molecules
Review
Recent Progress on Hydrogen Production from Ammonia
Decomposition: Technical Roadmap and Catalytic Mechanism
Xiangyong Huang 1, * , Ke Lei 1 , Yan Mi 2 , Wenjian Fang 2, *
Citation: Huang, X.; Lei, K.; Mi, Y.;
Fang, W.; Li, X. Recent Progress on
Hydrogen Production from
Ammonia Decomposition: Technical
Roadmap and Catalytic Mechanism.
Molecules 2023, 28, 5245. https://
doi.org/10.3390/molecules28135245
Academic Editors: Dai Dang and
Ning Yan
Received: 9 June 2023
Revised: 30 June 2023
Accepted: 2 July 2023
Published: 6 July 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Molecules 2023, 28, 5245. https://doi.org/10.3390/molecules28135245
and Xiaochuan Li 2
1 School of Energy and Environment, Anhui University of Technology, Ma’anshan 243002, China
2 School of Electrical and Energy Power Engineering, Yangzhou University, Yangzhou 225002, China
* Correspondence: huangxy@ahut.edu.cn (X.H.); fwjlf2227@163.com (W.F.)
Abstract: Ammonia decomposition has attracted significant attention in recent years due to its ability
to produce hydrogen without emitting carbon dioxide and the ease of ammonia storage. This paper
reviews the recent developments in ammonia decomposition technologies for hydrogen production,
focusing on the latest advances in catalytic materials and catalyst design, as well as the research
progress in the catalytic reaction mechanism. Additionally, the paper discusses the advantages and
disadvantages of each method and the importance of finding non-precious metals to reduce costs and
improve efficiency. Overall, this paper provides a valuable reference for further research on ammonia
decomposition for hydrogen production.
Keywords: ammonia decomposition; hydrogen production; thermocatalytic; non-thermal plasma-catalytic;
electrocatalytic; photocatalytic
1. Introduction
Reducing carbon emissions is a pressing global challenge. The development of clean
and renewable sources of energy, such as wind or solar, is an effective way. At the same time,
efficient and reliable energy storage and carriers are indispensable due to the intermittency
and variability of such natural energy sources. Hydrogen is considered an excellent energy
carrier due to its carbon-free, renewable, and environmentally friendly features [1–4].
However, low volume energy density and serious safety issues concerning storage and
transportation hinder its large-scale applications. A feasible approach is reversibly storing
hydrogen in liquid or solid hydrides (hydrogen carriers) and then generating hydrogen
through catalytic processes as required. Among potential hydrogen storage intermediates,
ammonia (NH3 ) is the most promising candidate due to its competitive advantages in terms
of hydrogen storage capacity, zero carbon emissions, availability, cost, and safety [5–8].
Ammonias’s hydrogen content is as high as 17.6 wt%, and the hydrogen volume den-
sity is about 123 kg-H2 /m3 , much higher than other modern hydrogen storage systems [5].
Moreover, ammonia is readily liquefied at room temperature (25 ◦ C) and a light pressure
of ca.10atm, resulting in a higher volumetric energy density than pressurized H2 [6,7]. In
addition, ammonia is widely used as an important chemical material in modern industries,
such as nitrogen fertilizers, refrigerants, and NOx-reducing agents. Due to the strong,
long-term demand, the infrastructure for its production, storage, and supply has been well
developed. As such, compared to other zero-carbon fuels, ammonia is a widely available,
practical, and affordable choice [8]. Furthermore, the extensive use of ammonia over the
years has contributed to developing safety codes and standards. Thus, ammonia safety has
been ensured.
Ammonia decomposition plays a crucial role in the renewable energy sources to
hydrogen user’s process, as outlined in Figure 1. The development of these technologies is
not synchronized. The production capacity of hydrogen and ammonia is not a significant
obstacle to meeting the high demand, while the current ammonia decomposition system
https://www.mdpi.com/journal/molecules
Molecules 2023, 28, x FOR PEER REVIEW
Molecules 2023, 28, 5245
2 of 25
Ammonia decomposition plays a crucial role in the renewable energy sources to hy-
drogen user’s process, as outlined in Figure 1. The development of these technologies is
2 of 25
not synchronized. The production capacity of hydrogen and ammonia is not a significant
obstacle to meeting the high demand, while the current ammonia decomposition system
does not allow mass hydrogen production with adequate purity. Therefore, ammonia de-
does not allow mass hydrogen production with adequate purity. Therefore, ammonia
composition may become the bottleneck of the hydrogen chain, which is why it is getting
decomposition may become the bottleneck of the hydrogen chain, which is why it is getting
dramatically increased attention [9–11].
dramatically increased attention [9–11].
Figure 1. The
Figure 1. The status
status of
of hydrogen
hydrogen production
production from
from ammonia
ammonia decomposition
decomposition in
in ammonia
ammoniaeconomy.
economy.
In
In the
the past
pastten
tenyears,
years,and
andespecially
especiallyininthe
thepast
pastfive, pioneering
five, research
pioneering and
research follow-up
and follow-
studies havehave
up studies resulted in new
resulted in conceptions, methods,
new conceptions, and materials
methods, for ammonia
and materials decomposi-
for ammonia de-
tion. These approaches and underlying mechanisms urgently need to be summarized and
composition. These approaches and underlying mechanisms urgently need to be summa-
understood in detail and are reviewed herein. This paper first analyzes the benefits and
rized and understood in detail and are reviewed herein. This paper first analyzes the ben-
drawbacks of various technologies and then describes their characteristics, principles, and
efits and drawbacks of various technologies and then describes their characteristics, prin-
mechanisms. Afterward, the composition, performance, and synthesis methods of a series
ciples, and mechanisms. Afterward, the composition, performance, and synthesis meth-
of catalysts are covered.
ods of a series of catalysts are covered.
2. Categories of NH3 Decomposition
2. Categories of NH3 Decomposition
The utilization of NH3 as a carrier for H2 has become more widespread due to its
The utilization
beneficial properties of
andNH 3 as a carrier for H2 has become more widespread due to its
importance in industrial settings, as well as its ability to mitigate
air pollution [2,12]. Compared to H2 , in
beneficial properties and importance NHindustrial settings, as well as its ability to mitigate
3 is more easily liquefied and stored, making it a
air pollution [2,12]. Compared
more feasible alternative. to H 2, NH3 is more easily liquefied and stored, making it a
more feasible alternative.
1 3
NH3 (g) → N 1 2 (g) + 3H2 (g)∆H = +46 kJ/mol
2 2
NH3 (g) → N2 (g) + H2 (g) ∆H = +46 kJ/mol
2 2
To produce clean H2 , various technologies have been developed, such as thermo-
To produce clean H2, various technologies have been developed, such as thermocat-
catalytic NH3 decomposition, photocatalytic NH3 decomposition, plasma-catalytic NH3
alytic NH3 decomposition, photocatalytic NH3 decomposition, plasma-catalytic NH3 de-
decomposition, and electrocatalytic NH3 decomposition. Figure 2 shows the advantages
composition, and electrocatalytic NH3 decomposition. Figure 2 shows the advantages and
and disadvantages of each method [10,11,13–18]. Understanding these methods is key to
disadvantages of each method [10,11,13–18]. Understanding these methods is key to de-
determining the current capabilities of the NH3 -to-H2 conversion technologies. Figure 3
termining the current capabilities of the NH3-to-H2 conversion technologies. Figure 3 com-
compares the performance of various technical methods for ammonia decomposition. The
pares the performance of various technical methods for ammonia decomposition. The
results were obtained under different conditions, enabling a thorough evaluation of the
effectiveness of each approach [10,19–25]. Further discussion has been explored regarding
the benefits and drawbacks of each approach below.
Molecules 2023, 28, x FOR PEER REVIEW 3 of 25
Molecules 2023, 28, x FOR PEER REVIEW 3 of 25

results
results were
were obtained
obtained under
under different
different conditions,
conditions, enabling
enabling aa thorough
thorough evaluation
evaluation of the
Molecules 2023, 28, 5245 3ofofthe
25
effectiveness of each approach [10,19–25]. Further discussion has been explored regarding
effectiveness of each approach [10,19–25]. Further discussion has been explored regarding
the
thebenefits
benefitsand
anddrawbacks
drawbacksof
ofeach
eachapproach
approachbelow.
below.

Figure 2. Advantages and disadvantages of different NH3 decomposition methods.

Figure2.2.Advantages
Figure Advantagesand
anddisadvantages
disadvantagesof
ofdifferent
differentNH
NH33decomposition
decompositionmethods.
methods.

Figure 3.
3. A comparisonofofvarious
varioustechnical
technicalmethods
methods forfor ammonia decomposition.(As(As
thethe evalua-
Figure 3.AAcomparison
Figure comparison of various technical methods ammonia
for ammonia decomposition.
decomposition. (As evaluation
the evalua-
tion
of of electrocatalytic NH 3 decomposition for H 2 production is mainly based on current density, no
tion of electrocatalytic3NH3 decomposition for2 H2 production is mainly based on current density,no
electrocatalytic NH decomposition for H production is mainly based on current density, no
comparison
comparison is made here with other technical methods) [10,19–25].
comparisonisismade
madehere
herewith
withother
othertechnical
technicalmethods)
methods)[10,19–25].
[10,19–25].

2.1. Thermocatalytic NH3 Decomposition

2.1. Thermocatalytic NH3 Decomposition
It should be
be notedthatthat withouta acatalyst,
catalyst, the temperature needed for ammonia
It should benoted
noted thatwithout
without a catalyst,the
thetemperature
temperatureneeded
neededfor
forammonia
ammoniade-
de-
decomposition
composition is quitehigh.
high.This
Thisisisdue
duetotothe
the strong
strong hydrogen
hydrogen bonds
bonds present within
composition is quite high. This is due to the strong hydrogen bonds present within
is quite within
ammonia molecules, which demand a high level of energy to break apart. As a result,
ammonia molecules break down into hydrogen and nitrogen [10,13,26,27]. Therefore, am-
monia decomposition without a catalyst is not practical, as it necessitates high temperature
Molecules 2023, 28,ammonia
x FOR PEER molecules,
REVIEW which demand a high level of energy to break apart. As a result, 4 of 25
ammonia molecules break down into hydrogen and nitrogen [10,13,26,27]. Therefore, am-
monia decomposition without a catalyst is not practical, as it necessitates high tempera-
Molecules 2023, 28, 5245 and energy
ture ammonia molecules,
consumption which
as well asdemand
having aa high level of energy
low reaction to break apart. cata-
rate. Consequently, 4 of 25
As a result,
lysts have beenammonia
created molecules
to hastenbreak down into
the sluggish hydrogen
kinetics and 3nitrogen
of NH [10,13,26,27].
decomposition andTherefore,
stimu- am-
monia decomposition without
late H2 production, as shown in Figure 4. a catalyst is not practical, as it necessitates high tempera-
ture
and and energy
energy consumption
consumption as well
as well as having
as having a lowa low reaction
reaction rate.rate. Consequently,
Consequently, cata-
catalysts
lysts
have have
been been created
created to hasten
to hasten the sluggish
the sluggish kinetics
kinetics of NHof NH3 decomposition
3 decomposition and stimu-
and stimulate H2
late H2 production,
production, as shownas shown in 4.
in Figure Figure 4.

