Clean Energy, 2023, Vol. 7, No.

1, 116–131

https://doi.org/10.1093/ce/zkac095
Advance access publication 9 March 2023
Review Article

Downloaded from https://academic.oup.com/ce/article/7/1/116/7074341 by National Taiwan University of Science & Technology (NTUST) Library user on 16 September 2023
Research progress in green synthesis of ammonia
as hydrogen-storage carrier under ‘hydrogen 2.0
economy’
Ge Li1, Ziran Ma1,*, Jia Zhao2, Jiali Zhou1, Shengpan Peng1, Yonglong Li1 and Baodong Wang1,3,*
1
National Institute of Clean-and-Low-Carbon Energy, Beijing 102211, China
2
Industrial Catalysis Institute of Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
3
NICE Europe Research GmbH, Stockholmer Platz 1, 70173 Stuttgart, Germany
*
Corresponding authors. E-mail: ziran.ma@chnenergy.com.cn, baodong.wang.d@chnenergy.com.cn

Abstract
Hydrogen energy is characterized by its environmental friendliness, high efficiency, lack of carbon emissions and wide range of ap-
plications. However, its transportation and storage are challenges that limit further development of the hydrogen-energy industry.
Ammonia is a carbon-free hydrogen-rich carrier. The storage of hydrogen in ammonia has unique advantages of high energy density,
easy storage and transportation, reliable safety, a mature industrial foundation and no tail-end carbon emissions. However, industrial
ammonia synthesis still heavily relies on the Haber–Bosch process, which accounts for significant energy consumption and green-
house gas emissions. Therefore, the development of green and sustainable ammonia-synthesis methods is extremely important and
urgent. Recently, ammonia-synthesis technologies such as electrocatalysis, photocatalysis, photoelectrocatalysis and biocatalysis
have successfully produced ammonia from nitrogen and water, resulting in lower costs. The nitrogen-reduction-reaction conditions
of these methods are mild and can be carried out under ambient temperatures and atmospheric pressure with low energy con-
sumptions. Meanwhile, these methods bypass the traditional hydrogen-production section and their routes are simpler. Therefore,
these technologies can be used to flexibly integrate renewable energy, including intermittent renewable energy, to achieve distrib-
uted ammonia synthesis. These benefits contribute to both global energy and environmental sustainability goals. In this study, the
mechanisms of ammonia synthesis under ambient conditions are reviewed and the technical difficulties of various catalysts for am-
monia synthesis are summarized. Based on the optimization strategies reported for various catalysts, the high-performing catalysts
reported for ammonia synthesis are reviewed and the developmental trend of this field has been forecasted.

Graphical Abstract

Performance optimization of
electrocatalytic ammonia synthesis

Improvement of catalytic
Selection of catalyst
device
Modification of catalyst
Noble metal base material
Battery structure improvement
Bionic site construction
Transition metal base Electrode structure design
material Table interface design
Control of electrolyte
Boron material, carbon Lattice defect regulation composition
material
Heteroatomic doping Non-aqueous system
Conductive polymer construction

Keywords: hydrogen 2.0 economy; ammonia synthesis; catalyst; ambient conditions; mechanism

Received: 30 September 2022. Accepted: 30 December 2022

© The Author(s) 2023. Published by Oxford University Press on behalf of National Institute of Clean-and-Low-Carbon Energy
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial License (https://creativecommons.org/
licenses/by-nc/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited. For
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 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ | 117

Introduction gas passes through an air-cooled, water-cooled exchanger and

ammonia cooler, and then enters the high-pressure ammonia
As a clean and efficient secondary energy source with a high
chamber to separate the liquid ammonia. The liquid ammonia
caloric value, high energy density and diverse sources, hydrogen

