i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7

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Review Article

An overview of organic liquid phase hydrogen

carriers

Abdennour Bourane, Mohamed Elanany, Thang V. Pham,

Sai P. Katikaneni*
Research and Development Center, Saudi Aramco, Dhahran 31311, Saudi Arabia

article info abstract

Article history: An overview study for assessing the feasibility of using organic compounds as hydrogen
Received 22 February 2016 carriers is conducted. A literature survey and preliminary molecular modeling work have
Received in revised form been carried out. Different classes of compounds have been investigated in the literature.
20 July 2016 Those are cycloalkanes, polycyclic alkanes, heteroatoms-containing hydrocarbons and
Accepted 20 July 2016 even ionic liquids. In addition to experimental work where catalyst development and
Available online xxx reactor design were sought for efficient and selective dehydrogenation of organic carriers,
computational modeling work had also been conducted by different research groups,
Keywords: principally to search for compounds with low enthalpy of dehydrogenation. Among the
Hydrogen carriers different compounds considered, the ones that meet more or less the required physical
Hydrocarbons (liquid in all state), toxicity/environmental, stability (to be recycled) and cost criteria for
Hydrogen content hydrogen storage and delivery purposes are within the cycloalkanes class. Methyl-
Enthalpy of dehydrogenation cyclohexane only seems to be the appropriate candidate. The economic viability of using
Methylcyclohexane such compounds is however pending to the releasable hydrogen content as the maximum
value is only about 7.2wt%. Among catalysts usually cited for the dehydrogenation of the
organic compounds, noble metal supported ones and mono or bi-metallic catalysts espe-
cially are having better performances in terms of activity and selectivity. Although the
combination of catalysts and organic compounds will give different reactivity and selec-
tivity, the polycyclic alkanes and heteroatom-containing hydrocarbons will usually be
more susceptible to side reactions during dehydrogenation forming coke, additional
partially dehydrogenated and decomposed products as well. No data are available as to the
life time of the catalyst in such reaction, but it is expected that deactivation might be a
concern. Different reactor configurations were considered in pursuit of high conversions
while limiting side reactions. Finally the computational modeling data obtained are in
agreement with the ones found in the literature. Although heteroatom-containing poly-
cyclic hydrocarbons are found to present lower enthalpy of dehydrogenation that would be
suitable for on-board dehydrogenation, as mainly sought by the different research groups,
their application as organic carrier seems quite difficult in regards of their hydrogen
content, their physical properties and the cost of synthesis.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: sai.katikaneni@aramco.com (S.P. Katikaneni).
http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Bourane A, et al., An overview of organic liquid phase hydrogen carriers, International Journal of
Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen storage materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen storage performance targets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen storage materials and technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
About hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Compressed hydrogen gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Liquid hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Metal and complex hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
High surface area sorbents and carbon-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Organic hydrogen carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Compounds investigated . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Catalytic systems and operating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Molecular modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Literature data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Computational modeling data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Viability of organic hydrogen carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Required characteristics for organic hydrogen carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogen content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Physical properties: starting material and dehydrogenated product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Compound stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Enthalpy of dehydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Toxicity and environmental impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Techno-economic analysis: methyl cyclohexane-toluene system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

the promising methods would be through the catalytic reac-

Introduction
The fossil fuels that are today the primary energy sources are
challenged, as societies in developed countries at least, are
requesting use of alternative energy sources that are cleaner
and sustainable. Hydrogen was found to be a promising
alternative energy carrier for decades already but the reali-
zation of a hydrogen economy is still facing multiple obsta-
cles. For the hydrogen production, steam methane reforming,
partial oxidation of fossil fuels or even water electrolysis are
the current established methods while new methods like
thermochemical water splitting using nuclear or solar heat or
other biological techniques are in early development phases.
In addition to its production, hydrogen storage and delivery
technologies are currently in commercial use but by the
chemical and refining industries only [1].
Hydrogen is indeed presently produced in limited number
of plants and to be used at the required location it is currently
transported by road via cylinders, tube trailers, and cryogenic
tankers. It is then stored as a discrete gas or liquid.
However for a widespread hydrogen use in energy appli-
cation and especially in transportation, hydrogen delivery,
storage and even conversion technologies barriers have to be
overcome [2].
Among options for meeting at least the delivery and stor-
age challenges and keeping oil as a hydrogen source, one of
tion pair of dehydrogenation of saturated organic materials
and the subsequent hydrogenation of their corresponding
aromatic products. The organic compound would indeed act
as a hydrogen carrier.
A vision of a global hydrogen energy chain using the
organic hydrogen carrier approach would involve hydroge-
nation of the organic compound near gas or oil fields with a
large reduction in the CO2 emission, as the generated CO2
through the hydrogen production process is planned to be
captured and injected into the ground for instance. The
hydrogen carrier would be transported to the consumer
countries by the usual sea-going chemical tankers, and it
would be stored in tanks on land, before being delivered to the
hydrogen stations by chemical trucks or even pipes used for
conventional fuels. The organic compound would then be
either dehydrogenated at the hydrogen station or directly on-
board the vehicle. This latter option seems quite difficult to
implement on a technical level and it would also be easier to
deal with CO2 generated through energy provided for the re-
action at the station as well. This overall scheme has a low
potential risk regarding safety and a small loss of hydrogen
through the transportation and also low cost, as the storage
and transportation would be carried out in the liquid state
under ambient pressure and temperature.
Organic molecules that can undergo reversible hydroge-
nation and dehydrogenation reactions have been investigated

Please cite this article in press as: Bourane A, et al., An overview of organic liquid phase hydrogen carriers, International Journal of
Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
by a number of research group [3e18] since the early 1980s
already [19]. But there is no commercial application of such
approach yet.
The overview on organic liquid phase hydrogen carrier is
focused on:

