Ammonia Borane: A potential Hydrogen storage material

Vineet Tiwaria
a Ashoka University, Haryana, India

Abstract
Example abstract for the astronomy and computing journal. Here you provide a brief summary of the research and
the results.
Keywords: keyword 1, keyword 2, keyword 3, keyword 4

1. Introduction ric hydrogen capacity of 19.6 wt%, which surpasses

The global energy demand has risen significantly in
parallel with population growth and industrial devel-
opment. However, the depletion of fossil fuel reserves
and the environmental impact of their combustion, in-
cluding the emission of harmful gases, have led to a
pressing need for alternative energy sources. Hydro-
gen energy has emerged as a promising solution due
to its high calorific value and minimal environmen-
tal impact. The quest for a clean and sustainable en-
ergy future hinges on the development of efficient and
practical methods for hydrogen storage and utilization.
Hydrogen, the most abundant element in the universe,
boasts exceptional energy density, making it a highly
attractive fuel source for applications ranging from trans-
portation to stationary power generation. However, its
gaseous nature at ambient conditions presents signifi-
cant challenges for safe and efficient storage and trans-
port. This has spurred intensive research into alterna-
tive hydrogen carriers - materials capable of storing
and releasing hydrogen in a safe and controlled man-
ner.
Among the numerous candidates out there, ammonia
borane (NH3 BH3 , often abbreviated AB) has emerged
as one of the most promising contenders for chemical
hydrogen storage. First synthesized in the 1950s by
Shore and Parry [1], AB boasts a remarkable gravimet-
the 5.5 wt% of liquid hydrogen and rivals that of many
complex metal hydrides [2]. Additionally, AB exists as
a white solid at room temperature and pressure, sim-
plifying its handling and transportation compared to
gaseous hydrogen. The allure of AB extends beyond
its impressive hydrogen content and physical proper-
ties. Unlike most complex metal hydrides, AB exhibits
favourable thermodynamics for hydrogen release. De-
hydrogenation, the process by which hydrogen is re-
leased from a carrier, can be achieved through either
thermal (heating) or hydrolytic (using water) pathways
[3]. Thermal decomposition liberates hydrogen at rel-
atively low temperatures (around 60°C) compared to
many metal hydrides, suggesting a potentially less energy-
intensive process [4]. Furthermore, the dehydrogena-
tion reaction is exothermic, meaning it releases heat,
potentially simplifying system design.
Despite these attractive features, significant challenges
remain in harnessing the full potential of AB for prac-
tical hydrogen storage applications. A central hurdle
lies in achieving reversible hydrogen release. The cur-
rent dehydrogenation processes for AB often lead to
the formation of complex polymeric byproducts, such
as polyaminoboranes (PNBs) [5]. These byproducts
exhibit significantly lower hydrogen content and pose
difficulties in regeneration, hindering the reusability

March 10, 2024

of AB as a hydrogen carrier [6]. Moreover, the de-
hydrogenation reaction often follows uncontrolled ki-
netics, releasing hydrogen in a rapid and potentially
unsafe manner [7]. Furthermore, while the dehydro-
genation temperature of AB is lower than many com-
plex metal hydrides, it still falls short of the ideal range
for onboard fuel cell applications (typically 30-80°C)
[8]. Lowering the dehydrogenation temperature while
maintaining efficient hydrogen release and reversibil-
ity requires the development of suitable catalysts. Ad-
ditionally, the release of ammonia (NH3) as a byprod-
uct during the dehydrogenation process necessitates the
development of efficient separation and potential rein-
tegration methods to avoid environmental concerns and
maximize hydrogen yield [9].
This paper aims to review the research that has been
done in the area of the synthesis, dehydrogenation and
regeneration of ammonia borane. We start by looking
at the various methods of the synthesis of the AB from
different routes. Then we move on to the most impor-
tant section, which is the dehydrogenation of AB. This
section includes various methods such as thermolytic
and hydrolytic dehydrogenation of AB, along with dif-
ferent catalyst-induced processes used to extract hy-
drogen from AB. The final section of this paper has a
discussion on the potential strategies and challenges of
the regeneration of AB by using the byproducts of the
dehydrogenation reactions.