Figure 4. Energy profiles for ammonia decomposition without catalyst and with catalyst.
Figure
Figure 4.
4. Energy
Energy profiles
profiles for
for ammonia decomposition without catalyst and with catalyst.
The catalytic dissociation of ammonia can be explained as a process where ammonia
The catalytic
The catalytic dissociation
dissociation of of ammonia
ammonia can can be
be explained
explained as as aa process
process where
where ammonia
ammonia
molecules are absorbed
molecules are
into the active site of the catalyst, leading to a sequence of reac-
molecules are absorbed
absorbedintointothetheactive
activesite
siteofof
the
thecatalyst, leading
catalyst, leading to atosequence
a sequence of reactions
of reac-
tions involvinginvolving
dehydrogenation
dehydrogenation and recombinative
and recombinative desorption
desorption [7,9,28]. The
[7,9,28]. [7,9,28].reaction
The reaction is
tions involving dehydrogenation and recombinative desorption The is generally
reaction is
generally accepted to occur
accepted
generally in several
to occur
accepted in occursteps,
to several as shown
insteps,
severalassteps,
shown in Scheme
as in Scheme
shown in1.Scheme
Firstly,
1. 1.there
Firstly, thereisis
Firstly, a amo-
theremolecular
is a mo-
lecular adsorption of adsorption
adsorption
lecular NHof 3 that
NHgenerates
3ofthat surface
NHgenerates
3 that generates
NHsurface
surface * at3the
3NH * at
NH active
the sites
3* active
at the of metal
sites
active ofsites
metalcatalysts.
of catalysts.
metal Then,
catalysts.
Then, NH3* undergoes
NH
Then, * incremental
undergoes dehydrogenation,
incremental dehydrogenation, resulting
resultingin the
in the
3 NH3* undergoes incremental dehydrogenation, resulting in the production of N* production
production of
of N*
N* and H*
atoms.
and H* atoms.and Finally,Finally,
N* and
H* atoms. N* and H* undergo
H* undergo
Finally, N* and H* recombinative
recombinative desorption,
desorption,
undergo recombinative leading to the
leading leading
desorption, release
to the re- of N
to the re-2
lease of N2 andandH2Hof
lease 2 into
into
N2 the thegas
and gas
H phase.
the These
phase.
2 into These reactions
gas phase.reactions
These culminate
reactionsinculminate
culminate the creation
in the of di-nitrogen
creation
in the of di- ofand
creation di-
di-hydrogen
nitrogen and on the surfaceon
di-hydrogen ofthe
thesurface
catalyst.of the catalyst.
nitrogen and di-hydrogen on the surface of the catalyst.
NH3(g) +∗⇋ NH3(ads)
NH3(g) +∗⇋ NH 3(ads)
NH +∗⇋ NH + H(ads)
NH3(ads) +∗⇋ NH3(ads) 2(ads)
2(ads) + H(ads)
NH +∗⇋ NH(ads) + H(ads)
NH2(ads) +∗⇋ NH2(ads)
(ads) + H(ads)
NH(ads) +∗⇋ N(ads) + H(ads)
NH(ads) +∗⇋ N(ads) + H(ads)
2N(ads) ⇋ N2(g) + 2 ∗
2N(ads) ⇋ N2(g) + 2 ∗
2H(ads) ⇋ H2(g) + 2 ∗
2H Elementary
Scheme 1.(ads)
⇋ H2(g)kinetic
+ 2 ∗steps for the ammonia decomposition reaction; (*) refers to an unoc-
cupied
Schemeadsorption
Scheme 1. Elementary kinetic sitefor
steps
1. Elementary on the
the catalyst
kinetic steps for[29].
ammonia thedecomposition reaction; reaction;
ammonia decomposition (*) refers(*)torefers
an unoc-
to an unoccu-
cupied adsorption site
pied on the catalyst
adsorption [29].
site on the catalyst [29].
Regarding the ammonia synthesis reaction, dissociative nitrogen adsorption is typi-
cally viewed as the rate-determining step. Nevertheless, there’s a possibility that recom-
Regarding theRegarding
ammonia synthesis ammonia synthesis
reaction, reaction,
dissociative dissociative nitrogen
nitrogen adsorption adsorption
is typi- is typi-
binative nitrogen
cally viewed as thedesorption could also
rate-determining step.impact the ratethere’s
Nevertheless, of theadecomposition
possibility thatreaction.
recombi-
cally viewed as the rate-determining step. Nevertheless, there’s a possibility that recom-
This
nativematter requires
nitrogen furthercould
desorption investigation
also impact andthe
research
rate ofto determine
the its actual
decomposition impactThis
reaction. on
binative nitrogen
the desorption
reaction
matter requires
could
kinetics.
further
also impact
Lucentini et al. and
investigation
theresearch
conductedrate of
a tothe
survey decomposition
and analysis
determine
reaction.
its actualofimpact
various oncatalytic
the reac-
This matter requires
systems.further
tion kinetics. investigation
The Lucentini
technological andand
et al.status research
conducted to determine
challenges
a survey of analysis
and ammonia itsofdecomposition
actual
variousimpact
catalytic on
were first
systems.
the reaction kinetics.
presentedLucentini et
in theirstatus
The technological al. conducted
paper.and Then, a survey
state-of-the-art
challenges and
of ammonia analysis
catalytic of various
systems and
decomposition were catalytic
related reaction
first presented
systems. The technological
mechanisms status
in their paper.were and challenges
Then,described in detail.
state-of-the-art of ammonia
catalyticFinally, decomposition
systemsthe andstructured
related reaction weremechanisms
reactors firstfor the
were described
presented in their paper. Then, in detail. Finally, the structured
state-of-the-art reactors for
catalytic systems andtherelated
decomposition
reactionreaction
mechanisms were described in detail. Finally, the structured reactors forthe the
of ammonia were explored [10]. In summary, the nitrogen desorption is dominant
Molecules 2023, 28, x FOR PEER REVIEW 5 of 25

Molecules 2023, 28, 5245 5 of 25

decomposition reaction of ammonia were explored [10]. In summary, the nitrogen desorp-
tion is the dominant slow step, but the complexity of the reaction increases with the cata-
lyst
slowcomposition,
step, but theactive phase,ofand
complexity thereaction
reaction conditions.
increases with the catalyst composition, active
Regarding the catalysts,
phase, and reaction conditions. there has been a growing interest in using transition metal-
basedRegarding
catalysts for NH3-to-Hthere
the catalysts, 2 conversion.
has beenAlthough
a growingRu-based
interest incatalysts have demon-
using transition metal-
strated excellentfor
based catalysts performance, they are less
NH3 -to-H2 conversion. practical
Although for large-scale
Ru-based catalystsapplications
have demonstrated due to
their highperformance,
excellent cost [30–32]. Therefore,
they are less Fepractical
and Ni-based catalystsapplications
for large-scale have emerged dueastopromising
their high
alternatives
cost [30–32].due to theirFe
Therefore, superior performance,
and Ni-based catalystsbut efforts
have are still
emerged underwayalternatives
as promising to further
reduce
due to costs, optimizeperformance,
their superior activity, and but increase
effortstheir operational
are still underway lifespan [33–38].
to further reduce Onecosts,
ap-
proach
optimize to activity,
improving andthe activity
increase of operational
their these catalyst systems
lifespan is to One
[33–38]. use rare earthto
approach element-
improv-
ing the
based activity of these
heteroatoms, such catalyst
as La and systems
Ce, forisdoping.
to use rareThisearth element-based
results in improvingheteroatoms,
the surface
such as La increasing
properties, and Ce, forthe doping.
number This results
of active in improving
sites, and enhancing the surface properties,
the catalytic activity increas-
of Fe
ing the
and number
Ni-based of active
catalysts sites, and
[39–43]. enhancing
Another approach the catalytic
is to createactivity of Fe and
multi-metal Ni-based
alloy-based
catalysts [39–43].
structures, which can Another
further approach
enhanceisthe to create
catalyticmulti-metal
activity byalloy-based structures,
providing better which
dispersion
can further enhance the catalytic activity by providing better dispersion
of the metal atoms, improving the stability of the catalyst, and increasing the resistance to of the metal atoms,
improving[28,44–49].
poisoning the stability of the catalyst, and increasing the resistance to poisoning [28,44–49].
Theconventional
The conventionalprocessprocessof of H
H22production
productionthrough
throughthermocatalytic
thermocatalyticNH NH33decompo-
decompo-
sitionisisslow.
sition slow.ItItrequires
requiresexternal
externalenergy
energyinput
inputtotoheatheatthethecatalyst
catalyst toto
at at least
least 400400℃°C forfor
a
a sufficient time, resulting in time delay and low energy efficiency.
sufficient time, resulting in time delay and low energy efficiency. Therefore, a more suit- Therefore, a more
suitable
able approach
approach forH
for the the H2 production
2 production process
process is needed
is needed that that
doesdoes not require
not require external
external en-
energy input. One such approach involves exposing a pretreated
ergy input. One such approach involves exposing a pretreated catalyst to a mixture catalyst to a mixtureof
of NH
NH 3 and3 and O2 gases
O2 gases at a specific
at a specific ratioratio at room
at room temperature.
temperature. This approach
This approach is knownis known
as low-as
low-temperature ammonia oxidation, and it removes the need
temperature ammonia oxidation, and it removes the need for the high-temperature de- for the high-temperature
decomposition
composition of NH
of NH 3 . The
3. The
reaction
reaction proceeds
proceeds as follows:
as follows:

3 +3 1/4O
NHNH 2 →
+ 1/4O HH
2 → 2 2++1/2N
1/2N22++1/2H
1/2H22O ∆H =
O ((∆H −75kJ/mol)
=−75 kJ/mol)
Katsutoshi Nagaokaetetal.al.studied
Katsutoshi Nagaoka studied hydrogen
hydrogen production
production using
using an acidic
an acidic RuO2/γ-
RuO2 /γ-Al 2 O3
Al 2O3 catalyst by exposing ammonia and O2 at room temperature, as shown in Figure 5
catalyst by exposing ammonia and O2 at room temperature, as shown in Figure 5 [50]. The
[50]. The exothermic
exothermic adsorptionadsorption
of ammonia of ammonia on the
on the catalyst catalyst
causes causes the
the catalyst bedcatalyst bedheat
to rapidly to
rapidly heat up to the auto-ignition temperature of catalytic ammonia, resulting
up to the auto-ignition temperature of catalytic ammonia, resulting in the oxidative decom- in the
oxidative decomposition
position of of ammonia
ammonia to generate to generate
hydrogen. hydrogen.
A differential A differential
calorimeter and calorimeter
a volumetricand gas
asorption
volumetric
analyzer were used in the study to measure the heat released by the heat
gas sorption analyzer were used in the study to measure the released
physisorption
by
of the physisorption
multiple ammoniaofmolecules
multiple ammonia molecules andofthe
and the chemisorption chemisorption
ammonia of ammonia
onto both the RuO2
onto both the
and acidic sitesRuO 2 and
on the acidic
γ-Al O
2 3 . sites
The on the
results γ-Al
showed2Oa3. significant
The results showed
amount of a significant
heat evolved
amount of heat
during both evolved during both processes.
processes.