Conduct a literature and patent survey on the potential of
using organic liquid phase compounds as hydrogen car-
riers and identify plausible
B new formulation with higher than 7.2% by weight cur-
rent hydrogen storage density and is stable after several
thousand repeated hydro/de-hydro cycles
B new highly active dehydrogenation catalyst that can
meet the variable hydrogen demand at a hydrogen
filling station
Perform preliminary computational modeling to provide
guidance for the new formulation of potential organic com-
pounds as hydrogen carriers.
Hydrogen storage materials
Hydrogen storage performance targets
Hydrogen is potential solution for reducing environmental
emissions from transportation vehicles using fuel cells. U.S.
DOE has set on-board hydrogen storage system targets for
2020 [20] using advanced hydrogen storage materials (Fig. 1)
[7e13].
System hydrogen gravimetric and volumetric densities are
key elements in the hydrogen storage performance targets
and the values reported can serve as a basis for R&D of po-
tential storing media. A value of 7.5wt% and 70gH2 L1 is
Fig. 1 e Energy Storage density e hydrogen content in organic chemical hydrides, compressed H2 tanks and metal hydrides
[7e11].
Please cite this article in press as: Bourane A, et al., An overview of organic liquid phase hydrogen carriers, International Journal of
Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
3
required for the “ultimate full fleet” target that would allow a
fuel cell car to run for about 500 kms. This value is from the
standpoint of the total onboard storage system and not just
the storage medium alone. The storage system would include
for instance interfaces with the refueling infrastructure, the
storage vessel itself, all storage media, any required insulation
or shielding, any regulators, electronic controllers, all onboard
conditioning equipment necessary to store the hydrogen
(compressors, pumps, filters, etc.), as well as mounting hard-
ware and delivery piping etc…
Consequently the gravimetric and volumetric capacities of
the material/media alone must clearly be higher than the re-
ported system targets. Depending on the material and on the
system design, material capacities may need to be a factor of
1.2e2 times higher than system capacity targets i.e. that the
material hydrogen gravimetric capacity should be between 9
to 15 wt% [21] which should be consequently our basis in
search of potential organic liquid phase hydrogen carriers.
Although these targets are for on-board vehicle hydrogen
storage media, they can also serve as a basis for materials that
would release hydrogen off-board like at the fueling station.
The material capacity to carry hydrogen will indeed have a
significant impact on the transportation cost as shown in the
study by TIAX LLC [22] where a 24% improvement in hydrogen
capacity would yield on average a 20% reduction in delivery
cost.
There are some studies reported on liquid organic
hydrogen carriers with hydrogen content of 5e8 wt%
[16e18]. Japan government is planning to demonstrate
onsite hydrogen production using liquid organic hydrogen
carriers such as methyl cyclohexane [7e13] and to validate
the technology validation underway at Chiyoda Corpora-
tion, as presented in Fig. 1 [7e13].
Another important point is the cost of the hydrogen stor-
age media. For on-board vehicle the new targets are not set yet
but the previous values indicate that the economics of
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
synthesis of the materials, hydrogenation/dehydrogenation
steps of materials are central to their successful use. This is
valid for on-board as well as for off-board hydrogen storage
media.
Finally the storing materials along with the possible by-
products that might be formed during hydrogenation/dehy-
drogenation must also be environmentally friendly.
Hydrogen storage materials and technologies
As seen above developing hydrogen storage and carrying
media having relatively high capacity on weight and volume
basis is very crucial and it is one of the major challenges the
hydrogen economy is facing today for its real launch.
Research into developing such materials is pursued along
with enhancement of the more conventional hydrogen stor-
age technologies like compressed hydrogen or liquid
hydrogen tanks.
About hydrogen
Hydrogen gas has a density of 0.09 g L1 at 0  C and 1 atm. The
liquid density is 0.07 g mL and the boiling temperature is
252.87  C. On a weight basis, hydrogen has nearly three times
the energy content of gasoline (120 MJ/kg for hydrogen versus
44 MJ/kg for gasoline) while on a volume basis the situation is
reversed and hydrogen has only about a quarter of the energy
content of gasoline (8 MJ/L for liquid hydrogen versus 32 MJ/L
for gasoline). Estimated 5 to13 Kgs [1 Kg hydrogen ¼ gallon of
gasoline energy equivalent] of hydrogen would be required for
light-duty automotive fuel cell vehicles to achieve a 500 kms
range. At room temperature and atmospheric pressure, 5 Kgs
of hydrogen occupies a volume of 60 m3 which would corre-
spond to a balloon of … ~5 m diameter. More practical solu-
tions have thus to be found to store hydrogen.
Compressed hydrogen gas
Carbon fiber-reinforced composite tanks for 350 bar and
700 bar compressed hydrogen are under development and are
already in use in some serial hydrogen powered vehicles. Inert
inner coating is however required to prevent the high pressure
hydrogen to react with the polymer. To have an idea, spherical
container having 55 cm in diameter (87 L volume equivalent)
would be able to carry out the 5 Kg of hydrogen considering a
700 bar pressure. Volumetric capacity, limits of high pressure
and also cost are key challenges met with this approach [6,21].
Liquid hydrogen
Liquid hydrogen seems more attractive as it has a higher mass
per container volume 0.07 g mL1 than for instance com-
pressed hydrogen at 700 bar (0.039 g mL1). The temperature
of liquefaction of hydrogen is however 252  C at atmospheric
pressure requiring some significant energy (over 30% of the
lower heating value of hydrogen). The critical temperature of
hydrogen being only 241  C, boil off is observed raising the
liquid losses issue along with cost, energy efficiency and
safety [6,21].
Metal and complex hydrides
Several metals and complex hydrides have the potential of
reversibly absorbing quite significant amounts of hydrogen
Please cite this article in press as: Bourane A, et al., An overview of organic liquid phase hydrogen carriers, International Journal of
Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
with theoretical quantities that may reach up to 18wt% in case
of complex hydrides like metal borohydrides LiBH4 [15,23e26].
However higher pressure and temperature are usually
required with most of these hydrides for both hydrogen up-
take and release. For instance magnesium borohydride can
release up to 10wt% of hydrogen but in a 300e400  C tem-
perature range. Similarly the rehydrogenation necessitates a
temperature of 400e500  C and a pressure of 800e950 bar H2.
Progresses are being made like for example with LiBH4 where
the temperature of dehydrogenation has been decreased from
410  C to 170  C after addition of MgH2 acting as “destabilizer”.
Other recent approaches consist in substituting the metal
borohydrides with heavy halide anions resulting in materials
with modified physical properties facilitating hydrogen up-
take [27] New recent research direction also include nano-
porous hydrides like geMg(BH4)2 that shows interesting
properties with higher hydrogen intake as hydrogen is stored
on both the inner surface and chemically bonded to boron [27].
Reactive hydrides composites where two or more
hydrogen-material containing compounds are allowed to
react during the release of hydrogen are also being recently
investigated. Examples of such composites are a combination
of metal borohydride and metal amide like LiBH4e2LiNH2
where the temperature for hydrogen release is lowered by
130  Ce250  C as compared with LiBH4 alone [27].
In case of metal hydrides lower hydrogen-storage prop-
erties are reported that can reach up to 7.6wt% for compo-
nents like MgH2. Current research work has also shown that
at this point the amount of hydrogen that this kind of ma-
terial can release in an absorption/desorption cycle might be
quite different from the amount it can hold theoretically and
some of them (e.g. LiAl4 or Ti(AlH4)4) are even not exhibiting
reversibility. In case of sodium alanate (NaAlH4) for instance
practical gravimetric capacities are only 3e4wt% to be
compared to 5.5wt% theoretical value [8]. The kinetics of
hydrogenation/dehydrogenation are also pointed out as
being slow. These features make these materials not really
suitable for on-board utilization yet and rather adapted for
use at the fueling station. Some metal hydrides can be uti-
lized near room temperature but they usually present a low
hydrogen mass density. Issues with material handling,
pyrophoricity and exposure to air humidity and contami-
nants need to be addressed as well in general with these
metal hydrides.
Some of these materials can be hydrolyzed in order to
produce hydrogen. This is the case for instance of MgH2
(contained initially in non-aqueous slurry) that reacts with
water to produce H2 and magnesium hydroxide (Mg(OH)2). H2
can be released in amounts as high as 11wt.%. Another com-
pound considered more recently is NaBH4. Upon reaction with
water, H2 is formed along with sodium tetrahydroxyborate. A
gravimetric hydrogen storage capacity of 7.3wt% is usually
reported with this kind of material [28]. Obviously this
approach seems to be difficult to implement on vehicles as
water and slurry must also be carried on-board in addition to
the spent fuel that may even be heavier than the starting
material. However this might be quite applicable off-board at
the fueling station.
Overall research work on hydrides needs to be continued to
reach a more energy efficient regeneration process including a
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
higher purity of the generated hydrogen to make the approach
more economically viable [6,21,29].
High surface area sorbents and carbon-based materials
Several high surface area sorbents e.g. carbon nanofibers,
graphite materials, metal organic frameworks, aerogels, etc…
are being studied for hydrogen storage. One advantage of the
sorbents is related to their fast hydrogen kinetics. Carbon
materials are paid particular attention with however issues
related to lack of reproducibility in hydrogen storage capacity
in case of carbon nanotubes and drawback of very low tem-
perature required. Some authors even claimed 60wt%
adsorption of hydrogen in specific carbon fibers [30] while
others claim to reach 6-8wt% at 196  C in high-purity single
walled tubes opened by sonication [31]. However the amount
of hydrogen that can be stored on such materials is usually
rather proportional to their specific surface area and generally
limited to 2wt% at a temperature of 196  C.
Metal-doped carbon nanostructured materials are also
considered where theoretical maximum reversible hydrogen
storage density of close to 9wt% are reported for instance with
scandium-based organometallic buckyball fullerenes [29].
Metal-organic frameworks (MOF) show also promising
storage capacities of hydrogen, by mostly physisorption, due
to their extremely high internal porosity. A maximum
hydrogen uptake of 5wt% has been reported for MOF-5 at 77 K
for instance. Similarly to other microporous materials the
storage capacity is found to depend linearly on the specific
surface area but is independent of the composition and the
structure. Possible higher storage capacities can be obtained
with these materials when having a higher heat of hydrogen
adsorption [32].
Other novel crystalline solids with high capacity for mo-
lecular hydrogen storage are under investigation. The solids
made up methane are claimed to contain the largest amount
of hydrogen of any compound (33.4 wt%). Other similar solids
composed of hydrogen-bonded water frameworks forming
what are called solid clathrate [33,34]. These kinds of com-
pounds are however synthesized under very high pressure:
3.5 GPa for CH4(H2)4 and 0.3 GPa [35]. Progresses are made to-
wards using less harsh conditions: addition of a promoter
molecule like tetrahydrofuran allowed synthesis of the
hydrogen hydrate at only 50 bars and 280 K. Stability of the
formed compounds at ambient conditions is another filed
where improvements are required. Hydrogen hydrate is stable
only up to 145 K at ambient pressure.
Organic hydrogen carriers
Compounds investigated
Cycloalkanes. The reaction of alkane dehydrogenation
yielding alkene and molecular hydrogen is highly endo-
thermic. High temperatures are usually required and use of a
metal catalyst usually leads to side reactions with formation
of coke. The free energy changes are however more favor-
able for the cyclic alkanes (or naphthenes) than for the linear
molecules because of the resonance energy of the product
aromatic ring [34] making these compounds potential
hydrogen carriers. Among cycloalkanes, cyclohexane (C6H12),
methylcyclohexane (C7H14), ethylcyclohexane (C8H16),
Please cite this article in press as: Bourane A, et al., An overview of organic liquid phase hydrogen carriers, International Journal of
Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
5
dimethylcyclohexane (C8H16), cyclooctane (C8H16) were
studied for their potential hydrogen storage [1,7e13,36e44].
The hydrogen content for these compounds is varying
between 7.2wt% (cyclohexane to benzene) and 3.6wt%
(cyclooctane to cyclooctadiene) considering a total
dehydrogenation.
At similar equilibrium conversion rate, the temperature of
dehydrogenation is found to be lower for the alkyl substituted
cycles due probably to the created inductive effect favoring
hydrogen release. All of these compounds including their
dehydrogenated products are liquids under ordinary temper-
