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Recent Advances in Liquid Organic Hydrogen Carriers: An Alcohol-

Based Hydrogen Economy
Vinita Yadav, Ganesan Sivakumar, Virendrakumar Gupta, and Ekambaram Balaraman*
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ABSTRACT: Energy storage and the use of abundantly available

feedstock without contributing to the carbon footprint are two
significant global challenges. In this regard, the development of
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high-performance, low-cost, sustainable, and environmentally

friendly energy storage and production systems is crucial to fulfill
the growing energy demands of the current society. The use of
hydrogen will diversify energy sources as it significantly reduces
greenhouse gas emissions and environmental pollution during
energy conversion. Although the hydrogen economy is quite
beneficial, hydrogen storage is still very challenging, and the
existing methods suffer from a lot of problems and drawbacks. The
conventional liquefaction and compression hydrogen storage
technologies are associated with several challenges, including low storage density, boil-off losses, relatively high costs, and safety
and transportation concerns. In recent years, liquid organic hydrogen carrier (LOHC) systems have attained a lot of importance as a
substitute for the traditional storage methods. Hydrogen storage and transport using LOHCs are based on two-step cycles, such as
(i) loading/storage of hydrogen by catalytic hydrogenation of H2-lean compounds and (ii) unloading/releasing hydrogen by
dehydrogenating the resulting H2-rich liquids. Since alcohols are widely accessible from various industrial processes or even from
biomass-derived precursors, the catalytic acceptorless dehydrogenation of alcohols is an attractive approach for future hydrogen
storage applications. Hence, the catalytic dehydrogenation-hydrogenation of alcohols can be used for the development of alcohol-
based LOHC systems which are economical, safe, and easy to handle. Further, they are similar to crude oils under ambient
conditions and thus are suitable for use in the current energy infrastructure. This Review covers several essential aspects of these
developing efficient and abundantly available LOHC systems for efficient hydrogen storage and transport applications. Additionally,
reversible LOHC systems based on the catalytic dehydrogenation-hydrogenation of alcohols and their corresponding carbonyl
compounds have been discussed.
KEYWORDS: alcohol, acceptorless dehydrogenation, dehydrogenative coupling, homogeneous catalysis, hydrogen, hydrogenation, LOHCs

■ INTRODUCTION
The rapid exhaustion of fossil fuels, anthropogenic emissions,
and ever-increasing energy consumption has led to an
increasing interest in the future energy system based on
renewable resources. Indeed, renewable energy sources, such as
wind, solar, geothermal, and biomass have attracted consid-
erable attention as alternatives to fossil fuels. However, some of
these sources, namely, wind and solar, are naturally
intermittent and fluctuating. Hence, it is necessary to find
alternative energy sources that can fulfill our future energy
demands. In this context, hydrogen is considered a clean and
efficient energy carrier because of its high energy content (120
MJ/kg) and clean-burning properties compared with fossil
fuels (Table 1).1−3 As an energy carrier, hydrogen can be used
for various fuel cell applications, such as mobile, stationary, and
portable power applications, without any greenhouse gas
emissions.4,5 Utilization of hydrogen as an energy source and
carrier is not a new concept and was recommended several
decades ago. In 1971, Jones initially proposed that liquid
hydrogen could replace fossil fuels in the 21st century.6 Later,
Salzano, Momirlan, and Bockris independently described a
hydrogen fuel economy and hydrogen storage concepts.7−9
Despite hydrogen’s potential as a clean and efficient energy
carrier, the production, storage, delivery, and end-use of the gas
pose significant challenges. Hydrogen is primarily produced
from fossil fuels such as natural gas and coal. However, in
recent years, renewable and sustainable energy sources have
shown considerable potential in hydrogen production. For
example, photocatalytic, thermochemical, or electrolytic water
Received: July 21, 2021
Revised: November 11, 2021
Published: November 23, 2021

