Article

pubs.acs.org/accounts

Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free

Hydrogen Economy
Patrick Preuster,† Christian Papp,‡ and Peter Wasserscheid*,†,§
†
Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058
Erlangen, Germany
‡
Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058
Erlangen, Germany
§
Forschungszentrum Jülich GmbH, Helmholtz-Institut Erlangen-Nürnberg for Renewable Energy (IEK-11), Egerlandstrasse 3, 91058
Erlangen, Germany

CONSPECTUS: The need to drastically reduce CO2 emissions will lead

to the transformation of our current, carbon-based energy system to a
more sustainable, renewable-based one. In this process, hydrogen will gain
increasing importance as secondary energy vector. Energy storage
requirements on the TWh scale (to bridge extended times of low wind
and sun harvest) and global logistics of renewable energy equivalents will
create additional driving forces toward a future hydrogen economy.
However, the nature of hydrogen requires dedicated infrastructures, and
this has prevented so far the introduction of elemental hydrogen into the
energy sector to a large extent. Recent scientific and technological progress
in handling hydrogen in chemically bound form as liquid organic hydrogen
carrier (LOHC) supports the technological vision that a future hydrogen
economy may work without handling large amounts of elemental
hydrogen. LOHC systems are composed of pairs of hydrogen-lean and
hydrogen-rich organic compounds that store hydrogen by repeated catalytic hydrogenation and dehydrogenation cycles. While
hydrogen handling in the form of LOHCs allows for using the existing infrastructure for fuels, it also builds on the existing public
confidence in dealing with liquid energy carriers. In contrast to hydrogen storage by hydrogenation of gases, such as CO2 or N2,
hydrogen release from LOHC systems produces pure hydrogen after condensation of the high-boiling carrier compounds.
This Account highlights the current state-of-the-art in hydrogen storage using LOHC systems. It first introduces fundamental
aspects of a future hydrogen economy and derives therefrom requirements for suitable LOHC compounds. Molecular structures
that have been successfully applied in the literature are presented, and their property profiles are discussed. Fundamental and
applied aspects of the involved hydrogenation and dehydrogenation catalysis are discussed, characteristic differences for the
catalytic conversion of pure hydrocarbon and nitrogen-containing LOHC compounds are derived from the literature, and
attractive future research directions are highlighted.
Finally, applications of the LOHC technology are presented. This part covers stationary energy storage (on-grid and off-grid),
hydrogen logistics, and on-board hydrogen production for mobile applications. Technology readiness of these fields is very
different. For stationary energy storage systems, the feasibility of the LOHC technology has been recently proven in commercial
demonstrators, and cost aspects will decide on their further commercial success. For other highly attractive options, such as,
hydrogen delivery to hydrogen filling stations or direct-LOHC-fuel cell applications, significant efforts in fundamental and
applied research are still needed and, hopefully, encouraged by this Account.

1. INTRODUCTION the only byproduct.3 If the applied hydrogen is produced from

The concept of using hydrogen as an energy carrier is not new.
As early as 1976, Jones postulated the use of hydrogen as
energy carrier not only to be desirable but inevitable on the
long-term.1 Since that time, numerous studies highlighting
various aspects of using hydrogen as an energy vector have
been published. These were summarized by Bockris in 2013 in
form of a historic record of scientific developments toward a
future hydrogen economy.2 The use of hydrogen as energy
vector has many advantages: (1) Combustion of hydrogen in
fuel cells or in combustion chambers typically liberates water as
renewable energy (e.g., by water electrolysis4) or without CO2
byproduct creation (e.g., by methane decomposition to carbon
and hydrogen5), a CO2-free energy system is possible. (2)
Hydrogen is characterized by a very high gravimetric energy
density. Its lower heating value is 33.3 kWh/kg or 120 MJ/kg−
no other energy carrier shows a higher gravimetric energy
density (see Figure 1).
Received: September 20, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.accounts.6b00474

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Figure 1. Energy density of various energy carriers in comparison: left side, volumetric energy density; right side, gravimetric storage density.
However, while the chemical industry produces and
consumes more than 60 million tons of hydrogen every
year,6 the introduction of hydrogen as energy vector is
struggling, mainly for two reasons: (1) Hydrogen has to be
produced from other forms of energy. This is different from our
previous understanding of energy carriers. Moreover, hydrogen
production from coal, oil, and gas (e.g., by steam reforming or
partial oxidation)7 liberates CO2 as byproduct. For example, 1
ton of hydrogen produced by methane reforming has been
reported to liberate more than 10 tons of CO2.8 In renewable
energy scenarios, hydrogen is expected to be produced by
electrolysis of water. However, this method of hydrogen
production is, at today’s gas and electricity prices, still more
expensive than hydrogen production from natural gas. While
production costs for 1 kg of hydrogen from electrolysis have
been reported to be around 3 € kg−1,9 the same amount
produced from methane is about half this cost, depending on
the local gas price. (2) It is complicated and costly to store and
transport large amounts of elemental hydrogen. As shown in
Figure 1, the excellent gravimetric energy storage density of H2
comes with an extremely low volumetric energy density under
normal conditions of only 0.01 MJ/L or 3 Wh/L. This is a
direct consequence of the low density of hydrogen under
ambient conditions (0.0898 g/L at 0 °C and 1 bar).10
Moreover, hydrogen is easily combustible with air in very
broad concentration ranges (Table 1). It is characterized by low
Table 1. Relevant Properties of Hydrogen for a Safe and
Secure Handling10,11
ignition limits in air (%) 4−75
ignition energy in air (mJ) 0.02
flame temperature (°C) 2045
boiling point (K) 20
diffusion coefficient in air (cm2 s−1) 0.610
ignition energy and high diffusion rates in gases, liquids, and
even solids. At room temperature, hydrogen shows a negative
Joule−Thomson coefficient thus heating up when expanded.