atures and pressures.
Polycyclic alkanes. Several polycyclic alkanes were mentioned
in the literature including:
- The ones containing only six membered rings in their
structure like decalin (C10H18) [45], tricyclic alkanes like
tercyclohexanes (C18H32) [46] or perhydro-anthracene
(C14H24) [47], tetracyclic alkanes like perhydro-pyrene
(C16H26) [48,49], and other higher containing number of
rings compounds like hydrogenated forms of chrysene
(C18H30), picene (C22H36), coronene (C24H36) and even hex-
abenzocoronene (C42H18) [48].
- The ones containing six and five membered rings in their
structure like perhydro-fluorene (C13H24) [47,48] or perhy-
drofluoranthene (C16H26) [47].
The available hydrogen content from these compounds is
varying between 7.2wt% (decalin to naphthalene) and 7.4wt%
(dehydrogenation to coronene) considering a total dehydro-
genation. It seems that no more than 7.5wt% of hydrogen can
be obtained from these organic compounds.
Among these compounds decalin (Tb ¼ 187  C) is the only
compound which is liquid at ambient conditions. However all
the others compounds are solid under the ambient condi-
tions and their dehydrogenation products, including naph-
thalene (Tm ¼ 80  C) derived from decalin, have even higher
melting points e.g. Tm ¼ 148  C for pyrene, Tm ¼ 438  C for
coronene. As a consequence solvents, e.g. toluene, have to be
used to obtain liquid solutions of such compounds with the
drawback of lowering the total hydrogen content of the
molecule. Pez et al. who are claiming most of the large
polycyclic hydrocarbons in EP1475349A2 [48] even propose to
utilize for instance mixtures of two or more components that
may form a eutectic melting at a lower temperature. For
example chrysene (Tm ¼ 250  C) and phenanthrene
(Tm ¼ 99  C) are reported to form a eutectic melting at 95.5  C
[49]. The introduction of substituents like n-alkyl, alkoxy or
ether groups on the ring structure of the polycyclic molecule
is also mentioned enabling to lower their melting point but
again at some cost of “dead weight” reducing the releasable
hydrogen content.
According to Cooper et al. [50] materials with higher en-
thalpies of hydrogenation will generally require higher tem-
peratures to dehydrogenate, and those with lower enthalpies
may no longer have an ability to be hydrogenated. According
to Fig. 2 below [50] that shoes calculated standard enthalpies
of hydrogenation for three structural classes of polyaromatic
hydrocarbons as a function of the number of fused aromatic
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
rings, the very large fused multi-ring aromatic systems would
be more appropriate as they have lower enthalpy of hydro-
genation. Experimental results of dehydrogenation of penta-
cene (DHhyd ¼ 17.5 KCal/mol H2) and coronene
(DHhyd ¼ 13.8 KCal/mol H2) under similar conditions seem to
confirm these data as only 0.15wt% of hydrogen are released
from pentacene compared to 1wt% for coronene [48]. Ac-
cording to the same authors, pi-conjugated aromatic mole-
cules comprising five-membered rings would also provide
effective reversible hydrogen substrates as they are found to
have a lower enthalpy of dehydrogenation than
the corresponding conjugated system in a six-membered
ring [48].
Nitrogen, sulfur and oxygen containing hydrocarbons. From
their computational data, Pez et al. [48] observed that an
introduction of N heteroatoms replacing carbons in polycyclic
aromatic hydrocarbons also generally results in a lower value
of the standard enthalpy of hydrogenation, i.e. a higher aro-
matic (or pi-conjugation) stabilization energy than their cor-
responding all carbon counterparts. As such the following
compounds were claimed: 1,4,5,8,9,12-hexaazatriphenylene,
C18H6N6 and its perhydrogenated derivative, C12H24N6 system.
The same authors also initially claimed ethyl carbazole
(C14H25N) as a potential carrier compound. 99.9% of hydrogen
could be released from the hydrogenated form with only
about 10 ppm of methane and 80 ppm of ethane formed.
However the maximum hydrogen content is only 5.7wt%,
which was not meeting the target for on-board vehicle use.
Phenantroline (C12H8N2) was later suggested as the theoretical
hydrogen content from the hydrogenated form is higher and
reaches 7.2wt% [50]. Carbazole (C12H9N) and acridine (C13H9N)
were also studied as potential hydrogen carriers with 6.7wt%
and 7.2wt% hydrogen content respectively from the hydro-
genated forms [47].
It has to be noticed that all the above cited dehydrogenated
compounds are solid at ambient temperature having a
melting point higher than 100  C. No data are available for the
dehydrogenated from for which high melting point are also
expected.
Low molecular weight aliphatic amines and di-amines are
claimed in US2010/0210878 patent application to produce their
corresponding nitriles along with hydrogen. For example 1,3-
diaminopropane from which a theoretical hydrogen content
of 10.8wt% is cited. During dehydrogenation this compound is
found to be converted into propionitrile with however for-
mation of NH3 as well. Low conversions are obtained at tem-
perature of about 200  C [51].
Substituted thiophenes are also proposed by ASEMBLON,
Inc. as carriers for storage, transport, and release of hydrogen
[52]. This is based on the discovery that finely dispersed sup-
ported metal catalysts readily carry out the cyclization and
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dehydrogenation reaction of alkyl sulfides to thiophene, at the
same time releasing hydrogen. For example, for the case of 2-
pentanethiol the reaction produces 2-methylthiophene and
hydrogen (5.7wt%).
In a chapter of his PhD thesis H. Zhao [53] investigated a
method for regenerating the above formed thiophene com-
pound by its catalytic hydrogenation accompanied with the
cleavage of one of the CeS bonds, also called selective ring-
opening, giving back the initial molecule. By doing so, an
additional mole of hydrogen can be indeed carried than with
the closed ring.
Other compounds containing sulfur or oxygen having a
formula R-XH were also claimed by ASEMBLON, Inc. for
hydrogen storage, wherein R can be an alkyl or aryl moiety
and X ¼ S or O [52]. Examples of such compounds are cyclo-
hexanol (C6H12O) which is dehydrogenated to phenol (6wt%
H2), or hexanethiol (C8H14S) which is dehydrogenated to the
disulfide (0.7wt% H2).
There are other prior art teachings on hydrogen storage
utilizing the reversible catalytic hydrogenation of simple ke-
tones, eg. acetone [54] to the corresponding alcohols, for
which the hydrogen storage capacities are however relatively
low.
Pez et al. [48] are claiming that by introducing the hydro-
genable ketone substituents into polyaromatic substrates,
with which it is conjugated, acceptable heats and hydrogen
storage capacities are achievable. Example of such com-
pounds is the pigment pyranthrone (C32H14O2).
Other oxygen-containing compounds are claimed in
US2010/0055513 pertaining to General Electric Company
Global Research [55]. Compounds having two secondary hy-
droxyl groups are claimed to have lower dehydrogenation
energy than cyclic hydrocarbons. As an example 2,3-
butanediol has DGdehy ¼ 15.2 KCal/mol H2 while decaline
has DGdehy ¼ 20.6 KCal/mol H2. These polyols compounds are
reported to also provide higher volumetric hydrogen capac-
ity. However the gravimetric hydrogen capacity of such
compounds is typically lower than the capacity of cyclic
hydrocarbons: 3.47wt% releasable H2 for cyclohexanediol
compared to 7.1 wt% for cyclohexane.
Ionic liquids. Some ionic liquids were considered for study as
hydrogen carriers in the literature with the claimed advantage
of dealing with compounds that have very low vapor pressure,
high density, and chemical and thermal stability and that are
not inflammable [56]. Imidazolium ionic liquids containing
cyclohexane moieties such as 1-methyl-3-[3-(cyclohexyl)pro-
pyl]imidazolium bis(trifluoromethanesulfonyl)imidate (R ¼ H
for below molecule) were prepared.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
Dehydrogenated compounds are solid compounds while
the hydrogenated compound is described as being a viscous
liquid for R ¼ H and as solid for R ¼ cyclohexane unit with a
melting point of 66  C. In case of R ¼ benzyl unit the com-
pounds are observed not to be stable under the hydrogenation
reaction conditions. Up to 12 atoms of hydrogen can be
released corresponding to maximum releasable hydrogen
content of 2.2wt% in case of R ¼ cyclohexane unit [56].
Benzimidazolines, including N,N0 -dimethyldihy-
drobenzimidazole, 1,3-dimethyl-2-phenylbenzimidazoline,
and 1,3-dimethylbenzimidazoline, were studied with
different palladium catalysts in acetonitrile suspensions/
solutions, and were found to release H2 even at
room temperature [57]. In case of dehydrogenation of N,N0 -
dimethyldihydrobenzimidazole compound, the internal salt
(2-(1,3-dimethylbenzimidazolium-2-yl)benzoate) is formed
along with one mole of hydrogen only making the releasable
hydrogen content of such compounds very low as seen below.
In addition the compound is mentioned to be stable in
solution and in solid state but at temperature up to 80  C. The
authors report that they were not able to reverse the hydrogen
evolution at this stage. This is probably related to the higher
stability of the salts against saturation as shown in Ref. [58].
Much lighter organic frameworks are being investigated to
improve the available hydrogen weight. Table 1 below sum-
marizes hydrogen content and physical properties of different
organic hydrogen carriers (hydrogenated and dehydrogenated
form) reported in literature.
Catalytic systems and operating conditions
Dehydrogenation. Noble metal based catalysts are usually the
ones reported in the literature for the hydrogenation/dehy-
drogenation reaction of organic compounds [42]. A well
known process in the refining industry is the catalytic
reforming where a Pt and/or Rhenium catalyst is used (various
versions of the process) to convert petroleum refinery naph-
thas, typically having low octane ratings, into high-octane
liquid products called reformates which are components of
high-octane gasoline. Among the major catalytic reforming
reactions happening is the dehydrogenation of naphthenes
(such as methylcyclohexane) to convert them into aromatics
(toluene). Depending upon the type or version of catalytic
reforming used as well as the desired reaction severity, the
reaction conditions range from temperatures of about
495e525  C and from pressures of about 5e45 atm [59].
Mono and Bi-metallic catalysts. In the case of the studies of
organic hydrogen carriers, platinum and bimetallic catalysts
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PteM (M ¼ second metal) are also well reported particularly
for highly selective dehydrogenation of the cycloalkanes
namely cyclohexane, methylcyclohexane, decalin and tet-
raline [3,50]. Addition of a second metal such as W, Mo, Re,
Rh, Ir, Pd and Sn, usually leads to a promoting effect resulting
from the electronic effect of the added metal to Pt which
improves the CeH bond cleavage, the stability of the formed
intermediates and the desorption of aromatic products. Or it
may be explained as the synergistic effect of the second
metal for the CeH bond cleavage and high hydrogen-reverse-
spillover or the hydrogen-recombination abilities of Pt,
facilitating the fast removal of hydrogen from the reaction
system and the chemical equilibrium shift in favor of prod-
ucts [39].
In an attempt of designing catalysts using less Pt, Ni-based
catalysts have been investigated considering use of Ni alone or
in combination with the Pt or other noble metals like Ruthe-
nium. These include Ni/C, Ru/C and NieRu and NiePt cata-
lysts for dehydrogenation reactions [45]. Particularly NiePt/AC
catalysts have shown high selective dehydrogenation of
cyclohexane with minimum use of Pt [60].
Taube et al. mention that the best known catalysts for the
dehydrogenation of methylcyclohexane included following
metals and oxide: Al2O3, V2O3, AleCr, NieP, AleTieV, Ru(SiO2),
CueNi, Co or AleCoeCreZn [19].
Addition of potassium, by impregnation method, into Pt/
Al2O3 has been considered by Okada et al. for the dehydro-
genation of methylcyclohexane in a fixed bed reactor at 320  C
[37].
Catalysts supports. Various supports are used for the
dehydrogenation catalysts including activated carbon in
granule or cloth form, metal oxide such as alumina, silica,
TiO2, MnO2, CeO2, Fe2O3, La2O3… or anodized aluminum
(alumite)… Different catalytic activity in terms of hydrogen
evolution rates are reported for the different supports used.
The difference in surface area, the metal dispersion (Pt) over
the supports, the better hydrogen spillover as well as the
metal-support interaction were pointed out for instance by
Shukla et al. [42] for dehydrogenation of methylcyclohexane
where the following order was obtained: La2O3 » TiO2 > Al2O3
> MnO2 > Fe2O3 > ZrO2 > CeO2. Reduced Pt loading to obtain a
higher metal dispersion on support, addition of a second
metal and the partial substitution of La by Y in LaNiO3 pe-
rovskites allowed the authors to further obtain an even higher
activity. The heat of conduction of the support was an
important parameter in the choice of the support for Kariya
et al. to obtain high rates of hydrogen production in a “spray
pulsed” configured reactor [15].
Catalyst particle size effect. The hydrogenolyis is the main
side reaction occurring leading for instance to methane for-
mation during the dehydrogenation of methylcyclohexane
[42]. It mainly prevails on relatively higher metallic grain size
while well dispersed metallic catalysts rather lead to the
dehydrogenation reaction.
Higher dehydrogenation reactions rates are reported with
well dispersed catalysts. Smaller particle sizes of Pt were
obtained with a reduction treatment with NaBH4 than with
H2 [39].
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7