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Table 1. A Comparison of the Energy Contents of Different
Fuels1
sample no. fuel energy content (MJ/kg)
1 molecular hydrogen 120
2 liquefied natural gas 54.4
3 propane 49.6
4 aviation gasoline 46.8
5 automotive gasoline 46.4
6 automotive diesel 45.6
7 ethanol 29.6
8 methanol 19.7
9 coke 27
10 wood (dry) 16.2
splitting into hydrogen (H2) and oxygen (O2), and electricity
from wind, solar, geothermal, or biomass are also currently
used to produce hydrogen.10−13
Despite extensive progress toward hydrogen production, the
storage and transportation of hydrogen have several
limitations, including a low volumetric energy density
(0.0108 MJL−1); safety issues; and the cost of cryogenic,
high-pressure compression cylinders or tanks.14−18 It is
therefore highly desirable to develop new methods for
convenient transportation and storage of hydrogen. Over the
past decades, many types of hydrogen storage technologies
have been investigated. For instance, hydrogen adsorption as
metal hydrides, in metal−organic frameworks (MOFs), and in
nanostructured materials have been studied.19−22 However,
these methods are limited by low hydrogen storage capacities
(HSCs), harsh conditions, high cost, and low energy efficiency.
The storage of hydrogen in chemical bonds of tiny organic
molecules, particularly organic liquids, is an appealing avenue
for future hydrogen carrier systems. Methanol,23 form-
aldehyde,24 and formic acid25 based hydrogen carrier systems
have been gaining considerable attention in the past few years.
The simplest alcohol, methanol, is emerging as a potential
candidate for an organic hydrogen carrier because of its 12.6 wt
% hydrogen content, ease of handling, and convenient
production of hydrogen .26 The dehydrogenation of aqueous
methanol is a three-step process. Initially, formaldehyde is
formed via dehydrogenation of methanol; then hydration of
formaldehyde yields methanediol, which again undergoes
dehydrogenation to afford formic acid; and the final step
results in CO2 production from formic acid (Scheme 1). This
Scheme 1. Description of the Basic Steps Involved in the
Dehydrogenation of Aqueous Methanol
overall process releases three molecules of hydrogen and CO2.
Similarly, formaldehyde and formic acid also release CO2 by
dehydrogenation. Although these hydrogen carrier systems are
quite promising, they suffer from several drawbacks, including
the release of CO2 from methanol and formaldehyde, toxicity,
and the low hydrogen storage capacity of formic acid (4.4 wt
%). In the context of environment viability, the hydrogen
carrier systems should have an HSC of 5.0 and 6.5 wt %,
respectively, set by the European Union and the U.S.
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government.27,28 Moreover, the H2 released from these
compounds cannot be efficiently reloaded since the liquid
carrier gets consumed. However, in recent decades, incredible
findings and significant milestones have been achieved in the
catalytic hydrogenation of CO2 to methanol both under
homogeneous and heterogeneous catalytic conditions (see
Supporting Information).29−32 Indeed, capturing the CO2 and
converting it to methanol can reduce the carbon footprint and
environmental feasibility of utilization.
An alternative hydrogen carrier system that has gained much
attention is the liquid organic hydrogen carrier (LOHC). By
definition, LOHCs are liquids or low-melting solids which
undergo reversible hydrogenation and dehydrogenation in the
presence of a suitable catalytic system. LOHCs are compatible
with present transport and refueling infrastructures and permit
high gravimetric and volumetric hydrogen storage under
ambient conditions. The LOHC system consists of a pair of
hydrogen-lean and hydrogen-rich organic compounds. Hydro-
gen is stored by converting H2-lean organic compounds to H2-
rich organic compounds in the catalytic hydrogenation
reaction, whereas the reverse dehydrogenation reaction of
H2-rich systems results in hydrogen release.33,34 This overall
process is reversible, and only hydrogen is released. The
LOHC concept is schematically illustrated in Scheme 2.
Although several hydrogenation and dehydrogenation reac-
tions of organic compounds are reported in the literature,35−37
there are certain requirements for these organic compounds to
become efficient LOHC systems:
High hydrogen storage capacity (volumetric and
gravimetric storage capacities >56 kg/m3 and >6 wt %,
respectively).
Low production cost and unlimited availability for a low
price.
Compatibility with existing energy infrastructure.
All compounds should have low melting point (<−30
°C) so that the use of external solvents can be avoided.
The high boiling point (>300 °C) of the LOHC system
is necessary to simplify hydrogen purification by
condensation.
Should be durable to undergo selective hydrogenation
and dehydrogenation for more cycles.
The LOHC compounds should be safe and nontoxic,
with high toxicological and eco-toxicological profiles
during transportation and usage.
Several promising LOHC systems based on hydrocarbons
and N-heterocycles, such as decalin-naphthalene, methylcyclo-
hexane-toluene, N-ethylcarbazole and perhydro-N-ethylcarba-
zole, 2-methyl-1,2,3,4-tetrahydroquinoline, and 2,6-dimethyl-
decahydro-1,5-naphthyridine have been reported.4,17,37−40
However, most systems have limitations, including high
hydrogen pressure and temperatures requirements for hydro-
genation and dehydrogenation reactions, low HSCs, and high
LOHC costs.
Since alcohols are easily manageable, inexpensive, and
widely available from various industrial processes and even
from renewable resources like lignocellulose biomass, they are
a good candidate for hydrogen storage applications.41,42
Alcohols undergo catalytic dehydrogenation to produce
carbonyl derivatives as hydrogen-lean byproducts, which can
be converted into the initial alcohols by hydrogenation.
Further, the dehydrogenation of alcohols can be performed
at lower temperatures as compared with N-heterocycles.