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is then stored. Energy capital recently began to enter the green-
energy is known as the ‘ultimate energy’. Although there are
ammonia industry on a large scale. The USA, the EU, Japan, Korea,
many advantages, it remains difficult to store and transport.
China and other countries have carried out green-ammonia pro-
The storage and transportation of hydrogen require pressures
jects. More than 40 large-scale green-ammonia projects have
exceeding 35 MPa, while the core materials and key equipment
been registered and approved using this technical route world-
of high-pressure hydrogen storage rely on imports, which results
wide.
in high prices for terminal hydrogen (≥60 yuan/kg). According
Third-generation ammonia synthesis departs completely from
to the goal of building 1 × 104 hydrogen-refuelling stations by
Haber–Bosch. It uses air or nitrogen (N2) as the nitrogen source
2050, infrastructure costs of 150–300 trillion yuan will be in-
and water (H2O) as a hydrogen source to introduce energy forms
vested [1–3]. In addition, high-pressure hydrogen is flammable
such as electricity from renewable energy sources and light en-
and explosive, and the weak safety of hydrogen is more prom-
ergy from solar energy into ammonia synthesis. Electrocatalysis
inent. Developing mature, safe and efficient hydrogen-storage
[11–59], photocatalysis [60–94], photoelectrocatalysis [95–117]
and transport technology based on China’s energy structure is
and biocatalysis [118–134] facilitate the activation of nitrogen
a ‘bottleneck’ problem in hydrogen-energy industry develop-
molecules to synthesize ammonia at room temperature and
ment.
pressure. This technology is regarded as the most promising
Due to the high terminal cost of hydrogen energy, ‘ammonia’
because it greatly reduces the cost of green-hydrogen produc-
has come into view. Ammonia (NH3) is a natural hydrogen-storage
tion without water electrolysis and the product is of high purity.
medium. At atmospheric pressure, ammonia liquefies at –33°C
There are many advantages: (i) the conversion rate of ammonia
for safe transportation. Presently, fertilizer production accounts
is not limited by the thermodynamic equilibrium under ambient
for >80% of the world’s ammonia use, so ammonia already has
conditions; (ii) the equipment is simple and safe; (iii) it solves
a complete trade and transportation system. Therefore, as a rich
problems associated with the Haber–Bosch method such as high
source of hydrogen, ammonia has great potential for hydrogen
energy input, inability to cope with fluctuations and the equip-
storage, direct use in fuel cells or reforming decomposition to
ment cannot be started and stopped at will, and creates a new
produce hydrogen. The sustainable production of ammonia (a
way for green electricity to convert into synthetic ammonia; (iv)
green alternative to the Haber–Bosch process) has been named
as a complement to the Haber–Bosch pathway, a miniaturized
one of the ‘Top 10 Emerging Technologies in Chemistry 2021’ by
photo/electrocatalytic ammonia-synthesis plant is expected to
the International Union of Pure and Applied Chemistry. Many sci-
achieve ‘distributed’ and ‘on-demand production’ of ammonia,
entists believe an ammonia economy is inevitable stemming from
which is complementary to the existing large, ultra-large and
‘carbon-neutrality’. A green and successful ‘ammonia economy’
centralized large-scale chemical plants; and (v) in some remote
will occur by 2040, i.e. the ‘hydrogen 2.0 economy’ [4–8].
areas with abundant solar and wind energy, ammonia provides
First-generation ammonia synthesis uses the Haber–Bosch
fertilizer for agricultural production and converts solar and wind
process with nitrogen (N2) and hydrogen (H2) as the raw materials
power generation into readily stored chemical energy, often dif-
(3H2 + N2 = 2NH3, △H298 K = –92.2 kJ mol–1, △G298 K = –32.9 kJ mol–1,
ficult to connect to the grid, and improves the clean-energy-
△S298 K = –198.76 kJ mol–1). The process requires high temperature
utilization rate.
(~450°C) and high pressures (~20–40 MPa) to improve the conver-
There are many reviews on the synthesis of ammonia at am-
sion rate. Moreover, the raw hydrogen in the Haber–Bosch pro-
bient temperature and pressure, most of which only analyse
cess comes from the gasification or reformation of natural gas,
either electrocatalysis, photocatalysis, photoelectrocatalysis or
coal or fuel oil, which consumes ~75% of the energy input and
biocatalysis, and little research covers the four kinds of catalysis
produces half of the CO2 during ammonia synthesis. This process
at the same time in one review. Therefore, we introduce these
suffers from high energy consumption, serious pollution and a
four kinds of catalysis at the same time in this paper to show
low energy-utilization rate [9, 10]. Therefore, the development of
readers the advantages and disadvantages of various catalysis.
sustainable and environmentally friendly ways to synthesize am-
The principles and process of electrocatalysis, photocatalysis,
monia by nitrogen-reduction reaction (NRR) at low temperature
photoelectrocatalysis and biocatalysis and their applications for
and low pressure or room temperature (RT) and pressure has at-
ammonia synthesis are described briefly, with a focus on the se-
tracted extensive attention.
lection of catalysts and the mechanism of ammonia synthesis.
Second-generation ammonia synthesis still utilizes the Haber–
Space limitations restrict our discussion to an overview of some
Bosch process, using green hydrogen and nitrogen to synthesize
of the issues and instead we provide key references to act as an
green ammonia, which is an important way to prepare green
entry point to some of these topics for the interested reader with
ammonia. The technology uses water electrolysis to produce
various professional backgrounds in various fields.
hydrogen, which generates green electricity from renewable en-
ergy sources such as solar, wind and tidal energy, and electrolyses
water into hydrogen and oxygen through electrolytic cell devices
1 Electrocatalytic ammonia synthesis
such as anion-exchange membrane (AEM) or proton exchange
membrane (PEM) [1, 2]. Pure ‘green’ hydrogen was produced Electrocatalytic ammonia synthesis electrochemically reduces
(99.999%) [3]. Nitrogen comes from air. Hydrogen and nitrogen are nitrogen to ammonia (ENRR) in a liquid electrolyte, a proton con-
mixed, enter the synthesis reactor and flow over the catalyst bed ductor ceramic membrane electrolyte and a molten salt elec-
after heat transfer inside the reactor. Under catalytic conditions, trolyte. Compared with the traditional Haber–Bosch process,
the reaction occurs at high temperature and pressure (molten iron electrochemical ammonia synthesis has advantages such as mild
catalyst) or low temperature and low pressure (ruthenium or Fe1– reaction conditions (ambient temperature and pressure), green
O-based iron catalyst). After the reaction, the high-temperature and sustainable electricity (renewable resources such as wind,
x
118 | Clean Energy, 2023, Vol. 7, No. 1
solar, and tidal energy), abundant raw materials (hydrogen from
water), simple equipment and easy operation.
1.1 Reaction principle
The chemical-reaction equation of electrocatalytic ammonia
synthesis is as follows:
N2 + 6e− + 6H+ Electrocatalyst 2NH3
(1) −−−−−−−−−−−−→
The standard electrode potential under standard conditions (25°C,
100 kPa) is 0.092 V (vs. the standard hydrogen electrode (SHE)).
The reaction potential under actual reaction conditions relative
to the reversible hydrogen electrode (RHE) is 0.23 V (vs RHE). In
theory, the reaction potential of electrocatalytic NRR is positive
compared with RHE. However, the reactants require activation
that carries an energy loss so the reaction potential is lower than
the theoretical potential—an overpotential. Based on existing
studies, the working potential range of NRR electrocatalysts is
generally −0.1 to –0.5 V (vs. RHE) [11].
This process requires adsorption of nitrogen molecules to the
catalyst surface, followed by electrochemical breakage of the ni-
trogen triple bond (N≡N) and attachment of hydrogen atoms to
those nitrogen atoms to form NH3. There are three main reaction
pathways for electrocatalytic NRR synthesis of ammonia: dissoci-
ation, association distal and association alternating pathway.
During dissociation, N2 molecules adsorb and bind to two ac-
tive sites on the catalyst surface. Severing the N≡N bond followed
by hydrogenation of the two activated nitrogen atoms yields NH3
molecules. During association, nitrogen molecules bind to an ac-
tive site on the catalyst surface after adsorption, but the N≡ N
remains partially intact. The distal pathway refers to nitrogen hy-
drogenation far from the active catalyst surface site to form a NH3
molecule and the remaining nitrogen atoms are hydrogenated to
form a NH3 molecule. The association alternating pathway refers
to the alternating hydrogenation of two nitrogen atoms to form
two NH3 molecules. Adsorption of N2 and N≡N cleavage by the
catalyst are important steps in ENRR.
When an aqueous electrolyte electrocatalyses NRR ammonia
synthesis, a hydrogen evolution reaction (HER) often occurs on
the catalyst surface because the process is under reducing po-
tential:
2H+ + 2e− Electrocatalyst H2
(2) −−−−−−−−−−−−→
HER will become a competitive reaction of the electrocatalytic
NRR synthesis of ammonia [11], which lowers the Faraday effi-
ciency (FE) of the NRR reaction. Therefore, electrocatalyst selec-
tion is also an important material design consideration.
The reaction mechanism of NRR on transition-metal nitrides is
different from NRR of general heterogeneous catalysts, since sur-
faces of transition-metal nitride had nitrogen atoms (nitride). On