Table 1 e Physical properties and hydrogen content of different organic hydrogen carriers reported in literature.
Hydrogen carrier Dehydrogenated H2 content Calculated Boiling Melting point
carrier (wt %) enthalpy point ( C) ( C)
(kJ/molH2)
Hyd. Dehy. Hyd. Dehy.
Cycloalkanes
Cyclohexane (C6H12) Benzene 7.1 68.6 81 6.5
Methylcyclohexane (C7H14) Toluene 6.1 68.3 101 111 126 93
Ethylcyclohexane (C8H16) Ethyl benzene
Dimethylcyclohexane (C8H16) Dimethyl benzene

Polycyclic alkanes
Tercyclohexanes (C18H32) Terphenyl 7.2 51e161 58e212
Pyrene (C16H26) 7.3 148
Chrysene (C18H30) 7.3 250
Picene (C22H36) 7.3 518 366
Coronene (C24H36) 7.4 525 438
Hexabenzocoronene
(C42H18)
Fluorene (C13H24) 6.7 295 116
Tetralin 3.0 64.2 207
cis-Decalin 7.3 64.0 193
Trans-Decalin 7.3 66.7 185
Cyclohexylbenzene 3.8 65.9 237
Bicyclohexyl 7.3 66.6 227
Cis-syn-1-Methyldecalin 6.6 63.9 213.2