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Scheme 2. Schematic Representation of Hydrogen Storage Concept Using LOHC Technology
Hence, alcohols are exciting candidates for sustainable
hydrogen production that can also act as rechargeable liquid
organic hydrogen carriers (LOHCs). This Review will discuss
transition-metal catalyzed acceptorless dehydrogenation of
bioalcohols from the perspective of hydrogen storage in
alcohols. Additionally, reversible LOHC systems have been
discussed with various catalytic dehydrogenation-hydrogena-
tion of alcohols and their corresponding carbonyl compounds.
■
ACCEPTORLESS DEHYDROGENATION OF
ALCOHOLS
The dehydrogenation of alcohols has been a widely explored
catalytic process from the beginning of the 21st century. Both
noble- and base-metal-based various homogeneous catalysts
have been investigated to efficiently dehydrogenate alcohols to
aldehydes, ketones, carboxylic acids, or esters. In acceptorless
alcohol dehydrogenation (AAD), alcoholic precursor under-
goes dehydrogenation, which results in the evolution of
hydrogen molecule is quite interesting. Since reverse hydro-
genation of these aldehydes, esters and carboxylic acids are also
widely explored using the same or different catalytic systems,
reversible acceptorless dehydrogenation/hydrogenation reac-
tions could be utilized as promising hydrogen storage systems.
Biomass-derived alcohols (methanol, ethanol, and polyols) are
potential candidates for hydrogen storage applications due to
their relatively high hydrogen content (Scheme 3). Moreover,
liquid alcohols can be utilized directly as a fuel by the existing
transportation infrastructure.
Scheme 3. Alcohol Mainly Used in Hydrogen Storage
Applications
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As discussed earlier, methanol has a high hydrogen storage
capacity and can be a good candidate for hydrogen storage
applications. The dehydrogenation of aqueous methanol
results in gaseous product (CO2), whereas anhydrous
methanol leads to formaldehyde and methyl formate (MF).
In the case of water contamination, formic acid and CO2 are
also produced as minor products. In 1985, the Maitlis group
reported the dehydrogenative transformation of methanol to
methyl formate by using 0.03 mol % of [Ru(PPh3)3Cl2]
catalyst at 150 °C for 18 h.43 Mechanistic studies on methanol
dehydrogenation with these types of catalysts indicated that
the presence of bulky and poor-electron-donating ligands could
accelerate the reaction rate.44 Further, the research group of
Saito used [Ru(OAc)Cl(PEtPh2)3] as a catalyst along with
acetic acid as an additive at 66 °C for this transformation and a
TON of 34 was obtained after 90 days.45 On the basis of
several experimental studies and the mechanism postulated by
Dobson and Robinson for the dehydrogenation of alcohols,46
Saito and co-workers proposed the mechanism for the
formation of formaldehyde from methanol by dehydrogen-
ation47 (Scheme 4). In 1988, Cole-Hamilton’s research group
reported the dehydrogenation of alcohol using [RuH2(N2)-
(PPh3)3] complex with the help of a base under light
irradiation at 150 °C.48,49 In addition to alcohols, diols,
polyols, methanol, and ethanol were also successfully
dehydrogenated with a turnover of 37 and 210 h−1,
respectively. The reaction mechanism proceeds via the
formation of ruthenium anionic species followed by β-hydride
elimination led to trihydrido species and the corresponding
carbonyl compound. Further, the hydrogen abstraction from
another alcohol molecule results in the formation of
[RuH2(H2)(PPh3)]. Finally, the catalytic loop completes
with the evolution of molecular hydrogen (Scheme 5). In
1990, another example of methanol dehydrogenation to methyl
acetate was reported by Shinoda and Yamakawa.50
They used a bimetallic Ru(II)−Sn(II) complex [Ru-
(SnCl3)5(PPh3)]3− and MeOH/MeNO2 (1:1) solvent mixture
under inert atmosphere at 65 °C, which showed low catalytic
activity and a turnover number of only 15.7 was obtained after
100 h. Mechanistic studies revealed that the rate-determining
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Scheme 4. Proposed Mechanism for Methanol
Dehydrogenation46
Scheme 5. Proposed Mechanism for the Dehydrogenation
of Alcohols Using [RuH2(N2)(PPh3)3] Complex48
co-workers developed another molecularly defined catalytic
system [CpRu(PPh3)2(SnF3)] based on bimetallic Ru/Sn site.
The complex [CpRu(PPh3)2(SnF3)] showed TONs up to 120
under similar reaction conditions (MeOH/MeNO2 (1:1)
solvent mixture at 140 °C). The improved activity might be
attributed to the fluoro-containing ligands compared to
chloride and bromide analogs as fluorine is more electro-
negative, which increases positive charge on the ruthenium
atom.52 Further, in the rate-determining step (β-hydrogen
abstraction), heterolysis of C−H bond might be facilitated by
the formation of intramolecular hydrogen bond, could also
contribute to the increased activity in the fluoro derivatives.
There is much potential research in aqueous-phase methanol-
reforming reactions that have been studied in recent years (see
Table 2, the catalyst for dehydrogenation of methanol). Since
many reviews have focused on the aqueous-phase reforming of
methanol,23,53 such topics are not included.
Ethanol is another promising candidate for use as a LOHCs
due to its high hydrogen output, abundant, economical, and
easy accessibility from renewables. Previously, the generation
of hydrogen from ethanol had been studied.47,48 Since ethanol
is, apart from methanol, an extremely challenging substrates
because of its relatively high energy barrier, a stable catalyst
system is required for its dehydrogenation. Further, the
dehydrogenation of ethanol can result in other side reactions,
lowering the reaction efficiency.54 The selection of a suitable
reaction condition is essential in the dehydrogenation of
ethanol. Indeed, ethanol dehydrogenation can lead to three
different products such as acetaldehyde (via AD), ethyl acetate
(via ADC), and acetic acid (Scheme 6).

