energies

Review
Hydrogen Carriers: Scientific Limits and Challenges for the
Supply Chain, and Key Factors for Techno-Economic Analysis
Davide Clematis 1, * , Daria Bellotti 2 , Massimo Rivarolo 2 , Loredana Magistri 2 and Antonio Barbucci 1,3

1 Department of Civil, Chemical and Environmental Engineering, University of Genoa, Via All’Opera Pia 15,
16145 Genoa, Italy; [email protected]
2 Thermochemical Power Group, DIME, University of Genoa, Via Montallegro 1, 16145 Genoa, Italy;
[email protected] (D.B.); [email protected] (M.R.); [email protected] (L.M.)
3 Institute of Condensed Matter Chemistry and Technology for Energy, National Research
Council (CNR-ICMATE), Via de Marini 6, 16149 Genoa, Italy
* Correspondence: [email protected]

Abstract: Hydrogen carriers are one of the keys to the success of using hydrogen as an energy
vector. Indeed, sustainable hydrogen production exploits the excess of renewable energy sources,
after which temporary storage is required. The conventional approaches to hydrogen storage and
transport are compressed hydrogen (CH2 ) and liquefied hydrogen (LH2 ), which require severe
operating conditions related to pressure (300–700 bar) and temperature (T < −252 ◦ C), respectively.
To overcome these issues, which have hindered market penetration, several alternatives have been
proposed in the last few decades. In this review, the most promising hydrogen carriers (ammonia,
methanol, liquid organic hydrogen carriers, and metal hydrides) have been considered, and the main
stages of their supply chain (production, storage, transportation, H2 release, and their recyclability)
have been described and critically analyzed, focusing on the latest results available in the literature,
the highlighting of which is our current concern. The last section reviews recent techno-economic
analyses to drive the selection of hydrogen carrier systems and the main constraints that must be
considered. The analyzed results show how the selection of H2 carriers is a multiparametric function,
and it depends on technological factors as well as international policies and regulations.
Citation: Clematis, D.; Bellotti, D.;
Rivarolo, M.; Magistri, L.; Barbucci,
A. Hydrogen Carriers: Scientific
Keywords: hydrogen carrier; compressed hydrogen; liquefied hydrogen; ammonia; methanol; LOHC;
Limits and Challenges for the Supply formic acid; metal hydride; techno-economic analysis; hydrogen storage
Chain, and Key Factors for
Techno-Economic Analysis. Energies
2023, 16, 6035. https://doi.org/
10.3390/en16166035 1. Introduction
Academic Editor: Vladislav A. Hydrogen is an attractive energy vector due to its high gravimetric energy density
Sadykov (e.g., 120 MJ/kgH2 vs. 55.6 MJ/kgCH4 for methane), and the potentiality to make power
production carbon-neutral. Nevertheless, its production is still highly dependent on fossil
Received: 31 July 2023 fuels and only 4% is derived from water electrolysis [1], and so relevant efforts are required
Revised: 12 August 2023
in making hydrogen an energy carrier suitable for a sustainable green economy. In the
Accepted: 14 August 2023
last decades, researchers have focused on several kinds of water electrolyzers, such as
Published: 17 August 2023
polymer electrolytes membrane (PEMWEs) [2,3], alkaline water electrolyzers (AWE) [4,5],
and solid oxide electrolyzers cells (SOEC) [6,7], which differ in component materials and
operating conditions. Moreover, in green hydrogen production, electrolyzers must exploit
Copyright: © 2023 by the authors.
the excess energy from the renewable energy sources (RES) grid, and then, in a reasonable
Licensee MDPI, Basel, Switzerland. scenario, hydrogen is not immediately used when produced, and so storage systems are
This article is an open access article required [8–13]. The hydrogen storage systems must display key features to be competitive
distributed under the terms and with conventional fuels (gasoline, methane, liquid natural gas) and other energy storage
conditions of the Creative Commons systems (batteries). They must provide high safety standards, allow fast hydrogen release
Attribution (CC BY) license (https:// when required, and be economically sustainable. Moreover, with hydrogen being the
creativecommons.org/licenses/by/ lightest element, it has the intrinsic limitation of a low volumetric energy density under
4.0/). ambient conditions, thus introducing storage and transport issues.

Energies 2023, 16, 6035. https://doi.org/10.3390/en16166035 https://www.mdpi.com/journal/energies

Energies 2023, 16, 6035 2 of 31

Currently, the most common method of hydrogen storage is to pressurize the gas in
high-pressure tanks (350–700 bar) [14,15]. The high pressure has the benefit of reducing
the volume required, but the compression work required has a negative impact on the
global energy balance, with a consumption equivalent to 11–13% of the energy contained
in the stored H2 [16]. In addition, other technological issues are still unsolved, limiting the
application of such an approach. The severe operating pressure places strong mechanical
stress on the vessels, which are mainly made of steel or aluminium. As such, the shell
must have a thickness able to tolerate the tension and meet safety requirements not only
under conventional operating conditions, but also during undesirable events such as colli-
sions [17]. The direct consequence is an increase in the weight of the hydrogen vessel, which
strongly impacts the suitability of this methodology for mobile applications. Furthermore,
molecular hydrogen can cause serious damage to infrastructure (metal tanks and pipelines)
due to the activation of phenomena such as H2 embrittlement, which reduces the lifetime
service of the structure itself [18,19]. Alternative materials such as carbon fiber reinforce-
ments have been investigated for lighter vessels, preserving mechanical resistance, but
despite the promising results, the material costs limit large-scale applications. Nevertheless,
hydrogen storage at high pressures could be interesting for stationary applications, and for
creating “hydrogen banks” able to store a high volume of hydrogen. This concept would
exploit the possibility of storing an elevated amount of hydrogen in salt caverns. These are
particularly favorable for this area due to their low permeability to H2 , thus reducing gas
leakages [20,21].
Hydrogen can be also stored in a liquid state, but this requires extremely low tem-
peratures (−253 ◦ C), which can be reached only by high energy-consuming cryogenic
loops [22–24]. The keeping of such low temperatures consumes at least 30% of the stored
energy, thus decreasing global efficiency [25,26]. On the other side, liquid storage operates
at a lower pressure than gaseous, reducing the vessel weight and improving safety condi-
tions. Nevertheless, the costs are still too high for widespread usage, and this method is
suitable only for niche applications where the release of hydrogen occurs in a short time,
based on relevant investments.
Lately, other alternatives have been developed for hydrogen storage; among them,
liquid carriers such as ammonia [27–29], methanol [30–32] and formic acid [33,34], as
well as systems based on more complex liquid organic hydrogen carriers (LOHC) [35–37]
or solid materials such as metal hydrides, could play a relevant role in the near future.
The interest in alternative hydrogen carriers has increased due to the possibility of their
operating in milder conditions (pressure and temperature) than those required by CH2 and
LH2 . In these systems, hydrogen is stored by means of the formation of bonds, as a result
of which the sustainability of all stages of the supply chain must be considered. Indeed,
despite the promising results already reported in the literature, this review shows that
several issues still arise, hindering their application at a large scale.
In this review, the main features of the above-mentioned hydrogen carriers have
been considered, focusing on their production, transport, and final hydrogen release,
highlighting for each of them the main challenges that must be faced in order to reach
full application and deep market penetration. In the last section, a thermo-economic
comparison is proposed based on the literature, highlighting the key factors that must be
considered for the selection of the most suitable technology.

2. Hydrogen Carriers Supply Chain: From Production to Hydrogen Release

In the last two decades, several alternatives have been proposed to overcome the
severe conditions required to employ CH2 and LH2 technologies. The most promising
approaches discussed in the following sections are based on the storage of hydrogen
through the formation of chemical bonds in a more complex molecule: the hydrogen
carrier. In Table 1, key physical features of the hydrogen carriers discussed in the next
section are compared with hydrogen and methane. In this review, methane is not closely
discussed as a next-generation hydrogen carrier, despite its large usage and the role that
Energies 2023, 16, 6035 3 of 31

it can play during the current energy transition. Although the CO2 methanation reaction
allows for the storage of hydrogen in methane by exploiting captured carbon dioxide,
and it shows full compatibility with the energy infrastructure, methane storage requires
severe conditions relating to temperature or pressure due to the physical properties of
methane (boiling temperature −161.5 ◦ C, volumetric energy density at ambient pressure
0.0378 MJ/L). Such intrinsic limitations have already been raised for pure hydrogen storage,
and high-pressure or cryogenic loops are used as they are competitive with other possible
energy vectors. These two approaches have a negative impact on process energy balance,
justifying the interest in the development of energy carriers that can store hydrogen under
milder conditions.

Table 1. Main physical characteristics of hydrogen, methane, and hydrogen carriers considered in
this review.

Boling Flash Point Inflammability Volumetric Energy

H2 Capacity
Carrier Temperature Temperature Range Density
(wt. %)
(◦ C) (◦ C) (Vol%) (MJ/L)
0.0107 (amb. pressure)
Flammable 2.757 (CH2 @ 350 bar)
Hydrogen −252.9 4–75% 100
gas 4.712 (CH2 @ 700 bar)
8.506 (LH2 @ −253 ◦ C)
0.0378 (amb. pressure)
5.800 (150 bar)
Methane −161.5 −188 4.4–17% 25
9.200 (250 bar)
22.200 (−163 ◦ C, 1 bar)
Ammonia −33.4 / 15–33.6% 17.8 12.700 (10 bar, −34 ◦ C)
Methanol 64.7 9.9 6–50% 12.5 15.8
Formic Acid 100.8 69 18–51% 4.3 7.2
Benzene 80 −11 1.2–8%
7.2 6.660
Cyclohexane 81 −18 1.3–8.4%
Toluene 111 4 1.1–7.1%
6.2 5.640
Methylcyclohexane 101 −6 1.2–6.7%
Naphthalene 218 80 0.9–5.9%
7.3 7.777
Decalin 185 57 0.7–5.4%
Dibenzyltoluene 390
212 / 6.2 6.786
Perhydrodibenzyltoluene 287
NaBH4 / / / 10.8 15.48
MgH2 / / / 7.6 15.84

Independent of its chemical composition, a suitable hydrogen carrier must provide:

• A sufficient hydrogen capacity (>5 wt. %);
• Easy and environmentally friendly production process;
• Not too harsh conditions and high stability during storage;
• Easy and safe handling during transport;
• Low energy consumption during hydrogen release;
• Option to be recycled.
This list identifies the main features that characterize the supply chain of hydrogen
carriers: production, storage and transport, and hydrogen release for final utilization. In the
following sections, all these stages, sketched in Figure 1, will be discussed for the hydrogen
carriers considered in this review. At the end of this section, Table 2 summarizes the main
challenges for each hydrogen carrier analyzed.
Energies 2023, 16, x FOR PEER REVIEW 4 of 30

Energies 2023, 16, 6035 4 of 31

hydrogen carriers considered in this review. At the end of this section, Table 2 summarizes
the main challenges for each hydrogen carrier analyzed.

Figure 1. Schematic
Figure representation
1. Schematic of the
representation of thesupply
supply chain
chain forfor hydrogen
hydrogen storage
storage and carriers
and carriers considered
considered
in this review.
in this review.

Table 2. Current
Table challenges
2. Current challengesfor
for hydrogen carriers
hydrogen carriers considered
considered inreview.
in this this review.