Figure 5. Schematic of the catalytic cycle developed for oxidative decomposition of ammonia
(reproduced with permission from [50], Copyright Science, 2017).
Molecules 2023, 28, 5245 6 of 25

2.2. Non-Thermal Plasma-Catalytic NH3 Decomposition

Thermocatalytic decomposition of NH3 generally occurs at a temperature above 873 K,
while traditional thermal reforming or decomposition of NH3 typically requires a high
temperature of about 1300 K. Despite the presence of a catalyst, the reaction temperature
is still relatively high, restricting the reaction’s useful applications. To start chemical
reactions at lower temperatures, researchers have investigated the potential of alternate
strategies involving electrical discharges or non-thermal plasmas [18,21,51]. Researchers
have explored the potential of plasma-catalytic NH3 decomposition. The results show
that non-thermal plasma can effectively transform NH3 into H2 with less influence from
the gas temperature [52–54]. The results of studies conducted on plasma-catalytic NH3
decomposition suggest that it can be produced with lower energy consumption and higher
efficiency [22,55–57].
Generally, the decomposition of ammonia induced through the direct application of
plasma is restrained due to the following reasons: (1) Energy efficiency: Direct application
of plasma does not now have any significant advantages in terms of energy use in contrast
to catalytic decomposition [58–60]. This is because, beneath equilibrium conditions, ammo-
nia can decompose at relatively low temperatures. (2) Plasma stabilization: When ammonia
undergoes direct-discharge conditions, it decomposes to produce nitrogen and high concen-
trations of hydrogen [61]. This makes it challenging to stabilize the plasma, which similarly
complicates the process of ammonia decomposition. However, one can still take advantage
of the benefits of plasma, such as the speedy introduction of high-temperature reaction
conditions. In the catalytic reaction system, plasma can function solely in the preliminary
start-up stage segment till the catalyst bed is heated up to the reaction temperature [14]. In
this case, hydrogen can be produced immediately at the beginning of the plasma system
via the capability of a decomposition reaction. At the same time, the catalyst can be heated
quickly via the warmth supplied via the plasma.
The mechanism for the plasma-assisted conversion of NH3 can be divided into two
parts. (1) Plasma mechanisms: These involve electron-induced chemistry, such as electron
impact reactions, quenching of excited species, and ion reactions. The energetic electrons
in the plasma interact with the NH3 molecules, leading to various chemical reactions.
(2) Thermal mechanisms: These involve conventional thermal mechanisms for thermally
induced chemistry. The heat generated by the plasma contributes to the overall conversion
of NH3 . Thermal energy helps break and form chemical bonds, facilitating the conversion
process. Bang et al. conducted an experimental and numerical study of the plasma-assisted
conversion of NH3 (Figure 6). They used a mixture of NH3 (1 mol%) diluted in N2 at
atmospheric pressure. This allowed them to investigate the effects of plasma on NH3
conversion under specific conditions [62]. They observed that the conversion of NH3 took
place even at room temperature during their study. They found a local peak in conversion
at around 600 K. This finding suggests that the plasma-assisted cracking of NH3 has the
potential to be cost-effective by reducing the temperature range required for the cracking
reaction. Lowering the temperature window for the cracking reaction can lead to energy
savings and improved efficiency in the conversion process.

2.3. Electrocatalytic NH3 Decomposition

The electrochemical process is also a promising alternative for onboard use, as hy-
drogen and nitrogen can be gained from the decomposition of ammonia at a moderate
temperature [17,63,64]. Liquid ammonia has a theoretical electrolysis voltage of 0.077 V,
significantly lower than water’s electrolysis voltage of 1.23 V [16,63]. When ammonia is
electrolyzed, hydrogen molecules are produced at the cathode, and amide ions are released.
Amide ions are oxidized at the anode to form nitrogen molecules. The electrolysis reactor
must be designed as a highly closed electrolytic cell under stringent experimental condi-
tions to prevent the oxidation and hydration of metal amides [63]. However, the current
efficiency is only 85% at a high cell voltage of 2 V due to the inevitable reverse reaction in
 Molecules 2023, 28, 5245 7 of 25

Molecules 2023, 28, x FOR PEER REVIEW 7 of 25

liquid ammonia. To make ammonia electrolysis practical, it is necessary to reduce the cell
voltage as much as possible at a high current.

Schematic of −1 −2
Figure 6.
Figure 6. Schematic of the
the primary
primarychain
chainreactions forfor
reactions (a) (a)
PCMech
PCMechand (b) (b)
−1 and PCMech
PCMechfor the the
−2 for

NH3/N
NH 3 /N
2 combination
combination
2 (1/99
(1/99 mol%)
mol%) with
with TgTg
= = 500
500 K,K, E/N
E/N = =
150 150 Td,
Td, and
and PdisPdis
= =
10 10
W. W. (reproduced
(reproduced with
with permission from [62], Copyright American Chemical Society,
permission from [62], Copyright American Chemical Society, 2023). 2023).

The electrocatalytic
2.3. Electrocatalytic NH3 decomposition can occur in an aqueous electrolyte under
NH3 Decomposition
certain pH conditions, either through the NH3 oxidation in an alkaline environment caused
by OHThe− electrochemical process is
ions after the adsorption of also
NH3 aonto
promising alternative
the electrode for onboard
or through use, as hy-
NH4 + oxidation
drogen and nitrogen can be gained from the decomposition of ammonia
by the oxidants such as hypochlorous acid in low pH environments [65–67]. However, at a moderate
temperature [17,63,64].
electro-corrosion Liquidkinetics
and sluggish ammonia has aelectrolytes
in acidic theoreticalcanelectrolysis
lead to lowvoltage of in
efficiency 0.077
the V,
significantly
electrochemical process. Alternative approaches to address this issue involve using alkaline is
lower than water’s electrolysis voltage of 1.23 V [16,63]. When ammonia
electrolyzed,
electrolytes for hydrogen molecules
electrocatalytic NH3 are produced atwhich
decomposition, the cathode,
have been and amide ions
extensively are re-
studied
leased. Amide
and offer ions are to
the potential oxidized
overcome at the anode toproblems
undesirable form nitrogen
relatedmolecules. The electrolysis
to acidic environments
towards
reactor electrode
must materials.
be designed as Ideally,
a highlyinclosed
an NHelectrolytic
3 decomposition system,
cell under NH3 is oxidized
stringent to
experimental
N at the
conditions
2 anode, while
to prevent theH O is reduced to H at the cathode, producing the
2 oxidation and 2hydration of metal amides [63]. However, gaseous H 2 and the
N2 fromefficiency
current an ammonia solution.
is only 85% atHowever, it isvoltage
a high cell well known
of 2 Vthat
duethetoside
the reaction
inevitableof OER
reverse
may be aincompeting
reaction process with
liquid ammonia. the Electrocatalytic
To make NH3 decomposition
ammonia electrolysis practical, it isat necessary
the anode.to re-
Anode
duce the cell reaction:
voltage as much as possible at a high current.
The electrocatalytic
2NH3 + 6OH NH − 3 decomposition can−occur
−→ N2 + 6H2 O + 6e Eθ = in an aqueous
−0.77 V vs. SHEelectrolyte under
certain pH conditions, either through the NH3 oxidation in an alkaline environment
caused by OHreaction:
Cathode − ions after the adsorption of NH3 onto the electrode or through NH4+ oxi-

dation by the oxidants such as hypochlorous acid in low pH environments [65–67]. How-
−
ever, electro-corrosion + 2esluggish
2H2 Oand + 2OH− in
−→ H2 kinetics Eθacidic
= −0.829 V vs. SHEcan lead to low effi-
electrolytes
ciency in the electrochemical process. Alternative approaches to address this issue involve
using alkaline electrolytes for electrocatalytic NH3 decomposition, which have been ex-
tensively studied and offer the potential to overcome undesirable problems related to
acidic environments towards electrode materials. Ideally, in an NH3 decomposition sys-
tem, NH3 is oxidized to N2 at the anode, while H2O is reduced to H2 at the cathode, pro-
ducing the gaseous H2 and N2 from an ammonia solution. However, it is well known that
 composition at the anode.
Anode reaction:
2NH3 + 6OH − ⟶ N2 + 6H2 O + 6e− Eθ = −0.77V vs. SHE
Cathode reaction:
Molecules 2023, 28, 5245 8 of 25
− − θ
2H2 O + 2e ⟶ H2 + 2OH E = −0.829V vs. SHE
Overall reaction:
Overall reaction:
2NH
2NH 3 ⟶
3 −→
3H
3H 2+
2+ NN Eθ = −0.059V
θ
2 2E = −0.059 V
The use
The use of
of electrocatalytic
electrocatalytic NH NH33decomposition
decompositiontotoproduce
produce H2Hhashasmanymany benefits,
benefits,in-
2
cluding simplicity and cost-effectiveness. However, problems remain,
including simplicity and cost-effectiveness. However, problems remain, such as slow such as slow kinet-
ics and poor
kinetics selectivity.
and poor To increase
selectivity. the electrocatalytic
To increase NH3NH
the electrocatalytic decomposition efficiency, var-
3 decomposition efficiency,
ious types of electrocatalysts have been studied, but their performance
various types of electrocatalysts have been studied, but their performance still cannot satisfy
still cannot
the requirements
satisfy of industrial
the requirements applicability.
of industrial Therefore,
applicability. it is important
Therefore, to develop
it is important new
to develop
high-efficiency
new ammonia
high-efficiency ammonia electrolysis electrodes
electrolysis electrodesforforhydrogen
hydrogenproduction,
production, as as shown
shown in in
Figure7.
Figure 7. Although
Although platinum
platinum and and other
other precious
precious metal-based
metal-based catalysts
catalystsareareeffective
effectivefor for the
the
processof
process ofelectrocatalytic
electrocatalyticNHNH33 decomposition
decomposition (alkaline
(alkaline water
water electrolysis),
electrolysis),their
theirhigh
high cost
cost
and limited availability are significant drawbacks [16,17,68–70]. Recently,
and limited availability are significant drawbacks [16,17,68–70]. Recently, catalysts based catalysts based
on transition
on transitionmetals
metalshave
have shown
shown promise
promiseforforelectrocatalytic
electrocatalyticNH NH33 decomposition
decomposition through through
variousstructural
various structuralandand morphological
morphological engineering
engineering techniques,
techniques, including
including alloyed/core-
alloyed/core-shell
shell formation,
formation, shape heteroatom
shape control, control, heteroatom
doping, and doping, and self-supporting
self-supporting materials
materials [40,66,71–73].
[40,66,71–73].
However, the However, the current
current density densityand
of oxidation of oxidation
selectivityand selectivity
achieved by achieved by these
these catalysts is
catalysts
still loweristhan
stillwhat
loweris than whatfor
required is practical
required application.
for practicalTherefore,
application. Therefore,
further researchfurther
and
development
research and in this area is necessary.
development in this area is necessary.

Figure7.7.Pt
Figure Ptand
andFeFecatalysts
catalystsdecompose
decompose ammonia
ammonia (reproduced
(reproduced with
with permission
permission fromfrom
[70],[70], Copy-
Copyright
right American
American Chemical
Chemical Society,
Society, 2017). 2017).