Scheme 6. Ethanol Dehydrogenation Routes

In 1977, Dobson and Robinson used the ruthenium and

step is the dehydrogenation of methanol to formaldehyde.
Further, it was presumed that the Ru(II)−Sn(II) bimetallic site
catalyzes the formation of acetic acid by isomerization of
methyl formate through a four-center interaction of soft Ru(II)
and hard Sn(II) with soft CO group and hard -OMe group
of methyl formate, respectively. Finally, this leads to migration
of the methyl group (from O to C).51 In 2000, Gusevskaya and
osmium complexes [M(OCORF)2(CO)(PPh3)2] (M= Ru, Os,
RF = CF3, C2F5, or C6F5) for the synthesis of various aldehydes
and ketones from primary and secondary alcohols respectively
via the dehydrogenation reaction.47 The dehydrogenation
reaction was carried at reflux temperatures in the presence of
12 equiv of trifluoroacetic acid to enhance the reaction. For the
primary alcohols, an initial rate of dihydrogen elimination
increases with the boiling point and ranges from 0.0075 mol
s−1 (mol of catalyst) −1 for ethanol to 2.27 mol s−1 (mol of
catalyst)−1 for benzyl alcohol. The catalytic cycle proposed
involves solvolysis of the catalyst and generates the

Table 2. Selected Catalytic Systems Used in the Dehydrogenation of Anhydrous Methanol

catalytic system solvent additive temp (°C) reaction time (h) TON TOF (h−1)
[Ru(PPh3)3Cl2] MeOH − 150 18 65 3.6
[Ru(OAc)Cl(PEtPh2)3] MeOH AcOH 66 90 34 0.4
[RuH2(N2)(PPh3)3] MeOH NaOH 150 2 74 37
[Ru(SnCl3)5(PPh3)]3− MeOH/MeNO2 − 65 100 15.7 0.15
[CpRu(PPh3)2(SnF3)] MeOH/MeNO2 − 140 40 120 3

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corresponding M-alkoxide species [M(OAlk)(OCORF)(CO)-
(PPh3)2] followed by β-hydride elimination to generate the
respective aldehyde (or ketone) and form the metal hydride
complex [MH(OCORF)(CO)(PPh3)2]. Further, the trifluoro-
acetic acid reacts with the hydride complex to regenerate the
catalysts and liberate dihydrogen. Later, Rybak and Ziółkow-
ski55 and Jung and Garrou56 independently tried to regenerate
Dobson and Robinson experimental results. However, short-
range alcohols like ethanol, isopropanol, and n-butanol
achieved lower conversions under comparable reaction
conditions using the ruthenium acetate complex. Jung and
Garrou explained that the poor activity and short catalyst
lifespan are due to its thermal decomposition and loss of
trifluoroacetic acid under the catalytic reaction conditions.
Hulshof and co-workers also reported the catalytic acceptorless
dehydrogenation of alcohols into aldehydes and ketones using
the same Robinson catalyst.57 Using 1 mol % catalyst and 12−
18 equiv of trifluoroacetic acid (with respect to catalyst),
various primary and secondary alcohols were dehydrogenated
selectivity to the respective carbonyl compounds in a short
reaction period at 130 °C. However, compared with Dobson
and Robinson’s work, conversion and selectivity obtained from
the dehydrogenation of primary alcohols were not appreciated.
This is attributed to other potential side reactions like aldol
condensation and decarbonylation of the aldehyde intermedi-
ate. Despite these encouraging earlier results, considerable
advances in simplified catalyst systems, stabilities, and activities
were still required for efficient hydrogen production. In 2007,
Beller’s research group reported the dehydrogenation of
isopropyl alcohol using Ru(II) catalytic system.58 Using
[RuCl2(p-cymene)]2 catalysts along with tetramethylethylene-
diamine (TMEDA), excellent catalyst stability (>250 h) and
high turnover frequencies (TOF) up to 519 h−1 were achieved
for the AD of isopropyl alcohol. Further, the same catalyst
system was used for the dehydrogenation of ethanol, obtaining
a TOF of 7.6 h−1 after 2 h. Subsequently, the Beller group also
reported a combination of [RuH2(PPh3)3CO]/PNPiPr catalytic
system for more efficient hydrogen production from ethanol
and isopropyl alcohol under neutral conditions (Scheme 7).59
Scheme 7. Ru-PNP Complex for the Efficient
Dehydrogenation of Alcohols to Aldehydes or Ketones59
The in situ generated ruthenium catalytic system showed
excellent reactivity in the dehydrogenation of isopropanol and
ethanol under mild conditions with a TOF (after 2 h at 100
°C) of 8382 and 1483 h−1 respectively. In 2012, Gusev60 and
Beller61 groups independently reported the efficient hydrogen
generation from ethanol and converted it to ethyl acetate
through the ADC (Scheme 8). Under very similar conditions,
both the ruthenium catalysts 1 and 2 efficiently catalyze the
dehydrogenative coupling of ethanol with excellent TONs
around 15 000 and 17 000, respectively. Also, the product ethyl
acetate was obtained in a close range (77% and 83% yields,
respectively). Catalyst 2 is air-stable, and the reaction was
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Scheme 8. Ru-PNP Complexes for Efficient
Dehydrogenation of Ethanol to Ethyl Acetate54,60,61
performed under an ordinary atmosphere. Moreover, Beller co-
workers have reported another method for effective hydrogen
generation from aqueous ethanol and bioethanol catalyzed by a
Ru(II)-complex, [Ru(H)(Cl)(CO)(iPr2PEtN(H)EtPiPr2)]
(3).54 Using this aliphatic Ru-pincer catalyst in the presence
of 8 M NaOH at 90 °C, a TON of 1770 after 1 h was achieved.
Aqueous ethanol dehydrogenation proceeded with good
selectivity and provided up to 70% acetic acid. Moreover, a
TON of 80 000 was obtained after 4 days, indicating the
robustness of this catalyst system (Scheme 8).
In 2016, the Milstein group reported another method for
C2-alcohols like amino alcohols, acceptorless dehydrogenation
to their corresponding C2-carboxylic acid salts, which was
successfully applied to synthesize a variety of amino acid
salts.62 Using 0.1 mol % ruthenium complex 4 in a basic
aqueous medium at 125 °C, a range of amino alcohols were
shown to have high reactivity and were obtained in good yields
(Scheme 9).
Scheme 9. Ru(II)-PNN Catalyzed Synthesis of Amino Acid
Salts from Amino Alcohol62
Interestingly, water is playing the dual role of acting as a
solvent and a nucleophile, from which the oxygen atom of the
carboxylic acid group was derived, with the liberation of
dihydrogen. Besides the precious metal-based catalytic systems,
the earth-abundant 3d-metal complexes are also known for the
acceptorless dehydrogenation of alcohols.63 The research
groups of Jones and Schneider reported the first iron-based
acceptorless dehydrogenation of alcohols.64 Using a minimal
amount of catalyst (0.1−1 mol %) of 5, a range of alcohols
including aliphatic, primary, and secondary alcohols and diols
were dehydrogenated to their corresponding carbonyl
derivatives such as aldehydes, ketones, esters, or lactones,
respectively, in average to good isolated yields (Scheme 10,
Table 3). Further, the catalyst showed good chemoselectivity
in the presence of both primary and secondary diols. Notably,
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Scheme 10. Iron-PNP (5) Complex Catalyzed Acceptorless Dehydrogenation of Alcohols64
Table 3. Overview of Selected Catalytic Systems Used in Ethanol or Polyols Dehydrogenation
the secondary alcohol only underwent dehydrogenation
without affecting the primary alcohol. According to the DFT
studies and control experiments, the active catalyst in the AD/
ADC reactions was proposed to be a pentacoordinate iron
amido hydride species 5′.
■
ALCOHOL−AMINE-BASED LOHC SYSTEMS
In 2015, Milstein and co-workers reported the ruthenium-
catalyzed reversible LOHC system based on amine-alcohols.
Acceptorless dehydrogenative amide formation from amino
alcohol (AA) and the reverse hydrogenation using the same
catalyst regenerate AA.65 They used PNN ruthenium pincer
complexes 4 and 6−9 that efficiently catalyze several
dehydrogenative coupling reactions of alcohols and amines
(Scheme 11). In this study, 2-aminoethanol (AE) was used as
an alcohol and an amine, which upon acceptorless dehydrogen-
ative coupling process can either form piperazine-2,5-dione
(glycine anhydride, GA) or the linear oligopeptide (LP). The
formation of GA as a major product is more advantageous
because it has a high hydrogen storage potential of 6.56 wt %
as compared with LP, which lowers the hydrogen storage
capacity of AE (for n = 6, 5.46 wt %). The reaction of 1 mmol
AE in low catalyst loading like 0.5 mol % of catalyst 6 and
KOtBu (1.2 equiv relative to 6) with 4 mL of dioxane solvent
at 135 °C for 12 h under argon atmosphere resulted in 78%
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conversion of AE, forming GA in 48% yield with linear
peptide. Further, the improvement in the reaction conditions
using catalyst 6 and the other bipyridine-based pincer
complexes 4 and 8 is shown in the lower conversion of AE.
By replacing the NEt2 group with an N(H)(tBu) amine group
in the pincer complex 6, the catalytic activity was enhanced.
Thus, using catalyst 9 in the presence of 1.2 mol % KOtBu (2.4
equiv relative to 9) and keeping the remaining conditions
same, the reaction resulted in 85% conversion of AE and 60%
yield of GA with 37 mL (77% yield) hydrogen (using reaction
1b). Later, the reverse hydrogenation reaction of GA was
performed using complexes 6 and 9. It was found that complex
9 was catalytically much more active compared with 6, and
almost quantitatively, conversion of expected product AE was
obtained with 0.5 mol % of 9 and H2 pressure (50 bar) at 110
°C. Pleasingly, the mixed products GA and LP obtained via the
dehydrogenation reaction were also hydrogenated under a
similar set of conditions, leading to an 85 wt % yield of AE,
which implies that the formation of LP does not impose a
major problem in the regeneration of AE.
The repeated dehydrogenation-hydrogenation cycles were
also carried out without the addition of additional catalysts,
and 81% of AE was detected even after the third cycle,
indicating that this system has the potential to be used in
hydrogen storage (Scheme 12).
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Scheme 11. Reactions of Amino Alcohol-Based Reversible Hydrogen Carrier System65