transition-metal nitrides, not only reactant N2 gas but also sur-
face nitride can be reduced to ammonia. Thus, the surface nitride
atoms in transition-metal nitrides also used as reactants in NRR
and follow the Mars–van Krevelen mechanism, which is generally
considered for catalytic oxidation reactions on transition-metal
oxides. In this mechanism, surface nitride rather than reactant N2
gas is first reduced to NH3 leaving a surface nitride vacancy. Then,
the reactant N2 gas regenerates the surface recovering the nitride
vacancy and can be further reduced to NH3 [12].
For noble-metal catalysts, such as Pd and Au, a surface-
hydrogenation pathway is proposed for the NRR. The potential-
determining step is *NNH formation on Pd and Au surfaces with
1~3 eV of free energy and the experimental NRR activity is ob-
served at lower overpotentials [12]. Using density functional
theory (DFT) calculations, Ling et al. [13] showed that the activa-
tion energy of *N2H2 formation via the surface-hydrogenation step
(N2(g)+2*H→*N2H2) is lower than the formation energy of *NNH
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(N2(g) + [H+ + e−}/ *NNH) on Pd and Au surfaces, indicating that
the N2 is activated by surface *H rather than surface metal atoms.
After *N2H2 formation via surface hydrogenation, the following re-
actions proceed by the addition of (H+ + e−) exothermically.
1.2 Study on catalysts of electrocatalytic
ammonia synthesis
In 1983, Sclafani et al. initially synthesized ammonia using iron
and stainless steel as cathode and anode in a potassium hy-
droxide electrolyte [14]. The leap of synthetic ammonia from
high temperature and pressure to ambient conditions occurred
and ushered in a new era of synthetic ammonia research.
Subsequently, some focused on the electrochemical synthesis of
ammonia in solid electrolytes with H+ conduction ability, such
as proton conductor ceramic films, under ambient conditions. In
1998, Marnellos et al. pioneered a new method of electrochemical
ammonia synthesis [15]. In their study, a porous palladium film
as cathode and anode and the SrCe0.95Yb0.05O3–δ(SCY) perovskite-
type ceramic film as the electrolyte were reported. H2 entering
the anode oxidized to H+ at 570°C and the ammonia-production
rate was 5 × 10–11 mol s–1 cm–2, which corresponded to a FE of 75%.
Molten salt electrolytes were used for electrochemical ammonia
synthesis because of their fast ion migration and diffusion, and
high conductivity. In 2005, Murakami et al. used porous nickel as
the electrode and molten alkali metal halide LiCl–KCl–CsCl–Li3N
as the electrolyte for electrochemical ammonia synthesis [16].
The ammonia-production rate at 400°C was 3.3 × 10–9 mol s–1
cm–2, which corresponded to a FE of nearly 72%. However, direct
ammonia synthesis through water and air is thermodynamically
non-spontaneous and suffers from high energy consumption,
low yields and high catalyst demand. In addition, the ammonia
yield and FE obtained in the laboratory were low, readily dis-
turbed by the environment and far from meeting the require-
ments of large-scale industrial production. Therefore, since 2012,
researchers have focused on the optimization of electrocatalytic
ammonia-synthesis experimental systems and the study of
electrocatalytic ammonia-synthesis catalysts [11].
Under ambient conditions, nitrogen adsorption and decom-
position kinetics are very slow, which leads to large overpotentials
of electrochemical nitrogen reduction and a very low synthesis
rate. In addition, competitive hydrogen evolution also reduces the
ammonia-synthesis rate at ambient temperature and pressure.
Reasonable selection and design of catalysts should improve the
reduction efficiency and reduce the reaction energy consump-
tion. Currently, electrocatalytic catalysts for ammonia synthesis
mainly include noble-metal catalysts, transition-metal catalysts
and non-metallic carbon catalysts.
1.2.1 Noble-metal catalyst
In 2012, Skúlason et al. [17] screened the ENRR activities of a
series of metal elements via theoretical calculations and reported
that Mo, Fe, Rh and Ru were located at the top of the volcano
map. However, these metals are highly susceptible to hydrogen
evolution. In addition, Sc, Y, Ti and Zr adsorb nitrogen atoms
better than hydrogen atoms and have certain ENRR activities, but
readily form corresponding oxides, so their ENRR performances
remain unclear.
Subsequently, many experimental and theoretical studies
have reported the feasibility of noble metals as catalysts for
ENRR, such as Au, Ag, Pt, Pd and Ru. Shi et al. [18], Li et al. [19]
 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ |
and Bao et al. [20] reported the following. (i) Au sub-nanoclusters
supported on a TiO2 surface prepared by liquid-phase reduction
electrocatalytically prepared ammonia at ambient tempera-
ture and pressure: at the optimal potential of –0.2 V vs. RHE, the
ammonia-production rate and the corresponding FE were 21.4
μg h–1 mg–1 and 8.11%, respectively [18]. (ii) CeOx–RGO (reduced
graphene oxide) prepared by liquid-phase reduction as carrier-
supported amorphous Au nanoparticles also electrocatalytically
synthesized ammonia at ambient temperature and pressure: at
the optimal potential of –0.2 V vs. RHE, the ammonia-production
rate and the corresponding FE were 8.3 μg h–1 mg–1 and 10.1%,
respectively [19]. (iii) Tetrahedral Au nanorods grown by seeding
were used for the electrocatalytic synthesis of ammonia at am-
bient temperature and pressure: at –0.2 V vs. RHE, the ammonia-
production rate and the corresponding FE were 1.648 μg h–1 mg–1
and 4%, respectively [20]. Wang et al. reported the use of carbon
as a carrier to support Pd, Au and Pt nanoparticles for room-
temperature electrocatalytic synthesis of ammonia. Under the
same reaction conditions, the ammonia-production rate and
FE of Pd/C far exceeded those of Au/C and Pt/C [21]. At the op-
timal potential of –0.05 V vs. RHE and phosphate buffer solution
(PBS) electrolyte, the ammonia-production rate and the corres-
ponding FE of Pd/C were 4.5 μg h–1 mg–1 and 8.2%. Followed by
the ammonia-production rate and FE of Au/C, which were 0.4 μg
h–1 mg–1 and 1.2%, and the lowest ammonia-production rate and
FE of Pt/C, which were 0.4 μg h–1 mg–1 and 0.2%. Yu et al. reported
a porous network-like Ag3Cu material for electrochemical reduc-
tion of nitrogen for ammonia synthesis at room temperature.
Since Ag3Cu has a very large specific surface area, it beneficially
exposes more active sites and electrochemical mass transfer in
electrocatalytic reactions. At the optimal potential of –0.5 V vs.
RHE and 0.1 M Na2SO4 electrolyte, the ammonia-production rate
of Ag3Cu is 24.59 μg h–1 mg–1 and the corresponding FE reached
13.28% [22]. The electrocatalytic performances of Ag3Cu, pure Ag
nanosheets and pure Cu nanosheets were also compared, and
Ag3Cu had the best catalytic performance. In conclusion, noble
metals have excellent ENRR activity and the composition and
surface morphology of the catalyst plays a significant role in its
catalytic effect.
1.2.2 Transition-metal catalysts
Noble-metal catalysts make industrial utilization difficult due
to high costs and scarce resources. Due to their unique d-orbital
structure and abundant electron cloud densities, transition-
metal catalysts facilitate weakening the stable N≡N triple bond
by activating and adsorbing nitrogen molecules. Therefore, the
application of transition-metal catalysts in the electrocatalytic
synthesis of ammonia has attracted extensive attention.
Inspired by the natural bacterial nitrogenase, Mo may be an ef-
ficient electrocatalytic catalyst for ammonia synthesis. Skúlason
et al. [17] verified the feasibility of electrochemical reduction of
nitrogen to ammonia by Mo at RE and pressure through DFT
calculations. Yang et al. successfully prepared Mo nanofilms by
electrochemical deposition and applied them to electrocatalytic
ammonia synthesis. At the optimal potential of –0.49 V vs. RHE,
the ammonia-production rate was 3.09 × 10–11 mol s–1 cm–2 and
the corresponding FE was 0.25% [23]. In addition to Mo, the fol-
lowing MO-related compounds were subsequently investigated. (i)
Nitrides and oxides: Ren et al. successfully prepared MoO2 and
MoN nanorods via sol-gel. Hydrogenation of the active inter-
mediate species *N2 to *N2H on the MoO2(100) crystal plane
occurred rapidly with an energy barrier of 1.26 eV, while hydro-
119
genation of *NH to *NH2 on the MoN(100) crystal plane also oc-
curred rapidly with an energy barrier of 0.66 eV. Therefore, MoN
has higher ENRR activity than MoO2. At the optimal potential of
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–0.3 V vs. RHE, the ammonia-production rate of MoN was 78.4
μg h–1 mg–1 and the corresponding FE was 4.5% [24]. (ii) Cheng
et al. synthesized Mo2C/C nanosheets and Mo2C nanorods via
sol-gel. The ammonia-production rate and corresponding FE of
Mo2C/C nanosheets in 0.5 M LiSO4 electrolyte at –0.3 V vs. RHE
were 11.3 μg h–1 mg–1 and 7.8%, respectively [25]. The ammonia-
production rate and corresponding FE of Mo2C nanosheets in 0.1
HCl at –0.3 V vs. RHE were 95.1 μg h–1 mg–1and 8.13%, respect-
ively. (iii) Sulphide: Li et al. prepared MoS2 and C3N4 composites for
the electrocatalytic synthesis of ammonia. At –0.3 V vs. RHE, the
highest ammonia-production rate was 18.5μg h–1 mg–1 and corres-
ponded to a FE of 17.8% [26].
In addition to Mo, other transition-metal-based catalysts (Ti,
V, Cr, Mn, Fe, Co, Ni, Nb and W) were studied. Skúlason et al.
found by DFT simulation that Fe is a highly active transition-
metal catalyst for the electrochemical synthesis of ammonia.
Subsequently, Zhao et al. used elemental Fe as a catalyst for the
electrocatalytic synthesis of ammonia. Those experimental re-
sults showed ammonia-production rates of 2.12 × 10–19 mol s–1
cm–2 and Faraday efficiencies of 1.43% at the applied potential