2. Synthesis of Ammonia Borane
The fundamental idea behind the formation of Ammo-
nia Borane is a reaction between a source of H3 N and
a carrier of BH3 . This idea might look quite simple
but it is not as straightforward as it seems. The chem-
istry behind this can be understood in two pathways:
the first being the classical pathway where Lewis acids
such as CO and Me3 N react with diborane to give the
monomeric donor-acceptor adducts, i.e. (CO)−BH3
and Me3 N−BH3 , respectively. With time, new alter-
nate synthesis routes emerged, in some cases involv-
2
ing complex chemistry. These routes are reported in
the following subsections.
2.1. Classical Pathways
Metathesis of ammonium and borohydride salts is the
most common and simple method to prepare ammo-
nia borane. It involves the reaction of an ammonium
salt (such as NH4 Cl or NH4 F) with a borohydride salt
(such as NaBH4 or LiBH4 ) in an organic solvent (such
as diethyl ether or tetrahydrofuran) at low temperature
(around 0 − 45o C). The reaction produces ammo-
nium borohydride, which decomposes spontaneously
into ammonia borane and hydrogen gas. The overall
reaction can be written as:
NH4 X + MBH4 → NH3 BH3 + H2 + MX (1)
where M is Na or Li and X is Cl, Br or F. The yield
and purity of ammonia borane can be improved by op-
timizing the solvent, the reaction time, and the molar
ratio of the precursors. The addition of some ammonia
or water can also enhance the yield.
The second main pathway is based on a base displace-
ment reaction, where ammonia (NH3 ) replaces the weak
base L of (L−BH3 ) in an organic solvent at tempera-
tures below zero. The general equation is:
L−BH3 + NH3 → NH3 BH3 + LH (2)
where the ligand L can be (CH3 )2 O, (CH2 )4 O, or (CH3 )2 S.
Higher temperatures favour the formation of diborane
B2 H6 , which can also react with ammonia to form AB
or diammoniate of diborane (H3 N−BH3 −NH3 −BH3 ).
The latter can be converted to ammonia borane by sol-
ubilizing it in diethyl ether or polyether with small
amounts of ammonia or diborane.
B2 H6 + 2 NH3 −−−→ 2 NH3 BH3
(3)
(symmetric cleavage)
This method involves passing diborane (B2 H6 ) gas into
liquid ammonia dissolved in an organic ether (such as
THF or diglyme) at -78°C. Depending on the solvent
and the ratio of B2 H6 and NH3 , the reaction can pro-
duce either AB or a mixture of AB and the diammoni-
ate of diborane (DADB).
B2 H6 + 2 NH3 −−−→ [NH3 BH2 NH3 ]+ [BH4 ]−
(4)
(asymmetric cleavage)
The diammoniate of diborane obtained from the de-
composition of NH4 BH4 in the solid state or the asym-
metric cleavage of B2 H6 and NH3 can further be dis-
solved in diglyme solvent containing a trace of dib-
orane to convert DADB to ammonia borane without
hydrogen evolution.
[NH3 BH2 NH3 ]+ [BH4 ]− −−−→ 2 NH3 BH3
(5)
(in diglyme with a trace of B2 H6 )
2.2. Alternative Pathways
The alternative pathways aim to regenerate ammonia
borane from its hydrolytic or thermolytic by-products,
such as boric acid (B(OH)3 ), tetrahydroxyborate anion
(B(OH)4 − ), ammonium (NH4 + ), and polymeric residue
(BNH x ).
−
From the borates, the species tri- (B(OCH3 )4 ) and
tetra-methoxyborate (B(OCH3 )4 − ) can be synthesized
and reacted with ammonium salts and reducing agents,
such as lithium aluminium hydride (LiAlH4 ), lithium
chloride (LiCl), or aluminium chloride (AlCl3 ), to yield
ammonia borane. The general equations are:
[NH4 + ] x [X x− ] + xB(OCH3 )3 + xLiAlH4 −−−→
(6)
xH3 N−BH3 + Li x X + xAl(OCH3 )3 + xH2
[NH4 + ] x [X x− ] + xB(OCH3 )3 + xLiCl + xAlCl3
(7)
−−−→ xH3 N−BH3 + Li x X + xAl(OCH3 )3 + xH2
The second method is a one-pot process where polyb-
orazylene is taken as a model residue. It is represented
with the formula BNH x (x<2). Polyborazylene is sus-
pended in liquid NH3 at −77o C and reduced by hy-
drazine N2 H4 for 24o C at 40o C.