Heteroatom containing hydrocarbons

Ethyl carbazole (C14H25N) 6.7 50.6
Phenanthroline (C12H8N2) 7.2 117
Acridine (C13H9N) 7.2 346 107
1,3-diaminopropane 10.8 56.7
2-methylthiophene 5.7
Cyclohexanol (C6H12O) Phenol 6
Hexanethiol C8H14S 0.7
2,3-butanediol
Cyclohexanediol 3.47

Ionic liquids
1-methyl-3-[3-(cyclohexyl)propyl]imidazolium 2.2 66
bis(trifluoromethanesulfonyl)imidate

Reactor systems and operating conditions. Different reactor
systems have been considered for the study of the dehydro-
genation of the organic hydrogen carriers. Those are batch-
wise [48,61], liquid film [40,45,62,63], fixed bed [37], mem-
brane reactor [36,64] or spray-pulsed systems [39,42].
Table 2 e Assessment of challenges for different organic
hydrogen carriers to meet required criteria for on-board
or off-board utilization.
For instance, a mixture of hydrogenated pyrene (65wt% of
hexadecahydropyrene C16H26 and 35wt% of decahydropyrene
C16H20) was dehydrogenated in a high pressure batch reactor
equipped with a customized grinding apparatus using a 5%
Rh/Carbon catalyst at 150  C under 1.6 bar hydrogen pressure
for 16 h 25wt% of the stored hydrogen within the initial
compounds was released with formation of a range of
partially dehydrogenated compounds along with the fully
dehydrogenated species: 9.1wt% pyrene (C16H10), and other
partially dehydrogenated forms 4.5wt% dihydropyrene
(C16H12), 0.4wt% tetrahydropyrene (C16H14), 20.3wt% hex-
ahydropyrene (C16H16), 0.3wt% octahydropyrene (C16H18),
19.4wt% decahydropyrene (C16H20) and 46wt% hexadecahy-
dropyrene (C16H26) [48]. Dehydrogenation of para-substituted
pyridine derivatives compounds in similar conditions
(T  200  C and Pd, Pt or Rh supported on C, SiO2, Al2O3) gave
also either a poor selectivity and high conversion or vice
versa [61].
Methylcyclohexane was dehydrogenated in a fixed bed
reactor using (0.1wt%)K-(0.6wt%)Pt/-Al2O3 as catalyst at 320  C
with a co-feed of hydrogen (5e20%Vol.). A methylcyclohexane
conversion of 95% was obtained with a toluene selectivity
>99.9%. Formation of benzene and methane through the side