of –1.2 V vs. RHE, which confirmed the above conclusion [27]. On
this basis, the ENRR activity of Fe compounds was further inves-
tigated. Chen et al. prepared a Fe3S4 nanoparticle material depos-
ited on carbon nanotubes and the electrochemical experiment
results showed ammonia production of 2.2 × 10–3 g h–1 m–2 [28].
Zhao et al. prepared Fe3S4 nanosheets as catalysts. At –0.4 V vs.
RHE, the ammonia-production rate was 75.4 μg h–1 mg–1 and the
corresponding FE was 6.45%. Theoretical calculations showed N2
adsorption on the Fe3S4 surface for activation and hydrogenation
[29].
1.2.3 Non-metallic carbon catalyst
For noble-metal catalysts, high prices, limited availability and
the formation of noble-metal–H bonds lead to a competitive
reaction of strong electrocatalytic hydrogen evolution, which
greatly reduces the FE. The unique d-orbital structure of the
transition metal and the rich electron cloud density of the
supplier facilitates weakening the N≡N triple bond to achieve
efficient nitrogen activation, but the d-orbital electrons of tran-
sition metals also facilitate metal–H bond formation. This leads
to the HER competition reaction and decreases catalyst NRR
selectivity. Therefore, researchers began to focus on cheap and
abundant non-metallic catalysts. Pure carbon materials are
electrochemically inert. Relevant studies confirmed the binding
energy between reactants and stable active intermediate spe-
cies improved by carbon surface modification or doping certain
heterogeneous atoms.
Mukherjee et al. reported use of a nitrogen-doped carbon ma-
terial rich in defects for electrocatalytic nitrogen reduction to
synthesize ammonia [30]. Using ZIF-8 rich in nitrogen and carbon
as the precursor, it was heat treated at different temperatures
to prepare nitrogen-doped carbon catalysts containing defects.
The heat-treatment temperature, heat-treatment time and the
nitrogen-reduction overpotential of ZIF-8 were optimized. The
production rate reached 3.4 × 10–6 mol cm–2 h–1 and the FE reached
10.2% at RT and pressure at –0.3 V vs. RHE in an alkaline elec-
trolyte. The catalyst showed excellent stability during an 18-h
continuous test. Recent studies reported that heteroatom doping
effectively regulated the electronic structures of carbon materials
120 | Clean Energy, 2023, Vol. 7, No. 1
and improved their ENRR activities. The adsorption and activation
of N2 increased with direct doping of N atoms on carbon mater-
ials, which enhanced its ENRR activity. In addition, adjusting the
electronic and geometric structure of the carbon materials and
the degree of N doping improved its catalytic activity. In addition,
Liu et al. also explored the ENRR performance of nitrogen-doped
porous carbon [31] and revealed the effects of nitrogen-doping
amount and nitrogen-doping type on ENRR performance by com-
bining experimental and theoretical calculations. Those results
showed the highest gas-production rate was 1.40 mmol g–1 h–l
at –0.9 V vs. RHE. DFT and experimental results confirmed that
pyridine-type nitrogen and pyrrole nitrogen were the active NRR
sites.
In addition, DFT calculations predicted weak adsorption cap-
acities of hydrogen on non-metallic substrates, which resulted
in many non-metallic electrocatalysts that are not conducive
to HER. Given that a proton is a Lewis acid, it is necessary to
develop carbon-based electrocatalysts with Lewis-acid sites
(electron-defective C atoms) to enhance the mutually repulsive
interaction between the Lewis-acid site and proton H to inhibit
HER. Liu et al. reported the development of a carbon-based cata-
lyst by introducing fluorine into a 3D porous carbon skeleton
(represented as F-doped carbon), effectively exposing a high ac-
tive site density for N2 adsorption and activation. At –0.2 V vs.
RHE, the highest FE of NH3 synthesized by F-doped carbon was
54.8%, 3.0 times (18.3%) that of the original carbon skeleton [32].
The ammonia-production rate of F-doped carbon was 197.7 μg
h–1 mg–1 at –0.3 V vs. RHE. The performance improvement of
F-doped carbon in N2 electrolysis comes from the binding-energy
enhancement of N2, which promotes decomposition of N2 into
*N2H. The electronegativity difference between fluorine and
carbon caused the F bound to the C atom to form a Lewis-acid
site. Therefore, the repulsive interaction between the Lewis-acid
site and the proton H inhibits HER activity; this enhances the
electroreduction selectivity of N2 to NH3. Due to its excellent
electrical conductivity, graphene is not only used in fuel cells but
also has unique applications in electrocatalysis. Wang et al. de-
signed metal-free boron-modified graphene at the atomic level
and used DFT to evaluate the catalyst structure and NRR cata-
lytic performance. The results show that the graphene edge can
effectively stabilize isolated boron atoms, with boron atoms at
the zigzag edge of graphene (B–ZZ–S) exhibiting the best per-
formance. It has a minimal free energy change of 0.85 eV via a
distal mechanism, which is lower than the Ru(0001) crystal plane
(1.08 eV) of the Ru-based catalyst. They believed that it is the
charge change between the NRR intermediate and the designed
boron-based catalyst that results in the high NRR activity [33].
Carbon-based catalysts prepared from biomass have the ad-
vantages of abundance and environmental protection, which
have attracted extensive attention. Zhao et al. chose alfalfa as a
raw material to prepare nitrogen-doped carbon materials with
multistage pore structures and obtained carbon materials with
different amounts of pyridine by adjusting the pyrolysis tem-
perature [34]. Those results showed that pyridine nitrogen played
an important role in N2 reduction to NH3 and also helped form
NH3 itself. The doped pyridine nitrogen hydrogenates to form
NH3, which generates a N vacancy on graphitic carbon, which
adsorbs and activates N2. The pyridine nitrogen–carbon ma-
terial prepared at 500°C optimized electrocatalytic nitrogen fix-
ation. In 0.005 M H2SO4 and at –0.5 V vs. RHE, the synthesis rate
was 1.31 mmol h–1 g–1 and the FE was 9.98%. This indicated that
biomass-derived nitrogen-doped porous carbon materials have
good potential in electrocatalytic nitrogen fixation. Although
non-metallic carbon catalysts are widely used in electrocatalytic
ammonia synthesis, they suffer from low ammonia-production
rates and FEs.
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The development of an efficient electrocatalyst is step one in
optimizing electrochemical ammonia synthesis. Table 1 shows
the activities of recently reported catalysts for ENRR reactions.
1.3 Electrocatalytic ammonia-synthesis process
The electro catalytic reaction takes place in a typical H-type elec-
trolytic cell. The electrochemical experiment was carried out on
the electrochemical analyser using a three-electrode system,
namely the prepared catalyst/CP electrode, platinum plate elec-
trode and Ag/AgCl electrode as the working electrode, counter
electrode and reference electrode, respectively. The loading
amount of catalyst is generally 0.2 mg cm–2. In order to prepare
the working electrode, the catalyst is dissolved in deionized water
and alcohol electrolyte. After ultrasound, it is added to Nafion
solution and then ultrasound continues to form a uniform solu-
tion. Finally, the catalyst solution is dropped onto the carbon
paper (CFP, 1 × 1 cm) and further dried in a drying oven at 60℃. In
the experiment, the electrolyte is purified by N2 and then the N2
reduction experiment is conducted. N2 electrochemical reduction
was carried out in N2 saturated electrolyte. After controlling the
potential electrolysis for 2 h, the electrolyte was collected in the
cathode cell for colour development, its absorbance was meas-
ured using an ultraviolet spectrophotometer and its ammonia
yield and FE were calculated.
The NH3 yield and FE were calculated as follows [31]:
C×V
VNH3 =
(3) t × mcat
where VNH3 is the ammonia production per mg of electrocatalyst,
µg·mg–1·h–1; C is the concentration of NH3 in the electrolyte,
µg·mL–1; V is the volume of electrolyte, mL; T is electrolysis time,
h; mcat is the electrode mass, mg.
3 × F × C × V × 10−6
FE = × 100%
(4) 17 × Q
where F is the Faraday constant, whose value is 96 500C mol–1; Q
is the total charge consumption during electrolysis, C.
To improve electrocatalytic NRR, the catalyst and
electrocatalytic device are equally important. The structure
of the electrolytic cell influences the reaction. The reactor
structure, electrode structure, electrolyte composition and
operating conditions all influence electrocatalytic efficiency.
The electrolytic cell structure used mainly includes four types:
a back-to-back electrolytic cell, a PEM electrolytic cell, an ‘H’
electrolytic cell and a single-chamber electrolytic cell [12]. In a
back-to-back electrolytic cell, a PEM or AEM separates the two
electrodes. During ammonia synthesis, water and nitrogen are
passed to the anode and cathode, respectively. Differently from
the back-to-back electrolytic cell, the PEM electrolytic cell is fed
with the electrolyte at the anode. The electrolyte water elec-
trolyses during ammonia synthesis and the H+ formed serves as
the proton source for nitrogen fixation. These two electrolytic
cells are gas–solid reaction systems, which effectively control
the generation of protons and inhibit hydrogen evolution. The
H-type electrolytic cell is used widely and comprises two re-
action chambers separated by a PEM, with electrodes directly
immersed in the electrolyte. Hydrogen evolution occurs during
ammonia synthesis, which affects the FE. For the electrolytic
cell of a reaction chamber, all electrodes are placed in the
same electrolyte, which oxidizes the ammonia produced by the
anode and leads to the deviation of the measurement results.
 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ | 121