Consequently, the handling of elemental hydrogen requires
investment into specialized equipment and dedicated infra-
structures.
Numerous hydrogen storage technologies have been
investigated in the recent decades. They all target to increase
the volumetric energy content without compromising on
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gravimetric energy density.12 As indicated by the title of this
contribution, we will not consider in the following state-of-the-
art technologies to store and transport hydrogen in its
elemental form as either compressed hydrogen (cH2, 200−
700 bar)13 or cryogenic hydrogen (l-H2, −253 °C).14
Moreover, we will restrict our discussion to technologies that
offer the potential for storage and transport of hydrogen on the
TWh scale and thus may potentially act as backbone of a future
hydrogen economy. For this reason, we will also not treat
hydrogen storage in the form of physisorption or chem-
isorption to solids.15
This contribution deals with the scientific foundations and
recent progress of technologies that aim for chemical hydrogen
storage by binding hydrogen to hydrogen-lean molecules in
catalytic hydrogenation reactions. To act as a hydrogen storage
system, the so-formed hydrogen-rich molecules should enable,
at least in principle, release of the stored hydrogen in a catalytic
dehydrogenation to close the storage cycle. Two classes of
hydrogen-lean molecules are distinguished: (1) Hydrogen-lean
molecules that are extracted from the atmosphere or exhaust
gas mixtures, like CO2 or N2. They form, after catalytic
hydrogenation, the well-known bulk chemicals formic acid,16
methane,17 methanol,18 Fischer−Tropsch products19 (depend-
ing on the applied catalyst and process parameters during the
hydrogenation process) or ammonia,20 respectively. (2)
Hydrogen-lean organic liquids that enable fully reversible
catalytic hydrogenation/dehydrogenation cycles. For these
compounds the term liquid organic hydrogen carriers
(LOHCs) has been coined (in an earlier publication also the
term “liquid organic carriers” was used21).
Note that LOHC systems enable hydrogen storage without
binding or releasing other substances from or to the
atmosphere. Pure H2 is obtained from LOHC dehydrogenation
after appropriate condensation of the liquid, ideally high-boiling
carrier molecule. The hydrogen-rich LOHC compounds can be
stored for extended times without energy losses and trans-
ported over long distances using established energy transport
logistics for liquid fuels (e.g., pipelines, ships, trucks). Thus,
transition to a hydrogen economy using existing and
depreciated infrastructure appears feasible. In the following,
we will limit our contribution to hydrogen storage and handling
using LOHC systems. While earlier reviews on the topic have
given a broad overview of liquid organic and inorganic hydrides,
their specific properties, and related catalyst systems for
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Scheme 1. Schematic View on Hydrogen Storage Using the Dibenzyltoluene (H0-DBT)/Perhydrodibenzyltoluene (H18-DBT)
LOHC System
Scheme 2. Schematic Representation of the Most Relevant Reaction Steps in Hydrogen Storage Using the N-Ethylcarbazole
(H0-NEC)/Perhydro-N-ethylcarbazole (H12-NEC) LOHC System
hydrogen release,22 our contribution focuses on a narrow set of
most promising LOHC systems and covers the full range from
fundamental catalytic aspects to first demonstrator applications.
2. AROMATIC HYDROCARBONS AS HYDROGEN-LEAN
STORAGE MOLECULES
Historically, the first research activities toward hydrogen
storage using LOHC systems date back to the 1980s. The
first oil crises promoted research at the Paul Scherrer Institute
in Switzerland toward the use of nuclear power for mobility via
water electrolysis, hydrogen storage, and on-board fuel cells.
Already at these early times, the advantages of LOHC systems
vs battery technologies (e.g., higher energy storage capacities,
shorter refueling times) were recognized.23 All these early
studies focused on the LOHC system toluene (TOL)/
methylcyclohexane (MCH). This system has a hydrogen
storage capacity of 6.1 mass % hydrogen (1.55 kWh/L) and
shows a comparatively high heat of hydrogenation of −68.3 kJ/
mol H2. For thermodynamic reasons, this leads to harsh
conditions in dehydrogenation if full conversion to TOL is
desired (typical conditions for 99% MCH conversion are 320
°C at 1 bar H2).24 At such harsh conditions, the formation of
side products by dealkylation or coking was typically observed
with the applied heterogeneous Pt25 or Ni catalyst systems.26 At
both hydrogenation and dehydrogenation conditions, all
reactants of the TOL/MCH storage system are gaseous. Due
to the relatively low boiling point of all components, extensive
condensation and purification steps are required to isolate pure
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hydrogen from the product stream. Another problematic
feature of the TOL/MCH LOHC system is its low flashpoint
that is below the temperature of dehydrogenation. Despite
these practical disadvantages, the Japanese company Chiyoda
Corporation has developed the TOL/MCH LOHC system into
a demonstrated technology and has recently announced its
large-scale application for hydrogen and energy logistics.27
Attempts to overcome some of the specific problems of the
TOL/MCH hydrogen storage pair while sticking to pure
hydrocarbon systems for full compatibility with the fuel
infrastructure led later to a closer investigation of the
naphthalene/tetralin/decalin,28 as well as the benzyltoluene
(H0-BT)/perhydrobenzyltoluene (H12-BT) and dibenzylto-
luene (H0-DBT)/perhydro-dibenzyltoluene (H18-DBT), stor-
age systems (hydrogen capacity = 6.2 mass %).29 While
naphthalene is solid at room temperature (mp = 80 °C), the
LOHC systems using technical mixtures of benzyltoluene or
dibenzyltoluene regioisomers turned out very attractive
(Scheme 1). They combine very wide liquid ranges (mp =
−34 °C; bp = 390 °C in case of H0-DBT) with excellent
thermal robustness, low flammabilities and very favorable
toxicological profiles. Most importantly, these mixtures are
already in large-scale technical use as heat transfer oils (e.g.,
under the trade name “Marlotherm”) for many decades, which
guarantees industrial acceptance, full registration, technical
availability at low price, and well established quality standards
in their production.