2.4.
2.4. Photocatalytic
Photocatalytic NH
NH33 Decomposition
The
The photocatalytic
photocatalytic methodmethod of of splitting
splittingNHNH3 3into
intoNN 2 and
2 and H2His2 also
is also a promising
a promising ap-
approach,
proach, asasit itcan
canbebecarried
carriedoutoutusing
usingrecyclable
recyclable catalysts
catalysts atat room temperature and and can
can
easily
easilycontrol
controllight exposure
light exposurewithwith
a switch. UsingUsing
a switch. sunlight to decompose
sunlight ammoniaammonia
to decompose through
photocatalysis is an artificial
through photocatalysis is anphotosynthetic reaction that
artificial photosynthetic occursthat
reaction in alkaline conditions
occurs in [15].
alkaline con-
As shown
ditions in As
[15]. Figureshown8, when the energy
in Figure 8, when ofthe
theenergy
irradiating
of thelight exceeds light
irradiating the band gapthe
exceeds of
the photocatalyst it creates electron-hole pairs. The resulting holes act as
band gap of the photocatalyst it creates electron-hole pairs. The resulting holes act as strong oxidants,
while
strongthe electrons
oxidants, in the
while theconduction
electrons in band
the can reduce Oband
conduction 2 to form hydroxyl
can reduce O2 radicals.
to form hy-To
achieve the photocatalytic degradation of ammonia, the electrons and holes
droxyl radicals. To achieve the photocatalytic degradation of ammonia, the electrons and generated on
the surface
holes of a semiconductor
generated on the surface of must have appropriate
a semiconductor mustreduction and oxidation
have appropriate abilities
reduction and
to interact abilities
oxidation with theto adsorbed
interact species
with theonadsorbed
the catalyst surface
species andcatalyst
on the producesurface
free radicals
and pro-or
other products.
duce free radicals or other products.
Photocatalyst + hv −→ e− + h+

2NH3 + 6h+ −→ N2 + 6H+

2H+ + 2e− −→ H2
 Photocatalyst + h𝑣 ⟶ e− + h+

2NH3 + 6h+ ⟶ N2 + 6H +

Molecules 2023, 28, 5245 9 of 25

2H + + 2e− ⟶ H2

8. Illustration
Figure 8.
Figure Illustrationofof
thethe
process of photocatalytic
process ammonia
of photocatalytic decomposition
ammonia (reproduced
decomposition with
(reproduced wit
permission from [15], Copyright Royal Soc Chemistry, 2020).
permission from [15], Copyright Royal Soc Chemistry, 2020).
So far, only a limited number of photocatalysts have been found to be effective in the
So far, only
decomposition of aanlimited
aqueous number
ammonia of solution.
photocatalysts have been
These include common found to be effective in th
photocatalysts,
decomposition of an aqueous ammonia solution. These
such as TiO2 , ZnO, ZnS, Mo2 N, and graphene, as well as their hybrid materials that include common photocatalyst
are
such
loaded aswith
TiO2metals
, ZnO,[15,74–83].
ZnS, Mo2Utsunomiya
N, and graphene, as welltheasphotocatalytic
et al. studied their hybrid activitymaterialsof that ar
TiO loaded with different metals on the decomposition of ammonia
loaded with metals [15,74–83]. Utsunomiya et al. studied the photocatalytic activity o
2 and explored the
NH23 loaded
TiO decomposition mechanism
with different by proposing
metals three reaction pathways
on the decomposition of ammonia [83]. As andshown
explored th
in Figure 9, route 1 involves the formation of NH radicals by removing one hydrogen
NH3 decomposition mechanism by proposing three reaction pathways [83]. As shown i
atom from each of the two NH2 radicals, while route 2 involves the coupling of adjacent
Figure 9, route
NH2 radicals to 1
forminvolves
NH2 -NH the .formation 0 of NH radicals by removing one hydrogen atom
2 Route 2 involves the formation of NH2 -NH2 through
from each of the
the formation of Htwo NH2 radicals, while route 2 involves the coupling of adjacent NH
2 N-NH3 . The activation energies for routes 1 and 2 calculated by
radicals to form NH
density functional theory (DFT)
2 -NH 2. Route
are 2362’kcal/mol
involvesand the74.8formation
kcal/mol,ofrespectively.
NH2-NH2 Of through
these the fo
mation
pathways, of route
H2N-NH 3. The activation
2 is considered energies
energetically morefor routesthan
favorable 1 and 2 calculated
route 1. Possible by density fun
reaction
pathways for the formation of N and H through NH -NH coupling
tional theory (DFT) are 236 kcal/mol and 74.8 kcal/mol, respectively. Of these pathway
2 2 2 2 were further divided
into two
route 2 isroutes: route 2, energetically
considered which involvesmore the coupling
favorable of NH
than 2 radicals
route to 1. form
PossibleH2 N-NH 2,
reaction path
and route 20 , which involves the interaction of NH2 with one NH3 molecule in the gas
ways for the formation of N2 and H2 through NH2-NH2 coupling were further divided int
phase. The activation energies of the two routes were estimated to be 74.4 kcal/mol and
two routes: route
59.2 kcal/mol, 2, which
respectively. involves
Therefore, it isthe coupling
plausible that ofNHNH 2 radicals to form H2N-NH2, an
3 decomposition occurs via the
route 2′, which
formation of NH2involves
-NH2 through the interaction
routes 2 and of 20 . NH
Razak2 with
et al.one NH3the
reported molecule in the gas phas
linear generation
The
of H2activation
from NH3 over energiesPd/TiO of2the two They
catalyst. routes werethat
suggest estimated
the productionto be of 74.4
H2 kcal/mol
from NH3 and 59
kcal/mol,
was initiated respectively.
by the interactionTherefore, it is plausible
of N atoms that NHThis
on the Pd surface. 3 decomposition
interaction led occurs
to the via th
dissociation of N-H bonds under the catalysis of photogenerated
formation of NH2-NH2 through routes 2 and 2′. Razak et al. reported the linear generatio electrons [84].
of H2Recently,
from NH Yuan et al. have discovered that Cu-Fe-AR, which is not an effective thermo-
3 over Pd/TiO2 catalyst. They suggest that the production of H2 from NH
catalyst, can function as an excellent photocatalyst for NH3 decomposition when exposed
was initiated by the interaction of N atoms on the Pd surface. This interaction led to th
to short-pulse laser illumination [85]. The formation of adsorbate–metal excited states by
dissociation of N-H
hot carriers leads to thebonds under
lowering the catalysis
of activation of photogenerated
barriers, active site cleaning, electrons [84].
and product
desorption, resulting in enhanced reactivity and stability of Cu-Fe-AR compared to tradi-
tional thermocatalysts. Under continuous-wave LED illumination, Cu-Fe-AR manifests
a high efficiency comparable to Cu-Ru-AR. Although Cu-Ru-AR exhibits slightly greater
reactivity due to photothermal heating, the study demonstrates that photocatalysis can
be efficiently performed with inexpensive LED photon sources, as shown in Figure 10.
The results suggested that abundantly available metals might serve as productive and
cost-effective catalyst substrates for plasmonic antenna-reactor photocatalysis.
Molecules 2023, 28, x FOR PEER REVIEW 10 of
Molecules 2023, 28, 5245 10 of 25

Figure 9.9.Reaction
Figure Reactionmechanism
mechanism of NH decomposition
of 3NH to N2 and
3 decomposition to NH2 2and
overHTiO 2 photocatalyst
2 over (repro- (repr
TiO2 photocatalyst
duced with permission from [83], Copyright Elsevier, 2017).
duced with permission from [83], Copyright Elsevier, 2017).

Recently, Yuan et al. have discovered that Cu-Fe-AR, which is not an effective the
mocatalyst, can function as an excellent photocatalyst for NH3 decomposition when e
posed to short-pulse laser illumination [85]. The formation of adsorbate–metal excite
states by hot carriers leads to the lowering of activation barriers, active site cleaning, an
product desorption, resulting in enhanced reactivity and stability of Cu-Fe-AR compare
 greater reactivity due to photothermal heating, the study demonstrates that photocataly-
sis can be efficiently performed with inexpensive LED photon sources, as shown in Figure
Molecules 2023, 28, 5245 11 of 25
10. The results suggested that abundantly available metals might serve as productive and
cost-effective catalyst substrates for plasmonic antenna-reactor photocatalysis.

Figure 10.
Figure Schematiccomparison
10.Schematic comparisonofofthe theenergy
energydiagram
diagram forfor photocatalysis
photocatalysis (excited
(excited states)
states) and
and ther-
thermocatalysis
mocatalysis (ground
(ground state)
state) on Cu-Fe-
on Cu-Fe- andand Cu-Ru-ARs.
Cu-Ru-ARs. RedRed arrowsrefer
arrows refertotoelectronic
electronic excitation
excitation on
on Fe-N,
Fe-N, andand
blueblue to Ru-N.
to Ru-N. OnlyOnly
the the
twotwo possible
possible RDSsRDSs
are are included
included for for simplicity;
simplicity; migrations
migrations of ni-
of nitrogen
trogen species
species areconsidered
are not not considered for same
for the the same reason
reason (reproduced
(reproduced withwith permission
permission fromfrom [85],
[85], Cop-
yright Science, 2022).
Copyright Science, 2022).