Table 1: The activity of typical catalysts for NRR reactions

Catalyst Electrolyte Electric potential (vs Ammonia formation Electric potential (vs FE Reference
RHE) (V) (maximum rate rate (μg h−1 cm−2)/μg RHE) (V) (maximum (%)

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of ammonia formation) h−1 mgcat) Faraday efficiency)

RuPt/C 1 M KOH 0.023 38.8/– 0.123 13.2 [12]

PdCu/NC 0.05 M −0.45 –/69.2 −0.45 24.8 [13]
H2SO4
FeNi@CNS 0.1M −0.2 16.52/– −0.2 9.83 [14]
nanocomposite Na2SO4
MoS2–xOy 0.1M HCl −0.35 35.0/– −0.3 9.86 [15]
nanosheets
Ti2N nitride 0.1M HCl −0.25 11.33/– −0.35 19.85 [15]
MXene
Li-intercalated 0.5 M −0.4 –/8.7 −0.4 18.2 [16]
TiO2 nanosheets LiClO4
Fe2O3–TiO2 1 M KOH −0.177 1.07/– 23 1.9 [17]
Boron 0.05M –0.6 8.39/– –0.3 9.87 [18]
carbonitride Na2SO4
(BCN)
Reduced 0.1M HC –0.116 –/7.3 −0.166 10.8 [19]
graphene oxide
(DrGO)
Vulcanized 0.1M −0.39 –/31.93 −0.39 30.9 [20]
FeMoO Na2SO4
Fe ion grafted 0.1M −0.6 –/9.66 −0.6 13.9 [21]
onto MoO3 Na2SO4
nanorods
Ag-doped Cu 0.1M −0.4 –/61.5 −0.4 20.9 [22]
nanosheets Na2SO4
Cobalt single- 0.01 M HCl −0.1 –/67.6 −0.1 56.9 [17]
atom catalyst
Ag4Ni2 0.1 M HCl −0.2 –/23.32 −0.2 78.97 [23]
nanoclusters
Single Mo atoms 0.05 M −0.05 –/3.6 −0.05 50.2 [24]
anchored H2SO4
on nitrogen-
doped graphene
Reduced 0.1 M HCl –0.116 –/7.3 –0.116 22.0 [51]
graphene oxide
(DrGO)
Single Nb atom 0.1M –0.5 –/21.3 –0.5 9.2 [52]
modified anatase Na2SO4
TiO2(110)