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However, all pure hydrocarbon LOHC systems suffer from
their relatively high heat of hydrogenation. In the case of the
H0-DBT/H18-DBT, the latter has been determined exper-
imentally to be −65 kJ/mol H2.30 As a consequence, catalytic
dehydrogenation has to take place at temperatures above 250
°C. This high temperature level makes the utilization of “waste
heat” to drive the endothermic dehydrogenation reaction more
difficult.
3. N-HETEROAROMATICS AS HYDROGEN-LEAN
STORAGE COMPOUNDS
The development of LOHC systems with significantly lower
heat of hydrogenation/dehydrogenation has been pioneered by
researchers of the company Air Products and Chemicals who
carried out a systematic theoretical screening of LOHC
candidates according to this criterion.31 The best studied
system identified in this screening is N-ethylcarbazole (H0-
NEC)/dodecahydro-N-ethylcarbazole (H12-NEC) (hydrogen
capacity = 5.8 mass %) (Scheme 2).
The dehydrogenation enthalpy of this system is 50 kJ/mol
H2. To tackle one drawback of H0-NEC, namely, its melting
point of 68 °C, Stark et al. have investigated eutectic mixtures
of different N-alkyl substituted carbazoles and found melting
points of optimized H0-N-alkyl carbazole mixtures down to 24
°C.32 Another drawback of N-alkyl carbazoles and their
hydrogenated counterparts is the tendency to split off their
N-alkyl substituent at temperatures far below the decom-
position temperature of the heteroaromatic ring structure.33
LOHC systems with a dehydrogenation enthalpy similar to
N-ethylcarbazole are indole/indoline (ΔHdehyd = 52 kJ/mol
H2)34 and 1,2,3,4-tetrahydroquinoline/quinolone.35 These
systems have been studied using homogeneous and heteroge-
neous catalysts, and dehydrogenation temperatures were found
to be remarkably low. For indoline dehydrogenation, Jessop et
al. found 81% dehydrogenation to indole using a Pd on silica
catalyst at only 100 °C (reaction time 1 h).34 In the case of the
dehydrogenation of 1,2,3,4-tetrahydroquinoline, the applied
homogeneous Ir-complex was able to reach 100% dehydrogen-
ation over 20 h at 138 °C (reflux of the solvent p-xylene).35
The use of other N-based heteroaromatic/heteroalicyclic
LOHC systems (e.g., pyridines/piperidines or perhydronaph-
thyridines/naphthyridines) has been very recently summarized
in a review by He et al.36 In brief, the presence of nitrogen in
LOHC molecules always improves dehydrogenation thermody-
namics and kinetics. However, it also promotes thermal lability
and opens reaction pathways to undesired degradation
products.
4. ALTERNATIVE LOHC SYSTEMS
Even lower down is the hydrogenation/dehydrogenation
enthalpy for boron containing LOHC systems. Müller et al.
give 36 kJ/mol H2 for the dehydrogenation of 1,2-dihydro-1,2-
azaborine.37 Hydrogen release from molecular liquids contain-
ing nitrogen and boron has attracted significant attention since
the 1960s.38 While H2 release has been reported at temper-
atures below 100 °C, many systems are solids and stability at
storage conditions of up to 60 °C and in contact with moisture
is a concern.39 Moreover, the reversibility of these systems is a
grand challenge. To date, no such system has been reported
that can be recharged with molecular hydrogen. If all these
technical issues could be solved, still scalability of boron
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containing LOHC systems due to a limited world production of
boron would be an issue, as pointed out by Crabtree.40
An alternative, very interesting concept has been recently
presented by Milstein et al.41,42 It leaves the traditional track of
hydrogen storage by hydrogenation of aromatic compounds.
The authors report instead a LOHC-system based on 2-
aminoethanol that is catalytically converted into the cyclic
peptide glycine anhydride while liberating 4 mol of hydrogen
per mol of cyclic dipeptide formed (hydrogen capacity = 6.6
mass %).43 The reaction conditions are mild (105−135 °C)
with the homogeneous Ru-complex (preferably carrying PNN-
H ligands) applied. The same complex is also able to catalyze
the reverse hydrogenation reaction (10−70 bar H2 pressure,
110 °C). However, none of the reported storage cycles was
100% selective or complete even after prolonged reaction times
(12−48 h for each individual step). Still, this new approach is
highly remarkable and opens new avenues for future develop-
ments.