3. Catalysts for NH Decomposition

3. Catalysts for NH33 Decomposition
The choice of catalyst is critical for the efficient decomposition of ammonia to produce
The choice of catalyst is critical for the efficient decomposition of ammonia to pro-
hydrogen at low temperatures, and different technologies require different catalysts. For ex-
duce hydrogen at low temperatures, and different technologies require different catalysts.
ample, the Ru group of catalysts is commonly used in thermocatalytic NH3 decomposition,
For
whileexample, the Ruisgroup
the Pt group of catalysts
suitable for both is commonly used
electrocatalytic andinphotocatalytic
thermocatalytic NHNH 3 decom-
3 decom-
position, while the Pt group is suitable for both electrocatalytic and
position. In addition to co-catalysts, such as Ru and Pt, photocatalysts are also required photocatalytic NH3
decomposition.
in photocatalytic NH3 decomposition [9,26,72,73]. In non-thermal plasma-catalytic NH3 re-
In addition to co-catalysts, such as Ru and Pt, photocatalysts are also
quired in photocatalytic
decomposition, Fe-basedNH 3 decomposition
catalysts have been[9,26,72,73].
the most studiedIn non-thermal
[48,51,54]. plasma-catalytic
Furthermore,
NH decomposition,
for 3the industrialization Fe-based catalysts
of hydrogen have been
production fromthe most studied
ammonia [48,51,54].
decomposition, Further-
catalyst
more, for the industrialization of hydrogen production from ammonia
support is vital as it has a synergistic effect on the catalyst’s performance. Therefore, this decomposition,
catalyst support
review will focusison vital as it has
precious a synergistic
metal catalysts, effect on the catalyst’s
non-precious performance.
metal catalysts, There-
multi-alloy
catalysts,
fore, this and
review other aspects,
will focus emphasizing
on precious the research
metal emphasis
catalysts, on various
non-precious catalysts
metal in
catalysts,
different NHcatalysts,
multi-alloy 3 decomposition
and othertechniques.
aspects,By understanding
emphasizing thethe uniqueemphasis
research roles catalysts play
on various
in different
catalysts technologies,
in different NH3researchers
decomposition can optimize performance
techniques. and improve
By understanding thethe overall
unique roles
efficiency of the ammonia decomposition process.
catalysts play in different technologies, researchers can optimize performance and im-
prove the overall efficiency of the ammonia decomposition process.
3.1. Precious Metal Catalysts
PreciousMetal
3.1. Precious metals are a significant type of catalyst material, with Ru-based materials being
Catalysts
particularly noteworthy for their exceptional performance in NH3 decomposition [7,9,10,31].
As a Precious
result, they metals are aextensively
have been significantstudied.
type of Thecatalyst material,
catalysis of NH3with Ru-based materials
decomposition on Ru-
being particularly noteworthy for their exceptional performance
based catalysts is primarily attributed to B5 active sites [31,86–88]. The B5-type 3site in NH decomposition
comprises
[7,9,10,31]. As a of
a configuration result,
threethey have been
Ru atoms in oneextensively
layer and two studied. The catalysis
additional Ru atomsofinNH decom-
the3 layer
position on Ru-based
directly above catalysts isstep
it at a monoatomic primarily attributed
on a Ru(0001) to [89],
terrace B5 active sitesin[31,86–88].
as shown The B5-
Figure 11. Thus,
type site comprises
the number of B5 active a configuration of three
sites is frequently linked Rutoatoms
the sizeinand
oneshape
layerofand
Ru two additional
nanoparticles onRu
atoms in thesurface
the catalyst layer [90,91].
directly above it at a monoatomic step on a Ru(0001) terrace [89], as
shown in Figure 11. Thus, the number of B5 active sites is frequently linked to the size and
shape of Ru nanoparticles on the catalyst surface [90,91].
Molecules 2023,
Molecules 28,28,
2023, x 5245
FOR PEER REVIEW 12 of 25 12 of 25

Figure 11. Scheme of associative adsorption of the two N atoms to form an N2 molecule in a B5-type
Figure 11. Scheme of associative adsorption of the two N atoms to form an N2 molecule in a B5-type
site: (1) N atoms diffusion to the B5-type site, (2) association of N atoms to form an N2 molecule, and
site: (1) N atoms diffusion to the B5-type site, (2) association of N atoms to form an N2 molecule, and
(3) desorption of the N molecule (‘three stages of the growth of an Ru particle’ reproduced with
(3) desorption of the 2N2 molecule (‘three stages of the growth of an Ru particle’ reproduced with
permission from [91], Copyright Springer, 2009).
permission from [91], Copyright Springer, 2009).
Kim et al. investigated the influence of the crystalline phase of alumina on the de-
Kim et of
composition al.NH
investigated the influence of the crystalline phase of alumina on the de-
3 over Ru catalysts supported on alumina [87]. The results show that
composition of NH over
the dispersion and morphology of
3 Ru catalysts
Ru are keysupported
factors foron H2alumina
production [87].
fromTheNH results
3 decom-show that
the dispersion
position and morphology
over Ru/Al of Ru
2 O3 catalysts and canarebekey factorsby
regulated fortheH2support
production from NH3 decom-
and calcination
temperature.
position overAmong
Ru/Al2O the Ru/Al2 Oand
3 catalysts 3 catalysts
can be calcined
regulated at by
various temperatures
the support and re- tem-
and calcination
perature. Among the Ru/Al2O3 catalysts calcined at various temperatures andrate
duced at 573 K, Ru/γ-Al 2 O3 with Ru particle sizes of 7~8 nm displayed the highest reduced at
of ammonia
573 K, Ru/γ-Aldecomposition. Feng et al. have demonstrated that Yttrium oxide (Y2 O3 )of
2O3 with Ru particle sizes of 7~8 nm displayed the highest rate
can
ammonia
effectively disperse and stabilize Ru nanoparticles as a functional support for catalysts [92].
decomposition. Feng et al. have demonstrated that Yttrium oxide (Y2O3) can effectively
Highly dispersed Ru nanoparticles on Y2 O3 (Ru/Y2 O3 ) were prepared, and the catalytic
disperse
activity ofand stabilize
ammonia Ru nanoparticles
decomposition as a functional
was evaluated. The results support
showedfor thatcatalysts [92]. Highly
at a relatively
dispersed
high weightRu gasnanoparticles on Y2O3of(Ru/Y
hourly space velocity 30,0002OmLg
3) were −1 h−prepared,
1 , the 5 wt.% andRu/Y
the 2catalytic
O3 catalystactivity of
ammonia
exhibited excellent catalytic activity, achieving near-complete NH3 conversion at 475 C, su- high
decomposition was evaluated. The results showed that at a relatively
◦

weight
perior togas hourly
many space velocity
Ru catalysts supportedof by
30,000 mLg
typical −1h−1,Cha
oxides. the et5 wt.% Ru/Y2O
al. reported 3 catalyst
the successful exhibited
loading of highly monodisperse Ru particles onto alkali-exchanged zeolite
excellent catalytic activity, achieving near-complete NH3 conversion at 475 °C, superior to Y support using
an ion-exchange
many Ru catalystsmethod coupledby
supported with a vacuum
typical oxides. calcination
Cha et al. treatment
reported [93].
theAs shown in loading
successful
Figure 12, the resulting Ru/M-Y catalysts exhibit an average particle size
of highly monodisperse Ru particles onto alkali-exchanged zeolite Y support using an ion- of approximately
1 nm and contain both nanometer- and sub-nanometer-sized Ru particles. Hu et al. re-
exchange method coupled with a vacuum calcination treatment [93]. As shown in Figure
ported the successful synthesis of stable ruthenium (Ru) clusters with a size of about 1.5 nm
12, the resulting
by reduction Ru/M-Y
of single catalysts
Ru atoms underexhibit an average
an ammonia particle at
atmosphere size550of◦ C
approximately
[94]. These 1 nm
and contain both nanometer- and sub-nanometer-sized Ru particles.
Ru clusters are uniformly dispersed on the surface of the ceria. The obtained supported Hu et al. reported the
successful synthesis
ruthenium cluster of stable
catalysts exhibitruthenium
exceptional (Ru)
activityclusters with adecomposition
for ammonia size of aboutwith 1.5 annm by re-
duction
extremelyofhigh
single Ru atoms
hydrogen under rate.
production an ammonia
Ru-based atmosphere
materials have atpotential
550 °C [94]. These Ru clus-
applications
in Photocatalytic
ters are uniformly NH3dispersed
decomposition
on theandsurface
Plasma-catalytic
of the ceria.NH3 decomposition.
The obtained Iwase et al. ruthe-
supported
have reported
nium that a Ru-loaded
cluster catalysts exhibitZnS photocatalyst
exceptional activitydemonstrated
for ammonia remarkable activity in with an
decomposition
decomposing an aqueous ammonia solution into H and N
extremely high hydrogen production rate. Ru-based materials have potential
2 2 with a stoichiometric amount
applications
under simulated solar radiation [79]. In this reaction, the Ru co-catalyst was crucial in
in Photocatalytic NH3 decomposition and Plasma-catalytic NH3 decomposition. Iwase et
promoting ammonia oxidation to N2 .
al. have reported that a Ru-loaded ZnS photocatalyst demonstrated remarkable activity
in decomposing an aqueous ammonia solution into H2 and N2 with a stoichiometric
amount under simulated solar radiation [79]. In this reaction, the Ru co-catalyst was cru-
cial in promoting ammonia oxidation to N2.
Molecules 2023,28,
Molecules2023, 28,5245
x FOR PEER REVIEW 13 of 25
13 25

Figure12.
Figure 12.(a)
(a)HAADF-STEM
HAADF-STEMimages,images,(b)
(b)particle
particlesize
sizedistribution,
distribution,and
and(c)
(c)EDS
EDSelemental
elementalmapping
mapping
imagesofofRu/M-Y
images Ru/M-Ycatalysts
catalysts(M
(M= =H,H, Na,
Na, K,K,
andand
Rb)Rb) (reproduced
(reproduced withwith permission
permission fromfrom
[93], [93], Copy-
Copyright
right Elsevier, 2021).
Elsevier, 2021).

OnOnthe
theother
otherhand,
hand,thethe support
support used
used also
also strongly
strongly affects
affects thethe catalytic
catalytic activity
activity of of Ru-
Ru-
basedmaterials.
based materials.Firstly,
Firstly, a support
a support with
with a high
a high specific
specific surfacesurface
area area can enhance
can enhance the dis-
the dispersal
persal
of of Ru nanoparticles,
Ru nanoparticles, leading toleading to improved
improved NH3 adsorption
NH3 adsorption capacitySecondly,
capacity [92–94]. [92–94]. Sec-the
ondly, the characteristics of the support itself can have a synergistic
characteristics of the support itself can have a synergistic effect with Ru nanoparticles, effect with Ru nano-
particles,
thereby thereby enhancing
enhancing catalytic[23,95–99].
catalytic activity activity [23,95–99].
For example, For example,
Jeon et al.Jeonsynthesized
et al. synthe- a
sized a Y-doped BaCeO perovskite and constructed a
Y-doped BaCeO3 perovskite and constructed a strong metal support interaction
3 strong metal support interaction
(SMSI)
(SMSI) interface
interface with Ruwith Ru particles,
particles, as shownas shown
in Figure in Figure
13 [95].13 The[95]. The catalyst
catalyst achievedachieved
100% NH 100% 3
NH3 decomposition
decomposition efficiency at 500 ◦at
efficiency 500 had
C and °C and had aHhigher
a higher 2 H
generation 2 generation
rate than rate
most than most
Ru-based
Ru-basedThe
catalysts. catalysts. The improvement
improvement in catalytic performance
in catalytic performance can be attributed can be attributed
to the promotion to the
of
Npromotion
2 desorption of N
by2 desorption
the SMSI by the
interface.SMSI interface.
Yamazaki et al.Yamazaki
studied Ruet al. studied
catalysts Ru catalysts
supported on
CeO 2 −PrOxon
supported CeO2−PrO(Ru/CP)
composites x composites (Ru/CP)
prepared prepared
through through coprecipitation
coprecipitation [99]. The study [99]. The
found
study
that thefound thatofthe
activity theactivity
Ru/CPofcatalyst
the Ru/CP catalyst
is higher thanis higher
that of than that of the
the Ru/CeO Ru/CeO
2 and Ru/PrO 2 andx
catalysts, and the Pr
Ru/PrOx catalysts, andcontent
the Pr(=Pr/(Ce + Pr)) reached
content (=Pr/(Ce the target
+ Pr)) reached thevalue
targetofvalue
33–67%. It was
of 33–67%.
Molecules 2023, 28, x FOR PEER REVIEW 14 of 25

Molecules 2023, 28, x FOR PEER REVIEW 14 of 25

Molecules 2023, 28, 5245 14 of 25
It was also revealed that increasing the Pr content in the catalysts enhanced the Ru disper-
sion but suppressed Ru metalation due to a strong “metal–support interaction”.
It was
also also revealed
revealed that increasing
that increasing the Pr
the Pr content content
in the in the
catalysts catalysts
enhanced theenhanced the Ru
Ru dispersion butdisper-
sion but suppressed
suppressed Ru due
Ru metalation metalation due“metal–support
to a strong to a strong “metal–support
interaction”. interaction”.

