these technologies include high energy consumption
and high carbon emissions. Thermochemical water splitting, biohydrogen, and photo-electrolysis are
long-term and clean technologies, but they require more technical development and cost reduction
to implement reformation technologies efficiently and on a large scale. A combination of water
electrolysis with renewable energy resources is an ecofriendly method. Since hydrogen is viewed as a
considerable game-changer for future fuels, this paper also highlights the challenges facing hydrogen
generation. Moreover, an economic analysis of the technologies used to generate hydrogen is carried
out in this study.

Keywords: hydrogen energy; fuel cell; electrolytic; photolytic; thermal technique

Citation: AlZohbi, G. An Overview of 1. Introduction

Hydrogen Energy Generation.
Hydrogen is known as the lightest and the most abundant element. It supplies en-
ChemEngineering 2024, 8, 17.
ergy to fuel the stars and the Sun. It is considered non-toxic, odorless, colorless, highly
https://doi.org/10.3390/
combustible, and unpolluted. Also, it is an energy carrier [1]; it scarcely exists by itself
chemengineering8010017
and should be generated from compounds that contain it. Hydrogen is versatile; it can be
Academic Editors: Kirtika Kohli and produced from varied resources, and it is used in a wide range of applications. It can be
Ravindra Prajapati converted into electricity using conversion devices like fuel cells [2]. The main advantages
Received: 18 November 2023
of hydrogen are its high electrochemical reactivity, theoretical energy density, safe combus-
Revised: 9 January 2024
tion products, and unbounded availability. However, hardness storage, low density under
Accepted: 24 January 2024
normal circumstances, and explosion hazards represent the main impediments to the use
Published: 1 February 2024 of hydrogen in fuel cells. Many sources could be used to generate hydrogen, like water,
fossil fuels, and renewable energy. According to its production method, hydrogen can be
classified as follows [3]:
- Gray hydrogen: fossil fuels are used to produce hydrogen, like natural gas and
Copyright: © 2024 by the author. oils; this kind of hydrogen releases a large amount of CO2 into the air during its
Licensee MDPI, Basel, Switzerland.
production process.
This article is an open access article
- Blue hydrogen: hydrogen is produced using fossil fuels, and it is accompanied by
distributed under the terms and
carbon-capture storage technology to decrease carbon dioxide emissions.
conditions of the Creative Commons
- Green hydrogen: hydrogen is generated by electrolysis powered by renewable energy,
Attribution (CC BY) license (https://
such as solar, wind, geothermal, nuclear, and waste energy. It is considered to be a
creativecommons.org/licenses/by/
4.0/).
clean technology to generate hydrogen.

ChemEngineering 2024, 8, 17. https://doi.org/10.3390/chemengineering8010017 https://www.mdpi.com/journal/chemengineering

ChemEngineering 2024, 8, 17 2 of 31

- Brown hydrogen: this type of hydrogen is considered to be the most affordable and
the most harmful to the environment due to the thermal coal that is used in the
generation process.
- Turquoise hydrogen: hydrogen is fabricated using methane pyrolysis technology that
yields solid carbon.
- Yellow hydrogen: this refers to the hydrogen generated by electrolysis using solar energy.
- White hydrogen: this type of hydrogen is geological, which is established in under-
ground deposits and formed via fracking. Presently, there are procedures to harness
and exploit it.
Hydrogen energy is versatile in terms of its usage and generation. Currently, it is used
in the production of methanol and ammonia, the fabrication of vitamins and pharmaceutical
products, and the hydrogeneration process of liquid oils. Also, hydrogen is used to extract
sulfur and nitrogen compounds in refinery processes [4]. It is used to produce steel by
replacing coking coal and to generate fuel for transportation. Moreover, some companies
are planning to use hydrogen to heat and cool buildings and to generate power to minimize
GHG emissions and improve efficiency.
Hydrogen energy is anticipated to be a sustainable fuel for the future. Recently,
the development of hydrogen technologies has gained more international interest and
attention due to the significant role that hydrogen can play in increasing energy security
and economic sustainability. Hence, hydrogen energy can sustainably cope with the global
growth in energy demand. In addition, hydrogen energy can be used to generate and
store energy and to deal with the intermittent nature of renewable energy sources [5].
Also, hydrogen can contribute to decarbonization in many sectors, including chemical,
transportation, and steel production, and therefore, it can enhance air quality, boost energy
security, minimize oil reliance, and cope with climate change. Moreover, hydrogen can
be produced from plastic waste materials through several thermo–catalytic processes;
therefore, it is considered to be a solid waste treatment [6].
The neutral carbon characteristic of hydrogen depends on the cleanliness of its gen-
eration method, the feedstock used, and the energy used in its generation process [7].
Therefore, it is essential to determine the hydrogen origin before considering it as a green
energy source. The kind of feedstock and energy and the desired end-use purity determine
the specified technology and hydrogen generation method. The objective of this paper is to
present a complete review of the operated and developed technologies used to generate
hydrogen with a focus on the feedstock and energy used, the advantages and drawbacks
of each technology, and its maturity. Moreover, the different uses of hydrogen and the
different challenges facing hydrogen energy generation are discussed in the current paper.
Also, since hydrogen is predicted to play a crucial role in the future, and since the economic
aspect is considered an important factor in expanding the hydrogen market, an economic
analysis is carried out in this paper.

2. Current and Future Uses of Hydrogen and Its Generation

Hydrogen can be fabricated and utilized on site. The main uses of hydrogen are oil
refining and ammonia production, which account for two thirds of hydrogen usage [8].
Hydrogen is combined with heavier oil in petroleum refineries to generate transport fuel.
Ammonia can be used as a fertilizer in agriculture, as a refrigerant gas, and in the fabrication
of explosives, pesticides, plastics, and other chemicals. Figure 1 displays the global annual
production of hydrogen and its usage between 2015 and 2030. Hydrogen generation will
increase: it reached 55 Mt of H2 in 2021 and is expected to reach 70 Mt of H2 by 2030. In
addition, it is noticeable that the main use of hydrogen is for ammonia production.
Overall hydrogen production is expected to increase from USD 150.20 billion in 2021
to USD 220.37 billion by 2028 [9]. Also, the overall hydrogen market bulk is anticipated to
attain USD 184.11 billion by 2028 [9].
ChemEngineering 2024, 8, 17 3 of 31

Figure 1. Annual hydrogen production and uses between 2015 and 2030 [10].

The hydrogen market scale is divided into three categories [11]:

− Small scale: the hydrogen capacity ranges from 0.5 MW to 1.7 MW, and the hydrogen
is used in hydrogen filling stations.
− Medium scale: the hydrogen capacity ranges from 33 MW to 1000 MW, and the
hydrogen is used for refineries.
− Large scale: the hydrogen capacity ranges from 66 MW to 333 MW, and the hydrogen
is used in industrial fields.
Several feedstocks are used to fabricate hydrogen, like water, fossil fuels (natural gas,
crude oil, and coal), and biomass. Figure 2 displays the current feedstock used in hydrogen
production. Non-renewable sources are mainly used in the hydrogen generation process.
A total of 48% are from natural gas, 30% are from crude oil, 18% are from coal, and 4% are
from water electrolysis [12]. In water electrolysis, the water is used to generate hydrogen,
and it requires electricity that is generated from fossil fuels or renewable energy.

Figure 2. Current distribution of types of feedstock used in the generation of hydrogen [12].

3. Main Approaches for Hydrogen Production

Many technologies are used to produce hydrogen, involving the steam reformation of
methane sources, coal and coke gasification, catalytic decomposition of natural gas, partial
oxidation of hydrocarbon, and water electrolysis. According to many research studies,
the largest quantity of hydrogen is produced by steam reformation at 48%, followed by
petroleum fraction at 30%, and coal gasification at 18%. The lowest is produced using water
electrolysis [13,14].
ChemEngineering 2024, 8, 17 4 of 31

The prime technologies of hydrogen generation use non-renewable energy, are very
energy intensive, and have a high temperature demand [13]. Consequently, the use of
these technologies contributes to polluting the air by emitting enormous quantities of
ashes and greenhouse gas emissions, including oxide carbon, nitrogen, sulfur, and heavy
materials. However, other technologies use renewable resources to generate hydrogen,
such as photo-electrolysis, thermochemical, and water splitting. Some of these technologies
are still at laboratory scale [15,16].
The classification of hydrogen generation is based on many factors, such as the tech-
nologies used and the sources of energy used. There are mainly two power sources used
in the process of hydrogen generation: fossil fuel and renewable energy (Figure 3). The
technologies used for hydrogen production can be classified into three groups: electrolytic,
photolytic, and thermal process.

Figure 3. Methods used to generate hydrogen.

3.1. Electrolytic Technique

In this technique, hydrogen is generated by feeding the electrolyzer with electricity
to dissociate water molecules into hydrogen and oxygen. Water comprises two atoms of
hydrogen and one atom of oxygen, and the dissociation of water will yield hydrogen and
oxygen. Since the two atoms are robustly bonded, stimulus and external agents are required
to facilitate the splitting of the water molecule. The external agents could be electrical
energy generated from renewable and non-renewable energy sources. Water electrolysis
comprises a cathode and an anode joined through a power supply and submerged in a
conducting electrolyte. The types of electrolytes used are an oxygen ion exchange ceramic
membrane, a proton-exchange membrane (PEM), and an aqueous solution containing
ions. After a direct current is applied, the electrons move from the negative terminal
of the power supply to the cathode to form hydrogen. The electrons, generated by the
electrochemical reaction, go back to the positive terminal of the DC supply. This technique
can be sustainable and clean if the electricity used is produced from renewable energy
sources. This technology is envisaged to be cheaper and more performant if renewable
energy resources are used, as power prices decrease during windy and sunny days. The
performance of electrolysis can be estimated using two methods: Faradaic efficiency and
energy efficiency of the cell. Faradaic efficiency is described as the fraction of the number
of moles of hydrogen generated by the charge passed. A Faradaic efficiency of 100% means
that every electron obtained by water oxidation is converted to a conformable proton
ChemEngineering 2024, 8, 17 5 of 31

to generate hydrogen. Faradaic efficiency is usually less than 100% owing to parasitic
electrochemical processes, such as the degeneration of elements of the electrochemical
processes. The energy efficiency of the cell is the ratio of the obtainable energy from
the hydrogen generated by the cell, using the heating value of hydrogen, to the energy
expended by the cell [17]. Water electrolysis can be classified into three classes based on
the operating temperature: low temperature (lower than 300 ◦ C), intermediate temperature
(300–700 ◦ C), and high temperature (higher than 700 ◦ C and below 1000 ◦ C) [18]. There
are six main technologies used in the water electrolysis domain: the alkaline electrolyzer,
electrolysis with a proton-exchange membrane (PEM) water electrolysis, steam electrolysis
using a solid oxide electrolysis cell (SOEC), anion exchange membrane (AEM), plasma
electrolysis, and seawater electrolysis (Figure 4a,b).