5. LOHC HYDROGENATION/DEHYDROGENATION
CATALYSIS
Catalysis plays a key role in hydrogen storage using LOHC
systems as both H0-LOHC hydrogenation for hydrogen
storage and Hx-LOHC dehydrogenation for hydrogen release
require promotion by suitable catalyst systems. Despite the fact
that a number of studies have applied homogeneous
catalysts,21,35,42,44−47 the practical need for decoupling storage
tank and reactor volume to independently adjust storage
capacity (in MWh) and release power (in MW) calls for
heterogeneous catalyst systems in large-scale storage applica-
tions. Therefore, we will restrict the following part to the
development of heterogeneous catalysts for LOHC hydro-
genation and dehydrogenation reactions.
5.1. Fundamental Aspects
While many applied studies have started with screening
commercial catalysts for LOHC transformations,27 efficient
catalyst optimization requires solid fundamental understanding.
To this end, the groups of Steinrück and Libuda have
investigated since 2011 the catalytic dehydrogenation of various
hydrogen-rich LOHC molecules on single crystalline surfaces
and supported model catalysts using a rigorous surface science
approaches, i.e. applying spectroscopic methods under ultra-
high vacuum (UHV) conditions.48 By combining synchrotron
radiation-based high resolution X-ray photoelectron spectros-
copy (HR-XPS), infrared reflection absorption spectroscopy
(IRAS), temperature-programmed desorption (TPD), molec-
ular beam experiments, and theoretical studies, these groups
were able to gain an unprecedented atomic/molecular-level
understanding of the relevant processes in LOHC dehydrogen-
ation catalysis. Some of the most instructive findings are
summarized in the following:
• In situ XPS during H12-NEC adsorption on Pt(111)33
and on Pd(111),49 followed by applying a heating ramp
revealed a reaction sequence that starts with the
desorption of H12-NEC multilayers followed by
dehydrogenation to H8-NEC through formation of a
central pyrrole unit. The latter dehydrogenates further to
H0-NEC. At even higher temperatures, a C−N scission
first forms carbazole before the LOHC molecule
disintegrates on the hot surface at even higher temper-
atures (Scheme 2).
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Scheme 3. Dehydrogenation of Dicyclohexylmethane (DCHM) on Pt(111) under the Conditions of a Surface Science
Experiment as Determined by a Combination of HR-XPS, TPD, NEXAFS, and IRAS

• Dehydrogenation catalysis of several perhydro-N-alkyl- molecules plays a crucial role for the high reactivity detected
carbazoles (with the alkyl groups being ethyl, propyl, or in surface science experiments.
butyl), compared on Pt(111) and on Al2O3-supported Pt 5.2. Applied Aspects of LOHC Hydrogenation
nanoparticles, showed no effect of the substituents on the
Hydrogenation of pure hydrocarbon aromatics with traditional
order of reaction steps and their onset temperatures.50
heterogeneous catalysts is performed in the chemical industry
• The undesired ethyl abstraction from H0-NEC to form on a million-ton-per-year scale, for example, benzene hydro-
high melting carbazole (mp = 245 °C) has been found to genation to cyclohexane for adipic acid production.55 In a
be a function of the Pt particle size. The structure similar manner the hydrogenation of H0-DBT is successfully
sensitivity of dealkylation was studied by HR-XPS on carried out using commercial Ru on AlOx catalyst (50 bar, 150
Al2O3-supported Pt model catalysts and Pt(111) single °C),29 and recent mechanistic studies have even elucidated the
crystals. On smaller, defect-rich Pt particles, the onset of hydrogenation order of the three aromatic rings applying 1H
dealkylation is shifted by 100 °C to lower temperatures NMR spectroscopy.56 The hydrogenation of carbazole
compared to large, well-shaped particles and a well- derivatives is also known in the literature but of significantly
ordered Pt(111) surface.51 less technical relevance so far. Already in the 1940s, Adkins et
• The dehydrogenation of dicyclohexylmethane (DCMH) al. have described the hydrogenation of different carbazole and
on a Pt(111) surface includes formation of a π-allylic indole derivatives using high temperatures and pressures (e. g.,
species coadsorbed with hydrogen (−70 to −10 °C), 200 bar H2, 260 °C).57 Following the seminal study by Pez et
followed by phenyl group formation and hydrogen al. at Air Products in 2006,31 a number of academic research
desorption at −10 to 60 °C, and finally, full dehydrogen- groups have significantly optimized the protocol for H0-NEC
ation (above 60 °C) accompanied by C−H bond scission hydrogenation. Table 2 gives an overview of applied conditions
at the methylene bridge (Scheme 3). The latter reaction and catalyst systems.