Figure 13. Schematic diagram of NH3 decomposition of Ru/Y-dosed BaCeO3 catalyst (reproduced
with permission from [95], Copyright American Chemical Society, 2022).
Figure
Figure 13.13. Schematic
Schematic diagram
diagram of 3NH
of NH 3 decomposition
decomposition of Ru/Y-dosed
of Ru/Y-dosed BaCeOBaCeO 3 catalyst (reproduced
3 catalyst (reproduced
with permission
Apart from
with permission from [95],
Ru-based
from Copyright
materials,
[95], Copyright American
Pt-based
American Chemical Society,
materials
Chemical 2022).
are also extensively studied in the
Society, 2022).
field of NH3 decomposition. While Ru-based materials are mainly used for thermocata-
Apart
Apart from
fromRu-based
Ru-based materials, Pt-based
materials, materials
Pt-based are also
materials areextensively
also extensivelystudied in the in the
studied
lytic of
field NH NH 3 decomposition, Pt-based materials are typically employed for photocatalytic
decomposition. While Ru-based materials are mainly used for thermocatalytic
field of NH 3 3 decomposition. While Ru-based materials are mainly used for thermocata-
and3 electrocatalytic
NH decomposition, NH 3 decomposition
Pt-based are[16,17,68,69,75,76,100].
materialsmaterials
typically for In
employedemployed a study by Kominami
photocatalytic and
lytic NH3 decomposition, Pt-based are typically for photocatalytic
electrocatalytic NH3 decomposition [16,17,68,69,75,76,100]. In a study by Kominami etTiO
et al., the photocatalytic NH 3 decomposition performance of metal-supported al., 2 cata-
and electrocatalytic NH3 decomposition [16,17,68,69,75,76,100]. In a study by Kominami
lysts
the was investigated
photocatalytic [76]. Pt/TiO2 exhibited
NH3 decomposition performance theofbest performance,TiO
metal-supported with the amount
2 catalysts was of H2
et al., the photocatalytic NH3 decomposition performance of metal-supported TiO2 cata-
investigated
and N2 reaching [76]. Pt/TiO
90 and2 exhibited
28 umol, the best performance,
respectively, after 4 with
h of the amount
light of H2 and
irradiation, N2
as shown in
lysts was
reaching 90 investigated
and 28 umol, [76]. Pt/TiO2 exhibited
respectively, after 4 h ofthe
lightbest performance,
irradiation, as withinthe
shown amount
Figure 14. of H2
Figure 14. The H2/N2 ratio was 3.2, consistent with the stoichiometric ratio of NH3 decom-
andHN/N
The 2 reaching 90 and 28 umol, respectively, after 4 h of light irradiation, as shown in
position.2 2 ratio et
Dong wasal.3.2, consistent with
successfully the stoichiometric
electrolyzed ratio of NH
liquid ammonia with3 decomposition.
metal amide as the
Figure
Dong et 14.successfully
al. The H2/N2 ratio was 3.2,liquid
electrolyzed consistent
ammonia withwith
the metal
stoichiometric
amide as ratio
the of NH3 decom-
supporting
supporting electrolyte using Pt electrodes [16]. In a subsequent study, they replaced the
position. using
electrolyte DongPt etelectrodes
al. successfully
[16]. Inelectrolyzed
a subsequentliquidstudy, ammonia
they replacedwiththe metal amide as the
Pt electrode
Pt electrode with a Pt/Rh/Ir alloy electrode, which tripled the current density [69].
supporting
with a Pt/Rh/Ir electrolyte using which
alloy electrode, Pt electrodes [16].
tripled the In a subsequent
current density [69].study, they replaced the
Pt electrode with a Pt/Rh/Ir alloy electrode, which tripled the current density [69].

Figure 14.
Figure 14. Schematic diagramof
Schematic diagram of Pt/TiO
Pt/TiO22 photocatalytic NH33 decomposition
photocatalytic NH decompositionperformance
performanceand
and reac-
tion mechanism
reaction (reproduced
mechanism with
(reproduced with permission
permission from
from [76],
[76], Copyright
Copyright Elsevier,
Elsevier, 2012).
2012).
Figure 14. Schematic diagram of Pt/TiO2 photocatalytic NH3 decomposition performance and reac-
tion
3.2. mechanism Metal
Non-Precious (reproduced with permission from [76], Copyright Elsevier, 2012).
Catalysts
3.2. Non-Precious Metal Catalysts
Although precious metal materials have excellent NH3 decomposition ability, their
3.2. Although
Non-Precious
high cost as precious
Metal
precious Catalysts
metalsmetal
limitsmaterials have excellent
their potential NH3applications.
for large-scale decomposition ability, their
Therefore,
high cost
researchers asare
precious
Although metals
precious
exploring metal
the limits their potential
materials
development have for large-scale
excellent
of non-precious NH applications.
3 decomposition
metal catalysts. Therefore,
ability,
Currently, their
researchers
high cost asare
non-precious exploring
precious
metals theCo,
suchmetals
as Ni, development
limits
andtheir of
potential
Fe have non-precious metal
for large-scale
demonstrated good catalysts.
applications.
NH 3 Currently,
Therefore,
decomposition
non-precious
activity metals
and areare
researchers being such astheNi,development
investigated
exploring Co,potential
as and Fe alternatives
have demonstrated goodcatalysts.
[6,9,10,101].
of non-precious metal NH3 decomposition
Currently,
Ni-based
activity
non-precious catalysts
and are beinghave
metals received
investigated
such as Ni, Co, significant
asand
potential attention
Fe have among[6,9,10,101].
alternatives
demonstrated numerous
good NH non-precious
3 decomposition
metal catalysts
Ni-based
activity and aredue to their
catalysts
being have lower cost
received
investigated and significant
assignificant
potential activity
attention
alternatives [7,102].
among The activity
numerous
[6,9,10,101]. of
non-precious
metal Ni-based
catalysts catalysts
due to their
havelower costsignificant
received and significant activity
attention among [7,102]. The activity
numerous of Ni-
non-precious
metalcatalysts
based catalysts is
due to their lower
primarily cost and
influenced by significant
the size ofactivity [7,102]. Thepresent
Ni nanoparticles activity on
of Ni-
the
based catalysts is primarily influenced by the size of Ni nanoparticles present on the
28, x FOR PEER REVIEW 15 of 25
Molecules 2023, 28, 5245 15 of 25

catalyst surface [103–105]. Deng et al. obtained Ni nanoparticles with varying particle
Ni-based catalysts is primarily influenced by the size of Ni nanoparticles present on the
sizes through direct thermal reduction of nickel-containing Ca-Al layered double hydrox-
catalyst surface [103–105]. Deng et al. obtained Ni nanoparticles with varying particle sizes
ides (LDH) and tested
through them
directforthermal
NH3 decomposition, as shown in Figure
reduction of nickel-containing Ca-Al 15 [104].double
layered Among hydroxides
these catalysts, the Ni/CaAlO
(LDH) x catalyst
and tested with
them for NH3Ni(NO 3)2 as the as
decomposition, precursor
shown in exhibited the best
Figure 15 [104]. Among these
NH3 decomposition performance,
catalysts, the Ni/CaAlOwithx an NH3 with
catalyst conversion
Ni(NO3 )rate of 99%
2 as the at 550exhibited
precursor °C. Thisthe is best NH3
decomposition performance, with an NH conversion rate of 99% at 550 ◦ C. This is because
because the average particle size of the Ni nanoparticles, 3 reduced with Ni (NO3)2 as the
the average
precursor, is the smallest (4.7particle size of thefor
nm), allowing Ni better
nanoparticles, reduced
dispersion on thewith Ni (NO
surface of3 )CaAlO
2 as thexprecursor,
is the smallest (4.7 nm),
and, thus, more effective adsorption of NH3. allowing for better dispersion on the surface of CaAlO x and, thus,
more effective adsorption of NH3 .

Figure
Figure 15. Schematic 15. Schematic
illustration of theillustration
synthesis of the
of Nisynthesis of Ni nanoparticles
nanoparticles derived derived
from the from the thermal
thermal re- reduction
of Ni-containing
duction of Ni-containing Ca-Al LDH Ca-Al LDH (reproduced
(reproduced with with permission
permission fromfrom [104],Copyright
[104], Copyright Elsevier,
Elsevier,2021).
2021).
Besides the size of Ni nanoparticles, the support used in Ni-based catalysts also plays
a crucial role in their catalytic activity. Currently, metal oxides such as CeO2 [43,106–109],
Besides the size of Ni nanoparticles, the support used in Ni-based catalysts also plays
Y2 O3 [110,111], Al2 O3 [112–114], and La2 O3 [115] are commonly used as supports for
a crucial role in their catalytic
Ni-based activity.
catalysts usedCurrently, metal oxidesThe
in NH3 decomposition. suchhighas CeO 2 [43,106–109],
activity of these metal oxide-
Y2O3 [110,111], Alsupported
2O3 [112–114],Ni-basedandcatalysts
La2O3 is [115] are commonly
typically due to the high used as supports
dispersity for Ni-
of Ni nanoparticles, the
based catalysts used
strong ininteraction
NH3 decomposition.
between the support The high and activity of these metal
Ni nanoparticles, and the oxide-sup-
presence of oxygen
ported Ni-based vacancies
catalysts on is typically
the support due to theLihigh
surface. et al.dispersity
successfully of used
Ni nanoparticles,
a Ni single-atom thesupported
CeO
strong interaction between2 (SA Ni/CeO
the support
2 ) catalyst for NH
and Ni nanoparticles,
3 decomposition into H
and the presence2 under of oxygen condi-
solar heating
tions [109]. The experimental results showed that at 300 ◦ C, the rate of NH decomposition
vacancies on the support surface. Li et al. successfully used a Ni single-atom supported 3
to H reached 3.544 mmol g −1 min−1 , which was superior to all non-precious metal cat-
2
CeO2 (SA Ni/CeO2) catalyst for NH3 decomposition into H2 under solar heating conditions
alysts and most precious metal catalysts. Based on this, they combined their self-made
[109]. The experimental results showed that at 300 °C, the rate of NH3 decomposition to
solar heating system, and the H2 generation rate of the catalyst under 1 sun reached
H2 reached 3.5441.58mmol mmol g−1gmin −1, which was superior
−1 min −1 , which was 100 times to all non-precious
higher metal catalysts
than the previous record. Do et al.
and most precious metal catalysts. Based on this, they combined
synthesized a series of Ni/AlCeOx composites using the cation-anion double their self-made solarhydrolysis
heating system, andmethodthe H 2 generation
and used them rate of the catalyst
as catalysts for NH3 under 1 sun reached
decomposition 1.58 mmol[114]. The
to H2 production
g−1 min−1, which experimental
was 100 times higher
results thanthat
showed thethe previous record. Do
catalyst exhibited et al. catalytic
excellent synthesized a
performance and
could completely decompose NH at around 550 ◦ C. The improved catalytic performance
series of Ni/AlCeOx composites using the cation-anion 3 double hydrolysis method and
can be attributed
used them as catalysts to the highly dispersed
for NH3 decomposition and reducible[114].
to H2 production Ni atoms, the increased amount of
The experimental
surface oxygen vacancies, and the significantly enhanced
results showed that the catalyst exhibited excellent catalytic performance and could com- NH 3 adsorption affinity.
Co-based materials have also been extensively studied as catalysts for NH3 decom-
pletely decompose NH3 at around 550 °C. The improved catalytic performance can be at-
position [116–118]. Many properties of Co-based catalysts are similar to those of Ni-based
tributed to the highly dispersed and reducible Ni atoms, the increased amount of surface
catalysts, and their catalytic activity is also influenced by the size of Co nanoparticles and
oxygen vacancies,the and the significantly
support enhanced
structure [119–125]. LeiNH 3 adsorption affinity.
et al. successfully prepared small Co nanoparticles
Co-based materials
dispersedhave also been
on N-doped extensively
carbon carriers studied
(Co/NC-X) as catalysts
by pyrolyzingfor NH 3 decom-
ZIF-67 in an N2 atmo-
position [116–118]. Many properties of Co-based catalysts are similar ◦ to those
sphere at different temperatures (X = 500, 600, 700, 800 C). They used them as catalysts of Ni-based
forcatalytic
catalysts, and their NH3 decomposition
activity is also to H 2 , as shown
influenced byintheFigure
size 16
of Co[125]. The Co NPsand
nanoparticles were evenly
distributed and highly dispersed on NC, resulting
the support structure [119–125]. Lei et al. successfully prepared small Co nanoparticles in high catalytic activity. Among these
catalysts, the NH conversion rate of Co/NC-600 at 500 ◦ C was 80%, and the H production
dispersed on N-doped carbon carriers 3 (Co/NC-X) by pyrolyzing ZIF-67 in an N2 atmos- 2
rate was 26.8 mmol g−1 min−1 . Yu et al. investigated the effect of BaNH, CaNH, and
phere at different temperatures (X = 500, 600, 700, 800 °C). They used them as catalysts for
Mg2 N3 on the catalytic activity of Co in the NH3 decomposition reaction [124]. In the
NH3 decomposition to H2, as shown in Figure 16 [125]. The Co NPs were evenly distrib-
uted and highly dispersed on NC, resulting in high catalytic activity. Among these cata-
lysts, the NH3 conversion rate of Co/NC-600 at 500 °C was 80%, and the H2 production
rate was 26.8 mmol g−1 min−1. Yu et al. investigated the effect of BaNH, CaNH, and Mg2N3
Molecules 2023, 28, x FOR PEER REVIEW 16 of 25
Molecules 2023,
Molecules 2023, 28,
28, x5245
FOR PEER REVIEW 16 of 25
16 of 25