Figure 4. (a) Visual representation of the working principle and the electrochemical reaction of the
alkaline electrolyzer, PEM electrolyzer, solid oxide electrolyzer, and AEM electrolyzer. (b) Visual
representation of the working principle of the plasma electrolyzer and seawater electrolysis [19,20].

Water electrolysis under alkaline conditions: Strong electrolytes, such as sodium or

potassium for positive ions, and hydroxide or chlorides as negative ions, are used in this
process to strengthen the solution to be able to transmit the ions with high motility. A
diaphragm is used to separate the anode and cathode. The alkaline electrolyte comes in the
cathode and anode areas, and water molecules can penetrate through the diaphragm to the
other region. When an electric current is applied, electrons move from the negative terminal
ChemEngineering 2024, 8, 17 6 of 31

of the DC course to the cathode and combine with the water molecule to create hydrogen
and hydroxide ions. Then, the hydroxide ions are moved to the anode by migration since
they have an opposite charge. In the anode, the hydroxide ions lose electrons and form
oxygen and water. The gas produced by the electrolysis is not able to move in a large
quantity through the diaphragm to the other area due to the impediment of the porous
diaphragm. Hydrogen and oxygen are composed and collected by gas receivers as oxygen
on the anode and hydrogen on the cathode. Nickel is used normally as electrode material
thanks to its good activity, easy accessibility, and its low cost. A concentrated solution of
potassium hydroxide (KOH) is normally used as an electrolytic solution due to its high
conductivity and fewer corrosion issues compared to other electrolytic solutions. This
technology is characterized by simplicity and low investment cost. The purity level of
oxygen and hydrogen can attain 99.7 and 99.9 vol.%, respectively. The operating tem-
perature is in the range of 80–90 ◦ C, and the operating pressure is around 3.4 MPa. The
performance of hydrogen generation is in the range of 45–80% [21]. This technology is more
effective when operating under low current densities (0.3 A/cm2 ) [22]. The disadvantage
of this technology is the highly corrosive effect of liquid electrolytes that shortens their
lifetime. Also, the cross-diffusion of oxygen and hydrogen between electrodes decreases
the purity of hydrogen, resulting in security matters linked to hydrogen explosion [23]. An
acidic/alkaline atmospheric water electrolysis is developed to generate hydrogen, in which
hydrogen is generated within an acidic solution, oxygen is released under alkaline condi-
tions, and a membrane is used in the center of the electrolyzer to curb neutralization [24].
This advanced technology generates four times more hydrogen than that of alkaline aque-
ous solution with 30% less energy consumption under the current density of 200 mA/cm2 .
An efficient catalyst can contribute to minimizing the overpotential of the OER and HER
in water splitting and enhance energy efficiencies. According to the authors of [25], the
catalysts Pt and IrO2 /RuO2 demonstrate high efficiency with low cost. The effect of temper-
ature on the efficiency on alkaline water electrolysis has been theoretically studied by [26]
through a developed model. Results have revealed that the rise of operating temperature
leads to improved system efficiency in the case of relatively high current density. The
catalytic activity of the role of the NiCoP catalyst for the hydrogen evolution reaction in
alkaline water electrolysis has been examined [27]. Results showed that the integration of
the catalyst nanoparticle on the carbon fiber support is efficient in the electrode preparation
and, therefore, increases the catalytic activity. The authors of [28] conducted a study to
estimate the impact of operating pressure on an alkaline water electrolysis system using
a developed numerical model. A comparison between the current–voltage polarization
curve and the experimental data is used to validate the developed system. Results showed
that using high-pressure water electrolysis acquires high-purity hydrogen without the need
for a water-adsorption device. In addition, the system becomes more performant with
suitable pressure, owing to the reduction of the power consumption of the balance of plant.
Proton-exchange membrane electrolyzer: in this process, a gas-tight thin polymeric
membrane with a cross-connected frame and effective acid character is used as an elec-
trolyte. Water is oxidized at the anode to generate oxygen, electrons, and protons that move
along the membrane to the cathode, where they are diminished and generate hydrogen that
babbles towards the cathodic gas manifold. The PEM electrolyzer is most suitable for low-
scale hydrogen generation. The maximum hydrogen yield is around 30 Nm3 /h, and the
power consumption is 174 kW [21]. The efficiency is in the range of 48–65%. The electrolysis
temperature is limited to below 80◦ due to the existence of the polymeric membrane. The
hydrogen purity reaches values up to 99.99 vol.% in the absence of auxiliary equipment
thanks to the solid polymer membrane, which can efficiently avert gas diffusion [21]. Also,
PEM can be performed at a high current density to enhance the hydrogen generation rate.
The hazard of the formation of a flammable mixture is low due to the weak gaseous per-
meability of the polymeric membranes. The main feature of the PEM electrolyzer derives
from its capability to perform under a changeable power feeding pattern. However, PEM
electrolyzers are characterized by high investment costs and shorter lifespans, resulting
ChemEngineering 2024, 8, 17 7 of 31

from noble metal catalysts, indispensable PEM, and corrosion-resistant current. The use
of molecular catalysts is viewed as a promising solution to the drawbacks of PEM [29].
Lately, several molecular water oxidation catalysts and HOR catalysts, which can bear high
acidity, have evolved [30]. The coupling of PEM with renewable energy sources is viewed
as a promising system thanks to its resilient response and high current densities. However,
this hybrid system faces the challenge of degradation caused by operating with volatile
current and constant current. According to [31,32], degradation rates between 0 mV/h and
230 mV/h were apprised under constant current. This can be explained by the oxidation of
the porous titanium, which acted as the transport player and the fluffy membrane [33]. In
addition, the degradation can be caused by mechanical degeneration [34], active material
losses [18], and material caducity [35]. The rise in operating temperature has a positive im-
pact on the efficiency and the power efficiency of the PEM system owing to the low quantity
of electricity needed by a cell that lessens with the rise of temperature [36]. Nevertheless,
the increase of temperature above 100 ◦ C negatively affects the stability of membrane. Heat
is produced in the current contractor through the operating of the PEM owing to joule
heating. The area of the membrane alongside the current contactor and the current contrac-
tor will have the same temperature. Although the inner part of the PEM is submerged in
water, the area of the membrane compressed on the current contactor is revealed to have a
localized greater temperature, causing it to be more sensitive to degeneration. Therefore,
monitoring and evaluating the heat generation rate and the stack temperature is important.
Even though the PEM is recognized for its dynamic nature, a high rise of current supply
will lead to a fast rise of the heat production and the operating temperature, resulting in
negatively affecting the stability and the longevity of the membrane.
Solid oxide electrolyzers (SOEs) are presented as an advanced concept of water elec-
trolyzers to increase efficiency by enabling water or steam electrolysis at high temperatures
(600–900 ◦ C) [37]. Since water splitting is an endothermic reaction, an increase in tem-
perature leads to a decrease in the decomposition voltage and the electricity demand.
Therefore, a remarkable improvement in power-to-hydrogen efficiency (up to 95%HHVH2 )
with external heat of 150–180◦ is attained, resulting in a decrease in the cost of hydrogen
generation [38]. The working principle of SOEs is based on feeding the cathode with steam
and recycled hydrogen, and the water is reduced to produce hydrogen. The oxide anions,
produced in the cathode, move to the anode through the solid electrolyte, where they
combine to form oxygen and close the circuit with the released electrons. In addition to the
high efficiency ensured by SOEC, expensive noble metal electrocatalysts are not required
thanks to the high running temperature. The two different architectures of SOEC are the
cathode-supported cell (CSC) and the electrolyte-supported cell (ESC). The main difference
between these two architectures is the thicker layer. The CSC comprises a thick cathode
upon which a thin anode and electrolyte are placed. However, the ESC encompasses a thick
electrolyte upon which a thin anode and cathode are placed. The electrolytes that are widely
used in this technology are ceramic material, Ni-based cermet, combined yttria-stabilized
zirconia (YSZ, 8 mol.% yttria-doped), and gadolinium-doped ceria. The main benefits of
YSZ are the conscientious stable efficiency under temperatures ranging between 700 and
850 ◦ C owing to a high ionic conductivity (10−2 –10−1 S cm−1 ). Gadolinium-doped ceria
is considered to be a useful electrolyte material owing to its high conductivity, while it
has a high sintering temperature (~1500 ◦ C) that is considered to be a challenge since it
limits co-sintering possibilities. Compared to traditional electrolyzers, this technology can
perform effectively with high power density. Notably, intense temperature waste heat
is supplied. This can be explained by the fact that the electrochemical transformation of
water under high-temperature conditions allows the storage of electricity and heat in the
generated hydrogen [39]. Since this technology is a high-temperature type of electrolysis,
it causes the rapid degradation of cells. Nuclear heat is one of the leading nominees to
run SOEC on a large scale, where heat is a byproduct. In addition, it can be incorporated
with solar collectors with the aim of storing energy and generating secondary fuel. The
causes of degradation of SOEs can be categorized into three classes: structural degradation,
ChemEngineering 2024, 8, 17 8 of 31