is a first unwanted decomposition step. Further heating
under the conditions of the surface science experiment Table 2. Overview of Various Catalyst Systems and Reaction
led to fragmentation of the diphenylmethane molecules Conditions for the Hydrogenation of N-Ethylcarbazole (H0-
on the surface already at 180 °C.52 NEC) as Described in Selected Publications
It is noteworthy that onset temperatures of catalytic active metal support temperature (°C) pressure (bar) refs
dehydrogenation or decomposition are always found much Ni 130−180 50−70 58
lower in the surface science experiments compared to real C/SiO2 130 70 59
conditions with the solid catalyst suspended in the LOHC Raney 120−230 50 60
medium. For example, the very low onset temperatures Ru 130 70 61
reported for dicyclohexylmethane under surface science AlOx 120−180 60−70 62−64
conditions (see above) is contrasted by the fact that no C 130 70 62
dehydrogenation activity is observed for such molecule with TiO2/SiO2 130 70 59
any Pt catalyst system at 1 bar hydrogen atmosphere below 200 Pt C 130 70 59
°C. Furthermore, decomposition of pure hydrocarbon LOHC
compounds observed under surface science conditions at 180
In brief, Ni, Ru, and Pt catalysts have been found suitable for
°C is typically not observed under real conditions below 350 °C
the hydrogenation of H0-NEC. Typical applied temperatures
to the same extent. Along the same lines, it has been found that
are between 120 and 230 °C, and hydrogen pressures are
the optimum temperature for H12-NEC dehydrogenation at
between 50 and 70 bar. Interestingly, the work of Ye et al.58
Pt(111) under surface science conditions is 110 °C,33 while
revealed indications for the mass transport of hydrogen being
optimum rates were found at 250 °C for the same reaction
the rate-determining step of the reaction. This is in contrast to
under real catalysis conditions.53 In order to close this
the finding by Wan et al., who described that the variation of
“temperature gap”, H12-NEC, otherwise volatile under UHV
stirrer speed under very similar conditions had no effect on the
was covalently linked to an imidazolium cation, forming a
observed reaction rate.63 The Ru-based hydrogenation catalyst
nonvolatile ionic liquid.54 In this way, it was possible to probe
was found to form H8-NEC as kinetically stable intermediate of
in situ the dehydrogenation of the “immobilized” and liquid
the H0-NEC hydrogenation reaction.62
H12-NEC close to equilibrium reaction conditions of real
heterogeneous catalysis by XPS and TPD. Interestingly, 5.3. Applied Aspects of LOHC Dehydrogenation
dehydrogenation was observed under these conditions at Also the dehydrogenation of cyclic aliphatic hydrocarbons is
identical reaction temperatures to the real catalysis experiment. well-known in the chemical and petrochemical industry. The
This demonstrates that the availability of free and reactive most important example is the so-called “platforming”, a
coordination sites in proximity to the adsorbed LOHC refinery process that converts alkanes into alkylated aromatics
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to boost the octane number of fuels. As indicated by its name,
the process uses Pt-containing catalysts to promote dehydro-
genation.65 Palladium and other metals have been also
described but their activity is generally significantly lower.66
MCH dehydrogenation is both an important reaction in the
platforming process and the key step in the hydrogen-release
using the TOL/MCH LOHC system. Therefore, a number of
studies have tried to improve lifetime, activity, and selectivity of
MCH dehydrogenation catalysts. Small additions of rhenium
have been found to enhance the stability of the catalyst.65
Moreover, doping with sulfur has shown beneficial effects.67
Furthermore, it has been shown that the active catalyst under
real conditions is not pure Pt but a carbon modified Pt−C
surface.68 Depending on the H2‑pressure, a balance between
formation and degradation of the carbon layer is established. At
hydrogen pressures below 1 bar, the catalyst deactivates much
faster due to cooking. Okada et al. have demonstrated that a
homemade Pt/AlOx dehydrogenation catalyst worked with
stable catalytic performance (LHSV = 2 h−1, T = 320 °C) with
99.9% toluene selectivity in MCH dehydrogenation for 3000 h
time on-stream.25 Also Ni catalysts have been found suitable for
MCH dehydrogenation. However, these catalysts are less active
compared to Pt and more prone to side product formation.69
Al-ShaikhAli et al. have very recently published a bimetallic
NiZn catalyst that reaches one-third of the MCH conversion of
a standard Pt catalyst (at 350 °C) with 90% selectivity to
toluene at high conversion.70 This is a quite remarkable result
compared to earlier reported Ni-based systems.
As described above, hydrogen storage in the benzyltoluene
(H0-BT)/perhydrobenzyltoluene (H12-BT) and dibenzylto-
luene (H0-DBT)/perhydrodibenzyltoluene (H18-DBT)
LOHC systems has significant advantages over the TOL/
MCH system, such as higher volumetric storage density, easier
hydrogen purification, and reduced toxicity. Brückner et al. have
studied the catalytic dehydrogenation of H12-BT and H18-
DBT using various commercial catalysts (310 °C, 1 bar H2) and
found that Pt on C and Pt on AlOx catalysts are by far more
active than the respective Pd analogues on the same supports.29
Different from dehydrogenation of pure hydrocarbon LOHC
systems, the dehydrogenation of nitrogen-containing alicyclic
compounds proceeds at lower temperatures due to their lower
reaction enthalpy. Here, we will restrict ourselves to the specific
case of H12-NEC dehydrogenation, as this is by far the best-
investigated compound. Table 3 gives an overview of catalyst
systems and reaction conditions that have been successfully
applied in the literature for this purpose.
In brief, H12-NEC dehydrogenation has been studied at 1
bar and at temperatures between 130 and 270 °C using various
active metals. At 270 °C, Peters et al. demonstrated
Table 3. Overview of Various Catalyst Systems and Reaction
Conditions for the Dehydrogenation of Perhydro-N-
ethylcarbazole as Described in Selected Publications
active temperature pressure
metal support (°C) (bar) refs
Ir homogeneous 150 1 44
Pd SiO2 150−170 1 71
AlOx 130−180 1 72
C 170 1 73
Pt AlOx 180−270 1 29, 72, 74
Ru AlOx 180 1 72
Rh AlOx 180 1 72
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dehydrogenation productivities of up to 10.9 g(H2) g(Pt)−1
min−1, which corresponds to a quite impressive Pt-based power
output of 22 kW g(Pt)−1.74 This performance was obtained
using a homemade egg-shell catalyst. H12-NEC dehydrogen-
ation was found to be heavily mass transfer influenced at
temperatures above 235 °C.