4 BNH + 5 N2 H4 → 4 H3 N−BH3 + 5 N2 (8)
3
The energy of this reaction is −64.7 kJ mol−1 . Am-
monia borane is obtained with a yield of 92%, the side
product being hydrazine borane N2 H4 BH3 . The latter
is thereafter converted to ammonia borane in ammonia
borane in liquid NH3 at −77o C, heating up to 60o C
for 24 hours, and cooling down to −77o C.
3. Dehydrogenation of Ammonia Borane
3.1. Thermolysis
Thermal decomposition of ammonia borane is carried
out as a two-stepwise exothermic reaction. There have
been several experimental studies that suggest that the
first step releases about 1 mol of H2 , along with residue
mainly containing polymeric aminoborane [BH2 NH2 ] x
with some aminoborane (BH2 NH2 ) and gaseous bo-
razine (B3 N3 H6 ). (Miranda 2007) has studied the am-
monia borane thermal decomposition reaction along
two paths. The hydrogen release along these paths can
be summarized as follows:
3.1.1. Route A - The polymeric ammonia-borane cycle
The release of hydrogen along this route can be under-
stood by the following three reactions:
Reaction-1: The formation of Polyaminoborane (PAB):
xBH3 NH3(s) → [BH2 NH2 ] x + H2(g) (9)
Reaction-2: The formation of Polyiminoborane (PIB):
[BH2 NH2 ] x → [BHNH] x + xH2(g) (10)
On further heating, this ultimately leads to the forma-
tion of boron nitride.
Reaction-3: The formation of boron nitride
[BHNH] x → xBN + xH2(g) (11)
The final reaction requires a very large temperature,
around 1500 K, for hydrogen release. Moreover, the
final product of this reaction, boron nitride, is very sta-
ble and makes the reverse reaction very impractical for
hydrogen storage.
3.1.2. Route B - The cyclic polymeric ammonia-borane cycle
Formation of cyclic polymeric compounds like borazine
(B3 N3 H6 ), cyclotriborazane (H2 BNH2 )3 and polybo-
razylene ([B3 N3 H4 ] x ) is an alternative route for the de-
composition of BH3 NH3 . The hydrogen release reac-
tions for this route can be listed as:
Reaction-4: Dehydropolymerization of borazine:
3BH3 NH3(s) → B3 N3 H6(g) + 6H2(g) (12)
followed by,
B3 N3 H6(g) → [B3 N3 H4 ] x + H2(g) (13)
Reaction-5: Borazine-cyclotriborazane cycle:
B3 N3 H6(g) + 3H2(g) ←→ (H2 BNH2 )3(s) (14) These catalysts, such as Co, Ni, Cu, and Fe, are more
Transformation of ammonia-borane into cyclotriborazane: show high activity for the hydrolysis of AB. The cat-
3BH3 NH3(s) → (H2 BNH2 )3(s) + 3H2(g) (15)
3.2. Hydrolysis
The hydrolysis of ammonia borane is a process that
involves the reaction of ammonia borane with water
to produce hydrogen gas and borate salts. This process
can be used as a potential method for hydrogen storage
and generation, as ammonia borane has a high gravi-
metric hydrogen density. However, there are some chal-
lenges and limitations associated with this process, such
as the stability, recyclability, and purity of the reactants and Ir-Ni, combine the advantages of both noble and
and products.
The hydrolysis of ammonia borane can be catalyzed
by following metal-based catalysts:
3.2.1. Noble metal-based catalysts
These catalysts, such as Pt, Rh, Ru, and Pd, show high
activity and stability for the hydrolysis of AB, which
can be expressed as:
NH3 BH3 + 2 H2 O → NH4 + + BO2 − + 3 H2 (16)
The catalysts can be supported on various materials,
such as carbon, alumina, silica, or zeolite, or stabilized
by polymers, such as laurate or PSSA-co-MA. The re-
action is exothermic and releases about 156 kJ/mol of
heat. The reaction rate and the hydrogen yield depend
on several factors, such as the catalyst type, loading,
and support, the reaction temperature, and the water
content. The reaction mechanism is often described by
the bimolecular Langmuir-Hinshelwood kinetic model,
which assumes that the reaction occurs between the ad-
sorbed species of ammonia borane and water on the
catalyst surface. The reaction kinetics are usually first
order with respect to the catalyst concentration and
zero order with respect to the AB concentration.