mechanical failure due to thermal stress, and chemical/electrochemical degradation. The

degradation of SOE cells depends on cell material, cell operating conditions, and processing.
The longevity of SOE cells during operation is affected by current density, gas supplied,
operating temperature, cell polarization, and steam-to-hydrogen transformation rate [40].
However, the stack degradation is a result of seals, interconnect contact degeneration, and
speeded-up cell degeneration due to pollution from tubing [41]. Despite the fact that the
SOE is a promising technology for wide-ranging hydrogen generation, it is still in the
development stage.
Anion exchange membrane (AEM) electrolysis is a propitious technology for large-
scale hydrogen generation. This technology integrates the merits of alkaline and PEM
electrolysis in a cell formed of a hydrocarbon-based anion exchange membrane and two
transition metals [42,43]. The benefits of this technology arise from the use of distilled
water or milder alkaline electrolytes rather than a concentrated KOH solution and the
feasibility of using an affordable catalyst, as in alkaline electrolysis, and the use of a solid
polymer electrolyte architecture, as in PEM electrolysis [44]. It is a cheap technology and
has low interchange with atmospheric CO2 [45]. Nevertheless, the disadvantages of current
AEM are low power performance, low ionic conductivity, important catalyst loading, and
moderate-range membrane stability with significant ohmic resistance loss [43]. An increase
in temperature increases the efficiency of AEM, and the integration of ionomers in the
electrode could enhance ion transport between the electrode and the membrane [46]. The
main weakness of AEMs is their restricted thermal stability, particularly at high pH [47]. The
degradation of AEMs at high temperatures and under fundamental circumstances is mainly
caused by two reasons: nucleophilic attack of hydroxide on N-alkyl groups and Hofmann
elimination [48]. Moreover, the electrochemical oxidation of the immersed phenyl group
oxygen evolution catalyst can lead to the degradation of AEMs [49]. The development
of stabilized functional groups on the polymer backbone enhances the chemical stability
of AEMs under alkaline circumstances, resulting in using this membrane under high
temperatures for long duration. AEMs should be fed with pure water, and the use of
ionomer/binder material is necessary. The use of pure water engenders low current
densities and the use of suitable liquid electrolyte conduct to improve the performance of
AEMs, such as 1% K2 CO3 or dilute KOH solutions.
Plasma electrolysis is viewed as an alternative and promising method for hydrogen
generation thanks to its ability to generate more hydrogen using less energy consump-
tion compared to hydrocarbon electrolysis. Plasma electrolysis can generate hydrogen
149 times more than hydrogen generated by Faraday electrolysis [50]. It comprises electrol-
ysis performed at high voltage that generates electrical sparks, resulting in the formation
of plasma in the electrolyte solution. In this technology, the surface current flows near the
water–plasma boundary to produce hydrogen in the proximity of the negative electrode
and oxygen in the vicinity of the positive electrode. Many factors affect hydrogen gen-
eration in plasma electrolysis, such as PH, conductivity, electrolyte solution, and voltage
discharge [51]. A rise in voltage leads to minimized electricity consumption and improved
hydrogen generation. Hydrogen generation can be enhanced by adding acetic acid to the
electrolyte solution and by deeply submerging the cathode in the electrolyte [52]. It has
been found that the ideal hydrogen generation was 50.71 mmol/min, attained at 700 V
with 0.03 M KOH, 10 vol.% ethanol, and 6.6 cm cathode deep, with an energy consumption
of 1.49 kJ/mmol [50]. The concentration of electrolytes influences the Faradaic efficiency
of plasma electrolysis. An investigation study on the effect of concentration of electrolyte
on the Faradaic efficiency of plasma electrolysis using various electrolytes with different
concentrations of the methanol additive with variables between 0 and 99.5 vol.%. Re-
sults demonstrated that the rise of conductivity of NaOH solution from 0.43 mS/cm to
16.68 mS/cm with the concentration of a methanol additive of 99.5 vol.% led to a rise
in the Faradaic efficiency from 325 to 850 with an applied voltage of 700 and to reduce
the energy consumption [53]. This is attributed to two reasons: the larger conductivity
of the electrolytic solution and the lesser energy losses and resistivity in the electrolytic
ChemEngineering 2024, 8, 17 9 of 31

cell. Also, the rise of conductivity of electrolytic solution leads to lessening the discharge
onset voltage in plasma electrolysis, which indicates that the bigger the conductivity of
the electrolytic solution, the easier the initiation of plasma at a smaller voltage, leading to
lessen the consumed energy. The Faradic efficiency depends also on the type of electrolyte.
According to [53], the use of KOH electrolytic solution can achieve thigh hydrogen energy
efficiency with a value of 40.8%. Moreover, the use of Na2 CO3 aqueous electrolytic solution
in plasma recorded the biggest energy efficiency with a value of 51.1%, attributed to the
CO and CO2 gases generated in the region of the discharge plasma performing as a forager
of the hydroxyl radicals [54]. The organic additive in plasma electrolysis has a significant
effect on energy consumption, energy and Faradaic efficiencies, and hydrogen production
rate. Ethanol can increase the hydrogen production rate by 21.4-fold, Faradaic efficiency by
12.8-fold, energy efficiency by 3.6-fold, and reduce energy consumption by 17.9-fold [53].
Methanol is viewed as promising for plasma electrolysis, since it can achieve an efficiency
of 51.5% compared to 46.3% obtained with ethanol additive.
The rise in temperature of the electrolytic solution leads to a rise in hydrogen genera-
tion and minimizes electrical energy consumption. An investigation study on the effect of
the temperature of the electrolytic solution, Na2 CO3 aqueous solution with a CH3 COOH
additive, on the electrical energy consumption and hydrogen production of plasma elec-
trolysis has been conducted by [52]. Results indicated that the rise to electrolytic solution
from 70 ◦ C to 75–80 ◦ C led to a lessened energy consumption of 11.8 × 103 kJ/mol(H2 ) to
5.3 × 103 kJ/mol(H2 ) and a rise in hydrogen generation from 0.61 g(H2 )/kWh to
1.36 g(H2 )/kWh. This can be attributed to a larger water-vapor concentration at the
high temperature of the electrolytic solution and the lower amount of energy consumption
required for heating the electrolytic solution and evaporating it near the discharge electrode.
Seawater electrolysis is a feasible solution to the grid-scale generation of carbon-free
hydrogen without depending on fresh water. The working principle of seawater is the
same as water electrolysis, with a little difference due to the chemical composition being
contingent on salts like sodium chloride. There are three processes to generate hydrogen
from seawater: (a) electrolysis to generate hydrogen, oxygen, and alkali; (b) electrolysis
to generate hydrogen, oxygen, chlorine, and alkali; and (c) electrolysis to generate hy-
drogen and sodium hypochlorite. The second method is the most functional. The use of
real seawater, which is a plentiful resource, can contribute to the mitigation of freshwater
consumption. This technology is characterized by larger hydrogen generation compared
to simulated seawater [55]. The hydrogen generation rate increases with the salinity of
seawater, which is attributable to the change in the electrolyte conductivity with the salinity
of the seawater. However, hydrogen generation from seawater electrolysis faces several
issues related to the lifetime, high capital and operating cost, change in seawater with
season and topology, foiling of the ion exchange membranes, deposit of solids, biofoul-
ing, and corrosive Cl− oxidation species [56]. The high concentration of various salts in
seawater with different competing redox processes and substantial pH variation lead to
the degeneration of the catalysts. One of the promising technologies to produce hydrogen
using less energy is based on replacing the OER with thermodynamically more beneficial
electro-oxidation processes. Electrosynthesis is another operation of this technology. The
benefit of salt-water electrolysis derives from its ability to evade the problems with chlorine
chemistry without minimizing the hydrogen generation performance and the electrolysis
current [57]. To generate hydrogen using sea electrolysis, the energy used should be priced
rationally enough to equalize the high consumption.

3.2. Photolytic and Biotechniques

Light is utilized to produce hydrogen by decomposing water. This technique comprises
photolytic biological production and photo-electrochemical production (PEC) (Figure 5).
Sunlight is used with specialized semiconductors (photo-electrochemical) to split water
photo-electrochemically, while microbes and micro-algae with sunlight generate hydrogen
using photolytic biological production.
ChemEngineering 2024, 8, 17 10 of 31

Figure 5. Types of processes used in biohydrogen production.