In full agreement with the surface science studies described
above, the dehydrogenation of H12-NEC proceeds in a
sequence of dehydrogenation and decomposition steps depend-
ing on the applied conditions. Yang et al. described, for
example, that the dehydrogenation of H12-NEC to H8-NEC
starts at Pd on AlOx already at 128 °C, while the
dehydrogenation of H8-NEC to H4-NEC requires a minimum
temperature of 145 °C, and complete dehydrogenation to H0-
NEC a temperature of 178 °C.72 The same study also
demonstrates that under the applied mild conditions only
0.003 mol % ethane (from the hydrodealkylation of the N-ethyl
group) is detected in the product mixture. Moreover, the
obtained product gas stream was claimed to be free of PEM fuel
cell poisons (PEM = proton exchange membrane). However,
even under these mild conditions, 2% of the NEC carrier
molecule was dealkylated to carbazole over 10 hydrogenation/
dehydrogenation cycles. The same group has also studied
systematically the activity of different metals in H12-NEC
dehydrogenation under comparable conditions and found the
reactivity order of Pd > Pt > Ru > Rh.73
6. APPLICATIONS AND OUTLOOK
Applications of the LOHC technology with potential to
contribute to a hydrogen-free hydrogen economy in the future
can be envisaged in the fields of energy storage, hydrogen
logistics, and hydrogen mobility.
For stationary energy storage, it is useful to discriminate
between grid and off-grid applications. In grid applications, the
storage unit is always connected to an energy supply or sink of
almost infinite dimension. The unit’s owner aims to fill the
storage with cheap energy at energy-rich times, while the unit
generates valuable energy in the form of electricity and heat at
energy-lean times. This concept is attractive for buildings,
business parks, or industrial sites if the energy price spread is
large enough, the yearly hours of energy surplus/shortage are
sufficiently high and the investment costs for the LOHC unit
are reasonable.75 Off-grid applications are economically more
attractive than on-grid applications as the electricity and heat
produced by the system does not compete at grid price level
but with other (usually more expensive) ways of off-grid energy
production, for example, a diesel generator. Examples for such
off-grid applications include tourist locations on secluded
islands, transmitting stations in the desert, or mining
exploration sites in the wilderness. Typical costs for electricity
from diesel generators in such locations are 0.6 €/kWh, which
allows to cover both the cost for renewable energy production
and the LOHC storage unit. In all attractive off-grid application
scenarios, the storage unit is embedded into an environment
with excess supply in renewable energy. However, temporal
energy demand does not fit the generation profile and
anticipated energy-lean times are too long to bridge the
resulting shortages with commercial battery systems. Figure 2
illustrates an example of off-grid power supply: Here, enough
sunlight is available in daytime to fill the LOHC hydrogen
storage and a heat storage system for overnight hydrogen
release from the LOHC system.
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research Article

Figure 2. LOHC-based unit for off-grid power supply: at energy-rich times, solar energy is used to operate photovoltaics and to charge both the
LOHC and the heat storage system.

Figure 3. LOHC demonstration unit at Fraunhofer IAO, Stuttgart: 100 kW dehydrogenation unit (horizontal vessel in the middle) heated by a
hydrogen burner (not visible behind the container) producing hydrogen for a 30 kW fuel cell (right in front). The total storage capacity of the unit is
1000 L of H18-DBT (tanks on the left) or 2.05 MWh based on the lower heating value (LHV) of the stored hydrogen.

A typical LOHC system for power storage involves the
following five elements: electrolysis, LOHC hydrogenation
unit, storage tanks, LOHC dehydrogenation unit, and fuel
cell.76 A recent important progress in stationary energy storage
is the so-called “OneReactor” concept77 that applies a
combined hydrogenation/dehydrogenation unit. This concepts
saves significant cost as only one reactor with its catalyst
inventory, piping, manifolds, and management system is
required. A great advantage of performing storage and release
in the same reactor is that the reactor is always at elevated
temperature. This greatly increases dynamics of the system as
heating up times of cold reactors are avoided. A requirement to
operate successfully the “OneReactor” is to have a catalyst
system or combination of catalysts at hand that works for both
hydrogenation and dehydrogenation with suitable activity and
excellent selectivity. To identify and further optimize such
catalyst systems is a very attractive research target.
G DOI: 10.1021/acs.accounts.6b00474
Energy and hydrogen logistics will play a key-role in an
increasingly renewable world as global regions with the highest
potential for renewable energy harvest are not identical to those
with the highest energy demand. A detailed evaluation of
LOHC-based energy and hydrogen transport has been recently
published based on two specific scenarios, namely, export of
renewable energy from Northern Africa (solar) and export from
Iceland (hydroelectric, geothermal, wind) to Germany.78 The
study concludes that energy transport via LOHC over long
distances is indeed quite promising. Compared to the transport
of compressed or liquid hydrogen, transport costs for LOHC-
based hydrogen are low, in particular due to the possibility to
use existing fleets of product tankers. Compared to electric
transmission, the fragmented energy delivery by dozens of
individual ships navigating in the open sea increases security of
supply. The additional storage function of the LOHC systems
allows for energy release at the time and at the location of
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
Figure 4. Process chain for operating a LOHC-based hydrogen filling station.