HydrogenHydrogen
Car- Carrier Current Challenges for Next Studies
Current Challenges for Next Studies
rier • Development of catalytic systems able to operate at lower temperatures and pressure than the
• Development of catalytic
Haber–Bosch process. systems able to operate at lower temperatures and pressure than the
Ammonia
Haber–Bosch • process.
Decrease the content of critical raw materials (CRM) and PGM elements in catalyst formulation.
• Development of alternative processes for ammonia synthesis (e.g., electrochemical synthesis).
Ammonia • Decrease
• the content
Increase of critical
the kinetics raw materials
of ammonia (CRM)
cracking under milderand PGMconditions.
operating elements in catalyst formulation
• Development of alternative processes for ammonia synthesis (e.g., electrochemical synthesis).
• Increase
• the kinetics
Integration of of ammonia
methanol cracking
synthesis with CCS under milder
technologies foroperating conditions.impact.
reducing environmental
• Boost the research on the electrochemical process for methanol synthesis.
•
Methanol Integration
•
of methanol synthesis with CCS technologies for reducing environmental impact.
Decrease the amount of PGM elements in the catalyst for methanol cracking.
• Boost •the research on the
Improve catalyst electrochemical
selectivity process forand
in both the hydrogenation methanol synthesis.
dehydrogenation process.
Methanol
• Decrease the amount of PGM elements in the catalyst for methanol cracking.
• • catalyst
Improve Improve the activity and
selectivity inthe selectivity
both of heterogeneous catalysis
the hydrogenation for formic acid synthesis.
and dehydrogenation process.
Formic Acid • Identification of green organic solvents for formic acid synthesis in liquid-state processes.
• Improve
• the activity of
Optimization and the selectivity
heterogeneous catalystofarchitecture
heterogeneous
for formic catalysis for formic acid synthesis.
acid dehydrogenation.
Formic Acid • Identification of green organic solvents for formic acid synthesis in liquid-state processes.
• • Replacement
Optimization of Pt-based catalysts
of heterogeneous catalystfor hydrogenation
architectureand fordehydrogenation.
formic acid dehydrogenation.
• Improve catalyst tolerance towards wet hydrogen and impurities.
•
Liquid OrganicReplacement
• of Pt-based
Improve catalysts
dehydrogenation forathydrogenation
kinetic milder conditions. and dehydrogenation.
Hydrogen Carriers
Liquid Organic • • Improve recyclability service life
Improve catalyst tolerance towards wet hydrogen by enhancing the selectivity of the dehydrogenation process
and impurities.
towards the desired unsaturated LOHC.
Hydrogen • Improve dehydrogenation kinetic at milder conditions.
Carriers • Improve
• recyclability
Development ofservice
a simplerlife by enhancing
process for hydrogen the selectivity of the dehydrogenation process
storage.
towards the•desired
Metal Hydrides unsaturated
Improve recyclability ofLOHC.
metal hydride (>1500 cycles).
• Improve hydrogen release under milder conditions (T < 85 ◦ C).
• Development of a simpler process for hydrogen storage.
Metal Hydrides • Improve recyclability of metal hydride (>1500 cycles).
• Improve hydrogen release under milder conditions (T < 85 °C).

2.1. Ammonia
2.1.1. Ammonia Production
Ammonia is one of the most widely produced chemicals, with worldwide produc-
tion, and it has an attractive hydrogen content of 17.6 wt. %. Today 96% of the
Energies 2023, 16, 6035 5 of 31

2.1. Ammonia
2.1.1. Ammonia Production
Ammonia is one of the most widely produced chemicals, with worldwide production,
and it has an attractive hydrogen content of 17.6 wt. %. Today 96% of the commercialized
NH3 is synthesized by the Haber–Bosch process, developed in the early 1900s [27,38]. In
this well-established industrial process, nitrogen (N2 ) and hydrogen (H2 ) react on magnetite
(Fe3 O4 ) used as a heterogeneous catalyst:

N2(g) + 3H2(g)  2NH3(g) (1)

The weakly exothermic reaction (−92.4 kJ/mol) is usually carried out in temperature
and pressure ranges of 350–550 ◦ C and 150–320 atm, respectively, to shift the equilibrium to-
wards the product. Despite the depth of knowledge regarding its synthesis and worldwide
utilization, the greenhouse gases (GHG) associated with the Haber–Bosch process are high,
accounting for 1.2% of the total GHG emissions [27]. Furthermore, the production pathway
and its environmental impact are key factors that make ammonia a valuable hydrogen
carrier. In this context, three possible approaches can be followed. The first action deals
with hydrogen production, which up to now has been based on methane, natural gas, oil,
and coal. This stage must be shifted to technologies based on water electrolysis powered by
RES, with a drastic reduction in GHG. The second action is focused on the development of
catalysts able to provide a significant industrial application under milder conditions, reduc-
ing the overall energy consumption, while the third is the aspiration towards a revolution
in process design, with alternative approaches for the synthesis of NH3 .
H2 production by water electrolysis is beyond the scope of this review, but updated
discussions about electrolyzers can be found here [9,39,40]. Focusing on the catalysts
used for ammonia synthesis, nowadays, the research is oriented towards material with
a significant catalytic activity at lower temperatures and pressure than the state-of-the-
art catalysts, and they must be economically sustainable. Several catalyst formulations
have been proposed, and the most promising materials are based on iron (Fe), ruthenium
(Ru), cobalt (Co), and nickel (Ni) [41,42]. As previously introduced, Fe-based catalysts
represent the reference for ammonia synthesis, and their compositions are similar to those
proposed by Bosch. The commercial catalyst has Fe3 O4 as its main active phase, with
the small addition of oxides used as promoters and stabilizers such as Al2 O3 (2.5 wt. %),
CaO (2.0 wt. %), K2 O (0.8 wt. %), SiO2 (0.4 wt. %), MgO (0.3 wt. %), and traces of TiO2 , ZrO2 ,
and V2 O5 , with a maximum service-life of 10 years [43]. The deactivation is mainly due to
the sintering between iron particles, enhanced by the formation of local hotspots. Moreover,
in the conventional Haber–Bosch process, where the H2 used for ammonia production is
derived from methane steam reforming, the presence of oxygenated compounds (CO, CO2 ,
O2 , H2 O) can produce surface poisoning. This is reversible if the exposition is limited to a
few weeks, but becoming irreversible if extended over time. Irreversible poisoning is also
induced by the presence of chlorinated and sulfur compounds [44].
Another class of catalysts already used at the industrial scale is based on Ru, such as in
the Kellogg process. The higher catalytic activity of Ru than conventional Fe-based catalysts
allows for a decrease in operating conditions (pressure and temperature). Considering
that ruthenium belongs to PGM, it is mainly used as the supporting phase on a cheaper
material for the sake of cost reduction. Indeed, the elevated cost is one of the key factors
that hinders its utilization as the main catalyst for industrial applications. Moreover, the
literature shows that, despite the promising catalytic activity, Ru-based catalysts suffer
from the presence of oxygen, as discussed for Fe-based catalysts, with fast deactivation, as
reported by [45].
To overcome the price issues related to ruthenium, other elements such as cobalt
and nickel have been considered as possible candidates for NH3 production. For these
elements, the catalytic activity can be improved using promoters. In 2022, Gao et al. [46]
reported that barium hydride (BaH2 ) can have a synergic effect with Ni, with a drastic
Energies 2023, 16, 6035 6 of 31

reduction in the activation energy from 150 kJ mol−1 (bare Ni-Mg-O catalyst) to 87 kJ mol−1 ,
enhancing nitrogen hydrogenation. Previously (2021), Sato et al. [47] also identified barium
has an element for boosting the activity of Co-based catalysts. They found that a simple
encapsulation of Co nanoparticles supported on MgO with BaO leads to an increase in the
NH3 synthesis rate to up to 80 times higher than that obtained without barium addition. The
presence of BaO, which facilitates strong electro-donation to Co surface atoms, decreases the
energy for the N≡N cleavage bond. It is noteworthy that the proposed catalyst formulation
also maintains promising activity under milder conditions (150 ◦ C, 10 bar), proffering the
development of less energy-consuming processes.
Alternative approaches proposed for ammonia synthesis are based on electrochemical
cells with different systems that can operate in a wide temperature range. High-temperature
systems (T > 400 ◦ C) are based on solid-state electrolytes (protonic or anionic), and N2 and
H2 are fed to the electrodes. The operating temperature is linked to the ionic conductivity
of the electrolyte and the catalytic activity of electrodes. Although systems operating at
over 600 ◦ C have been proposed to increase the sluggish kinetics, most of the works are
oriented towards temperatures lower than 600 ◦ C [42] for reducing operating costs. At
higher temperatures, yttrium and cerium are considered the main elements for electrolyte
formulation. At lower temperatures (400–450 ◦ C), carbonate-based materials have been
proposed, using Ag–Pd-based electrodes [48]. Nevertheless, the energy consumption
associated with this process and the low Faradaic Efficiency (FE) make this approach
unsuitable for competing with conventional ammonia processes, and further investigations
and improvements are required.
An attempt to decrease the energy demand has been made via the lowering of oper-
ating temperatures to below 100 ◦ C. The low-temperature electrochemical process for
ammonia synthesis is usually carried out in a basic solution (KOH) using a proton-
conducting membrane (e.g., Nafion® ). Common electrodes are made up of Pt (anode)
and Ru (cathode), and the utilization of Pt affects the purity required for water/hydrogen
in the inlet stream. This cell setup leads to a production rate of 2 × 10−11 mol s−1 cm−2 at
90 ◦ C with FE below 1%. A relevant improvement in production rate and current efficiency
(1.13 × 10−8 mol s−1 cm−2 at 80 ◦ C, with current efficiency of 90%) has been obtained with
an anode and cathode made up Ni–Sm0.2 Ce0.8 O2−δ and SmFe0.7 Cu0.3−x Nix O3 , respectively,
highlighting the possibility of achieving interesting performance, and the current necessity
to investigate new electrode systems [49].
Another electrochemical path recently proposed for distributed ammonia production
is based on the electrochemical reduction of nitrogen species, such as nitrates (NO3− ),
nitrites (NO2− ) and nitric oxide (NO) [50]. These processes have the advantages that the
double bond between nitrogen and oxygen is characterized by lower energy (204 kJ mol−1 )
compared to the triple bond of N2 (941 kJ mol−1 ), making the exploitation of these species
more interesting [50]. The efforts made to develop such electrochemical systems are
also justified by considering a circular economy view. Indeed, these ions are detected in
wastewater (NO3− , NO2− ) from agricultural and industrial sites, and NO is mainly present
in waste gases. Their presence in water or air represents a risk for both the environment and
human health [51,52], necessitating their removal. Based on these aspects, a proper design
of wastewater and flue gas treatments allows for obtaining a concentrated nitrogenous
stream that can be used as feed for the electrochemical process. Figure 2 summarizes
the main reaction path characteristic of ammonia production based on NO2− , NO3− and
NO. The key steps of the reaction involve the adsorption of the reactant on the cathode
surface, followed by an electron and proton transfer. It is important to keep in mind that the
limiting stage changes as a function of the starting nitrogenous species, with consequences
for electrocatalysts development.
Energies 2023,
Energies 16, x6035
2023, 16, FOR PEER REVIEW 7 7ofof30
31

Figure
Figure 2.
2. Main
Main reaction
reaction path
path for
for nitrogen
nitrogen species
species reduction
reduction at
at the
the cathode
cathode surface.
surface. Figure
Figure adapted
adapted
from [50].
from [50].