Scheme 12. Repetitive Dehydrogenation-Hydrogenation
Cycles
In subsequent work, Milstein and co-workers developed a
new LOHC system using commercially available, abundant,
and inexpensive ethylenediamine (ED) and ethanol as
hydrogen carriers.66 In this reaction, bipyridine-based pincer
complex 4 showed excellent activity with a catalytic amount of
base. For both hydrogenation and dehydrogenation, complex 4
showed excellent conversions. The dehydrogenative coupling
of ED and ethanol using 0.2 mol % catalyst 4 and 1 mL of
dioxane solvent at 135 °C for 24 h gave the expected product
N,N′-diacetylethylenediamine (DAE) in 92% yield with full
conversions of ED and ethanol and the monoamide N-(2-
aminoethyl)-acetamide (AEA) in only 8% yield, as well as H2
in 95% yield (Scheme 13). Further, the reverse hydrogenation
reaction using 0.2 mol % 4 and KOtBu (2.4 equiv relative to 4)
under 70 bar hydrogen pressure at 115 °C for 48 h afforded
complete conversion of DAE and ED in 92% of yield. Using
0.4 mol % catalyst 4 and less dioxane solvent (2 mL), large-
scale hydrogenation of DAE under the same set of conditions
for 10 h resulted in the quantitative amount of ED.
Plausible organic intermediates are shown for the dehydro-
genative coupling of ED and ethanol in Scheme 14.

Scheme 13. Ru-PNN Complex (4) Catalyzed Dehydrogenative Coupling of Ethylenediamine with Ethanol66