Figure 5. Schematic view of a direct LOHC fuel cell.
highest energy demand, a fact that adds significantly to the
economics of the transport path.
Figure 3 shows a very recently installed commercial
demonstrator for LOHC-based hydrogen logistics. This
demonstrator has been manufactured by Hydrogenious
Technologies GmbH, Erlangen,79 and installed at Fraunhofer
IAO, Stuttgart. The unit runs on H18-DBT that is delivered to
Stuttgart from Erlangen via road transport. The material is
charged in Erlangen using solar power, a PEM electrolyzer
(Siemens), and a LOHC hydrogenation unit (Hydrogenious).
The unit provides 30 kW power and is used as part of a micro-
smart grid80 to charge electric vehicles during the night at
Fraunhofer IAO, Stuttgart.
Note that from an actual economic viewpoint, it is not
favorable to convert hydrogen, stored and transported in
LOHC systems, back into electricity. In contrast, it is much
more attractive to use the stored hydrogen directly as fuel for
hydrogen mobility or in industrial applications. While 1 kg of
hydrogen (33.3 kWh LHV) provides 18.3 kWh electricity
(assuming a FC efficiency of 55%) resulting in a market value
of 2.2 € (assuming the German industrial electricity prize of
0.12 €/kWh), the market value of 1 kg of hydrogen at a
hydrogen filling station is between 9 and 12 €. Commercial
hydrogen delivery costs are between 5 and 55 €/kg depending
on purchase quantity, quality, and location. This price spread
gives an indication of the economic value of on-demand
H DOI: 10.1021/acs.accounts.6b00474
Article
delivery of hydrogen to various customers. Note that LOHC-
based hydrogen storage and transport is not restricted to green
hydrogen from water electrolysis but can also be based on
hydrogen from methane reforming or “waste” hydrogen from
chlor-alkali electrolysis processes.
LOHC-based hydrogen delivery to hydrogen filling stations
is a realistic technology target for the upcoming three to five
years. Major development targets deal with providing the
required hydrogen quality for fuel cell vehicles at low
investment into the LOHC dehydrogenation/compression/
purification unit. Options to provide the heat of dehydrogen-
ation at a hydrogen filling station include direct electrical
heating, burning of fuels (e.g., LPG or bioethanol), or heat
storage systems that are electrically heated from solar or wind
power at energy-rich times. Figure 4 shows the sequence of unit
operations that is required to operate such a hydrogen filling
station. As development goal for a future commercialization, it
is envisaged to operate the whole process chain in a 20 feet
container at the filling station (including the dispenser) and to
use either the existing fuel tanks of the station or a small tank
within the container for LOHC storage.
On a longer research perspective, also on-board hydrogen
generation on mobile platforms is a very attractive research
and development goal. Technical realization of this vision is
easier on heavy and large platforms, like ships or locomotives,
than on high performing small cars. On-board storage of the
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
diesel-like LOHC is straightforward, a double chamber tank
system is required to accommodate Hx-LOHC and H0-LOHC
in the same tank volume. During the refueling process, Hx-
LOHC is filled into the one chamber of the tank system, while
H0-LOHC is sucked off to empty the other tank chamber from
uncharged LOHC.81
For obvious reasons, the provision of the dehydrogenation
heat for hydrogen release is more challenging on mobile
platforms than for stationary applications. Some options, like
heat supply from a heat storage system, are impractical for
mobile applications. Basically, the following options remain:
• Electrical heating using the electricity produced by the
on-board FC is an obvious option, but it comes with the
shortest driving range. The reason is that the limited
efficiency of the FC enters twice the overall efficiency
calculation, for driving and for producing the electricity
equivalent for heating the endothermic dehydrogenation.
• On-board hydrogen combustion is the second option to
produce the dehydrogenation enthalpy. At least 27% of
the released hydrogen has to be burned for full hydrogen
release in the case of H18-DBT (assuming no heat
losses). Comparison with Figure 3 illustrates that
significant progress in power density of the conversion
units is needed to make this technology an option for on-
board energy delivery on road vehicles.
• Combining the endothermic LOHC dehydrogenation
reaction with metal hydride hydrolysis as an exothermic
hydrogen release process has been proposed by Jessop et
al.82 While the idea appears appealing on the first view,
handling of solid metal hydrides/oxides, controlled heat
release from these systems, and their on-board
regeneration is very challenging.
• Heat integration between the exothermic fuel cell
operation and the LOHC dehydrogenation is another
option. As only PEM fuel cells fulfill the dynamic
requirements for mobile applications, this requires on the
first view LOHC dehydrogenation at the temperature
level of PEM fuel cells (up to 180 °C).83 An alternative,
very interesting but still very immature option is the on-
board operation of a Direct-LOHC-fuel cell (D-LOHC-
FC, Figure 5). Conceptually, this option has the striking
advantage that LOHC dehydrogenation and fuel cell
operation takes place in one device and at one catalyst
thus saving both space and investment. In addition, the
D-LOHC-FC does not liberate elemental hydrogen from
the LOHC but only protons, a process that can take
place at the low temperatures of typical PEM fuel cells.
