International Journal of Hydrogen Energy 56 (2024) 1419–1434

Contents lists available at ScienceDirect

International Journal of Hydrogen Energy

journal homepage: www.elsevier.com/locate/he

Recent progress and techno-economic analysis of liquid organic hydrogen

carriers for Australian renewable energy export – A critical review
Valerie Sage a, 1, Jim Patel b, Philip Hazewinkel a, Qurat Ul Ain Yasin b, c, Feng Wang c,
Yunxia Yang b, Karen Kozielski b, Chao’en Li b, *
a
CSIRO Energy, 26 Dick Perry Avenue, Kensington, Western Australia, 6151, Australia
b
CSIRO Energy, 71 Normanby Road, Clayton North, Victoria, 3169, Australia
c
Department of Chemistry and Biotechnology, School of Science, Computing and Engineering Technologies, John Street, Hawthorn, Victoria, 3122, Australia

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

Handling Editor: Dr M Mahdi Najafpour Hydrogen, as a primary carbon-free energy carrier is confronted by challenges in storage and transportation.
However, liquid organic hydrogen carriers (LOHCs) present a promising solution for storing and transporting
Keywords: hydrogen at ambient temperature and atmospheric pressure. Unlike circular energy carriers such as methanol,
Techno-economic assessments (TEA) ammonia, and synthetic natural gas, LOHCs do not produce by-products during hydrogen recovery. LOHCs only
Hydrogen
act as hydrogen carriers and the carriers can also be recycled for reuse. Although there are considerable ad­
Liquid organic hydrogen carriers (LOHCs)
vantages to LOHCs, there are also some drawbacks, especially relative to the energy consumption during the
Catalyst development
Australian energy export dehydrogenation step of the LOHC recycling. This review summarizes the recent progresses in LOHC technol­
ogies, focusing on catalyst developments, process and reactor designs, applications, and techno-economic as­
sessments (TEA). LOHC technologies can potentially offer significant benefits to Australia, especially in terms of
hydrogen as an export commodity. LOHCs can help avoid capital costs associated with infrastructure, such as
transportation vessels, while reducing hydrogen loss during transportation, such as in the case of liquid hydrogen
(LH2). Additionally, it minimises CO2 emissions, as observed in methane and methanol reforming. Thus, it is
essential to dedicate more efforts to explore and develop LOHC technologies in the Australian context.

1. Introduction
Hydrogen (H2) is a central pillar of the low carbon energy transition
strategy, offering a unique way of storing, transforming, and trans­
porting renewable energy. H2 can enable large-scale renewable energy
integration and power generation, and help decarbonise transportation,
power generation, and industrial energy use. The Hydrogen Council is­
sued a report recently claiming that the hydrogen could represent 22 %
of the world’s final energy demand by 2050, which equates to 660
million tonnes (MT) of H2 annually [1].
Australia is in a unique position of becoming a major player in the
future hydrogen economy with high renewable hydrogen production
capacity owing to high solar radiation intensity, abundant land for large-
scale solar arrays, and abundant agricultural biomass resources, et
cetera. It is especially well suited to export large volumes of hydrogen to
the international market due to its geographical proximity to the major
Asian markets and its established trading relationships [2]. As such,
economical, sustainable, reliable, and safe ways of storing and trans­
porting large amount of hydrogen over long distances needs to be
investigated.
The general characteristics of ideal hydrogen storage media should
include high energy density, stability and safety, ease of operation, fast
kinetics, high purity of released hydrogen, long-term storage capability,
and considerable scalability. Hydrogen storage and transportation
technologies can be classified as either physical or chemical methods.
The physical approach includes compressed gaseous hydrogen (cH2) in
high-pressure tanks or underground caverns and liquefied hydrogen
(LH2) from cryogenic methods. Sorption methods include both physical
(reversible absorption in metal or hydrides) and chemical (those with
chemical bonds to solid or liquid storage materials such as polymers and
chelates) methods. Hydrogen can be liberated via a reaction pathway
from hydrogen mediums such synthetic liquid fuels such as methanol,
formic acid, liquified methane and ammonia, their derivatives, and
recyclable carriers such as liquid organic hydrogen carriers (LOHCs).

* Corresponding author.
E-mail address: Chaoen.Li@csiro.au (C. Li).
1
Current address: PtX and Alternative Fuels, Neste, Finland.

https://doi.org/10.1016/j.ijhydene.2023.12.269
Received 2 October 2023; Received in revised form 14 December 2023; Accepted 24 December 2023
Available online 5 January 2024
0360-3199/© 2023 The Authors. Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
V. Sage et al. International Journal of Hydrogen Energy 56 (2024) 1419–1434

The challenges associated with conventional hydrogen storage, such Table 1

as compression and liquefaction technologies include safety concerns, Comparison of different hydrogen storage technologies with strengths (+) and
low storage density, transportation efficiency, boil-off losses, and rela­ weaknesses (− ) [8].
tively high costs [2]. Moreover, the liquefaction of hydrogen requires a cH2 (700 LH2 Methanol H18-DBT
great amount of energy (more than 30 % of its energy content) [3]. Low bar) (− 253 ◦ C)
temperatures and/or high pressures are essential to store hydrogen by Energy density 5.0 8.5 15.9 6.7
solid adsorption, while normally elevated temperatures are needed to (MJ/L)
release the hydrogen. Unlike liquids which can use the existing fuel Reversibility Not relevant Not relevant – – No ++ Good
Maturity of + Existing + Existing ++ Good + Existing
infrastructures, solid systems require new infrastructures. The desire for
technologies
manageable hydrogen transportation methods compatible with inter­ Infrastructure – – No – – No +++ +++
national commodity export distances have led people to shift research compatibility Excellent Excellent
focus towards LOHCs. Transportation – Special – Special +++ +++
The processes of hydrogenation and dehydrogenation of LOHC sys­ configuration (gas truck (tube trailer, Ordinary Ordinary
up to 1000 tanker 4000 truck truck
tems are reversible, allowing for rapid reactions without consumption of kg-H2) kg-H2) (equiv. (1800 kg-
the carriers themselves and theoretically, only hydrogen is released 4000 kg- H2)
during the dehydrogenation step. Besides this, another advantage of H2)
LOHCs is that their properties are typically like liquid fuels such as diesel Transportation – Limited – Limited +++ +++
size & distance (short (long Unlimited Unlimited
and gasoline. They can be stored at ambient conditions in liquid form for
distances, distances,
a long period without any energy loss and can take advantage of the low high
existing energy infrastructure for storage and transport such as ships, demand) demand)
storage tanks, and fuelling stations. This capability can reduce long Storage time – Limited – – – Losses +++ +++
distance-transportation costs, handling risks, and capital investments Unlimited Unlimited
Safety – Concerns – Concerns ± As
[4–6]. LOHC systems allow H2 to be released at the required time and
+++
gasoline Excellent
location based on relative energy demand. It is particularly important Biodegradability Not relevant Not relevant +++ – – Poor
when considering the supply model from the export location, for Excellent
example, Australia and the Middle East where the hydrogen is produced Operability in + Feasible + Feasible +++ ± Limited
dynamic use Excellent today
with low-cost renewable electricity to somewhere such as Japan with a
Energy loss (%) in 6–15 30 + boil-off 19a 22
high energy demand [7]. Moreover, the transport of hydrogen in the conversion &
This is cze
form of LOHCs over long distances is essentially valuable and quite transportation of
promising compared to other hydrogen transport methods. Capital Transportation & 0.1–6b + 0.1–6b + 5.1d 0.7e dehydroge
transportation cost for LOHC-based hydrogen is low compared to other distribution cost 1.6–2.7c 1.6–2.7c
(A$/kg-H2) nation
forms of hydrogen transport due to the possibility of using existing fleets
of product tankers. The fragmented energy delivery by ships navigating a - generated from atmospheric/captured CO2, b - compression, liquefaction,
on the open sea increases security and volume of supply compared to storage, and transportation, c – exclude the cost of refuelling station, d - con­
electric transmission. Table 1 lists the strengths (+) and drawbacks (− ) version of hydrogen to methanol, and e − hydrogenation, dehydrogenation, and
of LOHC represented by perhydro-dibenzyltoluene (H18-DBT) in com­ transportation. 1 US$ = 1.5 A$ and 1 Euro = 1.63 A$.
parison with pure hydrogen both in compressed and liquified forms and
circular hydrogen carriers represented by methanol. 2. Classification of LOHCs
Despite the advantages of LOHCs as appropriate hydrogen carriers,
major challenges remain for large-scale development and deployment of LOHC systems are composed of pairs of hydrogen-lean (H0-LOHC)
this technology. The main challenge is the unfavourable dehydrogena­ and rich (Hx-LOHC) organic compounds that store and release hydrogen
tion enthalpy requiring high temperature and high energy input. This by repeated catalytic hydrogenation and dehydrogenation cycles (Fig. 1)
leads to numerous issues such as catalyst deactivation caused by coking [10]. Among them, three LOHC pairs have gathered particular interest
and degradation of the LOHC during multiple hydrogenation/dehydro­ in the last decade, methylcyclohexane (MCH)/toluene (TOL),
genation cycles. Another challenge is related to the fact that not all perhydro-dibenzyltoluene (H18-DBT)/dibenzyltouene (DBT), and
LOHCs are in a liquid state at all stages of the hydrogenated and dehy­ perhydro-N-ethylcarbazole (H12-NEC)/N-ethylcarbazole (NEC). The
drogenated cycle, leading to storage and transport issues. Intensive first two are currently under demonstration for stationary applications
research in catalysis development and dehydrogenation process have in Japan [11] and Germany [12] respectively, while the third is prom­
been pursued with outcomes to address both these challenges [9]. ising for mobile applications [13].
However, the need for robust processes that can promote the dehydro­
genation of LOHCs at convenient conditions from an industrial view
remains. Management and integration of the overall process heat is also
essential for improvement.
This paper provides a comprehensive review of recent progress in
LOHC technologies and the current state-of-the-art in research. The
study delves into LOHC systems that have gained considerable interest
and are currently being developed at scale, providing in-depth discus­
sion on these topics. Special attention is placed on the dehydrogenation
reaction of LOHCs and the catalysts required for this process. Addi­
tionally, a thorough evaluation and comparison of various LOHC sys­
tems are conducted, considering their properties, environmental
impacts, and techno-economics aspects (TEA). The aim is to showcase
the potential and suitability of LOHCs for hydrogen storage and trans­
port and to further enhance their commercial viability. Fig. 1. LOHC hydrogenation and dehydrogenation cycle. Reprinted with
permission from Ref. [10]. Copyright 2022 American Chemical Society with
open access license CC-BY–NC–ND 4.0.