Bio-photolysis: water is used as feedstock in this technology to generate hydrogen

using photonic energy. Bio-photolysis is characterized by its ability to generate hydrogen
using water in moderate environments featuring modest pressures and temperatures.
Furthermore, this technology is proven at a laboratory scale. Bio-photolysis is categorized
into two categories: direct and indirect. In direct bio-photolysis, the water is used as a
substrate in the presence of light and micro-algae, such as green algae and cyanobacteria,
under anaerobic circumstances to produce oxygen and hydrogen [58]. The overall reaction
of bio-photolysis is expressed as [59]:

2H2 O + light → O2 + 2H2 (1)

The disadvantages of direct bio-photolysis are its low performance of hydrogen genera-
tion, which is sensitive to oxygen, and its high need for light intensity. In addition, the need
for enormous cultivation of algae to entrap sufficient sunlight to supply enough energy
is a barrier. Moreover, the concentration and preparation of cell biomass, photosynthetic
capacity rations, and respiration are viewed as challenges [60].
Indirect photolysis comprises two phases: photosynthesis and dark fermentation.
In the first phase, photosynthesis is used for carbon fixation, which aims to convert the
inorganic carbon into an organic compound (carbohydrate) in an open tank. In the second
phase, the carbohydrate is transformed into hydrogen, carbon dioxide, and acetic acid via
dark fermentation or combined photo-fermentation and dark fermentation. The overall
reaction of the indirect photolysis is [59]:

6H2 O + 6CO2 + light → (C6 H12 O6 )n + 6O2 (2)

(C6 H12 O6 )n + 12H2 O + light → 12H2 + 6CO2 (3)

The acetic acid is converted into hydrogen and carbon dioxide using light and under
anaerobic conditions. Photosynthesis is characterized by a high hydrogen yield of 0.38 kJ/L/h,
and the photochemical performance is 10% reached from full solar irradiance [61,62]. The
ability to fix nitrogen from the atmosphere is one of the main benefits of this technique, besides
the unnecessary separation of hydrogen and oxygen. However, the disadvantage is the high
percentage of O2 in the gas mixture. Many micro-algae were assessed to test their ability to
generate hydrogen by using crude glycerol as a cheap source of exogenous carbon to evolve a
concurrent lipide and hydrogen generation process [63]. All micro-algae amassed large lipid
quantities of up to 20%, but an important quantity of hydrogen is generated by Chlorella sp.
under anaerobic circumstances. The integration of biohydrogen with the generation of lipids
by oleaginous micro-algae could be a promising technology for the long-term feasibility of
biofuel generation utilizing micro-algae. The biohydrogen generated by direct bio-photolysis
ranges from 0.015 to 1.084 mmol/L.h and by indirect ranges between 0.35 to 10.26 mmol/L.h,
determined by the culture circumstance, microorganism used, and feedstocks.
Dark fermentation (DF): this technology is among the biohydrogen production (BHP)
technologies used to generate hydrogen, and it does not require light [64]. It transforms
ChemEngineering 2024, 8, 17 11 of 31

organic matter into carbon dioxide, hydrogen, and non-gaseous products under anaerobic
or anoxic circumstances. The principle of the DF process is based on the use of carbohydrate-
rich biomass with pure or mixed bacteria, such as organic acids and ethanol, under suitable
conditions to generate hydrogen in a gas state and some organics products in a liquid state.
According to [65], biomass rich in sugars and carbohydrates is considered to be the most
appropriate feedstock for biohydrogen generation through DF. The overall reaction of dark
fermentation is [66]:

C6 H12 O6 + 2H2 O → 2CH3 COOH + 2CO2 + 4H2 (4)

This technology is considered to be favorable and propitious for biohydrogen genera-

tion since it converts the waste and residual biomass to clean energy instead of throwing
it away and polluting the environment [66,67]. DF is characterized by a high hydrogen
evolution rate, which is higher than that of other BHP technologies. Otherwise, the yield of
H2 per substrate consumed is low. Also, the high production of carbon-rich metabolites
and CO2 presents another drawback of this technology that should be treated by elimi-
nating CO2 or detaching it from H2 and by converting it to other substances like methane
(CH4 ) [68,69].
The main microorganisms used in DF for different substrates and the biohydrogen
yield are presented in Table 1.

Table 1. Microorganisms used in DF for different substrates.

Microorganism Substrate Biohydrogen Yield Reference

Clostridium thermocellum ATCC 27405 Sugarcane bagasse 4.89 mmol H2 /g mediumadded [70]
Clostridium saccharoperbutylacetonicum N1–4 Rice Bran 3.37 mol H2 /mol sugar consumed [71]
Enterobacter aerogenes CDC 819–56 Sago wastewater 7.42 mmol H2 /mol glucose [72]
Enterobacter aerogenes PTCC 1221 Rice straw 19.73 mL H2 /g straw [73]
Bacillus cereus Wheat straw 156.4 mL H2 /g VS [74]
Ethanoligenens harbinense B49 Glucose 113.5 mmol H2 /L [75]
Clostridium acetobutylicum YM1 Rice bran 117.24 mL H2 /g sugarconsumed [76]
Clostridium thermocellum ATCC 27405 Date seeds 103.97 mmol H2 /L [77]
Clostridium butyricum TISTR 1032 Food waste 362 mL H2 /g VS [78]
Clostridium beijerinckii PS-3 Oil palm 141 mL H2 /g substrate [79]

Photo-fermentation: this photosynthesis process is used to convert organic acids into

hydrogen and CO2 in the presence of anaerobic bacteria strains like Rhodopseudomonas and
Rhodobacter [80]. The operational process is based on the decrease of molecular nitrogen
due to the presence of nitrogenase (an enzyme produced by bacteria) that loses a proton
to hydrogen without the formation of oxygen. The overall reaction of this technology is
formulated as [81]:

CH3 COOH + 2H2 O + light → 2CO2 + 4H2 (5)

The advantages of this technology refer to the use of clean solar energy and the
conversion of organic waste into hydrogen. On the other hand, this technology is complex,
comprising biological, chemical, and physical procedures that depend on many factors that
affect the output of hydrogen generation, such as medium type, microorganism type, photo-
fermenter design, and light intensity [82]. Also, the drawback of this technology refers to the
low growth rate of anoxygenic that leads to decreases in its efficiency, which is two orders
of magnitude lower than that of dark fermentation. Moreover, photo-fermentation entails a
bigger reactor than dark fermentation for the same amount of hydrogen generation amount.
The combination of photo-fermentation and dark fermentation in two-stage processes leads
to a rise in the hydrogen output [83]. Photo-fermentation is viewed as a better technique to
generate biohydrogen compared to dark fermentation due to the higher hydrogen content
(up to 58.90%) and the performance in energy conversion (10.12%) [84]. Photo-fermentation
ChemEngineering 2024, 8, 17 12 of 31

also has better performance in hydrogen generation, with a maximum hydrogen generation
of 141.42 mL (g TS)−1 , compared to 36.08 mL (g TS)−1 for dark fermentation. Therefore, the
photo-fermentation could be considered to be a good option for biohydrogen generation.
However, photo-fermentation has lower performance in sunlight transformation and
biohydrogen generation compared to bio-photolysis.
Microbial electrolysis cells (MECs): this technology is used to generate hydrogen from
organic material using electrochemical devices. This technology is based on the microbial
oxidization of organic material to form CO2 , electrons, and protons that are minimized to
form hydrogen gas. The overall reaction of MECS is expressed as [85]:

CH3 COO− + 2H2 O + H+ → 2CO2 + 4H2 (6)

The reactions occur in a reactor called a microbial electrolysis cell (MEC), and the
microorganisms used are termed electricigens and act as biocatalysts. The biocatalysts
are used to boost voltage performance and generation rate and to minimize the activation
overpotential of a certain redox reaction [86]. Some microbes can create a biofilm on
the anode surface that can transform the chemical energy into electrical energy. The
generated electrical energy is used to generate beneficial output on the cathode, like H2
and CH4 [87]. This technology can generate a significant amount of biohydrogen with less
environmental impact.
The use of a photobioanode, which is based on the integration of bio and solar energy
on the same electrode, has been investigated in this technology. Results revealed that the
photobioanode with two edges—biocarbon material and photocatalyst—forms a biofilm,
resulting in enhanced extracellular electron transport and boosted exoelectrogens [88].
In addition, the use of metal-free carbon film based on CeO2 -rGO as a photobioanode
was tested, and a hydrogen evolution rate of 5 m3 /m3 /d was achieved when treating
wastewater [89].
Photocatalytic: in this technology, the water splitting into hydrogen is powered by
solar energy with the aid of the four-electron or two-electron method. The advantages of
this technology are the fewer environmental effects without the need for energy surplus,
the cost, and the large scale of hydrogen generation. The drawback of this technology is the
use of expensive noble metals, which are used as efficient redox-co-catalysts owing to their
high physico–chemical aspects, excellent catalytic activities, and electrical features [90].
Contrastingly, non-noble metal photocatalysts are regarded as propitious options for water
decomposition thanks to their good performance, good stability, and low price. The good
stability of non-noble metals avoids deactivation under some circumstances, making it
convenient for transforming wastewater into hydrogen. An overview of the non-noble
metal catalysts used in photocatalytic H2 evolution is presented in Table 2. Many strategies
have been mentioned in the literature to promote the photocatalytic H2 generation from
water splitting, such as dye-sensitization, raising the contact area and the intensity of the
interconnection, ion co-doping, metalloid doping, building ore-shell structures, building
ternary systems, and supervising the morphology of the catalysts [91].

3.3. Thermal Technique

Hydrogen is released from materials and organic materials using heat and chemical
reactions. The organic material could be fossil fuels such as natural gas, and the material is
water, and, in this case, the process is called thermochemical. The thermal technique in-
volves natural gas reformation, biomass, coal gasification, and thermochemical generation.
The methods followed by this technique are steam reformation, biomass gasification, and
partial oxidation.
ChemEngineering 2024, 8, 17 13 of 31

Table 2. An overview of non-noble metal catalysts used in photocatalytic H2 evolution.