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
reaction were obtained with a selectivity of around 0.02%.
Several other compounds were also obtained due to ring
cleavage reaction with a total amount of around 0.005% [37].
Kariya et al. [39] carried out catalytic dehydrogenation of
methylcyclohexane experiments using a spray-pulsed
reactor. Reaction rates obtained by this process are claimed
to be one-order (15e25 times) higher than the conventional
gas-phase reactions. The principle is to feed the reactant to
the reactor, in an atomized spray way, in pulsed injection
mode using a fine nozzle fitted at the top of the reactor. The
liquid reactant is rapidly vaporized on the hot catalyst surface.
After the reaction under high partial pressure of reactant,
unreacted reactant and products (hydrogen and dehydroar-
omatized hydrocarbon) are readily desorbed and removed
from catalyst because of high temperature of catalyst surface
and stream of evolving hydrogen, and then the catalyst sur-
face becomes to almost dry and clean. The catalyst surface is
kept at 250e350  C on the average. In the present system, the
aromatic products are desorbed and eliminated from the re-
action system more quickly than in the liquidesolid reaction
system because of the high temperature of catalyst. Thus,
both the reverse reaction and the site-blocking by the prod-
ucts are suppressed. The conversion of cyclohexane in the
wet-dry conditions was only 25e35%. While no by-products
were reported by Kariya et al., for the cyclohexane reactant,
methane and benzene were observed by Shukla et al. for
methylcyclohexane [42].
Hodoshima et al. reported efficient hydrogen supply from
decalin, tetralin or methyl cyclohexane with superheated
liquid-film type catalysis [45,62,63]. The superheated liquid-
film state is realized with an adequate mass-to-volume ratio
of catalyst to solution under boiling and refluxing conditions
by heating at 210  C and cooling at 25  C at atmospheric
pressure. During the catalytic dehydrogenation, hydrogen is
removed from the reaction medium, while condensable re-
actants and dehydrogenated products remain there [45,63]. In
such a system, the amount ratios of catalyst-to-reactant are
quite sensitive to the catalytic activities. Saito et al. observed
that the superheated liquid-film state, realized at the catalyst/
substrate amount ratio of 0.30 g/1.0 ml, could offer dominant
dehydrogenation activities with the carbon-supported plat-
inum catalyst by external heating between 210 and 280  C for
decalin or between 180 and 240  C for methylcyclohexane in
the reaction of 2.0 h under boiling and refluxing conditions.
Nearly 100% conversions were attained at 240 and 280  C for
methylcyclohexane and decalin, respectively, and the reac-
tivity of methylcyclohexane was higher than that of decalin
[63]. Under boiling and refluxing conditions, the hydrogen
generated does not remain in the reaction medium once it is
evolved as a gas, thus avoiding the equilibrium restriction.
However in such conditions higher dehydrogenation rates are
obtained with compounds that are less volatile as the required
reaction temperature is higher [40].
Membrane reactors were applied to recover the hydrogen
from cyclohexane dehydrogenation. Itoh et al. [36] using a
palladium membrane reactor have shown that the hydrogen
recovery rate becomes higher as the pressure on the hydrogen
permeation side is lowered below atmospheric pressure or as
the reaction pressure increases. As the perm-side pressure
was lowered, the conversion as well as the hydrogen recovery
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9
rate at 300  C was found to increase. About 80% of the
hydrogen contained in cyclohexane, depending on the oper-
ation condition was successfully recovered.
Hydrogenation
Polyaromatic compounds. The hydrogenation reactivities of
different polyaromatic hydrocarbons: pyrene (C16H10), fluo-
ranthene (C16H10), anthracene (C14H10), fluorene (C13H10) and
other nitrogen-substituted compounds such as acridine
(C13H9N) and carbazole (C12H9N) were studied using different
alumina or carbon supported noble metals at a hydrogen
pressure of 70 bars and a temperature range of 100e250  C in a
batch reactor [47]. Based on the combination of catalysts and
organic compounds different reactivities and selectivities
were obtained. Rhodium and palladium supported catalysts
were found to be the most active ones for hydrogenation of
the tricyclic aromatic compounds while platinum and palla-
dium were the most active ones towards fluoranthene. An
almost total dehydrogenation was only observed for nitrogen
containing compounds with carbon supported rhodium
catalyst. In other cases a range of partially hydrogenated
compounds was obtained with a higher selectivity towards
fully hydrogenated compounds with increasing temperature.
Coronene (C24H12) was hydrogenated under 69 bars
hydrogen pressure at 150  C in a high pressure reactor (batch)
using a Rh/C catalyst. Upon hydrogenation coronene added
3.5wt% hydrogen with a range of partially hydrogenated
compounds obtained along the fully hydrogenated species:
2wt% decahydrocoronene (C24H22), 27wt% tetradecahy-
drocoronene (C24H26) and 70wt% octadecahydrocoronene
(C24H30) [48].
Nitrogen containing compounds. N-ethylcarbazole hydro-
genation has been investigated on catalysts consisting of Ru
metal supported on high surface area silica-alumina, alumina
or TiO2 at 130  C under 70 bars of hydrogen pressure in an
autoclave reactor. Higher conversion and selectivity towards
fully hydrogenated species was obtained with Ru/Al2O3 cata-
lyst. Experimental work supported by theoretical study shows
that the hydrogenation is taking place in a stepwise manner
over the metal catalyst starting with the formation of the
pyrrole intermediate on the terraces sites that is further hy-
drogenated on low coordinated sites because of steric hin-
drance [65].
Carbazole (C12H9N) was hydrogenated under 69 bars
hydrogen pressure at 125  C using a Rh/C catalyst in a high
pressure reactor. After reaction and cooling down to room
temperature the hydrogenated carbazole was removed from
the reactor mixture by extraction with acetone, filtering of the
insoluble catalyst and drying under vacuum. The following
products were obtained: 88wt % dodecahydrocarbazole
(C12H21N), 6wt% octahydrocarbazole (C12H17N) and 6wt%
dicyclohexyl (C12H22) showing a decomposition of the carba-
zole and a high conversion towards fully hydrogenated com-
pound [48].
Hydrogenation of 2-methyl thiophene (2 MT) was con-
ducted at 20 bars in a temperature range of 150e325  C in a
continuous-flow trickle bed reactor. Sixteen total catalysts
were evaluated including alumina supported noble metals Pt,
Pd and Ru; alumina supported bimetallic noble metals PdePt
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
and PdeRu; silica supported transition metal phosphides WP,
Ni2P and MoP, and alumina supported transition metal sulfides
MoS, NiMoS and CoMoS. The major products obtained were
tetra hydro 2 MT, pentenes and pentanes although the targeted
compound was pentanethiol through the ring opening. Out of
the four groups of catalysts the four most active catalysts are in
the order Pt/Al2O3 > PdePt/SiO2 > WP/SiO2 > CoMoS/Al2O3.
Higher selectivity towards TH2MT was obtained at low tem-
perature and low conversion of 2 MT while desulfurized
products were obtained at higher temperatures [53].
Other nitrogen containing compounds like pyridine de-
rivatives were hydrogenated under 70 bars of hydrogen and in
a temperature range of 100e150  C. Several catalysts like Pd/
Al2O3, Pd/C, RuO2, PtO2, Rh/C were evaluated and a poor
selectivity towards hydrogenated compounds was obtained
with most of the catalysts (except RuO2), due probably to
hydrogenolysis side reaction. Indole derivatives were more
successfully fully hydrogenated using a Rh/C catalyst [61] at
180  C.
Molecular modeling
Literature data
Few works related to molecular modeling, especially looking
into molecular structures that would have a low enthalpy of
dehydrogenation, are reported.
Considering the fact that materials with higher enthalpies
of hydrogenation will generally require higher temperatures
to dehydrogenate, and those with lower enthalpies may no
longer have an ability to be hydrogenated, Cooper et al. from
Air Products and Chemicals, Inc. looked into the enthalpy
of hydrogenation of several polyaromatic compounds [50].
Standard enthalpies of hydrogenation were calculated for
Fig. 2 e Enthalpies of hydrogenation as function of fused aromatic rings [26].
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three structural classes of polyaromatic hydrocarbons as a
function of the number of fused aromatic rings (Fig. 2 above).
The very large fused multi-ring aromatic systems have the
lower enthalpy of hydrogenation and thus would require a
low temperature of dehydrogenation. The authors also
showed that when substituting some carbons in polycyclic
aromatic hydrocarbons by N heteroatoms a lower value of the
standard enthalpy of hydrogenation is obtained for the
resulting compounds, i.e. a higher aromatic stabilization en-
ergy than their corresponding all carbon counterparts (Fig. 3).
This value is further decreased when the hydrocarbons
contain the greatest number of pyridine-like aromatic sextets.
The incorporation of two N atoms in a six membered ring,
replacing carbons, seems to provide an even further advan-
tage, depending on the nitrogens relative positional substitu-
tion pattern.
The authors also observed that larger molecules repeating
the six-membered, five-member ring nitrogen containing
structure are calculated to have lower, more favorable,
enthalpy of hydrogenation than the molecules repeating the
five-membered ring nitrogen or oxygen containing structure
(Fig. 4).
Based on these findings ethyl carbazole and phenantrolene
were selected by Air Products and Chemicals, Inc. as com-
pounds to be considered as hydrogen carriers.
Moores et al. [66] conducted DFT calculations, also showed
that the substitution of carbon atoms by nitrogen ones into
cyclic hydrocarbons allows to lower the enthalpy of dehy-
drogenation of the compounds. For instance the substitution
of one CH2 fragment by NH in cyclohexane is found to cause a
reduction of 5.78 kcal/mol in the enthalpy of dehydrogenation.
The substitution by a second NH has different effect
depending on its position: ortho is unfavorable, while para
and especially meta lead to further reductions of 3.74 and
5.27 kcal/mol, respectively. Thermodynamically, triazinane
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7 11

Fig. 3 e Enthalpies of hydrogenation as function of N substitution [26].