Hydrogen evolution occurs during NRR, which reduces the FE.
Therefore, catalysts focused on hydrogen evolution inhibition
and catalytic device improvements have become top research
priorities.
1.4 Brief summary
Due to the limited activity of electrocatalysts and the fierce
competition of cathodic hydrogen evolution, the ammonia-
production rate and FE achieved by most studies remain
quite low. According to the US Department of Energy’s
ARPA-erefuel programme, the performance targets required
for electrocatalytic NRR commercialization are: ammonia-
production rate of 10–6 mol s–1 cm–2 at a current density of 300
mA cm–2 and a FE of 90%. Moreover, the catalyst must have
high stability; this requires a catalytic efficiency decrease of
<0.3% after 1000 h of electrolysis [13]. Performances achieved
by the current electrocatalytic NRR research institutes meet
the commercial standard.
In designing the electrocatalyst, the biomimetic strategy,
density of states analysis and DFT calculations help design the
catalyst structure and predict its catalytic performance. In add-
ition, the commonly used modification measures of catalytic
materials include: morphology and size regulation, lattice defect
construction, table interface design, heteroatom doping, vacancy
engineering and the synergistic effect among several measures
[31, 32]. The design and modification of catalysts are effective
measures to realize high nitrogen activation efficiency (Fig.1).
In terms of reactor structure, new reactors are designed and
developed according to the NRR system requirements. For ex-
ample, a microreactor can combine with the battery structure
design and the minimal characteristic size of the microreactor
strengths mass transfer during electrocatalysis. In terms of
the electrode, the electrode structure of the cathode requires
additional development to make its proton- and electron-
transport pathway more reasonable and create good conditions
for electrolysis. In terms of the electrolyte, there is continued
122 | Clean Energy, 2023, Vol. 7, No. 1
Performance optimization of
electrocatalytic ammonia synthesis
Selection of catalyst
Modification of catalyst
Noble metal base material
Bionic site construction
Transition metal base
material Table interface design
Boron material, carbon Lattice defect regulation
material
Heteroatomic doping
Conductive polymer
Fig. 1: Optimization methods for optimizing the performance of electrocatalytic ammonia synthesis
exploration of aqueous solutions with high N2 solubilities and
moderate proton-transfer rates based on molecular struc-
ture and charge interaction. After the reactor form, electrode
structure and electrolyte composition are determined, which
necessitates the determination of the actual electrocatalytic
operating conditions. Therefore, it is necessary to study the in-
fluence of temperature, pressure, working potential and other
system parameters to optimize the operating conditions and
ensure the electrocatalytic NRR runs continuously to improve
the economy of the process.
2 Photocatalytic ammonia synthesis
Solar energy, as one of the most important clean energy sources,
has seen significant recent achievements that include photocata-
lytic CO2 reduction (CORR), water splitting, organic synthesis and
nitrogen reduction. These achievements accelerate additional
solar-energy development. Photocatalytic ammonia synthesis not
only uses atmospheric N2 as a reactant but also solar energy as
a driving force, which provides new opportunities for green and
low-energy ammonia syntheses.
2.1 Reaction principle
Photocatalytic ammonia synthesis involves the following steps.
(i) The physical or chemical adsorption of N2 on the semicon-
ductor catalyst surfaces is the premise of the photocatalytic re-
action. (2) Photoexcitation of the catalyst: the catalyst absorbs
light and when the photon energy (hν) equals or surpasses the
activation energy of the material, photogenerated electrons (e–)
transition from the Valance Band (VB) to the Conduction Band
(CB) on the surface of the catalyst, enriching photogenerated
electrons in the CB. However, this creates many photogenerated
holes (h+) in the VB. (3) The synthesis of NH3 by multi-electron
hydro reduction of N2 on CB was completed. (4) NH3 detaches
from the catalyst to end the catalytic cycle. The reaction in-
volves water oxidation and the hydrogenation/reduction of ni-
trogen, as follows [60]:
2H2 O + 4h+ → O2 + 4H+
(5)
N2 + 6H+ + 6e− → 2NH3
(6)
2N2 + 6H2 O → 4NH3 + 3O2
(7)
(8) H2 O + NH3 → NH4 + + OH−
Whether photocatalytic reductions occur depends largely on the
redox potential of the adsorbed reactants and the band position
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Improvement of catalytic
device
Battery structure improvement
Electrode structure design
Control of electrolyte
composition
Non-aqueous system
construction
of the semiconductor photocatalyst. For nitrogen reduction to
ammonia, the CB of the catalyst should be higher (negative) than
the hydrogenation position of N2 and the oxidation capacity of
the hole should exceed the oxidation of H2O to produce oxygen.
The transition-state electron transfer and proton coupling at the
beginning of N2 activation of the reaction bottleneck the process
and seriously hinder the overall reaction kinetics [62]. Therefore,
two primary problems need solutions to efficiently activate ni-
trogen and increase ammonia production. First, a small band-
gap semiconductor photocatalyst with visible-light absorption is
preferred, activated by photons to generate an effective charge
and simultaneously meet the thermodynamic reduction poten-
tial of N2. Second, carrier recombination in the photocatalyst was
inhibited by catalyst modification design, which accelerated the
bulk phase charge transfer to the surface, enriched more reactive
electrons to the catalyst surface for nitrogen activation and im-
proved the efficiency of nitrogen photo fixation.
2.2 Study on photocatalytic ammonia catalysts
The photocatalyst is the most important part of a light-driven
nitrogen-fixation system, so it is urgent to design and prepare
efficient photocatalysts and a photocatalytic reaction system.
However, most monomeric semiconductors do not meet the re-
quirements of photocatalytic nitrogen fixation. Semiconductor
photocatalysts used in photocatalytic nitrogen fixation are div-
ided into one of the following categories: metal oxides, metal
sulphides, bismuth halide oxides, non-metallic semiconductors
and metal–organic skeleton materials [63–67].
2.2.1 Metallic oxides
In 1977, Schrauzer and Guth first reported that iron-doped ti-
tanium dioxide materials reduced nitrogen to ammonia under
ultraviolet light [68]. Because of the abundant UV light in sun-
light, this method has the advantage of being clean and renew-
able. How to use clean light energy to activate nitrogen molecules
to achieve high-efficiency ammonia synthesis under mild condi-
tions has attracted more and more attention. Rutile TiO2 plays an
extremely important role in NRR. The study demonstrated that
the production of NH3 and N2H4 increased significantly with iron
inclusion and the optimal Fe content was 0.2%. Fe doping accel-
erated the conversion of anatase-type TiO2 into rutile-type TiO2.
However, at >0.2%, the surface activity of the TiO2 active centre
decreased, which resulted in a catalytic activity decrease. Wu et
al. [69] reported that TiO2(B) nanotubes with very large specific
 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ |
surface areas (344 m2/g), ultra-thin shells and submicron-sized
cavities produced 106.6 μmol g–1 h–1 of NH3 at room tempera-
ture under simulated sunlight, which is 1.61 times that of TiO2
nanosheets. The enhanced photocatalytic activity was attrib-
uted to the high surface area, submicron-sized cavity struc-
ture and abundant nanotube surface defects, which enhanced
the light-absorption capacity and promoted the separation of
photogenerated carriers. Xie et al. [70] synthesized rutile TiO2
nanoparticles with large specific surface areas and abundant
oxygen vacancies for photocatalytic nitrogen fixation. Using
methanol as the hole scavenger, the TiO2 photocatalyst exhibited
high photocatalytic nitrogen-reduction ability and the optimized
efficiency was 116 μmol g–1 h–1, which is 6.5 times that of P25).
Yang et al [71]. used a solvothermal method to prepare 2D WO3–x
nanosheets rich in oxygen defects, which showed high photocata-
lytic NRR abilities under visible light, and the NH3 synthesis effi-
ciency was 82.41 μmol g–1 h–1. The ultra-thin structure of the WO3–x
nanosheets generated many oxygen vacancies that served as ad-
sorption and activation centres for N2. At the same time, oxygen
vacancies expanded the absorption of visible light and acceler-
ated the migration of photogenerated carriers, which effectively
activated the chemisorbed N2.
Sun et al. stripped ultra-thin MoS2 ultrasonically and the ex-
posed crystal surfaces were primarily the (001) and (110) planes.
Without adding a sacrificial agent, the ammonia-production rate
reached 325 μmol h–1 g–1 [72]. Azofra et al. designed theoretical
Fe-doped 2D MoS2 nanosheets and found that the excitation en-
ergy barrier dropped significantly to 1.02 eV when simulating am-
monia synthesis [73].
2.2.2 Bismuth halide oxide
In general, bismuth halide oxide (BiOX, X = I, Br, Cl) is a 2D ma-
terial with a square lattice structure. The lamellar structure of
the [Bi2O2]2+ plate provides sufficient space for atomic polariza-
tion to facilitate efficient photogenerated carrier separation and
transport. In addition, the special layered structure of BiOX easily
generates vacancies, which serve as active sites for catalytic re-
actions, and the indirect band gap also greatly hinders charge
recombination. Therefore, BiOX materials have received much
attention in photocatalytic nitrogen fixation. Lan et al. [74] suc-
cessfully prepared BI-modified BiOBr microspheres with abun-
dant oxygen vacancies using a one-step pyrolysis procedure
and used them as effective photocatalytic nitrogen-reduction
catalysts. Glycerol reduces metallic Bi in situ and deposited it
on the BiOBr microsphere surface. The oxygen vacancy (OV)
generated synchronously served as adsorption and activation
centres for nitrogen molecules. Compared with pure BiOBr, Bi@
BiOBr heterostructured microspheres have higher surface areas,
better visible-light utilization and more efficient photogenerated
carrier separation. They showed better visible photocatalytic ni-
trogen fixation and the ammonia yield reached 1350 μmol g–1 h–1,
which is 11.8 times that of pure BiOBr. Wang et al. [75] success-
fully combined bismuth metal (Bi) and indium vanadate (InVO4)
in a two-step hydrothermal method to synthesize a Bi/InVO4
nanosheet photocatalyst. The excellent photocatalytic activity of
Bi/InVO4 depended on the high nanosheet surface area, the light-
harvesting capacity, the surface plasmon resonance (SPR) effect
of Bi and the separation of electron holes.
2.2.3 Non-metallic semiconductor
Differently from traditional catalysts, the non-metallic semi-
conductor is a visible-light-responsive organic semiconductor
123
with low price, good thermal stability and low biological tox-
icity. It has many ideal catalyst characteristics, which have led
to wide adaptation and application in photocatalytic nitrogen-
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fixation research. The conductance and valence band potential
of g-C3N4 is –1.3 and +1.4 eV, respectively (vs. NHE, pH = 7), and
the band-gap width is ~2.7 eV. Compared with traditional cata-
lysts, its light-absorption region encompasses UV and visible
light, has good light absorption below 460 nm in the solar spec-
trum and expands the available range of light energies. Xue et al.
prepared porous few-layer G-C3N4 (PCL-G-C3N4) by simple mo-
lecular self-assembly. The few-layer and ultra-thin nature yielded
a larger specific surface area and exposed more active sites, while
its porous structure narrowed the band gap and improved the
light-absorption capacity and range [76].
2.2.4 Metal–organic frameworks
MOFs are porous nanomaterials formed by metal nodes and
organic ligands. MOFs have a series of unique structural and
physico-chemical characteristics that provide a new oppor-
tunity to design efficient photocatalysts. The theoretical band
gap of MOFs ranges from 1.0 to 5.5 eV due to the structural
properties of metal nodes and the effect of organic ligands.
Therefore, adjusting the structure and composition of MOFs
can significantly improve the photocatalytic performance of
MOFs. Specifically, MOFs provide tunable porosities, high surface
areas, high pore volumes, high thermal stabilities and differ-
ences in structural topological and physico-chemical properties.
Hu et al. developed violet-based radioactive MOFs (GD-IHEP).
Photocatalytic nitrogen-fixation results showed that optimized
GD-IHEP-8 had excellent photocatalytic activity and the yield of
NH3 reached 220 μmol g–1 h–1 under visible-light irradiation [77].
Li et al. [78] prepared a series of iron-based MOFs (MIL-101(Fe),
MIL-100(Fe) and MIL-88(Fe)) with excellent photocatalytic ac-
tivities for ammonia synthesis. They systematically compared
MIL-101(Cr) and MIL-101(Fe), which have the same molecular
structure but different central metal ions. The difference in
charge density indicated that there was little electron exchange
and transfer between Cr and N2, with electrons clearly concen-
trated at Fe and N2. Since nitrogen activation is an electron-
driven reaction, this confirmed that nitrogen fixation originated
from the Fe catalytic centre.
2.2.5 Multi-component composite photocatalyst
The advantages of a multi-component composite photocatalyst
are: (i) expanded light-absorption response range; (ii) efficient
separation of photogenerated carriers; and (iii) enhanced ad-
sorption and activation abilities of adsorbents on the cata-
lyst surface. The heterojunction construction increased the
defect sites on the catalyst surface, improved the separation
and migration efficiencies of photogenerated carriers at the
heterojunction interface and effectively inhibited carrier re-
combination. A narrow-band-gap semiconductor can sensitize
a wide-band-gap semiconductor effectively, so a heterojunction
photocatalyst has an excellent visible-light response. Therefore,
constructing proper heterojunctions should improve the
photocatalytic performance of semiconductor materials.
Common heterostructures include common heterojunctions,
Z-type heterojunctions, S-type heterojunctions and p–n-type
heterojunctions. At present, most heterojunction photocatalysts
are Z-type heterojunctions.
Liang et al. composed a three-phase heterostructure of g-C3N4,
WO3 nanosheets and CoOx nanodots. The defect site formed
124 | Clean Energy, 2023, Vol. 7, No. 1