temperature range of 300–550 °C, the formation rate of H2 was in the order of Co-BaNH >
Co-CaNH
temperature
reaction >range
Co-Mg
temperature Nrange
3. Notably,
of 2300–550 °C, thethe H2 ◦generation
formation
of 300–550 of rate
rateformation
C, the of rate
H2 was Co-BaNH
in the H2 at
oforder 500
of
was in°C reached
Co-BaNH
the > of
order 20
Co-CaNH
mmol g −1>min
Co-Mg 2N3. Notably,
−1, comparable tothe
the H 2 generation
active Ru/Al 2rate
O3 . of Co-BaNH
In-depth
Co-BaNH > Co-CaNH > Co-Mg2 N3 . Notably, the H2 generation rate of Co-BaNH at 500 C at
studies 500 °C reached
revealed that20
a [Co-
◦
mmol g−1 20
min
N-Ba]-like
reached
−1, comparable
intermediate
mmol −to
g−1 minspecies thewas
active
1 , comparable Ru/Al
formed 2Othe
at
to the 3. In-depth
interface
active Ru/Al studies
of Co revealed
metal and that a [Co-
BaNH, which
2 O3 . In-depth studies revealed
N-Ba]-like
led to
that intermediate
the higher catalytic
a [Co-N-Ba]-like species was formed
activity ofspecies
intermediate at
Co-BaNH.the interface of Co metal and BaNH,
was formed at the interface of Co metal and which
led to thewhich
BaNH, higherled catalytic
to the activity of Co-BaNH.
higher catalytic activity of Co-BaNH.

Figure 16. Schematic

Figure illustration of the synthesis of Co/NC-X (reproduced
with with permission
from from
Figure16.16.Schematic illustration
Schematic of the
illustration ofsynthesis of Co/NC-X
the synthesis (reproduced
of Co/NC-X permission
(reproduced with permission
[125],
[125], Copyright Elsevier, 2022).
fromCopyright Elsevier,Elsevier,
[125], Copyright 2022). 2022).

The
The
The NHNH
NH 3 decomposition
3 decomposition activity
activity of Fe-based
of Fe-based materials
materials is generally
is generally lower lower
than than
that of that of
3 decomposition activity of Fe-based materials is generally lower than that of
Ni-based
Ni-based materials
Ni-basedmaterials
materials andand
and Co-based
Co-based
Co-based materials
materials
materials due
duedue to
to the the higher
higher
to the bond
higher bond
energy
bond energy
of Fe-N
energy of Fe-N com-
com-com-
of Fe-N
pared
pared to
paredtotoNi-NNi-N
Ni-Nand and
and Co-N
Co-N
Co-N [9,101].
[9,101].
[9,101]. However,
However,
However, despite
despite this,
this,this,
despite researchers
researchers
researchers still
still still have
havehave great
greatgreat interest
interest
interest
inFe-based
inin Fe-based
Fe-based materials
materials
materials duedue tototheir
to their
due lowlow
their lowprice
price [36–38,52,55,57,126,127].
[36–38,52,55,57,126,127].
price [36–38,52,55,57,126,127]. Lu etLu etfound
al.Lu al.
et found
al.a hid-
founda hid-
a
denden active
activephase
phase in Fe-based
in Fe-based catalysts
catalystsfor NH
for 3 decomposition,
NH 3 decomposition,
hidden active phase in Fe-based catalysts for NH3 decomposition, with the highest dehy- with the
with highest
the dehydro-
highest dehydro-
genation
genationrate
drogenation ratecorresponding
corresponding
rate corresponding to to
an anevanescent
evanescent
to an Fe/Fe4N
evanescent Fe/Fe4N mixing
Fe/Fe4N phase
mixing [38].
phase
mixing However,
[38].
phase However,
[38]. the the
However,
deposition
deposition of excess
of excess nitrogen
nitrogen atoms
atoms on the
on Fe-based
the catalyst
Fe-based can
catalyst
the deposition of excess nitrogen atoms on the Fe-based catalyst can cause deactivation cause
can deactivation
cause deactivation and aand a
decrease
decrease inincatalytic
catalytic efficiency.
efficiency. Chen Chenet al.
et observed
al. observeda “particle
a size
“particle
and a decrease in catalytic efficiency. Chen et al. observed a “particle size effect” in the effect”
size in
effect” thein activity
the activity
ofactivity
ofFeFe
3O 4/Al
3O 2O23Ocatalyst
/Al
4of Fe3 O3 catalystin in
NH NH3 decomposition,
3 decomposition, with TOFs
with TOFsincreasing as the
increasing as size
the ofsizeFeof
3O4Fe3O4
4 /Al2 O3 catalyst in NH3 decomposition, with TOFs increasing as the size
nanoparticles
nanoparticles
of increased
increased
Fe3 O4 nanoparticles [57]. As shown
[57]. As[57].
increased shown in Figure
in Figure
As shown 17, this effect
17, this
in Figure was
17, effect also
waswas
this effect observed
alsoalsoobservedin in
observed
plasma-catalyzed
plasma-catalyzed NH NH3 decomposition.
3 decomposition.
in plasma-catalyzed NH 3 decomposition.

Figure 17. Schematic diagram of NH3 decomposition ability of Fe/Al2O3 catalysts driven by plasma
Figure
and
Figure 17. Schematic
17.
thermo as the sizediagram
Schematic of Fe3O4of
diagram NH
NH33decomposition
nanoparticles
of increasesability
decomposition ofofFe/Al
(reproduced
ability 22O
with
Fe/Al catalysts driven
O33 permission
catalysts fromby
driven plasma
[57],
by plasma
Copyright
and thermoAmerican
as the Chemical
size of FeSociety,
O
and thermo as the size of Fe33O44 2022).
nanoparticles increases (reproduced with permission from [57],
Copyright American
Copyright American Chemical
Chemical Society,
Society,2022).
2022).
Molecules 2023, 28, 5245 17 of 25

3.3. Multi-Metallic Catalysts

To overcome the limitations of single noble metal catalysts and single non-noble metal
catalysts in the large-scale application of NH3 decomposition, researchers are exploring
the use of multi-metallic catalysts. These catalysts offer a balance between cost and per-
formance, with low cost, good catalytic performance, and high stability. Additionally,
the composition and morphology of different metals in the catalysts can be regulated,
providing more possibilities for optimization.
At present, bimetallic catalysts are the mainstream of multi-metallic catalysts [28]. Com-
mon bimetallic catalysts include Ru-Ni [128–130], Ni-Co [42,46,49,131,132],
Ni-Fe [47,48,133], etc. Hansgen et al. developed a computational framework that utilizes
nitrogen binding energies to identify potential monolayer bimetallic catalysts [134]. Through
this framework, they were able to predict that Ni-Pt-Pt(111) would be an effective bimetallic
catalyst for NH3 decomposition, even exceeding the activity of Ru. Their calculations proved
to be successful in identifying this high-performing catalyst. Tabassum et al. synthesized
CoNi alloy nanoparticles that were well dispersed on mixed oxide support of MgO-CeO2 -SrO,
with potassium promotion, resulting in the K–CoNialloy –MgO–CeO2 –SrO catalyst, as shown
in Figure 18 [49]. This catalyst exhibited high efficiency in converting NH3 , with a conver-
sion rate of 97.7% under reaction conditions of 450 ◦ C and 6000 mLh−1 gcat−1 . The study
suggests that the active sites located on the metal/oxide interface promote the recombination
of adsorbed N atoms, leading to N2 desorption and a significant reduction in activation
energy barriers. Shiraishi et al. developed a bimetallic alloy nanoparticle-supported TiO2
photocatalyst (Pt0.9 Au0.1 /TiO2 ) with 90 mol% Pt and 10 mol% Au [20]. This photocatalyst
demonstrated effective decomposition of NH3 into H2 and N2 , with significantly higher
catalytic activity than Pt/TiO2 . The enhanced performance can be ascribed to the presence of
Au in the alloy, which reduces the Schottky barrier height at the metal/TiO2 interface, leading
to a more efficient transfer of conduction band electrons on TiO2 to the metal particles. Yi et al.
conducted a study where they prepared various bimetallic catalysts (Fe-Co, Mo-Co, Fe-Ni,
and Mo-Ni) and utilized them for plasma-catalyzed NH3 decomposition [22]. The results
revealed that the Fe-Ni catalyst displayed the highest catalytic activity compared to the other
catalysts. Further analysis indicated that the Fe-Ni catalyst had the highest NH3 adsorption
capacity, likely the primary reason for its superior catalytic activity. Jiang et al. investigated
various morphologies of NiCo2 N compounds. They specifically focused on the structure of
nanoneedles grown on 3D nickel foam. It was found that this particular structure exhibited
several advantages, including a significantly increased surface area, more exposed active sites,
enhanced charge transfer, and improved gas diffusion. Furthermore, the NiCo2 N composite
demonstrated the most optimal catalytic activity in both the hydrogen evolution reaction
(HER) and ammonia electrolysis [135].
Developing multi-metal catalysts containing three or more metal elements is a more
challenging task, but it also holds greater potential. Xie et al. successfully utilized a
novel high-entropy alloy (HEA) CoMoFeNiCu nanoparticles for highly efficient NH3
decomposition [44]. As illustrated in Figure 19, they overcame the miscibility limit of
bimetallic CoMo alloys by stably tuning the Co/Mo elemental ratio in CoMoFeNiCu HEA
nanoparticles. The HEA catalyst has a lower cost than Ru-based catalysts and exhibits
better catalytic performance than Co-Mo catalysts. At a reaction temperature of 500 ◦ C, the
optimal conversion efficiency of NH3 using this catalyst can reach 100%. Furthermore, the
alloy composition and surface adsorption properties of the HEA catalyst can be well-tuned,
demonstrating its immense potential for practical applications.
 its superior catalytic activity. Jiang et al. investigated various morphologies of NiCo2N
compounds. They specifically focused on the structure of nanoneedles grown on 3D nickel
foam. It was found that this particular structure exhibited several advantages, including a
significantly increased surface area, more exposed active sites, enhanced charge transfer,
Molecules 2023, 28, 5245
and improved gas diffusion. Furthermore, the NiCo2N composite demonstrated the18most of 25
optimal catalytic activity in both the hydrogen evolution reaction (HER) and ammonia
electrolysis [135].