3.2.2. Non-noble metal-based catalysts
economical and abundant than noble metals and also
alysts can be prepared by different methods, such as
solvated metal atom dispersion, seeding-growth, or in
situ reduction. The catalysts can be amorphous or crys-
talline and have different shapes, such as nanospheres,
nanorods, or core-shell structures. The catalytic activ-
ity is influenced by the metal particle size, crystallinity,
composition, and oxidation state.
3.2.3. Synergistic effects of noble and non-noble metal cata-
lysts
These catalysts, such as Au-Co, Au-Ni, Rh-Ni, Pt-Ni,
non-noble metals and exhibit enhanced catalytic per-
formance for the hydrolysis of AB. The catalysts can
be bimetallic alloys or core-shell structures, and have
different metal ratios and distributions. The synergis-
tic effects are attributed to the electronic, geometric, or
chemical interactions between the two metals, which
affect the catalytic activity and stability.
The main challenge of the hydrolysis of ammonia bo-
rane is the recyclability of the borate by-products, which
are highly stable and require harsh reducing conditions
to regenerate ammonia borane. Several chemical routes
4
have been proposed to achieve this, such as using methanol, vironment for the dispersion and stabilization of the
hydrazine, or lithium aluminium hydride as reducing
agents. However, these methods are still costly and
complex and may introduce impurities or side reac-
tions. Therefore, further research and development are
needed to improve the efficiency and sustainability of
the hydrolysis of ammonia borane for hydrogen stor-
age and generation.
3.2.4. Other potential catalysts
Boron-containing nanocomposites, thin films and
foams: These catalysts are based on the incorporation
of boron into different metal or metal oxide matrices,
such as Co-B, Cu-B, Co-Mo-B, Co-P, etc. The au-
thors suggest that the presence of boron may enhance
the catalytic activity by facilitating the formation of
metal-borohydride intermediates or by modifying the
electronic structure of the metal sites. Some of these
catalysts also exhibit magnetic properties, which en-
able their easy separation and recycling.
Bimetallic alloy and core-shell nanoparticles: These
catalysts are composed of two different metals, such as
Ni-Au, Ni-Pt, Ni-Pd, Au-Co, etc. The authors claim
that these catalysts show synergistic effects, where the
combination of two metals results in higher activity,
selectivity and stability than the individual metals. The
bimetallic catalysts can be prepared by various meth-
ods, such as co-reduction, seeding-growth, replacement
reaction, etc. The core-shell structure, where one metal
forms a core and another metal forms a shell, may offer
additional advantages, such as tunable surface prop-
erties, enhanced electron transfer, and reduced metal
leaching.
Metal-organic frameworks (MOFs): These catalysts
are porous crystalline materials that consist of metal
ions or clusters connected by organic ligands. The au-
thors report that some MOFs, such as Ni-based MOF,
can act as precursors for the in situ generation of metal
nanoparticles within the MOF matrix during the hy-
drolysis of AB. The MOF may provide a suitable en-
metal nanoparticles, as well as for the adsorption and
activation of the AB molecules.
In addition to the hydrolysis of ammonia borane, some
recent studies have also developed methanolysis of am-
monia borane to generate pure hydrogen at room tem-
perature over various catalysts, such as RuCl3 , RhCl3 ,
CoCl2 , NiCl2 , Pd/C, etc.
NH3 BH3 + 4 MeOH → NH4 B(OMe)4 + 3 H2 (17)
Hydrogen capacity from the above system is calculated
to be about 3.9 wt%, which is lower than that from the
hydrolytic system (about 7.8 wt%).
4. Regeneration of Ammonia Borane
The viability of ammonia borane in the field of chem-
ical hydrogen storage is strongly dependent on the re-
cyclability of the spent fuel into the borane. The dehy-
drogenation process typically follows an irreversible
path, leading to the formation of ammonia (NH3 ) and
polymeric byproducts like polyaminoboranes (PNBs).
PNBs are complex molecules with lower hydrogen con-
tent compared to AB. Their decomposition back into
AB is challenging, hindering the closed-loop cycle for
hydrogen storage using AB. The strategies for poten-
tial regeneration of AB includes the hydrolysis reac-
tion where the key aspect lies in the formation of am-
monia borane condensate (NH3 BH3 · H2 O) during hy-
drolysis. This ammonia borane condensate can be ther-
mally decomposed at moderate temperatures (around
100°C) to regenerate AB. This suggests a potential closed-
loop cycle.