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Scheme 14. Proposed Pathway for the Dehydrogenative
Coupling of Ethanol and Ethylenediamine (ED)
The research group of Milstein developed a new hydrogen
storage system based on the formation of bis-cyclic imide via
dehydrogenative coupling of inexpensive and readily available
starting materials like 1,4-butanediol and ethylenediamine
(ED) and then hydrogenation of bis-cyclic imide.67 Using
ruthenium complex 9 (1 mol %) and KOtBu (2 mol %), the
dehydrogenative coupling of ED and 1,4-butanediol in dioxane
(2 mL) at 120 °C for 24 h, given the complete conversion of
1,4-butanediol. However, bis-cyclic imide was formed in 55%
yield and 20% yield of lactone along with other products such
as oligoamides (Scheme 15). Furthermore, under similar
Scheme 15. Reversible Transformation of 1,4-Butanediol and Ethylenediamine67
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reaction conditions, the ruthenium complex 10, which is the
PPh2 analogue of complex 9, was used for the dehydrogenative
coupling of ED and 1,4-butanediol, resulting in 70% yield of
bis-cyclic imide and 84% hydrogen yield. The reverse
hydrogenation of bis-cyclic imide at 40 bar hydrogen pressure
using complex 9 (1 mol %) and KOtBu (3 mol %) in dioxane
resulted in 99% conversion of starting imide and more than
90% yield of 1,4-butanediol and ethylenediamine. A similar
reaction using complex 10 showed conversion of the bis-cyclic
imide in 65% only. The repetitive hydrogenation/dehydrogen-
ation between the spent fuel (bis-cyclic imide) and the charged
fuel (ED/1,4-butanediol mixture) using complexes 9 and 10
showed moderate efficiency for the imide formation up to two
cycles. The ruthenium complex 9 was also used in hydro-
genation of various cyclic imides to form diols and amines in
good to excellent yields.
In seminal work, the research group of Olah and Prakash
described methanol/amine based a reversible hydrogen storage
system. Indeed, hydrogen is generated in the presence of
ruthenium catalyst 3 or 11 via the dehydrogenative coupling of
methanol and amine and the reverse hydrogenation reaction
regenerates the starting CH3OH and amine by the same
catalyst, thus closing the cycle.68 Methanol is particularly
suitable in this type of hydrogen storage system because it
contains 12.6 wt % hydrogen; it is easy to handle; and it can be
manufactured by a variety of industrial processes. The reaction
of benzylamine and methanol with catalyst 11 in toluene
solvent at 140 °C for 24 h in a closed reactor resulted in an
88% yield of N,N′-dibenzylurea. While the reverse hydro-
genation reaction (60 bar of hydrogen pressure) happened
with a complete conversion of N,N′-dibenzylurea to methanol
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Scheme 16. Acceptorless Dehydrogenative Coupling Affording Formamide Using Methanol68

Scheme 17. Manganese-Catalyzed Acceptorless Dehydrogenative Coupling Affording Formamide Using Methanol69