NO
NO3−isisprobably
probablythe themost
mostappealing
appealingnitrogen
nitrogenion, ion,due
dueto toits
itsdiffuse
diffusepresence
presencein inwater
water
(wastewater,
(wastewater, surface water, groundwater). Based on the literature, the first reduction stage
surface water, groundwater). Based on the literature, the first reduction stage
of
of NO NO − to to NO 2− is
NO is the
the limiting
limiting step
step of
ofthe
the kinetic
kinetic mechanism.
mechanism. For
For industrial
industrial applications,
applications,
3 3
itit is
is necessary
necessary to to increase
increase the the NONO − concentration close to the cathode surface, to improve
3 concentration close to the cathode surface, to improve
Faradaic
Faradaic Efficiency
Efficiency (FE)(FE) and
andlimit
limitthe thecompetitive
competitivehydrogenhydrogenevolution
evolutionreaction
reaction (HER).
(HER). TheThe
simplest
simplest approach
approach uses uses selective
selective membranes
membranes to to form high-NO3−catholyte
form aa high-NO catholyteenvironment,
environment,
but
but the the most
most update
update studies
studieslooklookfor fordouble-purpose
double-purposecathode cathodematerials
materials[50]. [50].In Inthis
thisview,
view,
the electrode
the electrode provides both a high adsorption capacity and high electrocatalytic
both a high adsorption capacity and high electrocatalytic properties proper-
ties
for NO for 3−NO . The
. The high high adsorption
adsorption raterate locally
locally increases
increases NO3−NO
the the concentration,
concentration, support-a
supporting
ing
higher a higher FE. Carbonaceous
FE. Carbonaceous porous porous structures
structures have havebeen been recently
recently investigated
investigated due to due to
their
their
elevated elevated adsorption
adsorption properties,
properties, and the and the functionalization
functionalization of theirofsurface
their surface with met-
with metals, such
als, such asfurther
as copper, copper, further
allows forallows
ammonia for synthesis
ammonia at synthesis
low nitrateat low nitrate concentrations
concentrations [53]. Other
[53].
promisingOther adsorbents
promising adsorbents
include carbon include carbon nanotubes
nanotubes (CNTs)with
(CNTs) activated activated with poly-
polyaniline and
cobalt oxide
aniline (Co3 O
and cobalt )
oxide
4 [54].
(Co The
3 O 4 )presence
[54]. The of polyaniline
presence of makes
polyaniline the system
makes themore
system selective
more
towards towards
selective NO3− adsorption,
NO adsorption,
with a local withincrease in its concentration
a local increase at the cathode
in its concentration surface,
at the cathode
and the and
surface, Co3 O 4 supplies
the electrocatalytic
Co3O4 supplies activityactivity
electrocatalytic for its reduction to ammonia.
for its reduction to ammonia.
When NO
When NO2−isisthe themain
main nitrogen
nitrogen source,
source, thethe
keykey aspect
aspect thatthat
mustmust be considered
be considered in elec-in
electrocatalyst design * and the simultaneous limitation of the
trocatalyst design is theishighthe production
high production of Hthe
of H* and simultaneous limitation of the hydro-
hydrogen
gen evolution.evolution.
The most The most promising
promising systemssystems for sustaining
for sustaining this are
this reaction reaction
madeare upmade
of metalup
of metal nanoparticles (e.g., Ru, Cu) distributed on carbon-based
nanoparticles (e.g., Ru, Cu) distributed on carbon-based supports (e.g., carbon nitride) [55]. supports (e.g., carbon
nitride) [55]. oxide is mainly formed during the combustion process, after which it is
Nitrogen
Nitrogen oxide is mainly
present in the atmosphere. formed during
The reduction of NOthe to itscombustion
liquid phase process, after
is strictly which
limited byititsis
present
low in the atmosphere.
solubility. The strategies Thecurrently
reduction of NO
under to its liquid phase
development is strictlyperformances
for increasing limited by its
lowthe
are solubility.
usage of The strategieselectrodes
gas diffusion currently [56] under development
or solid electrolyte forcells
increasing
workingperformances
at high tem-
are the usage of gas diffusion electrodes [56] or
peratures [57]. Nevertheless, all these technologies used for ammonia production solid electrolyte cells working at from
high
temperatures [57]. Nevertheless, all these technologies used
nitrogen oxide and ions are still far from operability at the industrial scale, and further for ammonia production from
nitrogen
efforts willoxide and ionsinare
be necessary thestill
near farfuture.
from operability at the industrial scale, and further
efforts will be necessary in the near future.
2.1.2. Hydrogen Release from Ammonia
2.1.2. Hydrogen Release from Ammonia
Among the ensuing stages of supplying ammonia as a hydrogen carrier, hydrogen
Among the ensuing stages of supplying ammonia as a hydrogen carrier, hydrogen
release is the most challenging. Indeed, despite the fact that the storage and transport of
release is the most challenging. Indeed, despite the fact that the storage and transport of
NH3 is based on a deep and widespread knowledge base, ammonia decomposition is still
NH3 is based on a deep and widespread knowledge base, ammonia decomposition is still
facing issues that impact the process’ sustainability [58]. The reaction is thermodynami-
facing issues that impact the process’ sustainability [58]. The reaction is thermodynamically
cally favored over ◦400 °C, but the kinetics are limited by the high activation energy of N–
favored over 400 C, but the kinetics are limited by the high activation energy of N–H
H blond
blond cleavage
cleavage andand molecular
molecular nitrogen
nitrogen desorption.
desorption. For For
thesethese reasons,
reasons, the current
the current re-
research
search is looking for catalysts active at reasonably non-severe conditions, tuning
is looking for catalysts active at reasonably non-severe conditions, tuning their composition their
composition
and morphology, and morphology, and thebetween
and the interactions interactions between
the active the active phase/support.
phase/support. Theoretically,
Theoretically, the catalytic systems used for ammonia
the catalytic systems used for ammonia synthesis should also be synthesis should
able also be ablethe
to support to
support the decomposition reaction; nevertheless, the results clearly show the
decomposition reaction; nevertheless, the results clearly show the necessity of developing necessity
of developing
tailored tailored
materials materials
for process for process due
optimization, optimization, due toreaction
to the different the different reaction
pathways [58].
pathways
Promising[58]. Promising
active catalystsactive catalysts
are usually are of
made usually
alloysmade of alloys
between noblebetween noble
metals (Ir, Rh, metals
Ru, Pt)
(Ir, Rh, Ru, Pt) and transition metals (Co, Fe, Ni, Cu). Pioneering studies have been focused
Energies 2023, 16, 6035 8 of 31

and transition metals (Co, Fe, Ni, Cu). Pioneering studies have been focused on Fe-based
materials [59], due to their activity in relation to the synthesis reaction, while in the last few
years, studies have been more closely focused on noble metal catalysts, with a particular
focus on Ru-based materials [60]. These noble metal-based catalysts enhanced ammonia
decomposition thanks to the reaction affinity between ruthenium and nitrogen. Ru is the
most widely investigated element due to its high turnover frequency (TOF), in the order
Ru > Ir > Rh > Ni > Pt > Pd > Fe [58]. Considering the high cost of Ru, several strategies
have been proposed to reduce the catalyst cost or improve its activity. The first approach is
the modification of the intrinsic activity by changing the catalyst’s morphology. Indeed,
a decrease in Ru particle size usually increases the number of active sites available for
the reaction. On the contrary, it is important to remember that a smaller dimension of
the particle leads to higher surface energy, enhancing particle agglomeration in long-term
applications [61]. Based on Chen et al.’s analysis [60], a Ru particle size close to 8 nm seems
to be optimal for catalytic activity and long-lasting performance.
A further topic of concern in the current research is the reduction in noble metal load.
It has been proven that the activity of a catalyst can be enhanced both by the addition of
a promoter and the selection of a proper supporting phase. As regards the promoters, it
has been previously reported in relation to ammonia synthesis that the presence of small
amounts of transition metals, alkali, or alkali or rare earth metals, can improve catalytic
activity, and this characteristic remains valid for the ammonia decomposition process [62].
Despite the fact that the role of promoters is still under debate, the results suggest that
the presence of such compounds enhances both the kinetic rate and the stability over time.
Interesting results have recently been obtained [63]. Sayas et al. [64] decreased the Ru-load
by using nanosized particles (7 nm) coupled with K as promoters on the CaO support,
and a complete ammonia conversion was reached at lower temperatures (from 550 ◦ C to
480 ◦ C). For the authors, the presence of potassium hindered competitive H2 adsorption.
Promoters also have a beneficial effect on the activity of free-noble metal catalysts, such as
Barium in Co–Ce catalysts [63]. The microkinetic modeling proposed by Lezcano identified
that the Ba addition enhances the rate of N2 desorption, which is one of the suggested
kinetic-limiting steps.
Regarding the catalyst support, although it is not directly involved in the reaction,
it can provide important features, such as an improved dispersion of the catalytic phase,
high surface area, non-acidic environment, and good thermal and electrical conductiv-
ity. Promising results have been obtained with Al2 O3 , which is widely used in many
catalytic processes, as well as with other metal oxides or alloys, such as SiO2 [65], Y2 O3 [66],
Sm2 O3 [67], CeO2 [68], and La0.8 Sr0.2 AlO3 [69]. Possible alternatives for support, which
are currently under investigation, include carbon materials due to their high tunability in
terms of both shaping and chemical properties [70,71]. Recent studies have focused on
doping carbon with heteroatoms (nitrogen, oxygen, and sulfur) and CNTs [72,73]. If the
decomposition is affected by the electron transfer rate, then a highly conducting support
can improve process performance. In this regard, the presence of impurities introduces
defects that have a beneficial effect on electric conductivity.

2.2. Methanol
2.2.1. Methanol Production
The interest in methanol as a hydrogen carrier has increased due to its relatively high
content of hydrogen (12.5 wt. %), low volatility at ambient conditions (Teb = 64.7 ◦ C), and
compatibility with the existing infrastructure for storage and transportation. Consider-
ing the impact of this topic on scientific research, a separate section is dedicated to this
LOHC; Section 2.3 concerns formic acid, while Section 2.4 will be dedicated to describ-
ing more complex organic compounds that have been considered in the last few years.
In 2023, Lee et al. [19] referred to the view of George Olah regarding the development of
the methanol economy [74]. The employment of carbon-based hydrogen carriers, such
as methanol, fits the requirements for energy transition and achieving net-zero carbon
Energies 2023,
Energies 16, 6035
2023, 16, x FOR PEER REVIEW 9 9of
of 30
31

sustainable
emissions. Here, methanol production
sustainable must production
methanol be the result of the
must integration
be the result ofof thecarbon capture
integration of
and
carbonstorage
capture (CCS)andtechnologies
storage (CCS) and green hydrogen
technologies and greengeneration
hydrogen [75].generation [75].
The
The interest
interest in in methanol
methanol is is also
also confirmed
confirmed by by the
the annual
annual production,
production, which which has has been
been
undergoing
undergoing aa rising risingtrend.
trend.InIn2022,
2022,the
the global
global production
production hashas
beenbeen estimated
estimated at 100
at 100 Mt andMt
and the forecast is for an increase up to 190 Mt in 2030 [76]. Different approaches have
the forecast is for an increase up to 190 Mt in 2030 [76]. Different approaches have been
been
mademade available
available at theatindustrial
the industrial
scale,scale, as a function
as a function of composition
of composition feed.feed.
NaturalNatural gas,
gas, coal,
coal, and biomass
and biomass havehave beenbeen
widelywidely
usedused as carbon
as carbon sourcessources for this
for this synthesis.
synthesis. Neverthe-
Nevertheless,
less,
it hasitbeen
has been reported
reported that that the aim
the aim of this
of this review review
is theis evaluation
the evaluation of CHof CH
3 OH 3OH as hydro-
as hydrogen
gen carriers,
carriers, andand its production
its production acquires
acquires environmental
environmental relevance
relevance if the
if the reaction
reaction pathway
pathway is
is based on sequestrated CO2 and green H2. For this process, the most diffuse approach is
based on sequestrated CO 2 and green H 2 . For this process, the most diffuse approach is
based on heterogeneous catalysis with copper/zinc oxide (Cu/ZnO) [77]. The most active
based on heterogeneous catalysis with copper/zinc oxide (Cu/ZnO) [77]. The most active
and
and stable
stable catalytic
catalytic systems
systemsare areCuO/Zn/Al
CuO/Zn/Al 2O23 and
O3 and Cu/Zn/Al
Cu/Zn/Al 2O3. 2This hydrogenation
O3 . This hydrogenation pro-
process is characterized by quite low conversion rates [78],
cess is characterized by quite low conversion rates [78], and it occurs in temperature and it occurs in temperature and
and pressure ranges of 220–350 ◦ C and 20–100 bar, respectively. Indeed, some studies show
pressure ranges of 220–350 °C and 20–100 bar, respectively. Indeed, some studies show
that if
that if pure
pure CO CO22 isis used
used asas aa carbon
carbon source
source the the process
process is is less
less effective
effective thanthan when
when CO CO isis
contained in the feed. An early study [79] showed that at 70.92 bar and 250 ◦ C, the process
contained in the feed. An early study [79] showed that at 70.92 bar and 250 °C, the process
with pure
with pure CO CO22 hadhad aa yield
yield of
of 50%,
50%, which
which increased
increased up up toto 72%
72%withwithaamixture
mixtureof ofCO/CO
CO/CO22
(x
(xCO = 0.4). In 2018, Marlin et al. [80] evaluated the impact of
CO = 0.4). In 2018, Marlin et al. [80] evaluated the impact of synthesizing CH33OH with synthesizing CH OH with
CO rather than CO. Carbon dioxide is less reactive than carbon
CO22 rather than CO. Carbon dioxide is less reactive than carbon monoxide, and for this monoxide, and for this
reason, larger reactors are required. The advantages of operating with CO2 are its higher
reason, larger reactors are required. The advantages of operating with CO2 are its higher
selectivity towards the desired product, milder reaction conditions, and a less complicated
selectivity towards the desired product, milder reaction conditions, and a less complicated
and lower-cost vessel design.
and lower-cost vessel design.
When looking for a more sustainable methanol synthesis method able to operate at
When looking for a more sustainable methanol synthesis method able to operate at
milder conditions, CO2 electrochemical reduction seems to be one of the most promising
milder conditions, CO2 electrochemical reduction seems to be one of the most promising
routes [81,82]. Process performances are affected not only by the selection of the electrocat-
routes [81,82]. Process performances are affected not only by the selection of the electrocata-
alysts, but also by the operating conditions and reactor design. Most of the efforts have
lysts, but also by the operating conditions and reactor design. Most of the efforts have been
been focused on the synthesis of electrode materials selective towards methanol formation,
focused on the synthesis of electrode materials selective towards methanol formation, which
which involves the transfer of six electrons and suffers from the competition related to
involves the transfer of six electrons and suffers from the competition related to faster hydro-
faster hydrogen evolution. Further to the traditional issues that can affect the electrochem-
gen evolution. Further to the traditional issues that can affect the electrochemical conversion
ical conversion process (low selectivity, mass transfer limitations, high overpotentials),
process
a further (low selectivity,
important masstotransfer
aspect consider limitations,
is the lowhigh CO2overpotentials),
solubility (1.69a g/L further important
at 20 ◦ C and
aspect to consider
ambient pressure). is the low CO 2 solubility (1.69 g/L at 20 °C and ambient pressure).