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V. Sage et al.
Liquid organic carriers suitable for hydrogen storage should meet the
following requirements [14,15]: (1) low toxicity and environmental
impact compatible with established fuels such as gasoline and diesel, (2)
low cost of synthesis to allow viable economics and high technical
availability, (3) high gravimetric and volumetric hydrogen storage
densities meeting the target of minimum 5.5 wt% and 56 kg-H2/m3
proposed by the Department of Energy (DoE), United States [16], (4)
low enthalpy of dehydrogenation (<70 kJ/mol-H2 [17]) to enable low
reaction temperature and use of waste heat for dehydrogenation, (5) low
melting point (<− 30 ◦ C) and high boiling point (>300 ◦ C) at liquid state
favourable for hydrogen purification and transport [17], (6) high ther­
mal stability, (7) long life over multiple cycles, and (8) stable revers­
ibility with no significant degradation during recycling. A
non-exhaustive list of various LOHCs is presented in Table S1.
Normally LOHCs exhibit hydrogen storage capacities of approxi­
mately 6–8 wt% [18]. As mentioned in the Introduction, a primary
challenge in the widespread adoption of LOHCs as hydrogen carriers is
their high enthalpies of dehydrogenation, necessitating elevated tem­
peratures and substantial energy input. Fig. 2 presents the dehydroge­
nation enthalpies of several classes of LOHCs as functions of their
hydrogen contents and highlights the constraints posed by hydrogen
content and dehydrogenation enthalpy.
2.1. Cyclic alkanes
Cycloalkanes are the most used LOHCs including cyclohexane/ben­
zene, methylcyclohexane (MCH)/toluene, decalin/naphthalene, and
perhydro-dibenzyltoluene/dibenzyltoluene (DBT) pairs (Table S1). The
main attractiveness of these compounds resides in their lower prices (as
shown in Table 4) and larger production volumes in comparison with
other carriers such as N-substituted heterocycles, as many of them are
produced from petroleum and widely used as industrial chemicals.
Their hydrogen storage capacity is in the range of 6–8 wt% (60-62
kg-H2/m3) [18], but they present quite high energy barriers between 64
and 69 kJ/mol-H2 for hydrogenation/dehydrogenation, which requires
high temperature for hydrogen releasing [17]. While the hydrogenation
of most aromatic compounds is a relatively easy and well-known com­
mercial process with noble metal catalysts displaying excellent perfor­
mances, the respective dehydrogenation processes are not common
because aromatics can be extracted easily from crude oil. Therefore,
regardless their high dehydrogenation temperatures, cycloalkanes are
suitable for large scale and long-distance hydrogen delivery because of
their low prices, high purity of hydrogen generated, and abundances
Fig. 2. Hydrogen contents versus dehydrogenation enthalpies for
different LOHCs.
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
that the world annual outputs of benzene and toluene are around 50 and
10 million tonnes per year (Mt/year), respectively.
While cyclohexane and most of derivatives are liquids, some in their
hydrogenated forms such as decalin and bicyclohexyl are solids at
normal temperature. Solid materials are difficult to be fed to a hydro­
genation reactor and require an additional energy to be liquefied,
thereby decreasing the energy efficiency of the whole system and
making it complicated and less reliable. The use of a eutectic mixture of
two LOHC systems, biphenyl and diphenylmethane, was thus proposed
to maintain the system at liquid phase and a high hydrogen content. The
hydrogen content for the mixture of biphenyl and diphenymethane with
a mass ratio of 35:65 can reach 6.9 wt%. Individually, biphenyl and
diphenymethane exhibit hydrogen contents of 7.3 and 6.7 wt%,
respectively [19]. In addition, environmental and safety concerns arise
for several cyclic hydrocarbons as some are carcinogenic or flammable.
2.1.1. Methylcyclohexane (MCH)/toluene
The MCH/toluene system has a hydrogen storage capacity of 6.1 wt
% (1.55 kWh/L) and shows a comparatively high heat of dehydroge­
nation of 68.3 kJ/mol-H2, where the temperature as high as 320 ◦ C in
dehydrogenation is required for full conversion to toluene [6]. Due to
the relatively low boiling points (101 and 111 ◦ C, respectively, as shown
in Table S1) of the MCH/toluene system, the separation and purification
of hydrogen from the gas stream will be an issue. Another problem is
their so low flash points (− 4 and 4 ◦ C, respectively [20]) that is below
the temperature of dehydrogenation.
The Japanese company, Chiyoda Corporation, has developed this
system into a demonstrated technology, called SPERA Hydrogen®, as
shown in Fig. 3 [21–23], and has recently announced its large-scale
application for hydrogen and energy logistics. They have also devel­
oped a compact-type hydrogenation-dehydrogenation facility to fit for
fuel cell vehicle fuel stations, with a H2 storage and generation capacity
of 50 Nm3/h (4.1 kg/h) [22].
The features of the SPERA Hydrogen® system include (1) long term
storage and long-distance transport with very minor loss due to the
chemical stability of the system, (2) easy to handle because both H0-
LOHC and Hx-LOHC are liquid under ambient temperature and atmo­
spheric pressure, (3) use of existing oil infrastructure as the physical
properties of toluene and MCH are similar to gasoline, and (4) combi­
nation of proven technologies with use of conventional equipment
except for catalysts used for dehydrogenation.
Regarding the SPERA hydrogen project, Chiyoda together with other
members of the Advanced Hydrogen Energy Chain Association for
Technology Development (AHEAD) has successfully completed the
world’s first global hydrogen supply chain system by December 25,
2020, for supplying 210 tonnes of gaseous hydrogen (equivalent to
filling 40,000 fuel cell vehicles) per year [24]. The hydrogen is produced
via steam reforming of the gas derived from the natural gas liquefaction
plant of Brunei LNG Sendirian Berhad. A demonstration project was
developed to produce hydrogen from variable renewable energy and a
compact dehydrogenation facility was adapted to fuel cell vehicle fuel
stations.
2.1.2. Perhydro-dibenzyltoluene(H18-DBT)/dibenzyltoluene(DBT)
Dibenzyltoluene (DBT) as well as benzyltoluene (BT) has gained
attraction last decade as potential valuable LOHCs. They are heat-
transfer fluids commonly known under the trade names of Marlo­
therm® SH and Marlotherm® LH, respectively, with relatively low
prices (5.8–18.6 A$/kg [25]). Comparing to cyclohexane compounds,
they have advantages of non-toxic, non-mutagenic, non-carcinogenic,
non-explosive, high thermally stable, and as liquid under atmospheric
pressure over a broad range of temperatures (− 50 to 370 ◦ C for
H18-DBT), a theoretical storage density of 6.2 wt%, and low dehydro­
genation enthalpies of 63.5 and 65.4 kJ/mol-H2 for H12-BT and
H18-DBT, respectively, as shown in Table S1.
Due to the exist of different isomers of hydrogenated DBT, different
V. Sage et al.
Fig. 3. Chiyoda’s SPERA Hydrogen process [21].
reaction pathways for both the dehydrogenation and hydrogenation
may lead to the formation of different intermediates (H0, H6, and H12-
DBT), as shown in Fig. 4 [26]. This may result in an incomplete dehy­
drogenation/hydrogenation depending on the catalyst used and the
process conditions, which would translate to a storage capacity lower
than the theoretical value. However, as shown by Brückner et al. [27],
complete hydrogen release from H18-DBT is possible by proper catalytic
process, for example, in the presence of Pt on alumina catalyst under
appropriate conditions (310 ◦ C, 0.1 MPa) with negligible fragmentation
(<0.01 %) of the hydrogen carrier molecule. This enables the utilization
of the H0/H18-DBT system in repeated hydrogenation-dehydrogenation
cycles.
It is noted that DBT could be hydrogenated not only with pure
hydrogen, but also with H2 containing gas mixture with CH4 and CO2
[28,29]. This is economically attractive, as such mixture is readily
produced from various processes such as reforming, gasification, or
cracking reactions. Moreover, the hydrogen in this kind of mixtures is
not economically valuable before expensive separation and purification.
Recently, DBT was introduced as a LOHC by a German company,
Hydrogenous Technologies GmbH [30], with a focus on commerciali­
zation of hydrogen storage and release systems for industrial and mobile
applications [31,32]. Hydrogenous Technologies has developed a
compact, small-scale plant including containerised storage and release
units [6,33]. The storage unit provide mid to large-scale (10–6000
Nm3-H2/hour or 0.8–494.7 kg-H2/hour) H2 storage from industrial and
renewable sources, while the release unit can supply hydrogen to refu­
elling stations and industries at the scale of 10–800 Nm3-H2/hour
Fig. 4. Hydrogenation/dehydrogenation of DBT using (((5-methyl-1,3-phe­
nylene)bis(methylene))dibenzene isomer as an example. Regenerated with
permission from Ref. [26]. Copyright 2015 American Chemical Society.
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
(0.8–66 kg-H2/hour). The heat required by the endothermic hydrogen
release process can be supplied by the waste heat of the process, natural
gas, electricity, or the produced hydrogen. Fig. 5 presents on of these
unit which provides 30 kW of power and can deliver fuel cell quality
hydrogen (at 33 Nm3-H2/hour or 2.7 kg-H2/hour) to charge electric
vehicles.
They have deployed similar containers in the United States since
2017 and are projecting to do so in China. Hydrogenous Technologies is
now working in cooperation with Covalion to give LOHC technology a
stronger foothold in the hydrogen market [34,35]. It is also developing a
decentralised H2-logistics project and the deployment of LOHC-based
hydrogen refuelling stations throughout Germany (Power-to-X Koper­
nikus Project) [36].
2.2. N-substituted heterocycles
The pure hydrocarbon LOHC systems as mentioned above suffer
from their relatively high heat of hydrogenation. The incorporation of
nitrogen atom or boron-nitrogen couple into cyclic compounds has been
shown to facilitate the endothermal dehydrogenation process by
decreasing the enthalpy of the reaction, making these heterocycles
potentially viable as a hydrogen storage substrate [37,38].
Although the promising heterocyclic LOHCs such as perhydro-N-
ethylcarbazole (H12-NEC) or octahydro-N-ethylindole (H8-NEID) allow
full catalytic hydrogenation/dehydrogenation at lower temperature
than their corresponding cycloalkanes, they have lower hydrogen den­
sities (5.8 and 5.2 wt% respectively as shown in Table S1) than related
cycloalkanes. Some of the fully dehydrogenated products are also solid
Fig. 5. Hydrogenious LOHC containerised system. Reprinted with permission
from Ref. [6]. Copyright 2017 American Chemical Society.
V. Sage et al.
at room temperature. Another drawback in the use of heterocycles is
their degradation by C–N cleavage, disproportionation, alkyl transfer,
and other side reactions occurring during the dehydrogenation and
hydrogenation. It has been reported that these side reactions can be
minimized by the steric effect of ligands on the heteroatom, such as the
methyl and ethyl groups in NEID and NEC [39].
2.2.1. Dodecahydro-N-ethylcarbazole/N-ethylcarbazole
Carbazole and its derivatives are well suited as LOHCs. N-ethyl
carbazole (NEC) with its hydrogenated form, dodecahydro-N-
ethylcarbazole or named as perhydrocarbazole (H12-NEC) with the H2
storage capacity of 5.8 wt%, has gained interest due to its low enthalpy
(50.6 kJ/mol, as show in Table 4) and low temperature of dehydroge­
nation (130–270 ◦ C). This LOHC pair was firstly suggested by the
company Air Products and Chemicals and patented by Pez et al. [40].
However, NEC is produced from distillation coal fractions and its
availability is limited today with the current market price [41]. The
main drawback of NEC is its high melting point (70 ◦ C as shown in
Table S1). As the fully dehydrogenated H0-NEC is solid at room tem­
perature, this complicates the technical dehydrogenation process and
leads to additional difficulties in the transportation and delivery of the
spent fuels, making the concept of liquid-phase hydrogen storage un­
likely. Another drawback of carbazole-derived LOHC systems is the
chemical lability of the N-alkyl bond, leading to decomposition reactions