and benzylamine, this system has only 2.4 wt % H2 storage
potential because of the high carbon content of benzylamine.
In view of the hydrogen storage capacity, N,N′-dimethylethy-
lenediamine (DED, 6.6 wt %) was the most appropriate amine,
and the reaction of 1 mmol of DED and methanol (4 mmol)
with 1 mol % 11 and 5 mol % K3PO4 resulted in 86% H2 yield
at 120 °C in toluene solvent for 24 h (Scheme 16). When Ru-
MACHO catalyst 3 was used under a similar set of conditions,
90% H2 yield was observed along with 95% yield of DED in
the reverse hydrogenation reaction at 60 bar hydrogen
pressure. Moreover, scaling up the reaction (5 mmol) under
neat conditions (in the absence of solvent) also resulted in
moderate to good yield of dehydrogenated and hydrogenated
products (76% and 60%, respectively).
More recently, Liu et al.65 demonstrated the utility of an
earth-abundant manganese pincer complex in developing a
similar hydrogen carrier system as described by Olah and
Prakash. Notably, this is the first report of the catalytic system
based on cost-effective, sustainable, and efficient first-row-
14720
transition metals for LOHC systems. The dehydrogenative
condensation of methanol and N,N′-dimethylethylenediamine
(DED) with 2 mol % PhPNP-complex 12 and KOtBu (4 mol
%) in 1,4-dioxane at 165 °C for 16 h gave N,N′-(ethane-1,2-
diyl)bis(N-methylformamide) in 86% of yield and along with
92% (95.5% purity) yield of H2 (Scheme 17). Assuming that
the H2 produced during the reaction in a closed system would
inhibit dehydrogenation, the evolved hydrogen was released
after 2 h of reaction, and the reaction was then carried out for
another 6 h at 165 °C, which resulted in a higher yield of both
H2 and the desired product (98% and 97% yield, respectively).
In comparison to the ruthenium catalyst 3, this PhPNP-
complex 12 showed 97% selectivity for a formation of N,N′-
(ethane-1,2-diyl)bis(N-methylformamide) by the dehydrogen-
ative condensation of methanol and N,N′-dimethylethylenedi-
amine (DED). Further, the hydrogenation of N,N′-(ethane-
1,2-diyl)bis(N-methylformamide) required harsh reaction
conditions (180 °C, 80 bar of H2) to obtain N,N′-
dimethylethylenediamine (DED) in 94% yield by catalyst 12,
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ACS Catalysis pubs.acs.org/acscatalysis
Scheme 18. Hydrogenation/Dehydrogenation Reactions Involving Methanol, Ethylene Diamine, and Urea70
Scheme 19. Mechanism of the ADC of Ethylenediamine and Methanol
the same catalyst used in the dehydrogenation reaction. While
catalyst 13 was found to be the most active for this
hydrogenation reaction and resulted in 99% yield of DED
with catalyst 13 (2 mol %) and KOtBu (2.5 mol %) in dioxane
solvent at 110 °C for 16 h. Milstein and co-workers70
developed a similar hydrogen carrier system based on the
formation of ethylenediamine (ED) and methanol by
unprecedented hydrogenation of ethylene urea (EU) and its
reverse dehydrogenative coupling reaction in the presence of
Ru-catalysts 4, 6, and 9. Earlier, the same group established a
LOHC system based on ethylenediamine-ethanol/N,N′-
diacetylethylenediamine (DAE), with a hydrogen storage
capacity of 5.3 wt % (Scheme 13). However, because methanol
has one fewer carbon and the dehydrogenative coupling of ED
and methanol can result in the formation of ethylene urea
(EU), which has a lower molecular weight than DAE, the
hydrogen storage capacity of a system based on methanol
would be higher (6.45 wt % H2 capacity). Using 1 mol % 9 and
4 mol % KOtBu, the hydrogenation of EU under 60 bar
hydrogen pressure at 170 °C for 7 d in 2 mL dioxane preceded
with complete conversion and the products ED and methanol
were obtained in 100% selectivity (Scheme 18). Moreover,
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Review
with ruthenium catalysts 4 and 6, the reaction resulted in 100%
conversion and 100% yield of ED and methanol after 1.5 and 5
days. The catalyst 4 showed excellent activity for EU
hydrogenation even when the reaction time was reduced to
1 d, yielding 81% of ED and 77% methanol. Next, the
dehydrogenative coupling of ethylenediamine and methanol
(1:3) was carried out in a closed 25 mL Young-type Schlenk
tube using 1 mol % 9 and 2.2 mol % KOtBu in dioxane (2 mL)
at 150 °C for 48 h. This reaction yielded 99% H2 and 76% EU,
as well as intermediates N-(2-aminoethyl)formamide (FA) and
N,N′-(ethane-1,2-diyl)diformamide (DFA) in 15% and 9%
yields, respectively.
Other ruthenium pincer complexes 4 and 6 were also
examined for the dehydrogenative coupling of ED and
methanol, and neither the intermediate FA nor EU was
observed under similar reaction conditions. According to
mechanistic experiments, the dehydrogenative coupling of ED
and methanol using catalyst 9 proceeds via metal−ligand
cooperation (MLC) and results in the formation of FA and
DFA with the release of molecular hydrogen. DFA can be
transformed to FA in the presence of ED and then to EU via
the dehydrogenation reaction (Scheme 19).
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■
pubs.acs.org/acscatalysis
ALCOHOL-BASED LOHC SYSTEMS
In 2016, Gusev reported an interesting hydrogen storage
system based on ethanol/ethyl acetate couple via the reversible
dehydrogenation/hydrogenation reaction catalyzed by osmi-
um-based pincer complexes.71 The ADC of ethanol using 0.01
mol % 14 and 1 mol % NaOEt as a base at 90 °C resulted in
82% ethanol conversion to ethyl acetate (Scheme 20).
Scheme 20. Reversible Dehydrogenation/Hydrogenation of
Ethanol and Ethyl Acetate
Notably, the reverse hydrogenation reaction was catalyzed by
the dihydride osmium complex 15 at 50 bar of hydrogen
pressure. Indeed, after 1 h, relatively higher TONs of 730 were
observed.
Milstein and co-workers also described a liquid-to-liquid
organic hydrogen carrier system based on ethylene glycol
(EG), which is cheap, readily available, and renewable.72 With
a theoretical hydrogen storage potential of 6.5 wt %, ethylene
glycol might efficiently store and release hydrogen reversibly
using a ruthenium pincer complex. By utilizing 1 mol % of
acridine-based PNP ruthenium complex 16 and 2 mol %
KOtBu, 94% conversion of EG and 54 mL of hydrogen with
99.65% purity were obtained (Scheme 21). Further, using 1
mol % of dearomatized complex 17, the dehydrogenative
coupling of EG proceeded efficiently under base-free
conditions and yielded 97% conversion and 61 mL of
hydrogen (99.59% purity). Moreover, in the presence of 1
Scheme 21. Reversible Liquid Hydrogen Carrier System
Based on the Acceptorless Dehydrogenative Coupling of
Ethylene Glycol72
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Review
mol % of 17, the crude reaction mixture was fully
hydrogenated to EG in 48 h at 40 bar of H2 pressure. Under
neat conditions and reduced pressure (95 mbar), a large-scale
dehydrogenation of EG (2 mL) at 150 °C for 7 days afforded
94% conversion and 1295 mL (75% H2 yield) of hydrogen.
Using 0.5 mol % 17 and at 40 bar of H2 pressure, this crude
mixture was completely converted to EG after 60 h.
The mechanism of this reversible dehydrogenation/hydro-
genation of EG based on calculations using the density
functional theory has been illustrated in Scheme 22. There are
numerous challenges associated with the acceptorless dehy-
drogenative coupling of EG to 2-hydroxyethyl glycolate