Hydrogen Evolution
Class Catalyst Co-Catalyst Reference
Rate (µmol/h.g)
Metal CdS Loaded Ni3 CNPs, Loaded TiO2 1028–18,020 [92,93]
sulfide ZnS Doped Cu, doped In and Cu, loaded ZnO/g.C3 N4 301.25–973 [94,95]
CdS/ZnS - 686 [96]
Metal TiO2 Doped high content C, coated 1 T-MoS2 33.04–21,500 [95,97]
oxide ZnO Loaded g-C3 N4 NSs, Loaded CdS QDs 322–22,120 [97,98]
Metal-free g-C3 N4 Doped P, Doped B, and F 348–7020 [99,100]
Metal NiP, Doped Mo, doped Co 15,300–20,400 [101]
phosphide Cu3 P Hybridized MoP 5420 [102]

Steam reformation (SR): this is among the most widely used and the cheapest tech-
nologies to generate hydrogen [103]. Its features emerge from the low generation and
operational cost and the high operational performance. The most common feedstocks
used are methane sources like natural gases and hydrocarbons [104]. Methanol, ethanol,
and glycerol could be used in this technology. Methanol has many benefits related to
attainability and accessibility, vacancy of C–C bonds in its chemical structure, a large ra-
tio of hydrogen to carbon, cheapness and safety, and moderate operating circumstances
for its catalytic conversion into hydrogen. Moreover, methanol could be supplied from
renewable energy resources. Ethanol is viewed as more promising because one molecule of
ethanol can generate six moles of hydrogen during steam reformation compared to three
moles of hydrogen generated by methanol–steam reformation. Ethanol can be generated
from agricultural feedstocks and lignocellulose. Glycerol is generated from the biodiesel
industry and alcohol and vegetable oil through transesterification reaction as a byproduct.
The main feature of glycerol is its availability, in which one ton of biodiesel generation
transesterification of edible or non-edible oil could generate 100 kg of glycerol. This process
is endothermic and requires high temperature and pressure to burn the used raw material.
It is performed through three phases. The overall reaction is presented as [105]:

MSR reaction : CH3 OH + H2 O → CO + 3H2 (7)

Water − gas shift reaction : H2 O + CO(g) ↔ H2 + CO2 (8)

It begins by reforming the hydrocarbon raw material with steam under high pressure
(3–25 bar) and high-temperature steam (700–1000 ◦ C) and injecting them into a catalyst
reactor to obtain a mix of carbon monoxide and hydrogen (syngas) with a small quantity
of CO2 . The second phase, named the “water–gas shift reaction”, aims to generate more
hydrogen by reacting the carbon monoxide with water to generate carbon dioxide and
hydrogen using a catalytic. The last phase strives to purify the hydrogen by removing the
carbon dioxide and other impurities from the gas stream. Many processes can be used
in this phase, such as membrane or pressure swing adsorption. Despite the benefits of
SR, it has many drawbacks attributable to the thermodynamics reactions and reactant
features [106,107], such as the high generation cost and the high power, tough reaction
circumstances, and low reaction performance and operation constancy. These drawbacks
are due to the high stability of methane that requires high energy consumption and extra
tools to ensure the high temperature and pressure required to activate it. Also, the cost
and the reachability of the used noble metals catalysts restrain their use. In addition, SMR
releases greenhouse gas that affects the environment and raises the cost of SR to handle
these emissions. The catalyst used in steam reformation should have special properties, like
high catalytic activity, good heat exchange, excellent thermal stability, accepted lifespan,
low pressure decrease, and high mechanical stability. Developing cheap catalysts with
properties that meet the requirement of steam reformation catalysts is crucial mainly in
activating methane at low temperatures, reaching the equilibrium values over a short time,
and protecting from deactivation parameters such as preferential oxidation and carbon
ChemEngineering 2024, 8, 17 14 of 31

formation [108]. The most common catalyst used in SR is Ni-based catalysts, owing to their
low price and high catalytic activity. However, Ni-based catalysts suffer from coking and
sintering. Many studies have been carried out to solve these issues by developing new
agents, adjusting the structures of supported Ni catalysts, building self-supported Ni-based
catalysts, and searching for Ni-based solid solution catalysts [109]. Some non-noble metals
have a high catalytic activity compared to nickel, such as MoC2 /Al2 O3 , which achieved
better CH4 transformation compared to Ni/Al2 O3 under low-temperature conditions [110].
Non-noble metal catalysts have serious issues that should be addressed, such as carbon
deposition, aggregation caused by high temperature, and easiness of deactivation [111].
Noble metal catalysts, such as Ru, Ir, Rh, and Pd, have been used as catalysts in SR owing
to their excellent catalytic activity and durability. However, their high cost and some
issues related to aggregation and carbon deposition for some noble metals limit their
uses. Many studies have been conducted to enhance the performance of noble metals
while minimizing their loading quantity. Rh showed excellent catalytic activity in the
conversion of CH4 . A study has been conducted on the deposition of CeO2 on Rh, and
results showed that Rh/CeO2 achieves the highest methane transformation compared
to other noble metals [112]. The addition of CeO2 to Pt/Al2 O3 enhances its efficiency in
converting the CH4 [113], and the addition of 12 wt.% La2 O3 to Pt/Al2 O3 enhances the
catalytic activity and minimizes the particle size of Pt [114].
Dry reformation (DR) is one of the new technologies that has been developed to
overcome the different disadvantages of SR by improving the process of methane transfor-
mation. The chemical reaction of DR technology is presented by [93]:

CH4 + CO2 ↔ 2CO + 2H2 (9)

The advantage of DR comes from its ability to convert the greenhouse gases CH4 and
CO2 , using them as oxidants, into syngas, resulting in a decrease in their emissions. It
is used in processes that demand a high portion of CO in the synthesis gas. The compo-
nents H2 and CO of syngas might be used to generate chemical fuels, mainly H2 . It has
the same thermodynamics as steam reformation. Dry reformation of methane (DRM) is
viewed as a promising candidate for energy storage. For instance, DRM powered with
concentrated solar energy could empower the transformation of solar energy with lower
energy density into chemical energy with bigger energy density for steady and sustainable
exploitation [115]. Many studies have been conducted on the thermochemical storage
performance of DRM power by solar energy, which is defined as the fraction of chemical
energy generated to input solar energy. A thermochemical efficiency of 19.7% was obtained
by DRM reaction in a tubular and semi-cavity reactor powered by a solar dish system [116].
Moreover, the DRM reaction in a foam reactor heated by highly concentrated solar radiation
achieved a thermochemical efficiency of 45.58% at c.a. 600 ◦ C [117]. However, DR has
many disadvantages attributed to a larger energy consumption that renders its application
at an industrial scale unserviceable/ineffective, a higher tendency to coke (carbon with a
few impurities) forming, and low fineness of syngas. The carbon formation can paralyze
the operating catalyst that is used to decrease energy consumption. Two solutions could be
used to reduce the coke deposition, either by increasing the temperature above 1000 ◦ C
or by adding oxygen to the feed by changing the catalysts with rare earth metals. The
catalysts used in dry reformation could be noble metals (Ru, Pt, Rh, and Pd) and non-noble
metals (Co, Ni, and Fe). The main advantages of noble metal catalysts derive from their
excellent catalytic activity and high protection against coke deposition. According to a
study [118] on the efficacity of different noble metal catalysts (Ir, Rh, Pd, Ru, Pt at 5 wt.%),
Rh showed the highest catalytic activity and durability. However, their high cost is consid-
ered to be the main limitation to their use. Therefore, many studies have focused on the
use of non-noble metal catalysts, mainly nickel. The authors in [119] conducted a review
of the active metals dispersed over different support systems used in DRM reactions. The
catalytic activity of Ni/Sab-15 [120], Ni/A12 O3 [121], and Ni-MgO-Al2 O3 [122] on the CH4
and CO2 conversions has been examined and showed good results. Results also showed
ChemEngineering 2024, 8, 17 15 of 31

that the rise of Ni loading led to an improvement in the CH4 and CO2 conversions [122].
A novel adapted process based on using Ni as bifunctional materials for carbon capture
and methane dry reformation has been developed [123]. The process was based on using
NiO-impregnated CaO material and CaO-NiO composition, and the results showed a good
performance. Moreover, results pointed out that NiO-doped sodium zirconate ceramics are
excellent materials for CH4 dry reformation and CO2 capture. On the other hand, the main
issue with Ni catalysts is the apparent carbon deposition [124].
Performing a DRM reaction with solar energy could enable a high conversion of CH4
with a high energy storage efficiency and a high reaction temperature obtained from high
solar concentration ratios. The use of a selective membrane, such as an oxygen permeation
membrane reactor and three-side membrane reactor, could boost the conversion rate of a
chemical reaction [125,126], as well as its potential to minimize CO2 emission owing to the
smaller heat requirement and purer outcome steam from the reactor [127].
Partial oxidation (PO) is an exothermic reaction that takes place when the methane or
hydrocarbons react with a finite amount of oxygen to generate a syngas stream, a small
amount of carbon dioxide, and other compounds. The chemical reaction of partial oxidation
is [128]:
Cn Hm + 1/2nO2 ↔ nCO2 + 1/2mH2 (10)
The reaction cannot be achieved to compose carbon owing to the insufficiency of
oxygen. The interest in this technology is assigned to its rapidness, which is quicker than
steam reformation, and its need for a smaller reactor. Also, this method is characterized
by a high conversion of methane with an excellent specificity of hydrogen and high space
velocities (flow rate of the reactants/the reactor volume) of the catalyst [129]. PO has not
been commercialized owing to some issues related to small drops in CO selectivity due
to the overoxidation that leads to increased local temperature at the catalyst surface and
conduct to deactivate the catalyst due to its sintering and carbon deposition. The catalysts
used in the partial oxidation of methane (POM) are noble metals, perovskite oxides, and
transition metals (Fe, Ni, and CO) [130]. The transition metals are characterized by a
stimulant catalyst element for POM, and the species metal has an important contribution
to the methane transformation processes. The use of Ni-supported catalysts can foster the
generation of syngas due to the metallic nickel and the complete combustion of methane
due to NI species with an oxidation number bigger than 2. Perovskite-cased catalyst mate-
rials proved their high catalytic activity, their potentiality in constraining themselves from
carbon degradation, and their steadiness. Also, the perovskite catalyst can minimize the
sill/starting value required to produce the carbon deposition. In addition, the reaction of
oxygen species atop the perovskite that reacts with the carbon deposition could avoid the
carbon deposition. The partial oxidation of ethanol has many benefits compared with the
other thermal technologies, such as quick start-up, simple functioning without the need
for an external heat source, and short reaction time [131,132]. It has been demonstrated
that the combustion of porous media could be enhanced owing to its larger heat transfer
performance, larger flame temperature, and speedy flame [133,134]. Moreover, the en-
hancement of hydrogen generation could be achieved through a larger flammability limit
using super-adiabatic combustion through porous media combustion [135]. Pd-based and
Pt-based catalysts can be used in POM for hydrogen generation. The Pd-based catalysts
require preheating to drive POM, and the Pt-based catalysts can drive the POM with a cold
start [136].
Autothermal reformation (ATR) integrates two technologies—steam reformation and
fuel oxidation—in one consolidated reactor that comprises a combustion area and a catalyst
bed in a refractory-lined pressure shell. In this process, the exothermic reaction of fuel
oxidation provides the requested heat for the endothermic reaction of steam reformation.
The feedstock used in this process can be liquefied petroleum gas, naphtha, natural gas,
Fischer–Tropsch tail-gas, pre-reformed gas, or refinery off gas. This technique is performed
under pressures of between 30 and 50 bar, temperatures between 950 and 1050 ◦ C, an
ChemEngineering 2024, 8, 17 16 of 31

oxygen-to-carbon molar rate of 0.6–1, and a steam-to-carbon molar rate of 0.5–1.5 [137].
The chemical reaction of ATR is formulated as [138]:

CH3 OH + (1 − nH2 O) + 0.5nO2 ↔ CO2 + (3 − n)H2 (11)

The operational process of this technology starts with the desulfurization of the feed
gas to remove the sulfur, which should be preheated and pre-reformed before injecting
it into the ATR reactor using the referenced proprietary heater. After that, syngas is
produced by reacting the feed gas with oxygen and steam. Then, the generated syngas is
injected again into the same reactor for more reformation to attain high output, achieving
thermodynamic equilibrium. In the last stage, the syngas streams into a gas boiler, which
is used to cool down the syngas and produce high-pressure steam. The syngas can be
used in several applications, such as generating hydrogen by separating the components
of the syngas and using it as raw material for other synthesis processes (Fischer–Tropsch).
Also, the high-pressure steam can be used for power production. ATR is common for
smaller-scale hydrogen production, quicker power-up and reaction time than SR, higher
output H2 generation than POX, and lower operational cost and energy requirements [139].
The issue of this process is the choice of the catalyst that should serve the SR and the fuel
oxidation and correspondence to the used fuel. Also, for high-generation capacities, this
technology becomes cost-effective due to the large investment requested for an oxygen
generation station [139].
Noble metal-based catalysts, like Rh/Al2 O3 , can generate a high amount of hydrogen
in ATR, but their use is limited due to their high cost [140]. A non-precious-metal catalyst
could be used in the ATR of ethanol. A nickel-based catalyst is a good candidate, but it
generates low hydrogen at low temperatures. Moreover, the deactivation of the catalyst
is induced by rubbishing and carbon deposition on the surface of the catalyst. The en-
hancement of the catalytic activity and stability of Ni-based catalysts could be achieved by
adding some metals like Co, Cu, or Mo or utilizing different supports like CeO2 , La2 O3 ,
and Y2 O3 [141,142]. Moreover, iron is known as an active element in the water–gas shift
reactions. It can lessen carbon deposition and raise selectivity to carbon dioxide, which
is pivotal for the hydrogen-opulent reformat gases used as fuels for application in fuel
cells [143]. Moreover, iron has identical electronic properties to nickel. Therefore, it could
enhance the nickel-based catalysts. Ammonia decomposition is used to generate hydrogen
by operating an autothermal microchannel reactor. The effects of different operating condi-
tions on the performance of the reactor have been studied [144]. Results have revealed that
the best functional circumstances were achieved with a flow rate of ammonia of 0.4 NLPM,
with a fuel-rich calculation equable to a fuel equivalence rate of 1.2, and a combustible feed
flow velocity of 0.8 NLPM.
Plasma reformation: plasma is an ionized gas produced in several ways, such as
shocks, flames, and electric discharge. It is distinguished by high electrical conductivity.
Plasma has the potential to supply high temperatures appropriate for thermal decom-
position, decreasing activation energy via vibrational excitation-based reaction passage,
electron collision-created cleavage, and ions and radicals adequate for utilization in cat-
alytic reactions [145]. It has been experienced to be used in the generation of hydrogen
through the reformation process due to its high energy density. The whole reformation
reaction is similar to traditional reformation. The only difference is that the plasma is used
to generate the energy and the free radicals required to run the reformation processes. In
this technology, a catalyst is not required since plasma acts as the catalyst due to the high
energy density. The main benefit of this method is low power consumption compared
to steam reformation and electrolysis and operation at low operating temperatures. In
addition, the generation cost is low, and the steam/heat output might be used for other
procedures [146]. According to [147], increasing the temperature by adding a heater and
raising the input voltage of the coil leads to a rise in the hydrogen generation rate. The
drawbacks of plasma reformation are the need for electrical energy and the hardness of
the high-pressure process, which negatively affect the lifetime of the electrode because it
ChemEngineering 2024, 8, 17 17 of 31

raises electrode corrosion by the reduction of arc mobility [148]. Plasma can be classified
into thermal plasma and non-thermal plasma based on the method of deposition of energy
into the gas stream. The main benefits of non-thermal plasma reformation compared to
thermal technology are high yield, instantaneous boot time, and lower energy cost. The
gliding arc is based on a transitional non-equilibrium plasma, beginning as thermal arc
plasma. The gas flow or magnetic field extends it, and it is snuffed out after it converts
to non-thermal arc plasma. It is considered to be a non-thermal arc plasma due to the
temperature of converted gas in the scope, which varies between 2200 and 2500 K, and
it is enclosed by the temperature of cold plasma (300 K) and thermal plasma (more than
10,000 K) [149]. A non-thermal arc has the potential to generate an efficient plasma with
high effectivity and good astucity. It has been proved that the use of a gliding arc discharge
reactor with a vortex flow configuration can achieve the best reformation outcomes in the
matter of fuel transformation and low-priced energy needed for syngas generation [150].
The effect of different factors such as voltage, temperature, waveform, and feeding rate
on methanol transformation plasma–catalytic methanol–steam reformation under electric
discharge has been examined [151]. Results have revealed that the rise of frequency and
discharge voltage leads to improved methanol conversion controlled by electric discharge.
The main benefit of electric discharge is the amount of energy supplied, which is enough to
break the chemical bonds of methanol and steam. In addition, a square waveform has been
proven to be more efficient in methanol conversion compared to a sine waveform. Also,
a rise in absorption intensities of reactants on the active surface on the catalyst surface is
achieved by a strong electric field.
Pyrolysis is considered among the thermochemical technologies that convert biomass
into hydrogen. Pyrolysis is a well-known route for hydrogen production, in which
hydrogen-containing compounds such as hydrocarbons are the only reactants. In fact,
these compounds are decomposed by heating in the absence of oxygen and water to
achieve a high temperature (between 375 and 525 ◦ C) in a short period. In this regard, the
pyrolysis of biomass is a renewable source, and pyrolysis of methane and hydrogen sulfide
is used as feedstock. The output of the reaction is a liquid mixture produced in a gaseous
mixture that will then be liquified [152]. The overall reaction of pyrolysis is given by [153]:

1/2CH4 + 2O2 ↔ 1/2C + H2 (12)

Many factors affect the performance of generating hydrogen by pyrolysis, such as

temperature, the rate of biomass heating, the catalyst type, and the time interval [154–156].
The high temperature and the short process time led to an increase in the hydrogen yield.
Biomass pyrolysis requires low-pressure operation [157]. The feasibility of its application
using several feedstock materials is considered to be its main advantage, while the requisite
of a high amount of energy is the main drawback [158].
Biomass gasification is known as one of the thermochemical conversion technologies
to convert organic material into synthetic gas (syngas) and a solid product labeled char in
an enclosed gasifier at high pressure and temperature. Syngas is a combustible gas that
contains mainly hydrogen and carbon, and it can be used as a fuel source and intermediate
to generate chemical products. The char is a blend of untransformed organic portions,
predominately carbon and ash. Biomass gasification is regarded as a promising technology
for hydrogen-rich syngas and is characterized by high energy performance and low CO2
emissions [159]. It has been developed at a commercial scale. The feedstocks used in this
technology are biomass resources, like municipal and industrial wastes, and forestry and
agriculture leftovers [160]. The disadvantage of this technology is the high cost of hydrogen
generation, which can reach 3.5 USD/GGE, compared with the SR technology [161,162].
Thermolysis is a thermochemical process where water is decomposed into hydrogen
and oxygen using chemical reactions and, under high temperatures (500–2000 ◦ C), heat
is provided from concentrated solar power, wind energy, and waste heat from nuclear
reactors. This technology is characterized by carbon-free or low-carbon emissions. Also,
ChemEngineering 2024, 8, 17 18 of 31

this technology makes a locked loop that is fed only by water to generate hydrogen and
oxygen since the chemicals utilized in the operation are reused in each twirl.