by the CoOx interface strongly adsorbed N2 and the ammonia- 2.3 Photocatalytic ammonia-synthesis process
production rate approached 230 μmol h–1 g–1 without adding a To realize the large-scale application of photocatalytic ammonia
sacrificial agent [79]. Liu et al. synthesized a Z-Scheme Fe2O3/g- synthesis, it is necessary to optimize the reaction system in all

C3N4 heterostructure by combining the strong optical absorption
ability of g-C3N4 and the absorption ability of Fe2O3 to N2, and
the ammonia-production rate reached 47.9 mg L–1 h–1 [80]. Liu
et al. formed a composite heterojunction catalyst with MXene,
TiO2 and monolayer MXene, and achieved an ammonia-synthesis
efficiency of 250.6 μmol h–1 g–1 under visible light [81]. Yu et al.
synthesized g-C3N4 and RGO to obtain heterogeneous struc-
tures, which significantly increased the separation efficiency of
photogenerated electron–hole pairs and increased the ammonia-
production rate by 42 times compared with g-C3N4 [82]. Shi et al.
prepared WS2@TiO2 heterojunction materials, which accelerated
the separation and transport of electron–hole pairs; the photo-
catalytic ammonia-production rate reached 1.39 mmol h–1 g–1
[83].
The development of efficient photocatalysts is the basis to
optimize photocatalytic ammonia synthesis and these cata-
lysts have excellent NRR catalytic activity results (by calculation
or experiment). Table 2 lists the recently reported activities of
photocatalysts for NRR reactions.
The past 30 years have seen many breakthroughs in the field
of photocatalytic ammonia synthesis. However, chemisorption
and activation of nitrogen in photocatalytic nitrogen-fixation re-
actions are more difficult compared with electrocatalysis, which
is the main problem affecting the performance of photocata-
lytic nitrogen fixation. There are three main factors affecting ni-
trogen fixation of photocatalytic materials: (i) the crystal phase
structure—titanium dioxide anatase and rutile phases have very
different photocatalytic performances; (ii) band structure—for
semiconductor materials, the CB position and valence band de-
termine whether photocatalytic reduction occurs, and the band-
gap width determines whether the material reacts under visible
light; (iii) specific surface area—the specific surface area is one of
the important factors restricting catalyst performance. In general,
a material with a larger specific surface area exposes more de-
fects, more reaction sites and facilitates the reaction. Currently,
photocatalysts for ammonia synthesis more or less have certain
defects (low performance, complex synthesis methods, unstable
materials), requiring the exploration and development of new
materials.
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aspects, including photocatalysts, photo collectors, reaction sys-
tems and reaction conditions. Although a large number of am-
monia photocatalysts have been developed, their performance
is always difficult to reach the industrial application level, so
more work needs to be put into the improvement of the reac-
tion system. At present, the gas–liquid-phase reaction system is
widely used for photocatalytic ammonia synthesis under atmos-
pheric temperature and pressure. Photocatalytic reaction is usu-
ally carried out in a quartz reactor. After water is added to the
reactor, catalyst is added to the reactor and the mixture is stirred
ultrasonically. After nitrogen is introduced, the magnetic stirring
continues and finally the stirred mixture is put under the con-
dition of light for reaction. After the catalyst is separated after
sampling, the concentration of NH4+ in the solution is analysed
by using indophenol blue spectrophotometry.This reaction device
has some limitations, including the low solubility of nitrogen in
water, the inability to separate the product ammonia in time and
the competitive reaction of hydrogen evolution. The efficiency
and reproducibility of photocatalytic tests are affected by many
factors, including the light source, light intensity, reaction tem-
perature/pressure, reaction medium and reaction equipment.
2.4 Brief summary
Metal oxide, metal sulphide, bismuth halogenated oxide,
non-metallic semiconductors and metal–organic skeleton mater-
ials show good catalytic effects in the photocatalytic synthesis of
ammonia. However, many problems remain for industrial appli-
cation: (i) adsorption and activation of N2; (ii) low catalyst light-
absorption capacity; (iii) high electron–hole recombination rate; (iv)
low photoelectric conversion efficiency. Further catalyst modifica-
tions will improve the photocatalytic ammonia catalytic efficiency.
Common methods include: (i) defect engineering; (ii) morphology
control; (iii) element doping; (iv) heterostructure construction.
3 Photoelectrocatalytic ammonia synthesis
Currently, the ammonia-production rate of photocatalytic NRR
is still low and challenging problems such as photogenerated

Table 2: Photocatalytic activities of ammonia synthesis under different modification strategies

Strategies Catalyst Nitrogen source Sacrificial agent Ammonia-production rate (mmol gcat–1 h–1) Reference

Morphological control eBP NFs N2 Na2S/Na2SO3 2.37 [84]