(HEG), including EG chelation with the metal center, which
reduces catalyst activity, hydrogen bonding between the alkoxy
metal complex and neighboring EG, which may obstruct the β-
hydride elimination step, dehydrogenation of HEG to a α-keto
ester, which further decomposes to CO and aldehyde, and the
formation of undesired products with lower HSCs such as
((1,3-dioxolan-2-yl)methanol). Nevertheless, the acridine
ligand backbone in ruthenium complex 17 has unique
characteristics which are responsible for overcoming these
challenges. Moreover, the dehydrogenation of EG to HEG was
endergonic to a small extent, which indicates the feasibility of
reversible dehydrogenation/hydrogenation reactions.
Later, Fujita et al.73 developed a hydrogen carrier system
based on the formation of γ-butyrolactone by dehydrogenative
lactonization of 1,4-butanediol and regeneration of 1,4-
butanediol reversely through catalytic hydrogenation reaction.
The dehydrogenative lactonization proceeded successfully
under solvent-free conditions with an iridium catalyst 18
containing a functional 6,6′-dionato-2,2′-bipyridine ligand,
yielding both hydrogen and γ-butyrolactone in 96% yields
after 9 h (Scheme 23). The reverse hydrogenation of γ-
butyrolactone in the presence of 1 mol % 18 under 8 atm H2
pressure also proceeded quantitatively, and 1,4-butanediol was
obtained in 98% yield after 72 h. In addition, triethylamine and
6,6′-dihydroxy-2,2′-bipyridine were required as additives in the
hydrogenation reaction.
Another liquid-to-liquid organic hydrogen carrier system
based on ruthenium complex catalyzed reversible dehydrogen-
ative coupling of ethylene glycol (EG) with ethanol under
solvent and base-free conditions was disclosed by the Milstein
group.74 Although numerous LOHC systems based on the
amidation reaction of alcohols and amines have been
developed, the products obtained are solid at room temper-
ature and require the use of a solvent, which reduces the
hydrogen storage capacity (HSC). Initially, the intermolecular
dehydrogenative esterification of EG with ethanol using 1 mol
% Ru-16 and 1 mol % KOtBu in a solvent mixture of toluene
and DMF at 150 °C for 72 h, resulted in 87% yield of H2 with
greater than 99.85% purity (Scheme 24). Furthermore, under
base-free conditions, the reaction of EG and ethanol with the
stable dearomatized acridine PNP ruthenium complex Ru-17
yielded 80% hydrogen. A 50 bar H2 pressure was used to fully
hydrogenate the ester mixture back to EG and ethanol.
Because dehydrogenation with solvents reduces the system’s
HSC, EG and ethanol were reacted in large scale under
solvent- and base-free conditions resulting in a 71% hydrogen
yield and a 72% EG and ethanol yield from reverse
hydrogenation. In Scheme 25, the proposed catalytic pathway
for the dehydrogenative coupling of EG and ethanol is
provided.
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Scheme 22. A Plausible Mechanism of the Acceptorless Dehydrogenative Coupling of Ethylene Glycol
Scheme 23. Reversible Dehydrogenation (or Lactonization)
of 1,4-Butanediol into γ-Butyrolactone73
■
LIMITATIONS OF ALCOHOL-BASED LOHC
SYSTEMS
The hydrogen economy is the center of attention in several
developed countries. Because of the main concern of climate
change due to CO2 emission and environmental pollutants,
hydrogen will be an ideal replacement for all the conventional
energy options. At present, the economic feasibility of an
alcohol-based LOHC system with exciting methodology is
challenging to contribute to the hydrogen economy. Because
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Review
mostly noble metals-based catalysts are involved especially
ruthenium, iridium with expensive ligand system, replacing
these metals with earth-abundant, and inexpensive 3d
transition metals with cost-effective ligands and heterogeneous
catalytic systems could be a promising approach for
economically viable LOHC in near future. Thus, it requires
more developments and infrastructure for practical applica-
tions.
■ CONCLUSIONS AND FUTURE PERSPECTIVE
With rapid industrialization and population growth, the global
energy demand is continuously increasing. So far, carbon-based
fossil fuels such as oil, coal, and natural gas have met the
majority of energy demands. However, challenges like fossil
fuel depletion and anthropogenic global warming, as well as
their negative effects on human health and the environment,
have prompted a search for alternative energy sources to meet
the modern world’s energy demands. Hydrogen is widely
considered a clean and environment-friendly fuel because of its
high gravimetric energy density and clean-burning properties.
The conventional hydrogen storage technologies, including
compression and liquefaction, are costly and unsafe.
Furthermore, the chemical hydrogen storage methods such
as hydrogen adsorption in metal hydrides, metal clusters,
metal−organic frameworks (MOFs), and nanostructured
materials also suffer from several aspects. Liquid organic
hydrogen carriers (LOHCs), which store hydrogen in covalent
bonds of liquid organic compounds, are quite promising. In
this Review, we have covered several essential aspects of
developing novel, cost-effective, and abundantly available
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Scheme 24. Ethylene Glycol and Ethanol-Based Reversible LOHC System74
Scheme 25. Proposed Route for the Dehydrogenative
Coupling of EG and Ethanol
LOHC systems for efficient hydrogen storage and transport
applications. LOHCs are very similar to crude oil derivatives at
ambient conditions, thus using existing energy infrastructure.
Without any doubt, notable developments has been made in
the effectiveness of LOHCs hydrogenation and dehydrogen-
ation process; still, further research and development are
needed.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.1c03283.
Various catalysts used in the catalytic hydrogenation of
CO2 to methanol and price of transition-metals used in
the dehydrogenation reactions (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Ekambaram Balaraman − Department of Chemistry, Indian
Institute of Science Education and Research (IISER)
Tirupati, Tirupati 517507, India; Academy of Scientific and
Innovative Research (AcSIR), Ghaziabad 201002, India;
14724
Review
orcid.org/0000-0001-9248-2809; Email: eb.raman@
iisertirupati.ac.in
Authors
Vinita Yadav − Organic Chemistry Division, CSIR-National
Chemical Laboratory (CSIR-NCL), Pune, Maharashtra
411008, India; Academy of Scientific and Innovative
Research (AcSIR), Ghaziabad 201002, India
Ganesan Sivakumar − Department of Chemistry, Indian
Institute of Science Education and Research (IISER)
Tirupati, Tirupati 517507, India
Virendrakumar Gupta − Polymer Synthesis & Catalysis,
Reliance Research & Development Centre, Reliance Industries
Limited, Navi Mumbai 400701, India; orcid.org/0000-
0002-3896-1451
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.1c03283
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
E.B. acknowledges funding from Swarnajayanti Fellowship
(DST/SJF/CSA-04/2019-2020 & SERB/F/5892/2020-2021),
and SERB, India (Grant No: CRG/2018/002480/OC). V.Y.
acknowledges the UGC, India for fellowship. G.S. thanks
IISER-Tirupati for fellowship.
■
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