occurring at temperatures above 270 ◦ C [42].
The dehydrogenation of NEC is a stepwise process with formation of
different intermediates (H4, H6, and H8-NECs) at different temperatures
(Fig. 6) [43]. As these Hx-NECs have lower melting points than H0-NEC
(Table 2), partial dehydrogenation can be envisaged to form a liquid
mixture of hydrogenated NEC with hybrid degrees. Of course, this leads
to a decrease in hydrogen carrying capacity. For example, the dehy­
drogenation of H12-NEC at 90 % makes the hydrogen storage capacity
down to 5.3 wt% [5]. Another solution to avoid the solid state is
replacing the ethyl group with longer chain alkyls (e.g., the melting
point of N-propylcarbazole is 49 ◦ C). However, as the alkyl chain does
not participate in the dehydrogenation/hydrogenation cycle, such
structural modification reduces the gravimetric storage density of the
system.
Stark et al. [43] found that with the appropriate combination of
N-alkylcarbazoles, it is possible to achieve a considerable decrease in
melting point. For example, the binary mixture of NEC and NPC at
eutectic composition is liquid at 25 ◦ C with a hydrogen storage capacity
of 5.6 wt%, and the ternary eutectic mixture of NEC-NPC-NBC has a
predicted melting point of 12.6 ◦ C, whilst still offering a suitable storage
capacity of 5.5 wt%, 95 % of that of pure NEC.
The cyclic capability of H12/H0-NEC has been demonstrated by Yang
et al. [44] with over 10 cycles of hydrogenation and dehydrogenation at
180 ◦ C for 300 and 200 min, respectively. The gravimetric capacity at
Fig. 6. Intermediates for hydrogenation/dehydrogenation of N-ethylcarbazole
(H0-NEC)/perhydro-Nethylcarbazole (H12-NEC). Regenerated with permission
from Ref. [43]. Copyright 2016 American Chemical Society.
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
Table 2
Melting points of different N-alkylcarbazoles and their
hydrogenated derivatives at standard pressure [43].
Compounds m.p. (◦ C)
Carbazole
H0- 245
H4- 118
H12- 76
N-methylcarbazole 90
N-ethylcarbazole
H0- 70
H4- 9
H8- 43
H12- − 85
N-propylcarbazole 49
N-iso-propylcarbazole 121
N-butylcarbazole 58
the 10th cycle was maintained at 5.68 wt% with lightly less than 2 % of
degradation.
2.2.2. Pyridines, pyrroles, quinolines, and indoles
The use of other N-based hetero-aromatic/alicyclic LOHC systems (e.
g., pyridines, quinolines, pyrroles, and indoles) has been reviewed by
different researchers [8,38,45]. Some common rules for the design of the
compounds with favourable thermodynamics have been identified.
(1) Heterocyclic, particularly bicyclic, compounds are favourable
due to the low dehydrogenation enthalpy. Among them 5-
membered heterocyclic ring, N atom at the 1-position, and N
atoms or substituents in an 1,3-arrangement of a hydrocarbon
ring are most often used. It is because the N–H bond is weaker
than the C–H bond and the C–H bond adjacent to an N atom is
weaker than those adjacent to C atoms. In addition, the steric
hindrance around N atom increases the dehydrogenation rate.
However, certain azoles, e.g., imidazole, are resistant towards
hydrogenation.
(2) Increasing the number of fused aromatic rings decreases the hy­
drogenation enthalpies. However, large polyaromatic com­
pounds are solids.
(3) Dehydrogenation is more favourable for alkyl-substituted cyclic
hydrocarbons and rather for five-than for six-membered rings.
In brief, the presence of nitrogen in LOHC molecules improves the
thermodynamics and kinetics of dehydrogenation, making the use of N-
substituted heterocycles well realised under more moderate conditions.
Moreover, it also promotes thermal lability and opens reaction pathways
to undesired degradation products.
In comparison to the more volatile and flammable carriers such as
pyridine, pyrrole, and some derivatives, indole and its derivatives (e.g.,
N-ethylindole and 2-methylindole) have attracted more attentions
[46–49]. They, structurally like NEC, are easily got and possess prefer­
ential LOHC properties such as low-temperature dehydrogenation.
Other properties of indole and its derivatives, such as cost, toxicity,
stability, and kinetic barrier etc., are worth further evaluation and in­
vestigations. Moreover, some N-heterocycles are no longer in liquid
state after hydrogenation or dehydrogenation under ambient conditions,
which may not be practical especially for mobile applications. There­
fore, searching for organic compound that maintains its liquid state even
at the temperature as low as − 40 ◦ C is necessary.
3. Dehydrogenation of LOHCs
As mentioned above, the major drawback of LOHCs is the high en­
ergy required for the dehydrogenation step to recover hydrogen. The
unfavourable dehydrogenation enthalpies of LOHCs mean that the
dehydrogenation of cyclic hydrocarbons typically requires relatively
V. Sage et al.
high temperature (250–350 ◦ C [50]) and thus high energy input. This
may result in the formation of carbonaceous deposit over the catalyst
through the cleavage of the C–C bond of the aromatic ring on the acid
sites of the catalyst surface, leading to catalyst deactivation and degra­
dation of the LOHC during multiple hydrogenation/dehydrogenation
cycles. Therefore, efforts have been done in catalyst design to increase
the activity and thus to reduce the dehydrogenation temperature and
process intensification including reactor design and energy integration
to improve the energy efficiency. The combination of suitable catalyst
properties and an appropriate reactor working at the optimal operating
conditions determines the results in terms of conversion, selectivity, and
hydrogen yield, as summarised in Fig. 7 [51].
3.1. Catalysts for LOHCs dehydrogenation
Catalysis plays a key role in hydrogen storage using LOHC systems as
both H0-LOHC hydrogenation and Hx-LOHC dehydrogenation require
promotion by suitable catalyst systems [52–54]. The desired charac­
teristics for dehydrogenation catalysts are an active phase with intrin­
sically high selectivity for dehydrogenation and an activity sufficient to
generate the required hydrogen. This active phase should be dispersed
on a high surface area support with sufficiently large pores to withstand
coking and lowest amount of strong acid sites on the surface. The
development of robust catalysts is needed in future for reducing the
dehydrogenation temperature and for improving the kinetics of the
process. Based on the analysis and others considerations [51,55], the
following general observations and conclusions can be drawn regarding
the choice of catalysts for LOHCs dehydrogenation.
3.1.1. Selection of active metals
Cycloalkanes dehydrogenation have been largely investigated in the
last decade [6,8,38,45,51]. Shukla et al. [56] provided a review on MCH
dehydrogenation with focus on catalysts, supports, reactor systems, as
well as the kinetic and thermodynamic of the reaction. The development
of efficient catalysts is normally used to overcome the kinetic barrier.
Catalyst selection needs to consider hydrogen spill-over, C–H and C–C
bonds dissociation capacity, and hydrogen-recombination properties of
the metal although deactivation of catalysts due to coking is the main
issue to be overcome. The particle size of the catalyst has a profound
effect on dehydrogenation reaction. For dehydrogenation of
N-substituted heterocycles, metal catalysts are easily poisoned due to
the existence of lone electron pair in the hetero-atom nitrogen.
Within the large number of catalyst candidates for hydrocarbon
dehydrogenation, heterogenous Pt-based catalysts figure amongst the
most studied ones, due to its C–H bond activation capacity, combined
Fig. 7. Scheme of the parameters influencing conversion, selectivity, and yield
in the catalytic dehydrogenation of LOHCs. Regenerated with permission from
Ref. [51]. Copyright 2018 American Chemical Society.
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
with a lower capacity in the rupture of C–C bonds, resulting in intrin­
sically higher selectivity toward the dehydrogenation reaction than C–C
cleavage [51,55,56]. Since C–N and C–B bonds are easier to break than
C–C bonds, the importance of C–H bond activation capacity is even more
important for heterocycles LOHCs. Other metals, such as Pd, Rh, Ag, Ir,
Ni, and Mo, have also been studied although they are generally less
active [9].
For dehydrogenation of N-heterocycles, lower energy is required
compared with that of cycloalkanes. Noble metal-based heterogeneous
catalysts such as Pt, Pd, Ru, and Rh can also catalyse dehydrogenation of
N-heterocycles and the initial catalytic activity follows the order of Pd >
Pt > Ru > Rh [57,58]. Moromi et al. [59] have found that the catalytic
activity of noble metal nanoparticles supported on carbon is a function
of the d-band centre relative to the Fermi energy. Pt, Ir, Pd, Rh, and Ru
with an intermediate d-band centre exhibit higher catalytic activity than
metals with lower d-band centres (Ag, Cu) and the metals with higher
d-band centres close to the Fermi energy level (Ni, Co). For dehydro­
genation of heterocyclic LOHC, Pd-based catalysts overnumber Pt due to
preferential adsorption of heteroatoms onto the Pd surface. In the case of
homocyclic LOHC, Pt is overwhelmed in single metal and bimetallic
catalysts based on the pronounced C–H bond cleavage, and the ability of
Pt in C–C bond cleavage gives up to the higher H2 selectivity, better
catalyst stability, and steady LOHC recyclability [60]. The activity of
platinum would in fact be so high that catalyse side reactions such as
disproportionation, dealkylation, and C-heteroatom bond cleavage be­
sides the dehydrogenation [61]. The use of other catalysts such as Pd,
Rh, and Ru allows heterocycle dehydrogenation without substrate
degradation and with high selectivity toward hydrogen especially when
an alkyl protecting group is present on the heteroatom like in NEC.
Bimetallic catalysts have shown considerably higher activity for
dehydrogenation than monometallic catalysts. For dehydrogenation of
cycloalkanes, the addition of a second metal (such as W, Ir, Re, Rh, and
Pd, etc.) and/or promoter (such as Ca) is proved effective against coking
by improving the C–H bond breaking ability of Pt, the stability of in­
termediates, and the desorption of aromatic products [62]. Synergetic
effect of different metals can be observed when using the bimetallic
catalysts such as Pt–Pd and Pt–Rh for dehydrogenation. It is known that
Pd and Pt have good hydrogen spill over ability which is effective for the
elimination of hydrogen species from the reaction system to suppress the
reverse reaction, but Ru or Rh does not. In addition, Pt has higher
hydrogen-recombination ability than Ru, Rh, or Pd, while Rh shows high
C–H bond cleavage ability. Other transition metals (e.g., Sn and In) have
an electronic interaction with Pt, which can reduce the Pt–H binding
energy, limiting deep dehydrogenation and as consequence coke for­
mation. Sn also favour hydrogen spill over and coke migration from Pt
sites to the support, further contributing to catalyst stability [62].
Side reactions can occur during the dehydrogenation process, that
are deleterious as they can lead to catalyst deactivation by carbon
deposition and can decrease the purity of the hydrogen generated due to
the formation of light gaseous alkanes such as methane and C2s (ethane,
ethylene, and acetylene). Hydrogenolysis and coke formation are more
structure sensitive than dehydrogenation. Consequently, the addition of
any inactive species on the catalyst surface (e.g., Sn, In, K, Na, etc.)
would act as a diluent for the Pt sites, increasing the selectivity toward
dehydrogenation [51].
3.1.2. Selection of supports
Dehydrogenation reaction is particularly favourable on catalysts
well-dispersed on high surface area supports [63]. The rate limiting step
and rate constant for different catalysts were mainly related to the
physicochemical properties and adsorption and activation abilities to­
wards the reactants and intermediates, which has been revealed by the
dehydrogenation reaction kinetics [64]. Surface acidity, surface area,
and pore shape and size of the support are important for the catalyst
stability and reaction selectivity. The presence of a high density of strong
acid sites shifts the selectivity toward cracking reactions, leading to
 V. Sage et al. International Journal of Hydrogen Energy 56 (2024) 1419–1434