H2 O + heat → H2 + 1/2O2 (13)

The energy generated by wind farms could be used to perform an electrolysis process
and generate green hydrogen. The wind-driven hydrogen generation could enhance the
overall resource use of wind energy. The working principle is based on the use of energy
generated by wind to generate hydrogen in electrolytic cells and then to separate and purify
the produced hydrogen to compress and store it. Many studies have been performed to
evaluate hydrogen generation using on and offshore wind in many countries [163–165]. A
study has been conducted by [166] to assess the generation of hydrogen using wind farms
in Pakistan. Findings have indicated that the generation of hydrogen using wind energy
is commercially feasible in many cities in Pakistan, and the hydrogen generated could be
used to fuel many forms of transportation.
Solar energy is also used to feed electrolysis to generate green hydrogen. Two tech-
nologies use solar energy to produce green hydrogen: photovoltaic electrolysis and concen-
trated PV electrolysis. Many solar-driven hydrogen generation projects have been erected
to generate hydrogen using PV panels. In the past, the use of this technology was disap-
pointing due to the low performance of solar to hydrogen (2–6%) and the high capital cost
(40 USD/kg of hydrogen) [167,168]. Recently, many studies have been conducted to en-
hance efficiency and decrease the capital cost of this technology. A rise of solar hydrogen
efficiency to 12.4% could be attained by matching the maximum power output voltage of
the PV system with the operating voltage of the electrolyzer [169]. Also, an integration
of multi-junction PV with electrolysis could achieve a high efficiency, around 16% [170].
Moreover, a study showed that the optimization of hydrogen generation could be attained
using a DC/DC buck transformer with an MPPT and by controlling the water flux inserted
in the electrolysis [171]. Using a DC/DC buck transformer can enhance the acclimation
between the electrolysis and the PV generator, and the control of water flux can enhance
hydrogen generation.
Nuclear energy-driven hydrogen generation technology is viewed as a promising and
attractive way to generate green hydrogen. Nuclear energy is more advantageous than
renewable energy resources, which have many drawbacks related to density, magnitude,
goodness, and reliability [172]. Nuclear energy can produce hydrogen energy by means
of high-temperature thermochemical processes or using temperature steam electrolysis.
The working principle of this technique is based on the use of high heat generated by the
reactor to split the water into hydrogen and oxygen. The drawbacks of this technology are
the high corrosivity caused by high temperatures that affect the materials used and some
hazards caused by the extending process [173]. To achieve an effective electrochemical and
thermochemical performance, high temperatures are requested and can be obtained using
high-temperature reactors. Molten salt-cooled, gas-cooled, and liquid-cooled reactors are
some examples of reactors that can be used to generate hydrogen. The most economical
reactor to generate hydrogen is the high-temperature gas-cooled reactor (HTGR) [174].
The first high-temperature gas-cooled (HTGR) reactor was built in Japan by the Japanese
Atomic Energy Agency (JAEA). The development and commercialization of generating
hydrogen with nuclear energy using HTGR is attributed to the JAEA. Moreover, the issue
of nuclear waste with high radioactivity levels is solved by the development of accelerator-
driven systems through the turning of long-lived fission products (LLFP) and MA into less
dangerous nuclides diminished lives [174].

4. Comparison of the Technologies Used to Generate Hydrogen

A comparison of the technologies presented in the current paper and used to generate
hydrogen in terms of efficiency, advantages, and drawbacks is displayed in Table 3. It
can be noticed that the reformation technologies have the highest efficiencies, but they are
characterized by high energy consumption and high greenhouse gas emissions. Steam
ChemEngineering 2024, 8, 17 19 of 31

reformation and plasma reformation could attain an efficiency of 85%, compared to 75% by
partial oxidation and autothermal and 50% by biomass gasification.
In biological processes, micro-algae and bacteria are used to generate hydrogen by
means of biological reactions and using either organic matter or sunlight. This process
gains more attention owing to the large and easy attainability of feedstock material, low to
net-zero carbon emission, and economic competitiveness. In addition, this process might
use wastewater since bacteria and algae could be expanded/developed in wastewater.
However, the methods used in this process are characterized by low yield/efficiency and
require more research [175].
Water electrolysis technologies are considered to be clean and environmentally friendly
if combined with renewable energy resources. PEM and alkaline are used under low
temperatures, while solid oxide electrolyzers (SOE) are used under high temperatures.
PEM has the advantages of hydrogen gas purity and high current densities compared
to alkaline electrolysis. Anion exchange membrane (AEM) and PEM electrolysis have
analogous assemblies, while the membrane in AEM transport anions (OH–) is a substitute
for proton (H+). AEM and alkaline use the same process in the electrodes. AEM is cheaper
than PEM due to the use of cheaper membrane transport anions, and AEM does not use
noble metal catalysts. A high-purity hydrogen could be achieved using AEM at high
pressure compared to an alkaline electrolyzer. PEM electrolysis could achieve a higher
efficiency of 70% compared to AEM, alkaline, and SOE, which have an efficiency of 60%.
Seawater electrolysis is viewed as a promising method to generate clean hydrogen without
requiring a high demand for freshwater since it uses seawater and can achieve an efficiency
of 72%. However, the corrosion of the positive electrolyte by the negatively charged
chloride that exists in seawater leads to court the lifespan of the system. This drawback can
be overcome using layers loaded in negative charges to coat the anode; therefore, they can
repel the chloride and cease the degradation of the essential metal.

Table 3. Comparison of the technologies used to generate hydrogen.

Technology Efficiency Advantages Drawbacks Maturity Reference

Alkaline Long-term stability, cost-effective, low cost, Low current densities, low operational pressure,
50–78% Commercial [23]
electrolyzer mature technology, non-noble catalyst corrosive liquid electrolyte, crossover of gases
PEM High current densities and voltage efficiency, High cost of components, acidic corrosive
50–83% Commercial [23]
electrolyzer high gas purity, rapid system response environment, low durability
No electrode corrosion, since it performs with
Solid oxide
high temperatures, so no need for expensive Bulky design, durability issues, high cost, and
electrolysis 89% (lab) Medium-term [176]
catalysts and better ability to tolerate the complex fabrication
cells
presence of impurities, negligible pollution
Chloride resistance, oxidation resistance, alkali Low power performance, low ionic conductivity,
Anion
resistance, and diffusion and dialysis to recover important catalyst loading, and moderate-range
exchange 57–59% Commercial [43]
acid, regeneration is not required, high-purity membrane stability with significant ohmic
membrane
hydrogen resistance loss
Generate more hydrogen using less energy
Plasma
- consumption compared to hydrocarbon [177]
electrolysis
electrolysis
Capital costs of the water purification
Seawater Mitigation of freshwater consumption since equipment and the environmental problem
72% R&D [178]
electrolysis seawater is a plentiful resource arising from the need to dispose of the residual
salts removed during desalinization
High needs of light intensity, low performance,
Photolysis 10–11% CO2 neutral, O2 generation Long term [179]
expensive
Low yield of H2 per substrate
Dark Light is not mandatory required, and many consumed—concomitant production of
60–80% Long term [180]
fermentation substrates can be used as carbon source carbon-rich metabolites (i.e., organic acids,
alcohols) and CO2 , big reactor needed
Possibility of using different organic Photochemical performance is low, and
Photo- biomass—oxygen inhibition effects on hydrogen nitrogenase activity is restrained due to the
10% Long term [181]
fermentation generation is removed since photosynthetic existence of oxygen
bacteria do not have PSII Low efficiency
ChemEngineering 2024, 8, 17 20 of 31

Table 3. Cont.

Technology Efficiency Advantages Drawbacks Maturity Reference

Possibility to work at high pressure with low
Hydrogen can be consumed at the bioanode,
Microbial energy consumption, ecofriendly electrolyte,
bioanodes do not accept high temperatures and
electrolysis 78% low-cost material, self-sustained and Long term [182]
high substrate concentrations and are very
cells self-assembled electrocatalyst, oxidation of
sensitive to slightly acidic pH
organic compounds
Steam No oxygen required, lowest process
70–85% Highest greenhouse gas emission Commercial [183]
reformation temperature, good H2 /CO ratio
Large energy consumption, higher tendency to
Dry
Possibility to use CO2 coke forming, - [93]
reformation
forming and low fineness of syngas
Partial Very high processing temperatures,
60–75% Catalyst is not required, low methane slip Commercial [184]
oxidation Low H2 /CO, generation of heavy oils
Autothermal Low methane slip, requires less temperature
60–75% Needs air or oxygen, generation of GHG Near term [185]
reformation than POX, existing infrastructure, mature
No need for thermal activation, quick reaction
Plasma
9–85% start-up, long durability, reliable, small reaction Requires electrical energy Long term [148]
reformation
volume
Biomass CO2 -neutral-decrease the amount of energy Requires a large amount of land and very
35–50% Commercial [186]
gasification sources inefficient
Possibility of using several cheap feedstock Require high amount of energy, seasonal
Pyrolysis 35–50% Near term [187]
materials disponibility, Tar formulation

5. Barriers to Hydrogen Generation

Hydrogen energy is viewed as one of the most favorable alternative fuels to achieve
sustainable mass transport. It has the potential to decarbonize transport since it can be
exploited in fuel cells to power vehicles by converting H2 into electricity without emitting
harmful pollutants and greenhouse gases. A hydrogen vehicle emits less than 15 tons
if generated by renewable electrolysis compared to 40 and 45 metric tons of a diesel
vehicle [188]. Hydrogen fuel can power airplanes, domestic heating, steel production,
heavy commercial vehicles, and long-haul freight vehicles. In addition, hydrogen could
be an effective part of the transition to more sustainable energy. It can be used as energy
storage for intermittent renewable energy, in both the medium and long term, due to its
very high specific energy. However, hydrogen should be stored as gas at high pressure or
as a liquid at cryogenic temperature since it has a very low volumetric density. Moreover,
hydrogen can play a crucial role in the long-distance transport and trade of energy.
Despite all the advantages of hydrogen energy, its generation faces many challenges
that should be addressed to boost the evolution of the hydrogen market in the coming
years. These challenges are presented below.
- There are many existing technologies for hydrogen generation. Some of these tech-
nologies are cheap but pollute the environment, and others are expensive and clean.
Hydrogen producers face an important issue in choosing the best technology and the
source of energy used to perform the generation process.
- Hydrogen storage is considered to be a significant barrier since high space is required
to stock hydrogen owing to its low density, resulting in increasing hazardous accidents
due to the high flammability of hydrogen. Also, energy efficiency is a significant issue
for all hydrogen storage technologies. The round-trip efficiency of hydrogen storage
is 32% compared to 95% of battery storage [189,190]. Moreover, the cost of hydrogen
storage is expensive compared to the storage of petroleum fuels. The capital cost
of underground and aboveground hydrogen storage compared to battery storage is
shown in Table 4. It is observable that the charging and discharging cost of hydrogen
storage is higher than that of battery storage, but the discharging cost of hydrogen
storage is lower than that of battery storage.
ChemEngineering 2024, 8, 17 21 of 31

Table 4. Capital cost of hydrogen and battery storage [189,190].