Fig. 4 e Calculated standard enthalpies of hydrogenation for polyindoles, polypyrroles, and polyfurans [26].

(three NH in the structure) is the easiest to dehydrogenate, the weakening effect of adjacent nitrogen on a CH bond. The
reaction being endothermic by only 13.72 kcal/mol as favored dehydrogenation can be ascribed to the nitrogen atom
compared to 30.04 kcal/mol fro cyclohexane. The beneficial a to the double bond stabilizing the molecule by aromatic
effect on the thermodynamics is explained by the well known delocalization.

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12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7

Similar observations than the ones from Cooper et al. evolving considering hydrocarbons with different struc-
were also made regarding bicyclic compounds. Variations tures and chemical composition, i.e. presence of various
are observed depending on the ring size (5 or 6) and the nature heteroatoms.
of the heteroatom. Incorporation of N, or less satisfactory O,
into the heterocyclic compound facilitates dehydrogenation.
Pyrene ( C16H10) and chrysene
The dehydrogenation of the compound containing hetero-
atom within the five membered ring is favored as compared
to the one with the heteroatom within the six member ring.
Full dehydrogenation was found impossible with compound
( C18H12) are compounds having the same
containing oxygen atom in six membered ring while
enthalpy of mono-dehydrogenation is very high. Their
computational work was supported by experimental work number of aromatic rings that are however configured
with reactions happening even at 110  C using Pd/C or Rh/C. differently: the later has kind of linear structure while the
An external substituent N outside the ring can be even former has a more compacted structure. Enthalpy of full
more effective than a ring N in lowering the enthalpy of dehydrogenation of the corresponding hydrogenated forms
dehydrogenation as shown by Clot et al. [67]. Calculated with two C substituted with two N: C14H24N2 and C16H28N2 (see
values of 16.1 kcal mol1 and 15.7 kcal mol1 were indeed Fig. 5) are about 19.1 and 15.8 kcal mol1 of H2. The disposition
of the rings has an impact on the dehydrogenation enthalpy.
Comparison of C14H24N2 and C16H26 (hydrogenated form of
reported for pyridine ( ) and aniline ( ) for pyrene), which have similar structures but incorporated ni-
trogen atoms in case of the first molecule, shows that the
presence of nitrogen will help in decreasing the enthalpy of
dehydrogenation by about 1 kcal mol1 of H2.
instance. The effects are reported to be approximately addi-
Tetrahydrothiophene, tetrahydrofuran and tetrahy-
tive for lowering the enthalpy of dehydrogenation with
dropyrrole have similar structure but different heteroatom S,
outside ring substituent N or with ring N atoms for however
O or N at the same position in the ring. Enthalpy of dehydro-
certain positions only like a 1,3-arrangement or 1,3,5-
genation is found to follow the following order: N<<S~O with
arrangement in an arene ring for instance. Two adjacent N
values of 40, 50 and 51 kcal mol1 of hydrogen respectively.
lone pairs in an arene would suffer mutual repulsion and two
adjacent NH2 groups in the 1,2-isomer would indeed clash
sterically.
Electron-withdrawing groups are reported to aid in
lowering the enthalpy of hydrogenation [68] while enthalpy of
Viability of organic hydrogen carriers
dehydrogenation is mentioned to be lowered for substituted
cyclohexanes with electron-donating groups or with the
Required characteristics for organic hydrogen carriers
presence of a conjugated external substituent [61]. This later
Organic liquid carriers suitable for hydrogen storage, to be
substituent must not be easily hydrogenated otherwise the
used on-board vehicle or at the fueling station should be
whole compound would no longer be readily dehydrogenated.
molecules that meet at least the following criteria:
Using DFT calculations the authors showed that for hydro-

genated indole derivatives ( ), placing a heteroatom A. Low enthalpy of dehydrogenation to enable low pro-
cessing temperature
B. Low volatility to avoid additional system for separation
within both rings ( ) or introducing an outside ring
with hydrogen
C. Reversibility with no significant degradation to allow
recycling
D. Liquid state at all stages of hydrogenation/dehydroge-
substituent NH2 ( )is the most powerful method nation to avoid mass transfer limitation as with solid
components, separation, transport issues…
E. High weight (9wt% H2) and volume (70gH2/L) storage
densities which is also preferable for transport cost
for lowering the enthalpy of dehydrogenation without
F. Low toxicity and environmental impact of starting
lowering the hydrogen content, but recognized that this is
material and dehydrogenated product
likely to tremendously increase the cost of synthesizing the
G. Low cost of compound synthesis to allow viable
compound. Side reactions involving cleavage of the CeNH2
economics.
bond might also occur as well with such compounds.

In case of use on-board vehicle, dehydrogenation temper-

Computational modeling data atures should be preferably below the temperature of PEM fuel
cell waste (knowing that operating temperatures are below
Preliminary computational work using DFT has been con- 200  C) without sacrificing on the dehydrogenation rates.
ducted to focus on how the enthalpy of dehydrogenation is Compounds possessing an optimal heat of hydrogenation

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7 13

Fig. 5 e Enthalpy of full dehydrogenation of the corresponding hydrogenated forms with two C substituted with two N.

would also be preferable to allow use of the waste heat for
dehydrogenation.
Based on the literature survey conducted the below Table 2
can be drawn showing the challenges the different kind of
organic hydrogen carriers are facing towards meeting the
above set criteria.
Assessment results of the different organic hydrogen car-
riers in terms of meeting the key criteria set will be discussed
below.
one of the polycyclic alkane compound (hydrogenated form of
coronene (C24H36) with 7 rings). Other compounds of the
cycloalkanes class exhibit a maximum theoretical hydrogen
amount of 7.1wt% (cyclohexane). Unless a very active and
selective catalyst is available the practical values should be
even lower as side reactions are expected along with partially
dehydrogenated products (in case of the polycyclic alkanes).
The heteroatom-containing hydrocarbons and ionic liquid
exhibit much lower hydrogen content.

Hydrogen content Physical properties: starting material and dehydrogenated

product
The hydrogen content seems to be the most challenging cri-
terion for all the different classes of organic hydrogen carriers. The cycloalkanes are the only compounds that are liquid
A maximum theoretical content of 7.4wt% H2 was obtained for at ambient conditions. Their dehydrogenated counterparts