formation of methane and other light hydrocarbons, coke deposition on required to be supplied either or combined from other resources such as
the surface of the catalyst, and reduction in the purity of H2 [65]. The the waste heat of the process, natural gas, electricity, or the produced
presence of large mesopores (6–15 nm) should avoid channel clogging hydrogen, resulting in the reduction in the effective storage capacity of
and reduce the loss of accessibility to the active sites. the LOHC system.
It has been determined that the strong metal-support interaction of The established state-of-the-art stationary LOHC storage setup ap­
the catalyst facilitates hydrogen spill over, helping the reaction equi­ plies separate hydrogenation and dehydrogenation reactors with the
librium to move favourably toward the production of hydrogen [56]. In hydrogenation reactor operating at low temperature/high pressure and
this regard, metal oxide supports are particularly suitable as they exhibit the dehydrogenation reactor operating at high temperature/low pres­
strong metal–support interaction. They favour the small energy barrier sure to maximize thermodynamic driving forces for the respective re­
of H-migration from catalyst to substrates and subsequent proton actions. Heat integration and rate control are key to both stationary and
diffusion and therefore improve the forward rate of the reaction. They on-board applications to drive the economics of such a process. Without
form additional active sites on the surface under reduced conditions for it, 25–30 % of the combustion heat of the hydrogen from the LOHC
the dehydrogenation reaction. would have to be invested to fully release the hydrogen [74]. If this
Shulka et al. [56] demonstrated that perovskite support, La0.7Y0.3 hydrogen was then used in a fuel cell with 40–60 % of efficiency [75],
NiO3, is more effective than well-known metal oxide supports with the the overall efficiency from LOHC-bound hydrogen to electricity would
H2 production of 45 mmol/g-Pt/min and high selectivity towards the only be 28–45 %.
dehydrogenation reaction achieved by proper design of perovskite The LOHC dehydrogenation reactor is basically a gas generation
composition with substitution at the La-site. The loading of Pt at ca 1 wt device coping with high volume of hydrogen production. For example, 1
% is promising to minimize the use of Pt in catalyst composition and thus mL of H18-DBT will produce >650 mL of hydrogen gas [76]. The high
reduce catalyst cost. volume of the produced hydrogen can displace the LOHC and reduce the
LOHC’s contact with the catalyst, resulting in poor heat and mass
3.1.3. Catalyst design corresponding to different LOHC systems transfer as well as the reduction of residence time of the liquid inside the
Catalysts for the dehydrogenation of the most studied LOHCs: MCH, reactor [77].
H18-DBT, and H12-NEC to toluene, H0-DBT, and H0-NEC, respectively, Different reactor systems have been proposed and demonstrated for
are summarised in Table S2 [6,8,38,51,56,66]. performing LOHC dehydrogenation. Both steady and unsteady state
Pt/Al2O3 and Pt–Re/Al2O3 catalysts are promising for MCH dehy­ reactors have been studied including spray-pulsed, fixed-bed, batch-type
drogenation to toluene. The kinetics, the catalyst deactivation, the continuous stirred tank (CSTR), 3D structured monolith (SEBM),
thermodynamic equilibrium, and the sulphur impact on the MCH tubular, and pressure swing reactors [14,56,77]. The advantages and
dehydrogenation reaction have been reviewed in detail before [55,67]. disadvantages for different reactor systems employed for dehydroge­
The most active dehydrogenation process for MCH was reported by nation of cycloalkanes are summarised in Table 3 [56].
Kariya et al. [62], using a 3.82 wt% of Pt/Al2O3 catalyst at 300 ◦ C in It has been reported that horizontal tubular reactors are filled with a
batch mode to produce hydrogen at a rate of 1.7 mol/g-Pt/min. The fixed bed of catalyst but only half-filled with liquid which can easily
highest hydrogen productivity has been reported for cyclohexane using separate the gas from the liquid phase [78]. In this kind of reactors, heat
Pt/alumite (anodized aluminium) catalysts (3 g-Pt/m3) at 375 ◦ C in a is supplied via the reactor walls. The liquid flows horizontally through
non-steady spray pulse reactor with a H2 evolution rate of 3.8 the fixed bed of catalyst pellets while hydrogen escapes vertically into an
mol/g-Pt/min [68]. Chiyoda has announced the large-scale application empty gas volume without influencing the residence time of the liquid in
for hydrogen and energy logistics using a proprietary dehydrogenation the reactor. In this design, hydrogen evolution creates turbulence in the
Pt–S/Al2O3-based catalyst, a uniformly highly dispersed metal on sul­ liquid, thus significantly improving the heat transfer from the hot wall
phurised Al2O3 support [69,70]. At the temperature of 345–351 ◦ C (0.3 into the liquid. Multi-tubular or plate reactors can be more efficient for
MPa, 2 h− 1 LHSV), the MCH conversion has reached above 95 % and H2 larger systems.
yield above 98 % with barely any loss of activity over 10,000 h. As part of the Kopernikus P2X project [79], a micro-structured
Pt/Al2O3 catalyst were used to promote the hydrogenation of H0-
DBT and the dehydrogenation of H18-DBT combining both reactions in a
single reactor in the temperature range 290–310 ◦ C with the hydrogen Table 3
pressure being the only variable for shifting the equilibrium between Strengths and weaknesses for different reactor systems employed for dehydro­
hydrogen loading and release [71,72]. Cycle tests of hydrogenation and genation of cycloalkanes [56].
dehydrogenation integration reaction have shown that the hydrogen Reactor Strengths Weakness
storage efficiency was 84.6 % after five cycle tests. This way of operation
Batch reactor High conversion Favours liquid phase
reduces the investment for catalyst and reactor, drastically increases the reaction
hydrogen storage dynamics, opens novel opportunities for heat inte­ Fixed-bed reactor Continuous product formation Favours liquid phase
gration and catalyst regeneration, and can be applied to the one-reactor reaction and reverse
concept proposed by Preuster et al. [6]. reaction
Wet-dry multiphase High efficiency of reactants, Commercial feasibility
The current state-of-the-art in catalysis is the egg-shell Pt/γ-Al2O3 system or spray- high catalyst temperature, process, process
catalyst developed by Peters et al. [73] who obtained a hydrogen pro­ pulse system reverse reaction suppressed intensification
duction rate greater than 5 mol/g-Pt/min for the dehydrogenation of Monolith reactor Structured catalyst, avoid No direct experimental
H12-NEC, the highest production reported up to now. Pt productivity granular catalyst, high data available
catalytic geometric surface
was boosted by minimizing pore diffusion limitation by thin catalyst
area, maximising working
layers. volume, alternate wet-dry
condition and thin liquid film,
3.2. Dehydrogenation reactors catalyst regeneration
Micro-reactor Compact design, heat transfer Complicated design
limitation overcomes
The dehydrogenation of LOHC is endothermic and favoured at high Membrane reactor Reaction and separation High cost and
temperature. Equilibrium conversion is achievable with reaction tem­ carried out in one step maintenance
peratures in the range of 250–375 ◦ C depending on the reactant, cata­ Liquid film reactor Avoid liquid reactant Catalyst surface covered
lysts, and reactor system used. To provide the enthalpy of the suspension with catalyst with thin liquid film and
hinder drying
cycloalkane dehydrogenation at certain temperature, extra heat is