The
The electrochemical
electrochemicalgeneration
generationofofmethanol
methanoloccurs occurs atat
thethe
cathode
cathode where
where thethe
COCO 2 re-
2
duction takes place. As reported in Figure 3, there are several
reduction takes place. As reported in Figure 3, there are several competitive and more competitive and more fa-
vored
favored reactions
reactionsthat thatcancandecrease
decreasethe theoverall
overallefficiency;
efficiency;as assuch,
such,ititisisnecessary
necessary to to identify
identify
suitable conditions (electrode material, solution composition,
suitable conditions (electrode material, solution composition, pH, temperature, pressure, pH, temperature, pressure,
CO
CO22 concentration)
concentration) to to promote
promote CH CH33OHOHproduction.
production.

Figure 3. Possible reactions at cathode surface during electrochemical CO2 reduction for methanol
Figure 3. Possible reactions at cathode surface during electrochemical CO2 reduction for methanol
synthesis. Figure adapted from [81].
synthesis. Figure adapted from [81].
Energies 2023, 16, 6035 10 of 31

Independent of the final product, the initial step in the formation of the CO2•− radical
affects the process with a high overpotential (−1.90 V vs. SHE). This feature, coupled with
the aforementioned low CO2 solubility, requires targeted actions on the electrode material
and the solution composition (e.g., organic solvents to increase CO2 solubility), and a proper
reactor design for enhancing mass transport [36]. The design of a suitable cathode for
commercial application must consider high methanol selectivity, high Faradaic Efficiency
(FE), and long stability under operating conditions. The application of pure metals is
not suggested due to their low efficiency, and more complex compositions are preferred,
such as metal oxides and alloys. The selection of metal oxides (MO: Cu2 O, RuO2 , TiO2 ,
MoO2 , Co3 O4 ) as the electrode material is justified by their basic behavior that improves
CO2 adsorption on cathode sites [81]. One of the limitations related to MO is the lack
of high electrical conductivity, which can negatively affect the charge–transfer resistance.
In resolving this issue, approaches such as nanostructured morphology and couplings
between different materials have been proposed. Weak Cu2 O cathode performances have
been improved by Albo et al. [83] by mixing them with ZnO. The authors considered
different Cu2 O/ZnO weight ratios, and the maximum methanol formation rate was reached
with a ratio of 1:1 at −1.3 V vs. Ag/AgCl (3.17 × 10−9 mol cm−2 s−1 , FE = 17.7%). In 2021,
Guo et al. [84] reported a strong improvement in FE (FE = 88.6%) when using a MO-based
system by dispersing an atomic Sn site anchored on a defective CuO catalyst. In this case,
the enhancement is derived from the cooperation between Sn site–oxygen vacancy–CuO,
with the formation of a double-layer capacitance, larger CO2 adsorption capacity, and lower
charge–transfer resistance.
Recently, some promising results have been obtained using metal alloys. Huang et al. [85]
coupled the Sn–Zn bimetallic system with a 4-aminopyridine (Py) organic catalyst sup-
ported on carbon paper. A FE = 59.9% for methanol was reached and kept stable for
more than 25 h due to the synergic effect between the bimetallic system and the organic
compound. An impressively low potential for selective methanol production has been
determined by Bagchi et al. [86] with a CuGa2 catalyst. Electrochemical CH3 OH synthe-
sis occurs at −0.3 V vs. RHE and with a FE of 77.26%, optimizing cell design with a
flow–cell reactor.

2.2.2. Hydrogen Release from Methanol

The release of hydrogen from methanol requires a mild temperature (200–300 ◦ C) due
to the absence of C–C bonds, and the most diffuse path is the catalytic steam reforming of
methanol (SRM). In this process, it is extremely important to ensure the correct selection of
operating conditions and catalysts to minimize CO production, which is both highly toxic
and can introduce poisoning issues in downstream applications (e.g., PEMFC) [81,87]. For
these reasons, in methanol-to-hydrogen conversion, the cracking reaction is often coupled
with water gas shift, as reported in this reaction pathway:

CH3 OH + H2 O → CO2 + 3H2 ∆H◦ 298K = +49.7 kJ mol−1 (2)

CH3 OH → CO + H2 O ∆H◦ 298K = +90.7 kJ mol−1 (3)

CO + H2 O → CO2 + H2 ∆H◦ 298K = −41.2 kJ mol−1 (4)
The commercial catalyst composed of Cu/ZnO/Al2 O3 shows high activity towards
hydrogen and low selectivity for CO, due to a synergistic effect between Cu and ZnO. Nev-
ertheless, its stability over time is still an open issue due to the segregation of ZnO, particle
agglomeration, and the deposition of carbonaceous compounds leading to a progressive
loss of active sites. Different strategies have been applied to overcome these issues [88].
Cheng et al. [89] added magnesium to a CuZnAl–xMg formulation, identifying the opti-
mum level for catalytic activity at 5% = Mg. The addition of Mg promoted the substitution
of Cu2+ in the malachite phase of the catalyst precursor with Cu+ , while the stability allows
for improved interactions between Cu and ZnO.
Energies 2023, 16, 6035 11 of 31

A second group of catalysts for SRM is based on nickel, which is less active than Cu
and other noble metals, and it usually works at higher temperatures (250–500 ◦ C). On the
contrary, Ni provides good mechanical strength and higher resistance to poisoning. Ni
shows non-negligible interactions with carbon, meaning the deposition of methanol coke
with the formation of NiC is possible [90]. The presence of oxygen atoms could improve the
selectivity of Ni, thus reducing carbon deposition. In this regard, in 2022, Shen’s group [91]
proposed a Ni-based catalyst, focusing on its recyclability. They prepared a series of
NiO/NaF systems, wherein the oxide is the active phase and NaF is the supporting phase.
Catalysts with different loadings of NiO have been considered, and the 6% NiO/NaF
showed the best performance, with 94% CH3 OH conversion, 100% H2 selectivity, and 30 h
of stable operation at 450 ◦ C. The recyclability of catalysts has been successfully tested, and
after water washing followed by acid washing, the activity was restored to the initial values.
The catalyst’s stability can be enhanced using noble metal catalysts, which also have
high stability at high temperatures. Improved stability has been achieved by substitut-
ing the copper with palladium, such as in PdZn catalysts, but this introduces a twofold
drawback. Pd is a PGM with impacts on costs, and it is less active than Cu in the desired
reactions. A promising approach seems to the coupling between these two elements (Pd,
Cu), and their alloys showed both high catalytic activity and longer stability [92].

2.3. Formic Acid

2.3.1. Formic Acid Production
Several studies focused on using formic acid (CH2 O2 , FA) as a possible hydrogen carrier,
despite its gravimetric H2 capacity (4.4 wt. %) being lower than the desired 5% [37,93,94].
This interest is also justified by the well-established knowledge regarding its handling,
as well as its low toxicity, and the mild conditions required by the dehydrogenation
process [95,96]. From an industrial point of view, formic acid is mainly produced via the
hydrolysis of methyl formate derived from methanol carbonylation. A second route of FA
synthesis is as a coproduct in acetic acid production [97]. Nevertheless, the usage of formic
acid as a hydrogen carrier gains appeal if the synthesis route is based on captured CO2 , as
proposed for methanol synthesis. The reaction can ensue via heterogeneous thermocatalysis,
as well as with homogeneous catalysis or in innovative electrochemical systems. As regards
heterogeneous catalysis for the conversion of CO2 to FA, it is favored at high temperatures
and high pressure. Due to these harsh conditions and the difficulties in formic acid
selectivity, few works have focused on this reaction pathway [98]. The first catalyst for
heterogeneous formic acid synthesis was proposed in 1935, and it was based on RANAY®
nickel, operating between 200 and 400 bar and 80 and 150 ◦ C. Some improvements have
been reached by employing noble metal catalysts such as Pd/C, but due to the interaction
of formate with carbonaceous support, low conversion has been observed [35]. These
weaknesses shift the efforts towards homogeneous catalytic systems. In homogeneous
catalysis, Ru-, Rh-, Ir-, Pd-, Ni-, Fe-, Ti-, or Mo-based material have been proposed for the
hydrogenation of carbon dioxide in CO2 , both in water or in other kinds of solvents such as
dimethyl sulfoxide (DMSO) [37]. The activity is sensitive to the pH of the solution wherein
the reaction takes place. Enhanced activity has been identified in a system containing a base
because the subtraction of protons forces the desired reaction [98]. When the reaction occurs
in water, polar solvents or basic compounds such as sodium hydroxide or carbonates are
usually used, while amines are preferred as organic media. Another parameter to consider
is that the solubility of CO2 in solution is quite low, and a large-scale process could require
an extremely high volume. For overcoming this limitation, some works have proposed
operating under supercritical conditions. In the work of Puring et al. [99], supercritical CO2
was coupled with the electrochemical reduction of carbon dioxide for a more sustainable
process, as already discussed for methanol [100]. In this study, the cathode is made up of
copper on a carbon-based support, and the supercritical CO2 conditions, with a pressure
of 150 atm, drastically reduced the hydrogen evolution reaction and enhanced the current
efficiency, yielding a higher level of formic acid production (Figure 4).
 Energies 2023, 16, x FOR PEER REVIEW 12 of 30

Energies 2023, 16, 6035 supercritical CO2 conditions, with a pressure of 150 atm, drastically reduced the hydrogen
12 of 31
evolution reaction and enhanced the current efficiency, yielding a higher level of formic
acid production (Figure 4).

Figure4.4.Schematic
Figure Schematiccomparison
comparisonofofCO
CO2reduction
reductionforforformic
formicacid
acidsynthesis
synthesisatatambient
ambientconditions
conditions
2
(left side) and supercritical CO2 conditions (right side). From [100].
(left side) and supercritical CO2 conditions (right side). From [100].

2.3.2.Hydrogen
2.3.2. HydrogenRelease
Releasefrom
fromFormic
FormicAcid
Acid
In the
In the dehydrogenation
dehydrogenation reaction
reactionofofFA,
FA,thethefirst target
first in selecting
target the the
in selecting operating con-
operating
ditions and
conditions thethe
and catalyst is isthe
catalyst theinhibition
inhibitionofofthe
thereaction
reaction (6)
(6) with CO formation,
with CO formation, due
due to
to
safetyissues
safety issuesand
andthe
thedeactivation
deactivationof ofthe
thecatalyst:
catalyst:

CHCH 2O2  CO2 + H2

2 O2 → CO2 + H2
(5)
(5)

CHCH
2 O22O
→2 
COCO
+H+ 2HO2O (6)
(6)
Homogeneous catalysis
Homogeneous catalysis has has also
also been
beenwidely widelystudied
studiedforfor hydrogen
hydrogen release
releasefrom
fromFA
[101,102]. The most widely used catalytic systems are based
FA [101,102]. The most widely used catalytic systems are based on soluble metal complexes on soluble metal complexes
selective towards
selective towards the the reaction
reaction (5). (5). PGM-based
PGM-based catalysts catalysts (Rh,
(Rh, Ru,
Ru, Ir)
Ir) and
and Fe-based
Fe-based com-
com-
poundshave
pounds havebeenbeeninvestigated.
investigated.The Thefirst
firstworksworksproposed
proposedphosphine
phosphinecomplexes
complexessuch suchas as
IrH22Cl(PPh
IrH Cl(PPh33))33 and
and Rh(C
Rh(C66H H44PPh
PPh2)(PPh
2 )(PPh 3)32.)2The
. The Ir-based
Ir-based complexes
complexes show
showthethebest
bestdecompo-
decom-
sition kinetics
position kinetics withwith a rate
a rateof of7.36 mol
7.36 moll−1 lh−−11. hNoteworthy
−1 . Noteworthy results werewere
results obtained in theinearly
obtained the
2000s2000s
early by Laurenczy
by Laurenczy and Beller [103] with
and Beller [103]Ru–phosphine
with Ru–phosphine catalytic systems,
catalytic which allowed
systems, which
for selective
allowed FA dehydrogenation
for selective FA dehydrogenation without without the formation of CO. Inofthe
the formation CO.lastInfew
the years, re-
last few
searchresearch
years, activities have been
activities havefocused on the on
been focused development
the development of water-soluble catalysts
of water-soluble active
catalysts
in theinabsence
active the absence of organic
of organic additives
additives forforhigher higherenvironmental
environmental sustainability [102]. In
sustainability [102]. In
greaterdetail,
greater detail,the theresults
resultsavailable
available in inthe
theliterature
literaturesuggest
suggestthat thatthe
thecatalytic
catalyticactivity
activityofof
metalisishighly
metal highlyaffected
affectedby bythe theelectro-donating
electro-donatingability abilityof ofthe
theligands
ligandstotothe
themetal.
metal.This
This
hypothesishas
hypothesis hasbeen
beenconfirmed
confirmedby byOnishi
Onishietetal. al.[37,102],
[37,102],who whoconsidered
consideredCp*IrCp*Ircomplexes
complexes
0 -bipyridine. The catalyst with the
(where Cp = pentamthylcyclopentadienyl) bearing 2,2′-bipyridine. The catalyst with the
(where Cp = pentamthylcyclopentadienyl) bearing 2,2
−1 while the introduction of electro-
unsubstitutedligand
unsubstituted ligandhad hadaalow lowactivity
activity(TOF (TOF==30 30hh−1),), while the introduction of electro-
0 -position of bipyridine massively improved the performance
donativeOH
donative OHgroups
groupsatat4,4 4,4′-position of bipyridine massively improved the performance
−1 ). A further improvement can enable operation in a closed reactor, due to
(TOF==2400
(TOF 2400hh−1). A further improvement can enable operation in a closed reactor, due to
the spontaneous increaseininthe
the spontaneous increase thepressure
pressureduring duringthe thereaction.
reaction.
The
The current research is also dedicated to the developmentof
current research is also dedicated to the development ofheterogeneous
heterogeneouscatalytic
catalytic
systems.
systems. Interest in this area has increased due to the easier separation ofoftwo
Interest in this area has increased due to the easier separation two differ-
different
ent phases and the higher recyclability of such materials, which
phases and the higher recyclability of such materials, which also attracts industrial stake- also attracts industrial
stakeholders.
holders. Metal Metal nanoparticles
nanoparticles are attracting
are attracting the attention
the attention of several
of several groups
groups [104–106],
[104–106], be-
because of their high catalytic activity. Some aspects must be
cause of their high catalytic activity. Some aspects must be considered in the preparation considered in the preparation
of
ofmetal
metalnanoparticles,
nanoparticles,such suchas asthe
theagglomeration
agglomerationof ofsmall
smallparticles
particlesduring
duringthe thesintering
sintering
stage due to their high surface energy, and the interaction
stage due to their high surface energy, and the interaction between the metal-dispersed between the metal-dispersed
phase and the support. Hydrogen release from formic acid has been obtained using Au,
phase and the support. Hydrogen release from formic acid has been obtained using Au,
Pd, Ir, Pt, and Pd on carbon and alumina. For example, nanosized gold particles finely
Pd, Ir, Pt, and Pd on carbon and alumina. For example, nanosized gold particles finely
dispersed on an Al2 O3 support provided high activity and low CO production [37].
dispersed on an Al2O3 support provided high activity and low CO production [37].
2.4. Liquid Organic Hydrogen Carriers (LOHC)
2.4.1. Introduction to LOHC Loop
The usage of liquid organic compounds as hydrogen carriers requires unsaturated
molecules that can host hydrogen [107]. Indeed, the LOHC-based systems work by cou-
pling an unsaturated compound with its saturated form by means of a hydrogenation–
dehydrogenation loop, as reported in Figure 5. The interest in LOHC is justified by the
possibility of storing hydrogen at room temperature or milder conditions than CH2 and
 The usage of liquid organic compounds as hydrogen carriers requires unsatu
molecules that can host hydrogen [107]. Indeed, the LOHC-based systems work by
pling an unsaturated compound with its saturated form by means of a hydrogena
Energies 2023, 16, 6035 dehydrogenation loop, as reported in Figure 5. The interest in LOHC 13 is ofjustified
31 b
possibility of storing hydrogen at room temperature or milder conditions than CH
LH2 methods, and by the reduced production of CO2 and N2, as happens when CH
and
LH NH3 areand
2 methods, used, respectively.
by the Moreover,
reduced production of COin2 and
some N2cases, the chemical
, as happens when CHnature
3 OH of L
means that their storage and transport can rely on the exploitation of infrastructu
and NH 3 are used, respectively. Moreover, in some cases, the chemical nature of LOHC
means that their storage and transport can rely on the exploitation of infrastructure already
ready available in the petrochemical sector, such as tanks and pipelines, with a po
available in the petrochemical sector, such as tanks and pipelines, with a positive impact
impact
on on investments.
investments.

Figure 5. Loop for liquid organic hydrogen carrier.

Figure 5. Loop for liquid organic hydrogen carrier.
Hydrogenation is a catalytic reaction that occurs at high pressure (10–80 bar) and
Hydrogenation
intermediate temperatureis(100–400
a catalytic reaction
◦ C) with that occurs
heat release, whichatcan high pressurein(10–80
be exploited the bar)
intermediate
energy balance oftemperature
the system [36].(100–400 °C) with
The industrial heatis release,
interest focused on which
LOHC, can be exploited
which can i
energy balance of the system [36]. The industrial interest is focused on LOHC, whic
provide a hydrogen capacity of at least 5 wt. % [78]. Other distinguishing factors that drive
LOHC selection are the synthesis process (easy and cheap), the toxicity of the compounds
provide a hydrogen capacity of at least 5 wt. % [78]. Other distinguishing factors that
and the risk associated with their handling, and the complexity of final hydrogen release.
LOHC
The selection areprocess
dehydrogenation the synthesis process (easy
is an endothermic and cheap),
reaction, requiringthean toxicity of the compo
energy supply,
and the risk associated with their handling, and the complexity of
and it is usually set as the limiting stage; its sustainability is evaluated by considering final hydrogen rel
Thekey
two dehydrogenation
parameters, suchprocess is an endothermic
as the temperature required reaction, requiring
by the process and the anenthalpy
energy supply
it is usually set as the limiting stage; its sustainability is evaluated by considering
associated with the reaction. Then, the development of an LOHC-based system relies on the tw
parameters, such as the temperature required by the process and the enthalpy assoc
energy balance of the whole process, as well as the recycling efficiency of organic molecules
and catalysts.
with the reaction. Then, the development of an LOHC-based system relies on the en
Several classes of organic compounds have been considered as LOHC, and among
balance
them, of thecompounds
aromatic whole process, as well
have been as theasrecycling
identified efficiency
the best option, as wasofrecently
organiccon- molecules
catalysts.
firmed by Chu et al. [108]. As previously introduced, a complete study on LOHC must take
Several
into account classes
both the keyofsteps
organic compounds
(hydrogenation, havetransport,
storage, been considered as LOHC, and am
and dehydrogenation).
them, aromatic compounds have been identified as the best option, as was
This review discusses the most promising organic couples that have been reported in therecently
literature in the last few years.
firmed by Chu et al. [108]. As previously introduced, a complete study on LOHC
takeBenzene–Cyclohexane
2.4.2. into account both the key steps (hydrogenation, storage, transport, and dehydrog
Loop
tion).
TheThis
mostreview discusses
investigated systemthe most promising
is benzene organic couples
(BNZ)–cyclohexane that
(CHX), due tohave been rep
its high
in the literature in the last few years.
hydrogen capacity (7.2 wt. %). The saturation of BNZ to CHX occurs at 150 C and◦

40 bar, and homogeneous catalysis has been considered for hydrogenation, but the results
2.4.2.a Benzene–Cyclohexane
show lower efficiency and stability Loop
compared to the heterogeneous catalytic systems [37].
Bianchini et al. reported that the complex [Rh(5-C5 Me5 )Cl2 ]2 is active in the hydrogenation
The to
of benzene most investigated
cyclohexane at 50 ◦system
C and 50isbar,
benzene
and with (BNZ)–cyclohexane (CHX),
a base acting as a promoter due to its
[109].
hydrogen capacity
The bottleneck (7.2
of the wt. %). The
BNZ–CHX loopsaturation of BNZ
is the temperature to CHX
required foroccurs
hydrogen at release
150 °C and 40
and ◦homogeneous
(~300 catalysis
C), as is typical for has beenprocess,
an LOHC-based consideredas wellfor hydrogenation,
as the but the
catalytic selectivity withresults s
a lower
the possibleefficiency
formation and stability
of several compared
by-products to the heterogeneous
(e.g., cyclohexene, cyclohexadiene) catalytic
and thesystems
Bianchini et al. reported that the complex [Rh(5-C5Me5)Cl2]2 is active in the hydrogen
resulting decrease in process recyclability. As expected, Pt was one of the first materials to
be considered as a catalyst, but the latest studies are focused on more active and selective
of benzene to cyclohexane at 50 °C and 50 bar, and with a base acting as a promoter [
materials. Nevertheless, some materials recently proposed still contain Pt mixed with
The bottleneck
other elements. Wang etof al. the
[110]BNZ–CHX loopthe
recently studied is catalytic
the temperature
performance required
of PtPd for
alloyhydroge
lease (~300 °C),
nanoparticles as is typical
supported for an LOHC-based
on nitrogen-doped carbon. The process, as well
experimental as theshow
results catalytic
the selec
excellent catalytic activity with a TOF of 90.07 mmol g−1 metal min−1 and 100% H2 purity
Energies 2023, 16, 6035 14 of 31

at 180 ◦ C. The density functional theory (DFT) calculations suggest that the presence of
Pd promotes the specific adsorption and activation of CHX on the Pt surface. A similar
enhancement has also been seen when substituting Pd with Ru and Ir [110]. Extraordinary
Pt activity enhancement in a reversible hydrogenation–dehydrogenation catalyst has been
described by Chen et al. [111]. Here, single Pt atoms were supported on CeO2 nanorods,
and this system allowed a performance increase of 309 times compared to conventionally
supported nanoparticles. Noble-metal-free catalysts based on Fe, Ni, Cu, and Zn have been
considered. Many efforts have been directed towards Ni-based materials. The main issues
with Ni are the high hydrogenolysis, which leads to a low selectivity for cyclohexane to
toluene. In this category of catalysts, a widely used strategy consists of the addition of a
second transition metal. Despite the results remaining very different from those reported
for noble-based catalysts, the Ni–Cu bimetal system supported on activated carbon cloth
(ACC) showed a performance improvement [112]. The NiCu/ACC has a CHX conversion
and H2 yield of 25.78% and 19.41%, respectively, versus a CHX conversion of 7.64% and a
H2 yield of 5.75% for the Ni/ACC material. The positive effect of copper on nickel activity
was confirmed by Xia et al. [113], using a NiCu/SiO2 system. In this case, the addition of
copper and the presence of SiO2 as a supported phase provided excellent selectivity for
hydrogen release and benzene (99.5%) at 350 ◦ C.

2.4.3. Toluene–Methylcyclohexane Loop

The couple toluene (TOL)–methylcyclohexane (MCH) has been widely considered
due to its hydrogen capacity (6.2 wt. %), the mild toxicity of the MCH, and the low cost
of chemicals [114]. Moreover, both TOL and MCH are liquids under ambient conditions.
As regards the hydrogenation process, conventional catalysts based on Pt are used, with
a non-negligible impact on cost. In the last few years, low-Pt-content and Pt-free cata-
lysts have been proposed in the search for high catalytic activity and poisoning resistance.
Indeed, when Pt is used, an ultrapure H2 feed (>99.99%) is required to avoid its deactiva-
tion [115]. Many catalytic-supported systems have been proposed [116]. Alumina (Al2 O3 )
is usually the supporting phase, functionalized with a transition metal such as Ni, Co, or
Mo. Nevertheless, these catalysts provide lower activity than Pt towards hydrogenation,
requiring more severe operating conditions. Zhou et al. [116] proposed an Fe-promoted Mo
carbide catalyst; they investigated the effect of iron load (Fe:Mo ratio) and carburization
temperature (550–700 ◦ C) on catalytic activity and stability. The addition of iron slightly
affects the hydrogenation activity, while strongly improving the stability over time. The
observed degradation has been attributed to surface oxidation, and a re-carburization
treatment can recover the initial properties of the catalysts.
Recently, Wang et al. [115] addressed CO catalysts’ deactivation, proposing an innova-
tive Pt-free catalyst made of RuNi/TiO2 , which also promotes toluene hydrogenation in
the presence of carbon monoxide in a range of 1000–5000 ppm. A further positive effect is
represented by the mild operating conditions (atmospheric pressure and 180 ◦ C) required.
The improvement is related to the different bonding properties of Ru and Ni, which interact
with CO and toluene, respectively.
Nagasawa et al. [117] reported the promising electrohydrogenation of TOL using a
solid polymer electrolyte setup. The main advantage of such a process is the coupling of
hydrogen production by water electrolysis with toluene reduction in one reactor, according
to the following reaction scheme:

Anode: 3 H2 O → 3/2 O2 + 6H+ E◦ = 1.23 V vs. SHE (7)

Cathode: C7 H8 + 6H+ + 6e− → C7 H14 E◦ = 0.154 V vs. SHE (8)