Molecules 2023, 28, x FOR PEER REVIEW 18 of 25

Figure 18. Schematic illustration for the decorated CoNi alloy on the oxide support of MgO–CeO2–
SrO (reproduced with permission from [49], Copyright Royal Society of Chemistry, 2022).

Developing multi-metal catalysts containing three or more metal elements is a more

challenging task, but it also holds greater potential. Xie et al. successfully utilized a novel
high-entropy alloy (HEA) CoMoFeNiCu nanoparticles for highly efficient NH3 decompo-
sition [44]. As illustrated in Figure 19, they overcame the miscibility limit of bimetallic
CoMo alloys by stably tuning the Co/Mo elemental ratio in CoMoFeNiCu HEA nanopar-
ticles. The HEA catalyst has a lower cost than Ru-based catalysts and exhibits better cata-
lytic performance than Co-Mo catalysts. At a reaction temperature of 500 °C, the optimal
conversion efficiency of NH3 using this catalyst can reach 100%. Furthermore, the alloy
composition
Figure and surface
18. Schematic adsorption
illustration properties
for the decorated CoNi of theonHEA
alloy catalyst
the oxide can
support of be well-tuned,
MgO–CeO 2 –SrO
demonstrating
(reproduced its immense
with permission potential
from for practical
[49], Copyright applications.
Royal Society of Chemistry, 2022).

Figure 19.
19. HEA
HEAcatalysts
catalystsbreaking
breaking thethe miscibility
miscibility limitation
limitation of conventional
of conventional binary
binary alloysalloys (repro-
(reproduced
duced with permission from [44], Copyright Nature,
with permission from [44], Copyright Nature, 2019). 2019).

3.4. Other Catalysts

3.4. Other Catalysts
In addition to
In addition to metal
metalnanoparticles,
nanoparticles,some somemetal
metal nitrides
nitrides cancan also
also be be used
used as NH
as NH 3 de-3
decomposition catalysts,
composition catalysts, suchsuch
as Moas Mo 2 N [136–138],
2N [136–138], MnN MnN [139],
[139], Co3MoCo33NMo 3 N [140–142],
[140–142], etc.
etc. Huo
Huo
et al.etdesigned
al. designed
Mo2N Monanocrystals
2 N nanocrystals anchored
anchored on two-dimensional
on two-dimensional (2D)(2D) mesoporous
mesoporous sil-
silica/reduced graphene oxide (rGO) hybrid nanosheets
ica/reduced graphene oxide (rGO) hybrid nanosheets (Mo2N/SBA-15/rGO) (Mo 2 N/SBA-15/rGO) as NH
as an an NH
3 de-3
decomposition catalyst[136].
composition catalyst [136].Benefiting
Benefitingfrom fromthe
thehighly
highlydispersed
dispersed MoMo22NN nanocrystals
nanocrystals and
and
modest
modest Mo-N
Mo-N band
band strength,
strength, the
the catalyst
catalyst exhibits
exhibits excellent
excellent catalytic
catalytic performance
performance with
with anan
ammonia decomposition rate as high as 30.58 mmol g −1 min−1 . Srifa et al. synthesized
ammonia decomposition rate as high as 30.58 mmol g−1 min−1. Srifa et al. synthesized
Mo N-based catalysts
Mo22N-based catalystswith
withFe,Fe,Ni,
Ni,andandCoCo additives,
additives, as shown
as shown in Figure
in Figure 20 [141].
20 [141]. The NHThe3
NH 3 decomposition activities of Co 3 Mo 3 N, Ni 3 Mo 3 N, and Fe 3 Mo 3 N
decomposition activities of Co3Mo3N, Ni3Mo3N, and Fe3Mo3N catalysts were higher than catalysts were higher
than
Mo2NMo 2 N catalysts.
catalysts. Among Among
them,them,
Co3Mo Co3N
3 Mo 3N
has has
the thecatalytic
best best catalytic performance,
performance, andNH
and the the3
NH3 conversion efficiency reaches 94% at 550 ◦ C. The increase in catalytic activity can be
conversion efficiency reaches 94% at 550 °C. The increase in catalytic activity can be at-
attributed to adding Co, Ni, and Fe to increase the particle size and specific surface area of
tributed to adding Co, Ni, and Fe to increase the particle size and specific surface area of
the catalyst and promote the recombination and desorption of N atoms.
the catalyst and promote the recombination and desorption of N atoms.
Molecules 2023, 28,
Molecules 2023, 28, 5245
x FOR PEER REVIEW 19 of
19 of 25
25

Figure Schematicdiagram
Figure 20. Schematic diagramof of
MoMo N catalysts
2N2catalysts withwith the addition
the addition of Co,ofNi,
Co, Ni,Feand
and Fe for
for NH NH3
3 decom-

position (reproduced
decomposition with permission
(reproduced from from
with permission [141],[141],
Copyright RoyalRoyal
Copyright Society of Chemistry,
Society 2016).
of Chemistry, 2016).

Researchers havehave also

also developed
developed somesome NH
NH33 decomposition catalysts of sulfides and
carbides, but
but the performance is average. Kraupner et
the performance is average. Kraupner et al.
al. synthesized
synthesized mesoporous
mesoporous Fe Fe33C
C
with
with high crystallinity [143]. The material has transmission pores with a diameter ofnm
high crystallinity [143]. The material has transmission pores with a diameter of 20 20
and a high specific surface area (about 2 g−1 ).2 At
415 m415 ◦ C, the conversion rate of NH
nm and a high specific surface area (about m g−1).700At 700 °C, the conversion rate of 3
is
NH over
3 is 95%. Krishnan
over 95%. et al.etsuccessfully
Krishnan synthesized
al. successfully synthesizedMoSMoS2 -supported
2-supportedacid, andand
acid, alkaline
alka-
functionalized (Al, Ti,
line functionalized (Al,and Zr)-Laponite
Ti, and catalysts
Zr)-Laponite [144].[144].
catalysts The The
results show
results that that
show the presence
the pres-
of heteroatoms (Al, Ti, and Zr) in the Laponite framework plays a key
ence of heteroatoms (Al, Ti, and Zr) in the Laponite framework plays a key role in im-role in improving the
reducibility, acid-base functional groups, and textural properties of MoS
proving the reducibility, acid-base functional groups, and textural properties of MoS2. 2 . Among them,
the MoS2them,
Among /Zr-Laponite
the MoS catalyst has the best NH decomposition performance, and its NH3
2/Zr-Laponite catalyst 3has the best NH3 decomposition perfor-
conversion rate at 600 ◦ C degrees is 94%.
mance, and its NH3 conversion rate at 600 °C degrees is 94%.
4. Conclusions
4. Conclusions
Ammonia decomposition is a highly efficient, environmentally friendly, and sustain-
Ammonia decomposition is a highly efficient, environmentally friendly, and sustain-
able technology for hydrogen production that has attracted significant attention. This article
able technology for hydrogen production that has attracted significant attention. This ar-
explores the technical path and catalysts used for hydrogen production through ammonia
ticle explores the technical path and catalysts used for hydrogen production through am-
decomposition. The article discusses various technologies and their catalytic mechanisms,
monia decomposition. The article discusses various technologies and their catalytic mech-
highlighting their advantages and disadvantages and their potential for industrialization.
anisms,
The highlighting
review their
also covers advantages
recent progressand disadvantages
in catalyst researchandfortheir potential
ammonia for industri-
decomposition,
alization. The review also covers recent progress in catalyst research for ammonia
emphasizing the importance of finding non-precious metals to reduce costs and improve decom-
position, emphasizing
efficiency. Overall, thisthe importance
article provides of valuable
finding non-precious
insights intometals to reduce
the current statecosts
of NHand
3
improve efficiency. Overall, this article provides valuable insights into the current
decomposition for H2 production and the potential for future advancements in this field. state of
NH3 decomposition for H2 production and the potential for future advancements in this
field. Contributions: Conceptualization, X.H. and W.F.; investigation, K.L. and X.L.; writing—original
Author
draft preparation, X.H. and Y.M.; writing—review and editing, W.F.; project administration, X.H.; funding
Author Contributions:
acquisition, Conceptualization,
X.H. All authors X.H.toand
have read and agreed the W.F.; investigation,
published version of K.L. and X.L.; writing—
the manuscript.
original draft preparation, X.H. and Y.M.; writing—review and editing, W.F.; project administration,
Funding: The authors
X.H.; funding gratefully
acquisition, acknowledge
X.H. All theread
authors have financial supporttofrom
and agreed The University
the published versionSynergy
of the
Innovation
manuscript. Program of Anhui Province (grant No. GXXT-2020-006 and grant No. GXXT-2022-025).
Institutional
Funding: TheReview
authorsBoard Statement:
gratefully Not applicable.
acknowledge the financial support from the Institute of Energy,
Informed Consent Statement: Not applicable. (grant No. GXXT-2020-006 and grant No. GXXT-
Hefei Comprehensive National Science Center
2022-025).
Data Availability Statement: All necessary data of this review has been included in the paper and
Institutional
no Review
further data Board Statement: Not applicable.
is needed.
Informedof
Conflicts Consent Statement:
Interest: Notdeclare
The authors applicable.
no conflict of interest.
Data Availability Statement: All necessary data of this review has been included in the paper and
no further data is needed.
Molecules 2023, 28, 5245 20 of 25

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