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V. Sage et al. International Journal of Hydrogen Energy 56 (2024) 1419–1434

Table 4
Comparison of required criteria for LOHCs with advantages (+) and drawbacks (− ).
Criteria Toluene [55,67,68,70,91] DBT [27,71,72,92] NEC [40,43,44,93]

H2 density
Gravimetric (wt%) 6.2 6.2 5.8
Volumetric (kg/m3) 47.4 +57
Energy density (kWh/L) 1.6 1.9 2.5
Melting point (◦ C) − 127/-95 <-50/-34 − 85/-70
Boiling point (◦ C) 101/111 371/388 281/378
Dehydrogenation
Enthalpy (kJ/mol) 68.3 64.5 50.6
Temperature (◦ C) >300 270–320 180–270
Stability/Reversibility - C–C bond cleavage due to required + Stable compound - C–N bond cleavage limiting thermal stability
high temperature
- Catalyst deactivation (coking) - Catalyst coking - Side reactions during dehydrogenation
+ Alleviated with promoters (e.g., K) + Alleviated with promoters (e.g., K) - Catalyst coking
Liquid state + Liquid at ambient conditions, + Liquid over a board range of temperature - Hx-NEC solid at ambient temperature
- Gas at dehydrogenation temperature + Partial dehydrogenation or blending can be
– H2 requires purification envisaged but decrease in H2 storage capacity
Toxicity and - Toxic for health and environment + Non-toxic + Non-toxic
environmental impact - Flammable + Non-explosive
Cost (A$/kg) 0.21 [94] 10.40 [95] 116.75 [96]
Cost (A$/kg) and + Abundant + H0-LOHC readily available - Limited current production
availability + H0-LOHC readily available as
refinery products
Other + Like current fuels and compatible - Possible incomplete degree of dehydrogenation
with distribution network (Formation of different intermediates)
Technology Readiness 8 Demonstration project in Japan 9 Demonstration project in Germany 3 Lab-scale tests only
Level (TRL)