In this system, of concern is the development of an electrocatalyst able to favor the
hydrogenation of TOL to MCH, rather than hydrogen evolution, which is a competitive
reaction. The results show that a cathode made of carbon paper loaded with Pt is able to
sustain the desired reaction, highlighting the importance of the cathode layer’s thickness
Energies 2023, 16, 6035 15 of 31

and the catalyst load, as well as the high impact of mass transport features typical of the
electrochemical systems. Electrochemical hydrogenation has also been investigated by
Imada et al. [118], using a binary Pt-based alloy nanoparticle-loaded (50 wt. %) carbon
catalyst (Pt3 M/C). The authors considered several binary systems (Pt3 M) with different
metals (M = Rh, Au, Pd, Ir, Cu, and Ni), and the presence of metal boosts the activity of
commercial Pt/C. PtRh/C provides the highest activity, and the Tafel slopes obtained for
each catalytic system suggest that the kinetic mechanism is not affected by the metal.
The MCH dehydrogenation process is mainly based on Pt catalysts with a non-
negligible impact on process costs, which are also affected by the energy input required by
the endothermic reactions. Therefore, the main efforts made have been towards reducing
the amount of Pt in the catalytic formulation and decreasing the operating temperature.
Nevertheless, the replacement of Pt-based catalysts is not trivial due to the high catalytic
properties with a toluene yield of up to 99% [119]. Bimetallic catalysts seem to be a promis-
ing alternative, as reported by recent studies [37]. Increasing interest has been shown in
catalytic systems containing Ni coupled with a second transition metal. The presence of
such elements (Cu, Zn) reduces the activity of Ni towards the hydrogenolysis of the C–C
bond, increasing the selectivity towards toluene up to 97%.
An alternative strategy to reduce cost has been proposed in [120]. Lv et al. developed
a nickel single-atom cerium oxide catalyst to be used in a solar-heating catalytic MCH
dehydrogenation reaction. The H2 generation reached a rate of 2756 mmol g−1 h−1 at
400 ◦ C, and the design of the thermal catalytic device allowed for operating under solar
irradiation, without a secondary energy input.
A factor that can be considered during the dehydrogenation step is the recovery of
heat. Pashchenko [121] described the thermochemical recuperation of waste heat during
hydrogen extraction from LOHC, considering as a model the MCH–TOL system. The
thermodynamic analysis performed in temperature and pressure ranges of 100–400 ◦ C and
1–4 bar, respectively, showed maximum thermal efficiencies at 300–350 ◦ C and 1.5–2 bar.
These conditions allow for obtaining an acceptable MCH conversion rate and notable
separation between hydrogen and toluene.

2.4.4. Naphthalene–Decalin Loop

The naphthalene (NPT)/decalin (DCL) system is characterized by a hydrogen capacity
of 7.3 wt. %, and it has been considered as a possible hydrogen carrier in the last few
years [122]. Conventional catalytic systems for NPT hydrogenation operate in temperature
and pressure ranges of 250–400 ◦ C and 15–80 bar, respectively. A recent thermodynamic
and kinetic analysis carried out by Peng et al. [123] suggested that the optimal conditions
for NPT hydrogenation when using a commercial NiMo/HY catalyst are 400 ◦ C, 80 bar,
and a ratio of H2 /NPT equal to 4. The addition of hydrogen to NPT molecules can
lead to the formation of several by-products and aromatic hydrocarbons (e.g., tetralin,
butylbenzene, ethylbenzene), and to avoid this, it is necessary to seek an improvement in
catalyst selectivity towards decalin. Promising results have been obtained by Ma et al. [124]
by means of a surface-engineering approach. The molybdenum carbide (α-MoC) surface
was doped with Pd, and the addition of the noble metal promoted the generation of
vacancies in the Mo structure, as well as the selective hydrogenation of NPT to DCL.
The authors also investigated the dopant load, finding that the optimum performance
corresponded to 0.5 wt. % of Pd.
The saturation of naphthalene to decalin is favored when metal nanoparticles are used
as catalysts [125]. In the last few years, studies have also been dedicated to non-noble metal
catalysts. For these materials, possible actions to improve their activity relate to the selection
of the support and the synthesis method, or metal loading. Vargas et al. [126] prepared
Ni catalysts (4 wt. %) supported on SBA15 (amorphous silica) and Al-SBA15. The results
show that the addition of Al into the SBA15 structure caused the substitution of Si4+ with
Al+3 and the formation of Brönsted acid sites. This change had a positive effect on catalytic
activity, which was also influenced by the preparation route. Indeed, a higher activity
Energies 2023, 16, 6035 16 of 31

was reached when the EDTA was used as a complex agent during catalyst loading on the
support, rather than using nickel nitrate. The enhancement in selectivity in the presence of
EDTA is related to a better dispersion of the Ni particles and a greater amount of acid sites.
Nevertheless, these catalytic formulations are not able to compete with noble metal-based
catalysts at present. Therefore, part of the research is focused on how reductions in catalyst
load preserve the activity. As previously introduced, the performance of a supported
catalytic system depends on the intrinsic activity of the metal phase and its interaction
with the supporting phase. Zhang et al. [125] evaluated this relation in a catalytic system
made up of Pd supported on HY zeolite (SiO2 /Al2 O3 ). A detailed investigation allowed
for the determination of the most suitable SiO2 /Al2 O3 ratio, and the role played by the
active metal, acid sites, and zeolite mesopores’ volume in catalytic performance.
Most of the studies regard the dehydrogenation stage, which is the limiting reaction of
the whole process in LOHCs. Beyond pure noble metals, other catalytic systems have been
proposed. The current leading approach to catalyst development is based on a multicompo-
nent system, with the aim being to exploit synergistic effects. In some cases, noble metals
are coupled with a suitable support. In 2023, Luo et al. [122] investigated the synergy of Pt
and Pd in a bimetallic system. Firstly, the authors identified the optimum Pt load (3 wt. %)
when MgAl2 O4 is used as the supporting material. They also investigated a PtPd bimetallic
system (Pt:Pd = 4:1) dispersed on the same spinel structure. The synergistic effects of the
bimetallic catalysts allow for decreasing the amount of the catalyst by up to 1%, while pre-
serving the performance. The selection of MgAl2 O4 as a supporting phase is justified by the
results recently presented by Wang et al. [127]. This material has been compared with other
candidates used as supporting phases, such as Al2 O3 , mesoporous silica (MCM-41), and
active carbon (AC). The results clearly show the improvement correlated with the usage of
MgAl2 O4 due to the higher dispersion of Pt particles, which allows the formation of smaller
nanoparticles (average size of 1.24 nm) with enhanced activity. The authors also underlined
the strong effect of the method of synthesis of the supporting phase, and how properties
such as crystallinity, morphology, and surface acidity can affect the catalytic performance.

2.4.5. Dibenzyltoluene–Perhydrodibenzyltoluene Loop

The dibenzyltoluene (DBT)/perhydrodibenzyltoluene (18H-DBT) system with a hydro-
gen capacity of 6.2 wt. % has gained attention as an LOHC also due to the well-established
industrial production of DBT and its competitive price (EUR 2–4/kg), and the extensive
knowledge related to safety and handling issues [35,128]. The dehydrogenated product
(DBT) is noncarcinogenic and nonexplosive, representing a fairly rare advantage related to
benzene and its derivatives. Moreover, 18H-DBT has the main advantage of being liquid
and stable in a wide temperature range (−30 to 360 ◦ C). From a technological point of view,
the DBT–18HDBT loop shows excellent reversibility with a remarkable kinetic rate and a
competitive dehydrogenation enthalpy (65.4 kJ mol−1 ). As regards DBT hydrogenation,
a relevant reaction rate has been obtained by using a Ru/Al2 O3 heterogeneous catalyst,
which worked better than the Ru/C and Pd/Al2 O3 catalytic systems [35].
Hydrogen quality can influence the performance of the hydrogenation stage.
Jorschick et al. [128] investigated hydrogen storage in 18H-DBT in a temperature range of
150–260 ◦ C, evaluating the effect of wet hydrogen. Firstly, Ru and Rh have been identified
as very active for DBT hydrogenation below 200 ◦ C. The presence of water in the hydrogen
stream can affect catalytic activity, but at the same time, the authors underline that the
amount of water used in that research is several orders of magnitude greater than the real
application value. Further, these results suggest that it is possible to identify catalysts
that are active with wet hydrogen, avoiding the dry stage between the electrolysis and
hydrogenation, with a relevant impact on the overall energy consumption of the process.
The noble metals remain the reference catalysts for dehydrogenation, as reported
by Bruckner et al., who considered Pt and Pd on different supports (Al2 O3 , SiO2 , C) at
270 ◦ C [129]. The Ru/Al2 O3 catalytic system also provided promising activity in mild
conditions, operating at 10 bar and in a temperature range of 80–160 ◦ C [129].
Energies 2023, 16, 6035 17 of 31

Another route to increase the process performance is the reactor design, and this aspect
can play a fundamental role in process scale-up at the industrial level. Indeed, most of the
studies carried out at the lab scale have been performed in a stirred tank reactor, which is
usually affected by inefficient heat transfer and mass transport. Ali et al. [130] proposed
an innovative continuous microchannel reactor, which showed greater hydrogen release
compared with the stirred tank, which increased from 64.1% to 82.2% at 320 ◦ C after 20 h.
Moreover, this option allowed a decrease in the amount of catalyst used.
In all the LOHC systems proposed above, it is extremely important to avoid a non-
uniform temperature distribution within the dehydrogenation reactor [36]. Indeed, the
formation of colder zones leads to a slowdown of the kinetic rate. On the other hand, the
presence of hot spots can cause the decomposition of the dehydrogenated LOHC form,
with the risk of breaking C–C bonds and complicating the compounds’ recyclability.

2.5. Metal Hydrides

Metal hydrides (MH) are an interesting solution that can operate under milder con-
ditions than LH2 and CH2 , with a storage pressure no higher than 30 bar, one order of
magnitude lower than compressed hydrogen, simplifying the handling procedure. H2
reacts with metals or alloys in a reversible reaction, allowing its release, and this solution
seems to be promising for small–medium applications (up to 30 Nm3 H2 ) [23,131]. H2
release is one of the main drawbacks of MH-based system, requiring energy supply due
to the endothermal conditions. Moreover, the recovery and reuse of the dehydrogenated
metal form is still an open issue that must be faced. Indeed, the development of a storage
system based on metal hydrides must be based on loop concept, with the possibility of the
recovery of the dehydrogenated form, as already shown for LOHCs, and its regeneration
to the hydrogenated form.
A suitable metal hydride system should be able to operate the whole loop (H2 ad-
sorption/desorption) under conditions close to those of the downstream application. The
expected hydrogen capacity of 10 wt. % is a threshold value for metal hydrides. Some
materials, such as Mg(BH4 )2 and LiBH4 , could theoretically provide a hydrogen capacity of
14.9 wt. % and 18.5 wt. %, respectively, satisfying the requirements, but the operating con-
ditions (pressure, temperature) required for both the hydrogenation and dehydrogenation
processes, and the corresponding kinetic rates, are far from targets [132].
Sodium borohydride (NaBH4 ) has attracted attention in the last ten years due to its
noteworthy hydrogen capacity (10.8 wt. %), good hydrolysis management, and excellent
hydrogen purity. The hydrolysis mechanism is based on the following reaction:

NaBH4 + 2H2 O → NaBO2 + 4H2 (9)

Nevertheless, from a practical point of view, several drawbacks are blocking the
application of such a system as a hydrogen carrier, among them being the production of
hydrate sodium metaborate (NaBO2 ·xH2 O), which is hard to recycle [133]. Consequently,
efforts are being made to develop approaches that will allow a higher selectivity towards
H2 or an improvement in the NaBO2 regeneration process.
Barbucci et al. [134,135] demonstrated that effective thermochemical NaBH4 regeneration
can be obtained when working over 600 ◦ C and 12 bar. The complete conversion of NaBO2 has
been achieved in 90 min at 634 ◦ C and 30 bar of H2 . More recently, Ouyang et al. [133] obtained
enhanced regeneration under room conditions by milling sodium metaborate (NaBO2 ·2H2 O
and NaBO2 ·4H2 O) with Mg (molar ratio NaBO2 ·2H2 O:Mg = 1:5, and NaBO2 ·4H2 O:Mg = 1:9).
This approach improves both the regeneration yields, with a maximum of 68.55% for
NaBO2 ·2H2 O, and drastically reduces of the cost of the reducing method, which requires
the dehydration of NaBO2 and the preparation of MgH2 .
The magnesium hydride itself has been attracting the attention of several researchers,
and nowadays is one of the most widely investigated metal hydrides for hydrogen stor-
age [136,137]. This is due to its lighter weight compared to more complex metal hydride
systems, its hydrogen capacity (7.6 wt. %), its ease of supply, and its accessible costs (in
Energies 2023, 16, 6035 18 of 31