However, the complete conversion of AB to ammonia
and regenerable condensate remains a challenge. Op-
timizing the hydrolysis reaction for efficient hydrogen
generation and AB regeneration is crucial. In future,
exploring alternative regeneration methods beyond hy-
drolysis and thermal treatment might be beneficial. Chem-
ical reduction or other strategies are some of the poten-
5
tial areas that could be investigated. structure, researchers can potentially optimize hydro-
gen release characteristics while maintaining high hy-
5. Conclusion and Prospects drogen content. Such tailored derivatives could of-
fer a more controlled and efficient pathway for hydro-
Ammonia borane (AB), a white solid at room tem-
gen release. Additionally, developing efficient and ro-
perature, has captivated researchers in the quest for a
bust catalysts is crucial. Ideal catalysts should oper-
clean and sustainable hydrogen storage solution. Its al-
ate at lower temperatures, promoting selective hydro-
lure lies in its impressive theoretical hydrogen content
gen release and minimizing the formation of unwanted
of 19.6 wt%, surpassing liquid hydrogen and rivaling
byproducts.
many complex metal hydrides. Additionally, the dehy-
Regeneration strategies are also paramount for a viable
drogenation process – the release of hydrogen from the
closed-loop hydrogen storage system. While current
carrier – exhibits favorable thermodynamics, meaning
processes have limitations, research on optimizing hy-
it can occur at relatively low temperatures compared to
drolysis – the reaction of AB with water – and explor-
some metal hydrides. This presents a potential advan-
ing alternative regeneration methods like chemical re-
tage for onboard fuel cell applications. However, the
duction holds promise for improving the reusability of
path to practical utilization of AB for hydrogen storage
AB. Here, engineering considerations play a vital role
is not without its hurdles.
in designing practical systems. Reactor design needs
A central challenge lies in achieving reversible hydro-
to address issues of heat management, controlled de-
gen release. Current dehydrogenation processes often
hydrogenation kinetics, and efficient hydrogen separa-
yield complex polymeric byproducts like polyaminob-
tion. Moreover, integrating ammonia separation and
oranes (PNBs). These byproducts have significantly
its potential reintegration into the hydrogen release cy-
lower hydrogen content and pose difficulties in decom-
cle is critical for maximizing hydrogen yield and min-
position back into AB, hindering the reusability of AB
imizing environmental concerns.
as a hydrogen carrier. Furthermore, dehydrogenation
Unlocking the potential of AB for practical hydrogen
can be an uncontrolled process, releasing hydrogen rapidly
storage demands a multi-faceted approach. Fundamen-
and potentially creating safety concerns. Despite these
tal research delving into dehydrogenation mechanisms
obstacles, the potential benefits of AB warrant contin-
and byproduct formation is essential. Computational
ued research and development efforts. Several avenues
modeling can accelerate the process of identifying and
hold promise for unlocking its full potential. One key
designing efficient catalysts for controlled and selec-
area involves gaining a deeper understanding of the de-
tive hydrogen release. Synthetic chemists can con-
hydrogenation mechanisms and the structure-property
tribute significantly by exploring tailored AB deriva-
relationships governing byproduct formation. Compu-
tives with improved dehydrogenation behavior. Engi-
tational modeling offers a valuable tool in designing
neering advancements in reactor design and byprod-
novel catalysts that promote efficient and selective hy-
uct separation are crucial for translating promising re-
drogen release at lower temperatures. This not only
search into practical applications.
improves the efficiency of hydrogen extraction but also
In conclusion, ammonia borane presents a compelling
aligns with the ideal operating temperature range for
case for a sustainable hydrogen storage solution. Its
fuel cells.
high hydrogen content, favorable thermodynamics, and
Synthetic chemists can contribute significantly by ex-
existence as a solid at room temperature solidify its
ploring methods to tailor AB derivatives. By incor-
potential. However, overcoming challenges associated
porating functional groups or altering the molecular

6
with irreversible dehydrogenation, uncontrolled kinet-
ics, and byproduct management necessitates a concerted
effort across various scientific disciplines. Through
continued research focused on understanding dehydro-
genation mechanisms, catalyst development, regenera-
tion strategies, and engineering considerations, scien-
tists can unlock the full potential of AB and pave the
way for a clean hydrogen future.