1 A$ = 4.71 CNY.

multi-stage reactor concept with an intermediate separation of hydrogen
was applied for H18-DBT dehydrogenation [80]. Each reactor stage
consists of a micro-structured radial flow reactor designed for
multi-phase flow of LOHC and the released hydrogen. The hydrogen is
separated from the gas phase effluent via Pd–Ag membranes which are
integrated into a micro-structured environment. This approach can
counteract the increase in volume caused by continuous gas production
and simplify the discharge of the gas from the multiphase flow. How­
ever, this has not yet been demonstrated in large LOHC systems. Further
scope of improvement in reactor design is required to minimize the heat
requirement by improvement in heat transfer and improve the surface
area of the catalysts. Up-scaling of reactor also need to be pursued.
4. Applications of LOHC technology
Generally, LOHCs can be used for hydrogen storage for both static
and mobile applications to provide hydrogen for heat production or fuel
cell applications. The characteristics of different LOHCs set certain
constraints leading to different suitability for various applications.
LOHC technology is particularly well suited for energy export with long
distance transport and stationary storage applications, as it allows to
balance the mismatch in electricity supply and demand between loca­
tions, seasons, or time of day, and can be integrated into an existing
energy infrastructure, as illustrated in Fig. 8. Where renewable energy is
in surplus, LOHCs can be used to store excess energy (H2) which can then
be stored for a long term or transported to an alternate destination
where dehydrogenation is performed to recover hydrogen as the
renewable energy carrier.

Fig. 8. Renewable energy storage and usage concept using LOHC technology in mobile and stationary applications with the hydrogenation and dehydrogena­
tion cycle.

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V. Sage et al.
4.1. Stationary applications
LOHCs are well suited for stationary storage applications where the
power demand is quasi-permanent and the fluctuations of demand are
on a minute scale [81]. The heat generated during the hydrogenation
process and from the re-electrification process such as gas/steam turbine
or high temperature fuel cells can be used for the endothermic dehy­
drogenation. It has been demonstrated that the integration of heat be­
tween the hydrogenation and dehydrogenation units of
methylcyclohexane/toluene pair can produce enough electricity to run
an electrolysis unit without the need of extra energy source [82]. The
coupling of a solid oxide fuel cell (SOFC) and a LOHC dehydrogenation
system also has the advantage of heat integration between the
high-temperature exothermal SOFC process (exhaust heat >600 ◦ C) and
the endothermal dehydrogenation reaction. Preuster et al. [83]
demonstrated that the hydrogen-to-electricity efficiency in the dehy­
drogenation and SOFC sequence is 45 %.
For stationary storage, off-grid applications are economically more
attractive than on-grid applications as the electricity and the heat pro­
duced from the system cannot compete with the grid electricity price but
with other ways, for example, a diesel generator [6]. Examples for such
off-grid applications include remote tourist locations, transmitting sta­
tions, or mining exploration sites. Typical cost for electricity from diesel
generators in such locations is 0.89 A$/kWh [84] and the levelized cost
for a multi-MW scale diesel generator can drop down to 0.30 A$/kWh
[85] which can cover the costs for both the renewable energy production
and the LOHC storage units.
In all attractive off-grid application scenarios, the storage unit is
embedded into an environment with excess supply in renewable energy.
A one-reactor concept has also been proposed for stationary storage as a
combined hydrogenation/dehydrogenation unit [6,71]. It not only saves
a significant capital cost, but also greatly increases the dynamics of the
system as the reactor is always at elevated temperature so that the
heating up of the cold reactor is avoided. This scenario can be applied in
some special circumstances. For example, the H0-DBT can be hydroge­
nated in one compartment with presence of CO, CO2, CH4, etc. such as
syngas and bio-syngas, while the hydrogenated LOHC such as H18-DBT is
dehydrogenated in another side of the reactor to release pure hydrogen
[71]. However, this process requires a catalyst working for both hy­
drogenation and dehydrogenation with suitable activity and excellent
selectivity. The potential of such reactor was demonstrated with
dibenzyltoluene (DBT or H0-DBT) as LOHC and Pt/Al2O3 as the catalyst
[71]. Hydrogenation of H0-DBT and dehydrogenation of H18-DBT were
carried out at the same temperature (270–320 ◦ C) with the hydrogen
pressure being the only variable for shifting the equilibrium between the
hydrogen loading and release. The heat of hydrogenation can be pro­
vided at a temperature level suitable for effective dehydrogenation.
4.2. Mobility applications
Considering mobility applications, heat integration can be more
challenging due to the requirement of compact, lightweight infrastruc­
ture, and enhanced safety requirements. An on-board vehicle system
would combine a LOHC storage tank, a dehydrogenation reactor, and a
fuel cell, as shown in Fig. 9 [86]. Considering that about 5 kg of H2 are
Fig. 9. Concept of hydrogen car with LOHC as H2 supply [86].
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
necessary for an autonomy of 500 km, around 80–120 L of LOHC would
be required depending on the H2 content. On-board storage of LOHC is
straight forward with a dual fuel tank system to accommodate Hx-LOHC
and the H0-LOHC. During the refuelling process, Hx-LOHC is filled into
one tank, while H0-LOHC is removed from the second tank.
To use the waste heat generated from the fuel cell to drive the
dehydrogenation reaction, there needs to be a thermodynamic excess in
heat from the fuel cell, otherwise, extra heat generated from battery or
hydrogen combustion must be used, which will reduce the autonomy of
the fuel cell [4,6]. As a rule of thumb, the exact amount of hydrogen
used for heat generation depends on various parameters such as effi­
ciency and thermal control of the fuel cell. If all the required heat for
dehydrogenation needs to be generated by hydrogen, approximately 20
% of the stored hydrogen would be consumed. If assuming a fuel cell
efficiency of 55 %, this configuration would lower the efficiency of the
dehydrogenation/fuel cell-system to approximately 44 % [4], which is
still relatively high compared to a fuel combustion engine which is
normally between 20 and 40 % [87].
In addition, the storage system needs to be able to react sufficiently
fast in response to changes in power demand and production from the
fuel cell with a dynamic release of H2 from the LOHC [81]. Thus, the fast
supply of heat to the dehydrogenation reactor for H2 output is a chal­
lenge. Generally, the increase of the reaction temperature takes several
minutes with a slow response to H2 demand changes.
On-board operation of a direct LOHC fuel cell with LOHC dehydro­
genation and fuel cell operation taking place in the device without
release of elemental hydrogen has also been conceptualised (Fig. 10) [6,
88].
In this virtual-hydrogen approach, dehydrogenation is replaced with
the electrochemical step which releases protons and electrons combined
with oxygen reduction to generate power. The main parameters of
organic fuels for this purpose are energy density, fuel cell potential and
efficiency, reversibility of dehydrogenation and hydrogenation re­
actions, safety, and cost. This process is however a low technology
readiness (TRL) application. With this concept in mind, Sievi et al. [89]
proposed the use of an additional vector, 2-propanol/acetone, as a
hydrogen-transfer system between the LOHC and the fuel cell to increase
efficiency at mild conditions (<200 ◦ C) without the need for external
heat input. It involves a sequence of thermoneutral hydrogen transfer
from H18-DBT to acetone and the direct use of 2-propanol as the organic
fuel in a proton-exchange membrane (PEM). 2-propanol can then be
re-oxidised to acetone.
To our best knowledge, mobility applications are currently far from
technical deployment due to the difficulties associated with on-board
dehydrogenation and the safety issues associated with the carriers
themselves. Although there is room for further improvement of the
proton transfer and electrocatalytic oxidation [89], the potential of the
Fig. 10. Schematic of the direct LOHC fuel cell concept. Reprinted with
permission from Ref. [6]. Copyright 2017 American Chemical Society.
V. Sage et al.
approach with respect to energy efficiency, power density and safety is
clearly recognisable.
5. Evaluation of LOHCs
5.1. Comparison of related properties
All the LOHC systems mentioned above have their advantages and
disadvantages regarding their chemical and economical properties such
as hydrogen capacity, dehydrogenation enthalpy, thermal stability,
handling, toxicity, costs, and availability, etc. The comparison in ad­
vantages/strengths (+) and drawbacks/weaknesses (− ) of the most
studied LOHC systems, taking toluene, dibenzyltoluene (DBT), and N-
ethylcarbazole (NEC) as examples, are listed in Table 4. These properties
have been evaluated and rated on a relative scale by Niermann et al.
[90] to clearly assess these LOHC systems for different applications.
Fig. 11 illustrates the assessment of the properties for the LOHCs
mentioned above as well as for methanol for comparison [90]. It is noted
that the gas flow means how fast the hydrogen releasing is from the
examined LOHCs.
The weightings of LOHC properties differ for the intended applica­
tions. For stationary storage applications, the property scenarios include
the availability and cost of the LOHC for large-scale applications, high
stability which reduces the need for LOHC replacement and lowers the
operating cost, and low energy demand. For energy transport, one may
consider the availability of the LOHC which strongly influences the
economic feasibility, high safety, low toxicity, ease of handling, and
other legal requirements to simplify the transport. For mobility appli­
cations, the most important factors are storage capacity and energy
density which directly affect the size and weight of the fuel system and
driving range of the vehicle, good dynamic behaviour with low cold
starting time and fast hydrogen release, low dehydrogenation temper­
ature which may be supplied by the waste heat from this PEM fuel cell,
and simple process design with very little additional requirement.
Based on these criteria, DBT is one of the most suitable candidates for
Fig. 11. Assessment of different chemical and economic parameters for toluene, DBT and NEC as LOHCs compared with methanol [90]. DH – dehydrogenation,
relative scales with 10 as the highest positive value.
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
transport and storage applications with toluene a second strong candi­
date especially for transport. Despite their high enthalpy of dehydro­
genation, these systems are suitable for outdoor and large-scale
hydrogen preparation mostly owing to their low price, the possibility to
integrate the heat from hydrogenation or other sources, and the high
purity of the hydrogen generated.
For mobile applications, NEC seems the LOHC of choice. The major
drawback is its high melting point (solid at ambient temperature) which
can be alleviated by partial dehydrogenation, however, to the detriment
of storage capacity. Cost and current production can also limit its
practical application. Mass production could significantly lower the
price in the future, making it suitable for stationary applications.
Methanol can potentially be applied in all three application fields due to
its properties however the dehydrogenation temperature (>350 ◦ C) and
gas flow are obvious the drawbacks.
5.2. Energy consumption analysis of LOHC in comparison with other
carriers
As mentioned throughout this paper, the energy consumption for
hydrogen recovery from LOHC is a concern for the application of this
technology. However, in comparison the hydrogen recoveries from cir­
cular hydrogen carriers such as methane and methanol at temperatures
higher than 800 and 500 ◦ C, respectively, the energy consumptions for
hydrogen recovery from LOHCs are much smaller because their dehy­
drogenation temperature is around 250 ◦ C only.
Li et al. [97,98] calculated the energy consumption metrics for major
chemical pathways based on the plant with the production of hydrogen
of 150 tonne/day and the transportation distance of 10000 km (the
rough distance from Australia to Asia), as shown in Fig. 12. To compare
with other delivery pathways, the boiled off H2 from the liquid hydrogen
scenario was considered to refrigerate back to the tanker. The fuel
consumption for a cargo was set as 0.21 kg/kWh [99].
Electrolysis is the most energy consumptive step for all hydrogen
delivery pathways. The differences reflected in this step are due to the
V. Sage et al.
Fig. 12. Energy consumption metrics for different carriers [97,98].
efficiency differences of hydrogenation step and subsequent steps,
where all scenarios are normalised to the final consumption step. The
results indicate that methanol scenario has lower hydrogen efficiency
resulting from the lower conversion within the methanol synthesis re­
action [100]. For liquid hydrogen scenario, the liquefaction step is a
high energy consumer [101]. For the substitute methane scenario, steam
reforming to release hydrogen is an energy intensive step [102]. Dehy­
drogenation energy consumption follows the order of NH3 < methyl­
cyclohexane < methanol < CH4. For the cargo transportation, the extra
energy consumption for methylcyclohexane is contributed by the return
load with toluene [21].
5.3. Techno-economic analysis (TEA)
Detailed economic analysis of the entire hydrogen supply chain has
been conducted by various researchers, covering hydrogen production,
storage, transportation, and distribution. While several technologies
show promise, economic and environmental aspects of the hydrogen
supply chain, especially from production to fuelling station with sea­
sonal storage and transport, can vary based on the chosen technology
and individual conditions, such as the distance between production and
demand. The most suitable option largely depends on the specific
application and the specific context. For example, the storage of gaseous
hydrogen in salt caverns is already implemented at a full industrial scale;
however, its applicability is limited in certain regions due to diversity in
geological conditions.
The most common hydrogen supply chains currently rely on pure
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International Journal of Hydrogen Energy 56 (2024) 1419–1434
hydrogen provided as compressed gas (cH2) or cryogenic liquid (LH2).
However, high-pressure storage tanks remain cost intensive while the
liquefaction of hydrogen is energy intensive. A multifunctional steel
layered hydrogen storage vessel (MSLV) ranging from 0.5 to 25 m3
under the pressure from 160 to 860 bar which was made in China costs
525–900 A$/kg-H2 [103]. In practical applications, the specific energy
demand for hydrogen liquefaction is approximately 10 kWhel/kg-H2,
which is slightly less than 30 % of the lower heating value (LHV) of
hydrogen (33 kWh/kg-H2) [104]. Both storage options are also con­
cerned with high safety requirements: high pressure for gaseous storage
and a low temperature for cryogenic storage. Additionally, storing
hydrogen in the form of circular hydrogen carriers incurs high cost in the
hydrogen recovery stage. Therefore, LOHCs offer a potentially cheaper,
safer, and more easily manageable and transportable alternative,
allowing for long-term storage without hydrogen losses.
As mentioned above, the overall cost of using different storage and
transport media varies across different studies as different conditions,
factors, characteristics, and boundary parameters are used in each study.
It is therefore not possible to compare the direct costs, however, the
relative costs between the different media could be examined. Fig. 13
presents the total hydrogen costs (production, storage, transport,
release) from different techno-economic studies, comparing LOHCs
represented by MCH in most studies, methanol, ammonia, and LH2 or
cH2 as storage and transport media [98,105–108]. It is noted that only
the hydrogen production from other resources such as natural gas [109]
than electrolysis was not compared in this study.
The levelized hydrogen production costs based on the year of
V. Sage et al. International Journal of Hydrogen Energy 56 (2024) 1419–1434