Charging Cost Discharging Cost Storage Cost

Technology
(USD/kW) (USD/kW) (USD/kW)
Battery 196 60 218
Hydrogen
942 574 0.08
underground
Hydrogen above
942 574 35
ground

- A hydrogen-fueled vehicle might be less preferable since less space will be available
for commuters due to the high space of hydrogen storage [191]. Also, the mileage that
the vehicle can travel before recharge presents a barrier since the vehicles require a big
storage capacity, resulting in bigger space in the vehicle. This issue could be solved
through electric vehicles using fuel cell batteries, which have some issues related to
the cost and the resources that are not renewable [192]. Furthermore, the installation
of recharging stations required for hydrogen-fueled vehicles causes a problem since
investors will not invest in the installation if they are not sure that people will buy and
use hydrogen vehicles [193]. Another issue related to the long process of the design
and installation of infrastructure is the road networks and pipelines required for fuel
charging stations.
- The expanding hydrogen market is facing the impediment of the ability of the existing
technologies to meet the hydrogen demand that is projected to increase in the coming
years with a competitive cost.
- The use of hydrogen for transportation, electrification, and heating is less effective
than direct technology since hydrogen is an energy carrier and not a primary energy
source, resulting in a high conversion loss.
- The carbon capture and storage (CCS) used in the generation of blue hydrogen is
unproven at scale and expensive since it requires equipment, materials, and infrastruc-
ture for transportation and storage, causing an increase in the cost of the generated
energy. In addition, the CO2 captured in CCS is used in enhanced oil recovery to liber-
ate unreachable oil into the depleted oil wells, resulting in increasing CO2 emissions
into the atmosphere. Also, the leakage of CO2 during transportation and at the site
of underground storage causes an immediate menace to human and animal welfare,
even if accident rates are very low.
- The generation of hydrogen through electrolysis consumes a huge amount of water.
In addition, the water used in the electrolysis process should be purified before using
it. Therefore, the capital cost of hydrogen generation increases with the cost of water,
purification, and transportation.

6. Economics of Hydrogen Generation

6.1. Cost of Hydrogen Based on Hydrogen Types
An analysis of the hydrogen-based energy system has been conducted [194]. The
findings pointed out that the global future energy system will be established mainly on
electricity and hydrogen. The cost of hydrogen relies on technologies used to generate
hydrogen and the feedstock used. Among the different types of hydrogen (colors), the
lowest cost of hydrogen generation is gray hydrogen, with a price range from 0.88 to
2.31 USD/kg of H2 [195]. The cost of blue hydrogen is higher owing to the necessity
to use devices/systems to capture and store carbon, and it ranges between 1.32 and
3.30 USD/kg of H2 [196]. The generation cost of green hydrogen through electrolysis is the
most expensive, and it ranges from 2.42 to 9.01 US USD/kg of H2 [195,196].
Figure 6 displays the cost of blue hydrogen, generated with coal and gas, and green
hydrogen in 2019 and a future estimation of their costs [197]. It can be noticed that the cost
of blue hydrogen generated with gas is the lowest, and the cost of green hydrogen is the
ChemEngineering 2024, 8, 17 22 of 31

highest. Blue hydrogen is 2–3 times cheaper than green hydrogen. Nevertheless, the cost
of green hydrogen is projected to drop significantly, by up to 60%, to reach a minimum
value of 1.5 USD/kg by 2050. Many issues affect the cost of green hydrogen, such as the
renewable electricity price, operating hours, and the electrolyzer investment cost [198].
Innovation and enhanced efficiency are required to maximize the electrolyzer’s ability to
reach multi-gigawatt (GW) levels. The drop in electricity price and the investment cost of
electrolysis facilities are fundamental to producing a competitive green hydrogen.

Figure 6. The global cost of hydrogen generation [197].

6.2. Cost of Hydrogen Generated Based on the Technologies Used

Currently, the most predominately used and economical technology for hydrogen
generation is the steam reformation of methane. Around half of all global hydrogen is
generated using steam reformation, with a generation cost of 7 USD/GJ. Partial oxidation
of hydrogen showed a competitive price for hydrogen generation. Nevertheless, a carbon
capture and storage system should be integrated to minimize the greenhouse gases gener-
ated by thermochemical technologies, and in this case, a rise in hydrogen price by 25–30%
must be considered [61].
Gasification and pyrolysis of biomass are among the thermochemical technologies
used to generate hydrogen. The cost of hydrogen generation by gasification and pyrolysis is
costly, about three times greater than the cost of hydrogen generated by steam reformation
technology. Therefore, these technologies are generally not deemed as cost-competitive
for steam reformation. The cost of hydrogen generated by gasification and pyrolysis of
biomass ranges from 10 to 14 USD/GJ and from 8.9 to 15.5 USD/GJ, respectively. The
generation cost depends on different factors, including the equipment, accessibility, and
cost of raw materials [1].
Generating hydrogen using water electrolysis is considered to be the simplest and
most efficient process without byproducts. However, the generation of hydrogen through
water electrolysis is costly due to the cost of electricity needed to split the water and the cost
of water. Decreasing the electricity prices and increasing the operating hours are crucial for
hydrogen generation through electrolysis [199].
An economic analysis of the different hydrogen generation technologies has been car-
ried out [200]. Results demonstrated that the most economical technology is the generation
ChemEngineering 2024, 8, 17 23 of 31

of gray hydrogen. In addition, the study indicated that alternative technologies could be
economically competitive in the future. Gasification and pyrolysis have the potential to
be competitive over time [201]. Also, results showed that hydrogen-generated power by
solar energy is the most ecofriendly process. The main technologies to generate hydrogen
by 2030 will be steam reformation of natural gas and catalyzed biomass gasification. In
addition, coal gasification and electrolysis will be used to a limited extent. Hydrogen
production using solar energy is arguable in a given context and is questionable but also
possible. The use of solar energy will most likely rise by 2050 [1].
A comparative study of the different hydrogen generation technologies in terms of
efficiency and cost has been performed [195]. Findings showed that hydrogen generation
based on fossil fuels is not in phase with the transition toward a sustainable energy future.
Also, the study pointed out that in the case of the generation of blue hydrogen, substantial
fugitive methane emissions happen, which is not taken into consideration in most studies.
Moreover, the study discussed the possibility of decreasing the cost of electrolysis in the
future. The introduction of a global hydrogen market is viewed as an important key
player since it would enable countries with suitable circumstances for renewable energy
generation to generate hydrogen at lower costs [202].
The cost breakdown of different technologies used to generate hydrogen is displayed
in Table 5. The highest investment cost is recorded for PEM electrolysis, with a value of
3163 (USD/kW), and the lowest is for the SMR technology. Steam reformation and steam
reformation with CCUS have the highest operating time and the lowest energy price.

Table 5. Cost breakdown of gray, blue, and green hydrogen [202].

Alkaline SMR with

PEM SMR
Electrolysis CCUS
Investment cost (USD/kW) 2836 3163 1090 1939
O&M (USD/kW) 42.54 48 51.27 57.82
Efficiency (LHV) 64 66 76 69
Operating hours 3000 3000 8322 8322
Energy price (USD/kW) 0.044 0.044 0.033 0.033

7. Conclusions
Hydrogen energy is viewed as the most available fuel worldwide and as one of the
prime options for storing renewable energy. It is an energy carrier used to store and
transport energy generated from other resources. Hydrogen energy is versatile. It can
be generated from several types of feedstocks and using a wide variety of technologies.
This paper presents an overview of the existing technologies used to generate hydrogen
from fossil and non-fossil fuels. These technologies are classified into three categories:
electrolytic, photolytic/biotechnique, and thermal. In electrolytic technology, electricity is
used to break water into oxygen and hydrogen, and the electricity used can be from fossil
fuels or renewable energy. Light energy, microbes, and micro-algae are used in photolytic
and biotechniques to break water into hydrogen and oxygen. In the thermal process, energy
is used to liberate hydrogen from several feedstocks, such as coal, natural gas, and biomass,
which incorporate hydrogen in their molecular bodies. Also, hydrogen can be generated
from feedstocks (like water) by combining heat with a closed chemical cycle. Results
showed that the most mature technologies are steam reformation and biomass gasification.
The actual technologies used for the generation and exploitation of hydrogen do not
conform with the environmental sustainability goals. The electrolytic process could be a
sustainable option if renewable energy is used; however, its cost and efficiency depend on
the cost and efficiency of the renewable energy resources used. Photolytic and biotechnique
methods are auspicious methods to generate hydrogen, but they are in the early stages of
development, and they are not feasible on a large scale. Gasification and thermochemical
technologies are economically feasible and competitive compared to reformation methods.
ChemEngineering 2024, 8, 17 24 of 31

The different barriers affecting the growth of the hydrogen energy market are high-
lighted in this paper. These barriers include low efficiency, high capital cost, and high
storage volume and cost. In the case of the electrolysis process using renewable energy,
hydrogen generation faces more challenges related to the extra cost of renewable energy,
the cost of water, its purification, and its transportation. More research studies should
be addressed to overcome the different challenges and boost the growth of the hydrogen
market in the coming years. The capital cost of hydrogen generation and storage should be
minimized by decreasing the cost of materials and components, increasing the efficiency of
the used technology, and dropping the cost of renewable energy.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: No new data were created.
Conflicts of Interest: The authors declare no conflict of interest.

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