2023 Mg ~ USD 3/kg). The current drawback that blocks its application at a large scale is
represented by the conditions required for MgH2 synthesis (hours at 400 ◦ C and 30 bar) and
the slow kinetic rate of hydrogen release [138,139]. The reaction occurs in a heterogeneous
system where the H2 gas phase interacts with the Mg solid phase. Based on updated
knowledge, the rate-determining step is the dissociation of H2 molecules on the Mg surface,
due to electronic configuration. Indeed, this stage is favored in transition metals that have
an orbital d that can easily interact with the hydrogen orbital, which is not available for Mg.
Mg dehydrogenation can be enhanced by the addition of catalysts, as was recently
reported [140]. In this paper, Kumar Sing et al. proposed a systematic investigation of the
effects of catalysts based on transition metals from groups 4–6 (TiO2 , ZrO2 , HfO2 , V2 O5 ,
Ta2 O5 , CrO3 , MoO3 , WO3 ). The results clearly show that the ball-milling dispersion of oxide
on MgH2 enhanced the desorption rate, and the best performances have been achieved
using TiO2 , ZrO2 , V2 O5 , and CrO3 , with promising performance results around 200 ◦ C.
The analysis suggests that the process benefits transition metals with multi-oxide states
2+ and 3+ . Dong et al. [137] used ab initio molecular dynamics simulations to describe the
positive effects related to the formation of a heterojunction between MgH2 and the single-
atom catalyst (MgH2 /SAC) by using transition metals. Although the calculations identified
a reduction in the activation energy for hydrogen desorption, the authors underline the
need for further investigations to achieve a deeper comprehension of the mechanism,
and the better tailoring of the material properties. Ismail [24] proposed to destabilize
MgH2 stability with the addition of NaAlH4 . The resulting Mg–Na–Al system has a lower
decomposition temperature, superior cyclability, and improved kinetic performances, due
to the formation of Al12 Mg17 and NaMgH3 in situ during H2 release.
A valuable approach for improving the performance of metal hydrides that requires
further investigation is nanostructural engineering [132]. The reduction in particle size
has a positive effect on the surface thermodynamic properties, as was predicted in 2005
by Wagemans et al. [141]. More recently, the effects of particle size on Mg-based metal
hydrides have been reported, with a performance enhancement achieved by decreasing
the particle size to lower than 10 nm. Future studies, seeking a full comprehension of
the mechanisms that act on the nanostructured systems, must be devoted to evaluating
their stability over time, due to the possible agglomeration issue related to the high-energy
surface. An example of the effectiveness of reducing particle size has been reported by
Zhang et al. [142]. They successfully produced ultrafine MgH2 nanoparticles (4–5 nm) with
a hydrogen capacity of 6.7 wt. % at 30 ◦ C, and furthermore, the first trial of its stability has
reported it preserving its performance over 50 cycles at 150 ◦ C.
The discussion presented above for each hydrogen carrier highlights the current
challenges that must be faced, and they are summarized in Table 2.

2.6. Integration with the Downstream Power Processes

All the approaches presented above have a final common stage of hydrogen release.
This review is mainly dedicated to hydrogen storage; nevertheless, in this section, the main
parameters that must be considered are briefly summarized to give key aspects related to
the integration of the storage system and final user. Based on a model wherein hydrogen is
fed to a fuel cell for power generation, the key aspects that must be taken into account in
full process design are as follows.
• Fuel cell selection
The fuel cell technology changes as a function of the application features (power size,
mobile/stationary, continuous/discontinuous), and this affects the requirements of the
hydrogen inlet stream. Indeed, the H2 purity, H2 mass flow, and operating temperature
are strictly related to the selected fuel cell and the application size. Low-temperature fuel
cells (e.g., PEMFC), which mainly use Pt-based electrocatalysts, are highly sensitive to
hydrogen impurities, such as carbon-based compounds and ammonia. Further, in the
case of hydrogen storage, when NH3 or LOHC is used, a high-purification stage will be
necessary, affecting the plant cost. On the contrary, high-temperature fuel cells (e.g., SOFC)
 gen impurities, such as carbon-based compounds and ammonia. Further, in the case of
hydrogen storage, when NH3 or LOHC is used, a high-purification stage will be necessary,
affecting the plant cost. On the contrary, high-temperature fuel cells (e.g., SOFC) are less
sensitive to these compounds, and can work easily in the presence of impurities. As ex-
Energies 2023, 16, 6035 pected, the fuel cell operating temperature and pressure will also affect the 19
overall
of 31 ener-
getic balance, and so it is important to evaluate the matching between the conditions of
H2 release and the fuel cell.
• Storage
are of CO2toand
less sensitive unsaturated
these compounds,LOHCs
and can work easily in the presence of impurities.
As expected, the fuel cell operating temperature and pressure will also affect the overall
When hydrogen
energetic is stored
balance, and in a carbon-based
so it is important to evaluatecompound,
the matching we mustthe
between consider the recov-
conditions
ery of the
of H unsaturated LOHCs, as well as CO2 and CO, when methanol and formic acid
2 release and the fuel cell.
are used.
• This action
Storage of CO2 could impact the
and unsaturated process via the challenges imposed on mobile ap-
LOHCs
plications, with
When stricterisconstraints
hydrogen on the volume
stored in a carbon-based and weight
compound, we mustofconsider
the system.
the recovery
of the unsaturated LOHCs, as well as CO2 and CO, when methanol and formic acid are used.
3. Techno-Economic Analysis
This action could impact the process via the challenges imposed on mobile applications,
with stricter constraints on the volume and weight of the system.
The worldwide use of hydrogen as an energy vector in power applications, and the
consequential development
3. Techno-Economic Analysisof a hydrogen-based economy, require techno-economic anal-
yses for each of the solutions
The worldwide proposed
use of hydrogen above.
as an energyThe assessment
vector must consider
in power applications, and theallcon-
the stages
previously
sequentialdiscussions,
developmentand of a the final application
hydrogen-based (mobile/stationary,
economy, continuous/discon-
require techno-economic analyses
tinuous) has
for each of athestrong impact
solutions proposedon above.
the selection of themust
The assessment proper technology.
consider Moreover,
all the stages previ- this
section highlights the strong correlation between all the technological factors and the
ously discussions, and the final application (mobile/stationary, continuous/discontinuous)
has a strong impact on the selection of the proper technology. Moreover, this section high-
strong influence of policy in developing a hydrogen network. Figure 6 sketches the main
lights the strong correlation between all the technological factors and the strong influence
parameters
of policythat must be considered
in developing in a techno-economic
a hydrogen network. Figure 6 sketchesanalysis.
the mainThis sectionthat
parameters addresses
the most
must beupdates
considered studies on techno-economic
in a techno-economic analyses
analysis. This sectionof the hydrogen
addresses the most carriers
updates previ-
ously introduced.
studies on techno-economic analyses of the hydrogen carriers previously introduced.

Figure 6. Main factors that must be considered in a techno-economic analysis aiming at the selection
Figure 6. Main factors that must be considered in a techno-economic analysis aiming at the selection
of a hydrogen storage system.
of a hydrogen storage system.
In Table 3, the key features that can affect the techno-economic analysis and the selec-
tion of hydrogen carriers are summarized and grouped according to the factors introduced
in Figure 6. A deeper discussion of these points is given after the table.
Energies 2023, 16, 6035 20 of 31

Table 3. Summary of the key features of factors that must be considered during the techno-economic
analysis of hydrogen carriers.

Factor Key Features for Techno-Economic Analysis

• Hydrogen carriers’ production must be coupled with RES to be economically sustainable [143].
• In an RES-based scenario, ammonia-based systems have lower carbon emissions than LOHC,
and the minimum cost is reached with the TOL–MCH supply chain [143].
• For RES-based power-to-X solutions (X = hydrogen, methanol, ammonia, and methane), the highest
Hydrogen carrier
energy efficiency is reached for hydrogen, and the lowest for methane [144].
production
• The replacement of the Haber–Bosch approach for ammonia synthesis is hindered by the high cost
of alternative methods [76].
• The final cost of hydrogen carriers is sensitive to the price of the water electrolyzers required to
produce green hydrogen, and to electricity costs [76].

• Dehydrogenation of LOHC has too high a cost for large-scale applications [145–147].
Hydrogen release • For industrial applications, the integration of the endothermic hydrogen release stage with
industrial waste heat can improve economic sustainability [145].

• For carbon-based hydrogen carriers, it is necessary to evaluate the economic impact of CO2 capture
Hydrogen carrier
technologies (for methanol and formic acid) and the recovery of unsaturated LOHC after hydrogen
recyclability
release [148–150].

• The shipping industry is one of the hardest sectors to abate due to severe constraints regarding
weight and volume, coupled with high power demand [151].
• In the shipping sector, the key parameters to be considered for evaluating techno-economic
sustainability are the ship’s size and the navigation time [151].
• PEMFC fed by H2 has been shown to be the most economic option for trips up to 7 days, while
Application sector on-board CH3 OH steam reforming can be considered for a longer time, and ammonia only if an
and size SOFC is used [151].
• For sizes larger than 5 MW, new technologies stop being able to substitute internal combustion
engines in the shipping sector [152].
• Regarding the substitution of diesel-powered trains with hydrogen carriers, metal hydrides are not
suitable due to process layout, as well as LOHC. Possible solutions could include using ammonia
and CH2 [153].

• Importance of the availability of a renewable energy sources grid [154].

Infrastructure network • The choice of the hydrogen carrier has a strong impact on the development of correlated
infrastructure, such as port refueling stations [155].

• Transport has a strong impact on small–medium H2 production [154].

• For small–medium production and long transport distances, the best solution is LOHC [143,154],
Transport Length and CH2 is best for short transport distances [154].
• Hydrogen exportation as ammonia is competitive if it is directly used; otherwise, LH2 could be
preferred [156].

• The location of the production of hydrogen carriers has a strong impact on process cost [154].
Geographical position • The decentralized production of hydrogen carriers can represent a possibility for growth at
isolated sites [157].

• Application of incentives [76].

Policy • Increase in carbon taxes [76].
• Necessity to develop a transnational logistic for hydrogen carriers’ supply chain [155].

All the factors introduced in Figure 6 and Table 2 are strongly interconnected, and
Ibagon et al. [154] discussed the strong interdependency of different factors, such as the
availability of RES, production capacity, the kind of electrolyzer, the storage system, and
carrier transport. The authors addressed case studies for four different locations in Uruguay.
Energies 2023, 16, 6035 21 of 31

This example is relevant because Uruguay has a deep renewable energy grid, and this
is one of the factors required to have sustainable hydrogen production. It is noteworthy
that Ibagon et al. also considered penalties associated with hydrogen production deficits
in their simulations. They verified that renewable energy availability is the main factor
for large hydrogen demand (250 tH2 /d), with a range of 47–57% of the levelized cost of
hydrogen (LCOH). The development of an accurate model to forecast renewable energy
production is then needed for large-scale applications, along with a deep knowledge
of the application site. The transport has a greater impact on small–medium hydrogen
productions (1.72 tH2 /d and 15 tH2 /d), and for such sizes, the best transport options are
trucks with liquid organic hydrogen carriers for long distances, and compressed hydrogen
for shorter distances.
The integration of the hydrogen supply chain with renewable energy sources and
green hydrogen production is vital to decrease the overall production costs and CO2
emissions. Based on these two assumptions, Lee et al. [143] compared different hydrogen
carriers (LH2 , NH3 , TOL-MCH, H0-18HDBT, and methanol) via techno-economic and
environmental investigations for large-scale marine transportation. The results show that
in a renewable power scenario with green H2 production, the ammonia system yields the
lowest carbon emissions (2.23 kgCO2 -eq/kgH2 ), with an LCOH of 4.92 USD/kgH2 , while
the lowest cost was achieved with the TOL–MCH supply chain (4.57 USD/kgH2 ).
The coupling between renewable sources and a power-to-X (P2X) solution has also
been discussed by Bellotti et al. [144]. In this work, the authors considered four possible
P2X pathways (hydrogen, ammonia, methanol, and methane) produced using RES and a
10 MW PEM electrolyzer. The highest energy efficiency (61.5%) was obtained with power-
to-hydrogen (P2H), and the lowest with power-to-methane (45%). Nevertheless, P2H is
the worst option in terms of volume required (316 m3 ), while the best storage solution in
terms of volume and energy density is power-to-methanol (P2M), with a volume of 30 m3
and 4.3 MWh/m3 . Power-to-ammonia (P2A) is the best solution in terms of H2 stored
in the fuel (108 kgH2 /m3 ). The economic analysis on expected investment (CAPEX and
OPEX) shows that the main costs are related to the electrical energy (50%) and the PEM
electrolyzer CAPEX (30%) and OPEX (10%).
The production of hydrogen carriers strongly impacts the economic sustainability of
the process. Currently, industrial processes, such as Haber–Bosch for ammonia, are cheaper.
Further, it is fundamental to develop strategies of production that reduce the final costs.
In 2023, Palone et al. [76] propose a techno-economic analysis of hydrogen generation
and storage with a chemical loop derived from waste high-density polyethylene. The
work is oriented towards the circular economy approach, and chemical looping, wherein
different synthesis processes are coupled, has been used to investigate the simultaneous
production of CH3 OH and NH3 . The analysis showed a significant decrease in CO2
emissions compared with conventional routes. The main operating cost is represented by
electricity (66% of overall OPEX), which is also the parameter most prone to fluctuations.
On the other hand, the final price evaluation and the competitiveness of such a process are
also sensitive to other variables such as the cost of electrolyzers for hydrogen production,
as well as the applications of incentives or an increase in carbon taxes.
For the formic acid-based process, the main challenges are the competitiveness of
green hydrogen and steam generation for synthesis, which, up to now, are not as significant
as the costs of conventional FA production [95]. Moreover, the lack of heterogeneous
active catalysts that are easily separable from reaction products hinders the diffusion of the
process, which currently bears costs related to the separation and recovery of homogeneous
catalysts [158]. In 2016, the techno-economic analysis presented by Pérez-Fortes et al. [148]
highlighted the potential of using formic acid as a hydrogen carrier, but at the same time, it
underlined the necessity to overcome technological issues related to catalyst development
and operating conditions.
The formic acid- and methanol-based processes acquire relevance when coupled with
carbon capture and storage (CCS) technologies, and a consequent reduction in overall
Energies 2023, 16, 6035 22 of 31