Fig. 13. Comparison of various economic studies on the overall hydrogen production costs from LOHCs in comparison with circular carriers and LH2 or cH2 [98,
105–108] where MeOH – methanol, L-SNG – liquified sythetic natural gas, FA – formic acid, HNP – hydorgenated napthalene, HDBT – hydorgenated dibenzyltoluene,
HNEC – hydorgenated N-ethylcarbazole, HAB – hydorgenated 1,2-dihydro-1,2-azaborine, T - tank, cav – cavern, JP – Japan, and AU – Australia.

2018–2019 calculated by Li et al. [98] (Fig. 13b) are in a similar range
with the study carried out by Autrey et al. [105] (Fig. 13a). The trans­
port of compressed hydrogen by sea [106] (Fig. 13c) costs much higher
than inland usage [105] (Fig. 13a). All these three groups in 2019
estimated the hydrogen life cost via most media around 10 A$/kg-H2.
The International Energy Agency, USA, predicted the cost in 2030 will
drop less than 6 A$/kg-H2 and in 2050 will further drop less than 5 A
$/kg-H2 [107] (Fig. 13e). Wijayanta et al. predicted the hydrogen cost in
Japan by 2030 produced inland in comparison with imported from
Australia (Fig. 13d). They concluded that it is still slightly cheaper if
imported from Australia. The hydrogen production cost is a dominating
factor. However, all studies in Fig. 13 indicate that the goal of producing
hydrogen by electrolysis for $2 per kilogram [110] should be achiev­
able. Generally, hydrogen carried via MCH/toluene pathway has similar
overall expensive to methanol pathway, however, the synthesis of
methanol and the hydrogen recovery from methanol costs more due to
the lower conversion rate of the synthesis and the higher temperature
applied in the recovery process (Fig. 13a and b). Liquid hydrogen might
be a cheaper prospect if the practical considerations of liquid hydrogen
cargo storage can be managed [111].
Niermann et al. [90,106] carried out a techno-economic analysis of
various LOHCs and circular carriers for intercontinental ship transport