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Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
14 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7

are also liquid making these compounds suitable for
transportation using conventional means (trucks, pipes).
Boiling points (melting points) of compounds like cyclo-
hexane or methylcyclohexane are 81  C (6.5  C) and 101  C
(126  C) and their dehydrogenated counterparts benzene
and toluene respectively have values of 80  C (5.5  C) and
111  C (93  C).
Polycyclic alkanes compounds like tercyclohexanes iso-
mers (containing three rings) have melting points ranging
from 51 to 161  C [69]. Their dehydrogenated counterparts
have melting point ranging from 58 to 212  C. Although data
were not available for hydrogenated forms of polycyclic al-
kanes having more than three rings in their structure, one can
guess that these compounds will not be liquid at ambient
conditions as well. Their dehydrogenated forms are however
solids in the conditions of interest.
Data for heteroatom-containing compounds with accept-
able hydrogen content like e.g. perhydro N-ethyl-carbazole
cited by Air Products and Chemicals, Inc., is also not available
but the dehydrogenated form N-ethyl-carbazole has a melting
point of 66  C.
Compound stability
The compound stability would be dependent on the oper-
ating conditions used during the hydrogenation/dehydro-
genation steps. Higher temperatures are usually required
for the endothermic dehydrogenation reaction while lower
temperatures are sometimes necessary to avoid decompo-
sition. A key factor is the catalyst which has to be designed
in such way to minimize as much as possible the side re-
actions like hydrogenolysis. It has been seen above that e.g.
the particle size of the impregnated metals has an impact
on the selectivity. It has also been seen that the structure of
the substrate itself has an impact on the final products. For
instance cyclohexane dehydrogenation would not give
other products than benzene while methylcyclohexane
would give small amount of methane and benzene in
addition to toluene. CeN or CeO cleavage reactions are
also observed during hydrogenation with heteroatom-
containing compounds.
Enthalpy of dehydrogenation
The hydrogenation of the organic carrier is assumed to be
done at the industrial scale using existing technologies and
though it is not as crucial as the dehydrogenation step which
is planned to be carried out either on-board the vehicle or at
the fueling station. Low enthalpy of dehydrogenation is then
important in order to perform this step at lower temperature
as possible for practical and economic reasons and also to
increase the thermodynamic efficiency of the energy storage
system. Among the classes of compounds that would have
low values is e.g. the heteroatom-containing class. Tempera-
tures of about 200  C were reported for different N-containing
hydrocarbons. Coking of catalyst might however occur more
easily with such kind of compounds. Other classes (except
ionic liquids) seem to require high temperature like for
methylcyclohexane (~320  C) to have satisfactory conversions.
Reactor configuration might help in shifting the equilibrium
conversion, like for instance using membrane reactors.
Toxicity and environmental impact
Cycloalkanes considered as hydrogen carriers and their
dehydrogenated products are components that are usually
found in the gasoline, diesel and jet fuel. Regulations are
however targeting compounds like benzene, classified as
hazardous air pollutant, with e.g. EPA requiring that, beginning
2011 refiners must meet an annual average gasoline benzene
content standard of 0.62 vol% on their gasoline nationwide [70].
Data are lacking for polycyclic alkanes. More information is
available for the corresponding dehydrogenated compounds
usually referred as polyaromatic hydrocarbons or PAHs. For
instance the PAHs of 2 or 3 ring groups such as naphthalenes,
fluorenes, phenanthrenes, and anthracenes are reported to
have toxicity which tends to decrease with increasing mo-
lecular weight [71]. These PAHs are usually used as in-
termediates in pharmaceuticals, agricultural, lubricating
materials, and chemical industries.
Some of the heteroatom-containing compounds are also
commonly used in the dye and pharmaceutical industry like
N-containing hydrocarbons acridine or quinoline.
Cost
For cycloalkane compounds like cyclohexane or methyl-
cyclohexane, their dehydrogenated counterparts benzene and
toluene can be readily available as raw materials from
naphtha refinery stream for instance. In a typical FCC light
naphtha stream about 3wt% of toluene and 4wt% of methyl-
cyclohexane are present. Toluene can also be produced in the
processes of making gasoline via a catalytic reformer or in an
ethylene cracker with a final separation (either via distillation
or solvent extraction) that takes place in a BTX plant. Cost of
cyclohexane or methylcyclohexane are reported to be about
1$/kg [72,73].
For polycyclic alkanes, their polyaromatic hydrocarbon
counterparts are found in coal tar or result from the hydro-
cracking refining process [48] for instance. Further processing
is needed to obtain these compounds and thus their cost is
expected to be higher than the ones of cycloalkanes. As an
indication, price of pyrene from Sigma Aldrich catalog is about
120$ for 10 g of sample while price of methylcyclohexane is
about 240$ for 1 L [74].
Heteroatom containing hydrocarbons would usually have
to be synthesized. A compound like 1, 10-phenanthroline
considered by Air Products and Chemicals Inc, may be pre-
pared by two successive Skraup reactions of glycerol with o-
phenylenediamine, catalyzed by sulfuric acid, and an
oxidizing agent, traditionally aqueous arsenic acid or nitro-
benzene [75]. Reported price in Sigma Aldrich catalog for such
compound is about 540$ for 100 g of sample. N-ethyl-carba-
zole which was another organic carrier also initially consid-
ered by Air Products and Chemicals Inc, has a reported price of
about 210$ for 500 g of sample [74].

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Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.167
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 7
Techno-economic analysis: methyl cyclohexane-toluene
system
Techno-economic and pre-feasibility of methyl cyclohexane
(MCH) -toluene system as hydrogen carrier is reported earlier
[76]. The pre-feasibility study was based on the production of
MCH using toluene hydrogenation using renewable hydrogen
in Saudi Arabia and its transportation to Japan for producing
on-site hydrogen at gas refueling station by dehydrogenation
of MCH. Further, the study also included with the dehydro-
genated by product, toluene is transported back to Saudi Ara-
bia. Based on above assumptions, a detailed techno-economics
is ported and compared with other approaches [76]. These
studies indicated that MCH system is one of the potential
hydrogen carriers for on-site hydrogen production and its
production cost is lower than other options considered in the
study. However, the production cost using MCH is higher than
centralized hydrogen production using natural gas with CO2
capture with hydrogen delivery via pipeline (this study did not
factor in capital costs of building LNG related infrastructure).
Conclusions
The following conclusions can be made from the literature
survey and preliminary in house molecular modeling that
have been carried out for assessing the feasibility of using
organic compounds as hydrogen carriers.
Different classes of compounds have been investigated in
the literature. Those are cycloalkanes, polycyclic alkanes,
heteroatoms-containing hydrocarbons and even ionic liq-
uids. In addition to experimental work where catalyst devel-
opment and reactor design were sought for efficient and
selective dehydrogenation of organic carriers, computational
modeling work had also been conducted principally to search
for compounds with low enthalpy of dehydrogenation.
Among the different compounds considered, the ones that
meet more or less the required physical, toxicity/environ-
mental, stability and cost criteria are within the cycloalkanes
class. The economic viability of using such compounds is
however pending to the releasable hydrogen content as the
maximum value is only about 7.2wt%.
Among catalysts usually cited for the dehydrogenation of
the organic compounds, noble metal supported ones and
mono or bi-metallic catalysts especially are having better
performances in terms of activity and selectivity. Although
the combination of catalysts and organic compounds will give
different reactivity and selectivity, the polycyclic alkanes and
heteroatom-containing hydrocarbons will usually be more
susceptible to side reactions during dehydrogenation forming
coke, additional partially dehydrogenated and decomposed
products as well. Different reactor configurations were
considered in pursuit of high conversions while limiting side
reactions.
Finally the preliminary computational modeling data
studies are in agreement with the ones found in the litera-
ture. Although heteroatom-containing polycyclic hydrocar-
bons are found to have low enthalpy of dehydrogenation
especially suitable for on-board dehydrogenation as mainly
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15
sought by the different research groups, their application as
organic carrier seems quite difficult in regards of their
hydrogen content, their physical properties and the cost of
synthesis.
Acknowledgments
The authors would like to thank one of the reviewers for the
constructive suggestions. Also, the authors would like to
acknowledge Saudi Aramco management for the permission
to publish this paper. C.F. Dean and O. R. Koseoglu are also
acknowledged for the fruitful discussions on refining
processes.
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