emissions can be achieved. Bellotti et al. [150] proposed a techno-economic analysis for
the integration of a CCS plant within a coal plant with a system for methanol production.
The sustainability of the process is not only dependent on technological design and system
integration, but it is heavily influenced by national and transnational policy, and a key role
is played by the cost of EU ET CO2 emission allowances. The integration between carbon-
based hydrogen carriers and CCS technologies has also been reported by Cui et al. [149]. In
this case, the authors focused on evaluating the cost of transporting hydrogen as methanol
and ammonia. Methanol is preferred only at a small scale (<2 tH2 /h), and if its synthesis
occurs only in the proximity of a CCS plant. Ammonia is more competitive for larger-scale
production and in cases wherein an infrastructure for CO2 capture is not already available.
The literature review highlighted a lower number of techno-economic analyses that
consider metal hydrides as hydrogen carrier. Nevertheless, a remarkable techno-economic
analysis has been proposed by Rivarolo et al. [159], and the results highlight the advantages
offered by metal storage compared with CH2 .
As sketched in Figure 6 and Table 3, the application sector and the required power
sizes also influence the selection of hydrogen carriers, and one of the hardest challenges
is related to the shipping industry [151]. Up to now, there has been no technology able
to completely substitute the currently used fuel engines given the power demand. In the
last few years, many candidates have been proposed, such as hydrogen, ammonia, and
methanol. As reported by Kistner [151], the navigation time and the ship’s size are the most
important parameters that must be considered during carrier selection. H2 -fed PEMFCs
result as the best economic option for trips up to 7 days. On-board CH3 OH steam reforming
could be profitable from both economic and environmental points of view, and for a longer
time. Ammonia could be considered only if it is used in the presence of SOFC, but further
evaluations of NOx emissions will be necessary.
The complexity of marine sectors and the necessity of differentiating applications has
been deeply discussed in [152], wherein a user-friendly tool, called HELM, is presented.
The algorithm allows for the direct comparison of different technologies, considering key
aspects of the propulsion system such as volume, weight, cost, and emissions, as well
as the size of the ship. For small applications (<5 MW), the usage of CH2 coupled with
PEMFC is suggested as an alternative to internal combustion engines (ICEs), while the LH2
is not so attractive, due to the need for complex auxiliary systems. With an increase in size
(>5 MW), the innovative technologies will not be able to completely replace ICE, but the
most valuable solutions for use in the future seem to be ammonia and methanol. An on-
field marine application has recently been proposed by Cavo et al. [156]. Here, an advanced
controlled method has been developed for the thermal management of a metal hydride
system coupled with polymer electrolyte fuel cells installed on-board the hydrogen vessel
ZEUS. System validation dynamically verified that the heat generated by fuel cells was able
to supply the thermal energy required by MH tanks under different navigation conditions
and during the transient state. On the contrary, ammonia applications can exploit the
advantages of their hydrogen capacity and utilization efficiency, and the low costs of
production, along with the possibility to use them directly in NH3 -powered fuel cells.
Another sector currently evaluating the possibility of applying hydrogen power sys-
tems is railway transport, in relation to the substitution of diesel-powered trains. The
recent analysis of Xu et al. [153] compared different hydrogen carriers (ammonia, LOHC,
MH) and the storage of CH2 and LH2 . Despite its attractive storage density value, the MH
application is hindered by the harsh operating conditions that, at the current stage, seem
unsuitable for this application. Also, LOHC utilization is not ready to be applied at a large
scale due to the harsh conditions required by the dehydrogenation process.
The strong impact of the scale factor has also been discussed in a rigorous economic
and environmental analysis performed by Dickson et al. [147], which compared liquid hy-
drogen (LH2 ), ammonia (NH3 ), and LNG with methanol, DBT/18H-DBT and TOL/MCH.
The scenario of medium-level market penetration favors NH3 and CH3 OH, with levelized
costs of USD 3.6 and 3.78/kgH2 , respectively. The LH2 option becomes competitive at
Energies 2023, 16, 6035 23 of 31

high-level market penetration, with a cost of USD 2.12/kgH2 , due to the strong impact of
the dehydrogenation process when an LOHC is used. A positive evaluation of using LH2
for hydrogen exportation has also been supported by Hinkley et al. [146], who considered
a case study of a power station used to produce 600 MW of hydrogen and three different
hydrogen carriers. The exportation of H2 as NH3 becomes more competitive only if ammo-
nia is directly used, thus avoiding the cracking stage. Nevertheless, NH3 has the advantage
of being easier to ship, along with a well-established knowledge base at the industrial level.
The loop TOL/MCH is considered less promising due to the toxicity of the compounds
used, and the high energy demand related to H2 release.
Geographical location affects choices when developing hydrogen-based systems, but
at the same time, H2 ’s economic factors can represent a possibility of growth for isolated
sites. Schöne et al. analyzed the potential applications of a decentralized system for
hydrogen production in Kenya [157]. The authors pointed out that, despite the promising
technological attractiveness of hydrogen-based energy systems, the key to a broad diffusion
will be decreasing the costs of such plants.
The interconnection between the factors sketched in Figure 6 is made evident in the
case study analyzed by Godinho et al. [155]. Indeed, they not only concluded that LOHC
transportation by shipping is sustainable only for short- to medium-distance shipping,
but they also clearly showed how the approaches selected for shipping will influence and
drive port infrastructure development and related investments, due to the high impact
of such a sector on energy demand. In more detail, Godinho et al. highlighted how the
economic sustainability of LOHC is strictly related to both technical development and
political actions. Favorable transnational legislation in the EU could lead to a logistic cost
in the period 2030–2050 ranging between EUR 0.30 and 0.37/kgH2 for DBT-PDBT and EUR
0.24 and 0.34/kgH2 for TOL-MCH. The promising and competitive prices are also related
to the possibility of exploiting existing storage and transportation infrastructures with
few modifications.
The sensitivity of H2 cost to all of the supply chain factors has also been investigated by
Zhang et al. [160] in 2022. They evaluated the cost associated with the import of MCH from
Saudi Arabia to Huizhou in China. The study considered the dehydrogenation and purifica-
tion processes after transportation, with costs of EUR 3.46 and 4.1/kgH2 , respectively. These
costs are unsustainable for large-scale applications, and the study identified two actions
that can help to overcome such drawbacks. The first one has been introduced in Section 2.4,
and it regards the high energy consumption of the dehydrogenation stage. The above
analysis underlines the importance of developing catalysts for MCH dehydrogenation that
remain active under milder conditions. Li et al. [145] focused on the balance of plants,
proposing the integration of an endothermal catalytic stage with industrial waste heat, or in
combination with high-temperature hydrogen power systems, such as those using molten
carbonate fuel cell (MCFC) and solid oxide fuel cell (SOFC). The latter action is related to
the scale of importation, and an increase from 10,000 tons/year to 100,000 tons/year is
estimated to reduce the cost by more than 60%.
Another interesting analysis of the supply chain’s impact on the final hydrogen cost
was undertaken by Rasool et al. [161], which elaborates on eight different scenarios. The
authors consider two alternatives for hydrogen production (alkaline and membrane),
four carriers (CH2 , LH2 , CH3 OH, and NH3 ), and three different export destinations from
Australia (Singapore, Japan, Germany). The analysis shows the high complexity of decision-
making due to the multilevel systems involved. Furthermore, the study also highlighted
the impact of the parameters that can be considered decision criteria, such as the expected
levelized cost of hydrogen (ELCOH) or the expected levelized cost of energy (ELCOE).
Based on ELCOH, the best option is the storage of hydrogen derived from alkaline elec-
trolyzers in NH3 , with costs of USD 8.6, 8.78, and 9.63/kgH2 if exported to Singapore, Japan,
and Germany, respectively. On the other hand, the ELCOE implies that methanol has the
best effects on the supply chain, with corresponding prices for the three destinations of
USD 73.34/GJ (Singapore), 74.21/GJ (Japan), and 77.65/GJ (Germany).
Energies 2023, 16, 6035 24 of 31

4. Conclusions and Perspectives

This review critically discusses the most promising hydrogen carriers for hydrogen
storage, which are essential to the transition towards cleaner and more sustainable energy
production. For each hydrogen carrier considered, the state-of-the-art for its production
and final release has been discussed and compared with the latest and most innovative
approaches proposed in the literature. The current research frontiers indicate that ammonia,
metal hydrides and carbon-based compounds (methanol, formic acid, and LOHC) can
act as hydrogen carriers, allowing the storage of hydrogen under milder conditions than
conventional compressed and liquefied hydrogen. Nevertheless, the analysis also highlights
that, although promising results have been reached in the last few years, more effort will
be required in the future to overcome the issues that remain unsolved.
From a scientific point of view, the first problem that researchers must face is related
to catalyst formulation for the hydrogenation and dehydrogenation stages. The next-gen
catalytic materials must be able to operate under milder conditions (pressure and tempera-
ture) than state-of-the-art materials, and should contain lower quantities of PGM elements,
which will reduce their price. For carbon-based hydrogen carriers, integration with CCS
technologies will be fundamental, as will be considering the possibility of recovering and
reusing the unsaturated form of LOHC after hydrogen release. Also, we must improve
metal hydrides’ recyclability, and make hydrogen from them release faster at temperatures
below 85 ◦ C.
These scientific developments must be coupled with techno-economic analyses in
order to reach the deeper market penetration of hydrogen technologies. In Section 3,
it is evident that the hydrogen economy is dependent on many factors, and some of
these are not related to scientific knowledge. A strong influence in the next few years
will be exhibited by national and transnational policies and decision-makers’ actions,
which will drive investments and infrastructure development, thus determining the fate of
hydrogen carriers.

Author Contributions: Conceptualization, D.C., L.M. and A.B.; investigation: D.C., D.B. and M.R.;
writing—original draft preparation: D.C., D.B. and M.R.; project administration: L.M. and A.B. All
authors have read and agreed to the published version of the manuscript.
Funding: This work was partially supported by the Project “PNRR programme project NEST-
NETWORK 4 ENERGY SUSTAINABLE TRANSITION, Spoke 4” (PE0000021).
Data Availability Statement: All necessary data in this review are included in the paper.
Conflicts of Interest: The authors declare no conflict of interest.

List of Abbreviations
18H-DBT perhydrodibenzyltoluene
AC active carbon
ACC activated carbon cloth
AWEs alkaline water electrolyzers
BNZ benzene
CAPEX capital expenditure
CCS carbon capture and storage
CH2 compressed hydrogen
CHX cyclohexane
CNTs carbonanotubes
CRW critical raw materials
DBT dibenzyltoluene
DCL decalin
DMSO dimethyl sulfoxide
ELCOE expected levelized cost of energy
ELCOH expected levelized cost of hydrogen
FA formic acid
FE Faradaic efficiency
Energies 2023, 16, 6035 25 of 31

GHG greenhouse gases

HB Haber–Bosch
HER hydrogen evolution reaction
ICE internal combustion engine
LH2 liquefied hydrogen
LNG liquefied natural gas
LOHC liquid organic hydrogen carrier
MCFC molten carbonate fuel cell
MCH methylcyclohexane
MH metal hydride
NPT naphthalene
OPEX operational expenditure
P2X power-to-X
PEMWEs polymer electrolyte membrane water electrolyzers
PGM platinum-group metals
RES renewable energy source
SAC single atom catalyst
SOECs solid oxide electrolyzers cells
SHE standard hydrogen electrode
SRM steam reforming of methanol
TOF turnover frequency
TOL toluene

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