Assuming that a D-LOHC-FC could reach one day the
same hydrogen efficiency as today’s hydrogen cars (0.7
kg H2 consumption per 100 km driving range), a car with
an 80 kg LOHC tank content (carrying a LOHC system
with 62 g of releasable H2/kg LOHC) would offer a
maximum driving range of ca. 700 km.
Note that the D-LOHC-FC process handles no elemental
hydrogen. Liquid, hydrogen-charged LOHC is pumped into the
device, and electric power is delivered together with uncharged
LOHC. Without doubt, efficient D-LOHC fuel cells would
bring the vision of hydrogen-free, but still hydrogen-based
energy converters much closer. But is this feasible? Already in
2003, Kariya et al. reported on the successful operation of a D-
LOHC-FC based on cyclohexane.84 The authors claim good
performance (open circuit voltage = 920 mV, maximum power
I DOI: 10.1021/acs.accounts.6b00474
Article
density = 14−15 mW cm−2). In contrast to direct methanol fuel
cells,85 the problem of undesired crossover of the fuel through
the membrane is reduced. D-LOHC-FC concepts operating on
N-containing LOHC systems were later published by Driscoll
et al.86 (using indoline and N-benzylaniline as fuels) and Ferell
et al.87 (using mainly H12-NEC and perhydrofluorene as fuels).
A thermodynamic evaluation of several different LOHC fuels
for direct fuel cell concepts has been presented by Arauja et
al.88 Also the patent literature covers D-LOHC-FC concepts.89
However, significant problems are still encountered on the
way to making D-LOHC-FC fuel cells efficient and robust.
These include compatibility issues between the membrane and
the LOHC materials, problems of electropolymerization, and
generally low power outputs due to the slow kinetics. It is so far
unpredictable whether the power output of D-LOHC-FCs will
ever be sufficient to enable their reasonable use on mobile
platforms. Therefore, the theoretical possibility of operating D-
LOHC fuel cells on vehicles one day should not prevent
anybody from establishing 700 bar hydrogen filling stations
today for the next decade of hydrogen mobility. Having said
this, it is also true that the topic of D-LOHC-FC is fascinating
with many interesting challenges for fundamental research.
In conclusion, it appears from the current state of knowledge
that LOHC systems offer significant potential to become a
leading concept among the different options of chemical energy
storage. Different from storage options for elemental hydrogen,
the concept enables storage and transport of very large amounts
of energy in existing infrastructures. Different from other
“power-to-X” concepts, no additional reactants have to be
isolated from gas mixtures or the atmosphere and very pure
hydrogen can be provided from LOHC storage systems. The
scientific and technological progress of the last five years toward
robust LOHC systems and efficient hydrogen storage/hydro-
gen release processes is very encouraging and supports the
vision of a future hydrogen economy in which much of the
applied hydrogen may be bound to high boiling liquids. This
would not only facilitate a stepwise transition into the hydrogen
economy, it would also make this economy look similar to our
current energy system. This is a very relevant point to gain
public acceptance for this kind of breakthrough toward a more
sustainable energy system.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: wasserscheid@crt.cbi.uni-erlangen.de.
ORCID
Peter Wasserscheid: 0000-0003-0413-9539
Notes
The authors declare the following competing financial
interest(s): Peter Wasserscheid is co-founder of the company
Hydrogenious Technologies GmbH (www.hydrogenious.net)
that is mentioned in the Account.
Biographies
Patrick Preuster is group leader at the Institute of Chemical Reaction
Engineering of the Friedrich-Alexander-University Erlangen-Nurem-
berg (FAU) (www.crt.cbi.fau.de) for energy conversion technologies
using LOHC systems. His particular research focus is on catalytic
conversion units with high power density.
Christian Papp is group leader of the “surface and in situ spectroscopy
group” at the Chair of Physical Chemistry II at the Friedrich-
Acc. Chem. Res. XXXX, XXX, XXX−XXX
Accounts of Chemical Research
Alexander-University Erlangen-Nuremberg (FAU). His current
research focuses on the fundamental understanding of surface
processes on the atomic and molecular level.
Peter Wasserscheid heads the Institute of Chemical Reaction
Engineering of the Friedrich-Alexander-University Erlangen-Nurem-
berg (FAU) since 2003. In addition, he acts as founding director of the
Helmholtz-Institute Erlangen-Nuremberg for Renewable Energies
(www.hi-ern.de) and as director of the IEK-11 at the Forschungszen-
trum Jülich (www.fz-juelich.de) since 2013. He is cofounder of the
company Hydrogenious Technologies GmbH (www.hydrogenious.
net) that is mentioned in the article.
■
ACKNOWLEDGMENTS
The authors thank Prof. Hans-Peter Steinrück, Prof. Jörg
Libuda, Prof. Wolfgang Arlt, Prof. Eberhard Schlücker, Dr.
Andreas Bösmann, Dr. Daniel Teichmann, Dr. Caspar Paetz,
Dr. Berthold Melcher, and Dr. Martin Schneider for fruitful
discussions and helpful advice. Moreover, the authors thank the
Energie Campus Nürnberg, the Bavarian Hydrogen Center and
the German Science Foundation through its Cluster of
Excellence “Engineering of Advanced Materials (EXC 315)”
for financial support. C.P. wants to thank H.Z.B. for the
allocation of synchrotron beamtime.
■
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L DOI: 10.1021/acs.accounts.6b00474
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