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V. Sage et al. International Journal of Hydrogen Energy 56 (2024) 1419–1434

of hydrogen (5000 km) and long-term storage (60 days). Their results
showed that methanol and hydrogenated DBT had the lowest total costs
for storage and transport, followed by MCH (Fig. 13), and that LOHCs
are well suited for long-term storage and long-distance applications.
Expensive raw materials such as NEC and azaborine increase the overall
cost of the LOHC system compared to toluene or DBT. Transport cost is
comparably low for all LOHC carriers as it can use the current distri­
bution infrastructure. The release cost includes the dehydrogenation,
hydrogen burner and hydrogen purification. Despite high energy
requirement for LOHC dehydrogenation, this cost is relatively insignif­
icant. If the dehydrogenation heat requirement is covered by the waste
heat from high temperature fuel cell rather than by hydrogen burning,
the overall energetic efficiency improves with decrease of 4.9–9.8 A
Fig. 14. Greenhouse gas (CO2) emission comparison for different H2 storage
$/kg-H2 in system cost [106]. Amongst all LOHCs, DBT appears to be the
and transport options. Reprinted with permission from Ref. [118]. Copyright
most economical one in term of hydrogen production costs, slightly 2018 Elsevier.
cheaper than toluene. The higher cost of DBT, which is about 4 times
more expensive than toluene, is offset by the lower cost of hydrogen
(LOHC-own) with all transports performed by trucks [118].
release due to the lower temperature of dehydrogenation and easier
While LOHCs are favourable from an economic point of view, they
separation of pure hydrogen due to its higher boiling point.
are the least favourable environmental option with the highest ecolog­
Studies from Germany have looked at the cost of LOHCs (DBT)
ical impact [112,117]. The detrimental environmental impact of LOHCs
compared to other hydrogen carriers for domestic scaled applications
is due to the high energy requirement of the dehydrogenation step,
with continental transport over a shorter distance with maximum of 500
which emits great amount of GHG especially if the heat is provided by
km using road trailer [112,113]. With these criteria, several combina­
natural gas. When using produced hydrogen to heat the dehydrogena­
tions of storage (cavern and tank) and transport (pipeline and trailer)
tion reaction, the environmental impact of this step is significantly
can be envisaged for different forms of hydrogen (cH2, LH2, LOHC).
reduced. When comparing the two LOHC compounds directly, both
Reuß et al. [112] demonstrated that LOHC-based pathways are
options show similar results, but slight differences can be seen. The
economically advantageous for the supply of hydrogen for the mobility
production of DBT causes more emission than that of toluene. This ad­
sector and are highly promising compared to cH2 and LH2 especially for
vantages, position of toluene, however, is thwarted with the higher heat
smaller-scale hydrogen demand. However, when using LOHCs as a
and electricity demand for dehydrogenation of toluene. Toluene is
storage or transport medium this corresponds to the highest energy
however much more toxic than DBT and this will influence its clearance
demand, heat integration and therefore low-cost renewable heat supply
for road and maritime transport.
will be required to remediate the issue caused by the low dehydroge­
In addition to their environmental impact regarding GHG emissions
nation pressure and a potentially high greenhouse gas (GHG) footprint
during the storage, transport, and usage chain, their toxicity and eco­
in the circumstance that heat was to be supplied by the combustion of
toxicity profile need to be considered. The toxicology of LOHCs can be
natural gas [114]. LOHCs were found to be the most cost-effective op­
evaluated in comparison to fossil fuels. Two important benefits of LOHC
tion compared to diesel and methanol when considering the entire
systems in comparison with crude oil-based fuels is that fuels are burned
process chain from production to the filling station [115]. For mobile
whereas LOHCs act as a hydrogen carrier and can be in theory indefi­
applications, due to the high hydrogen-to-electric-fuel efficiency of
nitely reused. Moreover, LOHCs are simple compounds which makes the
LOHCs and the low energy consumption during driving compared to
assessment and risk management much less complex than fossil fuels
diesel or methanol, the amount of hydrogen required per kilometre of
[119].
travel is the lowest for fuel cell LOHC vehicles.
Benzene and toluene are under restricted use in Europe due to human
It has been proven that the largest factor determining the cost of
carcinogenicity and reproductive toxicity, respectively. Moreover, high
producing hydrogen using electrolysis is the cost of electricity [116].
aquatic toxicity and poor biodegradability of cyclohexane and methyl­
Locations with major potential for cheap renewable energy production
cyclohexane mandates their classification as toxic to aquatic organisms
are therefore preferred, with hydrogen production via electrolysis and
and have a potential persistence in the environment. As such, benzene/
storage during times of low electricity prices. In the Australian context,
cyclohexane and toluene/MCH LOHC systems present a high hazard to
with large potential for renewable electricity from wind and solar,
human as well as the environment and are, in this regard, inferior to
LOHCs offer thus huge potential for domestic storage, transport, and use
other LOHC systems and the currently used energy system based on
of hydrogen, and very importantly for hydrogen export over long dis­
diesel [120]. On the other hand, the hydrogenated forms of alkylcar­
tance. LOHCs therefore present an economical solution for the inter­
bazoles exerted a moderate cytotoxicity but are not biodegradable.
continental transport of large volume of hydrogen.
For transcontinental hydrogen export (e.g., from Australia to Asia),
the problematic of transport via ship is largely different from the
5.4. Environmental impacts
transport via pipeline. In this context, the transport of LH2 via tankers
will have a larger environmental impact due to the continuous required
Over a couple of studies, Wulf et al. [117,118] performed a life cycle
energy during transport.
assessment (LCA) of several supply chain architectures to provide
hydrogen to refuelling stations in a domestic context with transport
6. Conclusions and outlooks
under 500 km, the segments including the LOHC for transport and
storage. Unfortunately LOHC technique have more significant environ­
Hydrogen stored in the form of LOHCs has obvious benefits to
mental impact in comparison with the compressed hydrogen with
Australia as a potential hydrogen export enabler minimizing the capital
cavern storage and pipeline transport which has the lowest greenhouse
cost of infrastructure such as transportation vessels, reducing hydrogen
gas (GHG) emission of ~1.5–1.8 kg-CO2/kg-H2 [118]. Fig. 14 compares
loss during transportation such as in the case of LH2 and CO2 emission
the greenhouse gas (GHG) impact of the H2 liquefied with grid
which apply to methane and methanol export commodities.
(LH2-grid) or wind (LH2-wind) power electricity and LOHCs produced
Despite the advantages of LOHCs, the concept is still not yet widely
from DBT and toluene with the dehydrogenation using the energy from
commercially developed. Various LOHC systems still face different
the combustion of natural gas (LOHC-DBT and LOHC-Tol) or hydrogen

1431
V. Sage et al.
challenges. The primary drawback of LOHCs is the high energy demand
required for the dehydrogenation step. The reaction is strongly endo­
thermic and demands considerable energy input to achieve high
hydrogen production, thus impeding the economic and practical
viability of LOHC systems. However, this issue can potentially be miti­
gated through heat integration and reuse from exothermic processes.
The integration of a heteroatom in the LOHC system (e.g., NEC) can
reduce the dehydrogenation enthalpy, and these systems might be more
suitable for mobile applications, with heat integration with the fuel cell.
However, their higher costs and the fact that the fully dehydrogenated
NEC is a solid at ambient temperature remain an issue. However, partial
dehydrogenation and alkyl-chain substitution to form a mixture of the
hydrogenated forms of NEC as liquid can be envisaged [5,43]. Rational
development of new LOHCs with required properties will be attractive.
Future cost reductions can be expected by large scale realization of
such systems. The high dehydrogenation temperature (>250 ◦ C espe­
cially for MCH/Toluene and DBT systems) can also lead to degradation
of the LOHCs, catalyst deactivation, and coking during multiple hy­
drogenation and dehydrogenation cycles. In addition, the low boiling
temperature of LOHC system such as MCH/toluene can results in some
quality issue of the released hydrogen and might require further puri­
fication investment especially if used in combination with a fuel cell.
Although certain LOHC systems (such as toluene and DBT) have been
commercially demonstrated, the development of chemical processes and
technical devices essential for their large-scale implementation is still in
an early phase. Further research and development are therefore neces­
sary, particularly in the areas of catalysts, reactor systems, heat inte­
gration, process optimization, and rational development of LOHCs. The
potential for optimization offered by this technology remains largely
untapped and requires more extensive exploration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
The authors would like to thank the financial support received from
Victoria Hydrogen Hub (VH2), Hydrogen Future Science Platform and
Hydrogen Mission of CSIRO. Special thanks are extended to Dr Patrick
Hartley for his support to this project, Drs Seng Lim, Doki Yamaguchi,
and Nawshad Haque for their support at the early stage of this project.
Finally, we extend our appreciation to Miss Zhe Chen for her assistance
in partly conducting literature study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijhydene.2023.12.269.
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