PFL-g-C3N4 N2 Methyl alcohol 8.20 [76]
Element doping Metal Ru@GaN NWs N2 Na2SO3 2.40 [85]
Non-metal B−C3N5 N2 Methyl alcohol 0.42 [86]
Defect project SV-1T-MoS2 N2 Methyl alcohol 8.22 [87]
g-C3N4−V N2 – 0.32 [88]
TiO2−H2-DA N2 Methyl alcohol 3.00 [89]
Heterojunction Type II NCN/MgO N2 Ethyl alcohol 4.55 [90]
p–n TiO2/BiOBr N2 Methyl alcohol 1.43 [91]
Z-scheme MOF@DF-C3N4 N2 Methyl alcohol 2.33 [92]
S-scheme ZnO/ZnSnO3/CDs Air Ethyl alcohol 0.77 [93]
Others LSPR MoO3−x N2 Methyl alcohol 0.44 [94]
MOFs Gd-IHEP-8 N2 – 0.22 [135]
FLPs 10B/10Mo−C3N4 N2 Methyl alcohol 1.68 [136]
 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ |
­ lectron–hole pair recombination and low solar-energy utiliza-
e three advantages: (i) under an external bias, the photogenerated
tion remain. In addition, testing requires sacrificial agents, which
affect the quantitative detection of NH3 by complexing with NH3.
In contrast, controlling the reaction potential or current density
readily controls electrocatalytic NRR; the reaction system is
simpler than photocatalysis. However, some challenges such as
low reaction rate, low FE, low stability, more interference in the
test process and inconsistent test standards remain. Therefore,
coupling solar energy and electric energy with the synergistic ef-
fect of photocatalysis and electrocatalysis should improve the
ammonia-production rate and FE.
3.1 Reaction principle and process
Photoelectrocatalytic nitrogen reduction is generally divided into
three processes: (i) a semiconductor is excited by light to produce
photogenerated electrons; (ii) an external bias directionally trans-
fers photogenerated electrons to the catalyst surface; (iii) the
catalyst reduces N2 fixed on the catalyst surface to NH3, N2H4 and
other nitrogen-containing compounds.
The as-synthesized catalysts were coated onto carbon pa-
pers as working electrodes. In general, catalyst was dispersed
in anhydrous ethanol following by the addition of Nafion solu-
tion. Then, the mixture was sonicated to form a suspended solu-
tion. Afterward, the suspended solution was cast by dropping
on carbon paper (1.5 × 3.5 cm) and dried under vacuum at 25℃.
The NRR test was operated in the photoelectrochemical reactor
with the applied potential of –0.65 V vs. Ag/AgCl under simulated
solar light illumination (1 sun with AM 1.5-G filter) for 2 h. During
the test, N2 gas was continuously bubbled into the electrolyte of
Na2SO4 (the electrolyte was purged with N2 for 30 min prior to
the test). This procedure was repeated for five cycles, in which
the electrolyte solution was changed before starting every new
cycle. The amount of NH3 production was determined using the
indophenol blue method.
For the photoelectrocatalytic system, the external bias voltage
promotes the reaction to improve the reduction ability. The re-
actor is usually set up with a three-electrode system, comprising
a working electrode, counter electrode and reference electrode.
The electrode catalyst serves as the working electrode, where
the NRR mainly occurs. Usually, a platinum sheet is used as the
anode with the main oxygen-reduction reaction. To prevent fur-
ther oxidation of ammonia, a Nafion membrane was placed be-
tween the photocathode and anode, allowing only the passage of
ions. The common way to prepare the photoelectric electrode is to
attach the semiconductor material of the photoelectric electrode
to the transparent conductive oxide coated glass with low work
function, such as indium tin oxide or fluorine doped tin oxide
(FTO), and use it on the electrode clamp. In general, the working
electrodes were prepared as follows: 5 mg of photocatalysts were
dispersed in 2 mL anhydrous ethanol to make the slurry of the
materials. Then, the slurry was coated onto an FTO glass elec-
trode (1 × 1 cm) by using the drop-casting method. Next, the
as-prepared electrodes were dried naturally overnight under
vacuum. Transient photocurrent response was performed by
using an electrochemical workstation based on a standard three-
electrode system using the as-prepared catalyst/FTO cell as the
working electrodes.
Photocatalysis and electrocatalysis have unique advantages.
Combining photocatalysis and electrocatalysis, electrocatalysis
benefits the directional transfer of the photocharge, photo-
catalysis reduces the electric potential of nitrogen electrocatalysis
and slows down the competitive hydrogen reaction. There are
125
charge moves directionally, which benefits the photogenerated
charge and hole separation; (ii) electrocatalysis facilitates the en-
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tire reaction; (iii) photoelectrocatalysis is an electrode reaction,
which simplifies activity testing of the catalyst, such as electro-
chemical impedance, linear scanning curve (LSV), etc. It is helpful
to explore the mechanism of catalytic reduction by measuring
the catalyst activity using an electrochemical workstation.
3.2 Study on photoelectrocatalysis catalysts
Photoelectric catalytic reaction (PEC) is based on electro catalytic
redox reaction and uses light energy to reduce the overpotential
of the NRR, which will be beneficial to the improvement of FE
and ammonia yield. Catalysts with cost-effectiveness and ef-
ficiency advantages are essential for nitrogen reduction. This is
a potential technology research direction. Previous studies have
shown that photoelectrochemical processes have been applied to
many reactions, such as water decomposition, removal of toxic
organic dyes, conversion of carbon dioxide (CO2) into fuel and oxi-
dation of water. However, the efficient synthesis of ammonia by
photoelectrochemistry has not been widely explored.
The early research on photoelectrochemical NRR mainly fo-
cused on the preparation of photocatalysts (coating, loading
or growth) on photo electrodes and the photo-driven NRR was
carried out without applying bias potential. Zhu et al. reported
that the solvated electrons generated by ultraviolet-light exci-
tation of B-doped diamond can drive the dynamically inert NRR
process [96]. It was found that the ammonia production in the
photoelectrochemical dual-compartment H-cell was higher than
that in the single-compartment cell. In this system, B-doped dia-
mond is excited and releases electrons into solution to generate
solvated electrons that can directly participate in the high-energy
NRR process. This process is solving the problem of weak N2 ad-
sorption on the catalyst surface. In addition, Li et al. introduced
oxygen defects into the rutile TiO2 photo-electrode surface by
atomic-layer deposition. Researchers proved that the surface OV
of the TiO2/Au/a-TiO2 photoelectric electrode and the plasma-
excited Au nanoparticles have a synergistic effect on enhancing
the photoelectric catalytic NRR performance [97].
Later, in order to solve problems such as the low dissolved con-
centration of N2 in aqueous solution and the hydrogen evolution
(HER) competitive reaction, Zheng et al. designed and prepared
a hydrophobic aerophilic heterostructure photocathode, which
can significantly inhibit the HER competitive reaction in the
photoelectrochemical cathode cell [98]. The researchers coated
gold nanoparticles/polytetrafluoroethylene and a thin titanium
layer (Au PTFE/TS) on the surface of a silicon (Si)-based photo
electrode commonly used in the photocatalysis system. The
hydrophobic PTFE porous framework on the photocathode elec-
trode prepared in the experiment can become the gas-diffusion
layer of N2, thus forming a rich N2 atmosphere on the surface of
the Au PTFE/TS photocathode. In addition, the Si substrate can
be excited to generate photogenerated electrons after absorbing
sunlight and the Au nanoparticles (NPs) dispersed on the PTFE
surface open up an electron-transport channel for the N2 reduc-
tion reaction. The contact-angle experiment reveals the hydro-
philicity of the Si-based photocathode after integrating the Au
active site and the hydrophobicity of the porous PTFE skeleton.
The aerophilic property of the Au PTFE/TS sample makes the
interaction between the N2 molecule and photoelectric electrode
greatly enhanced after the introduction of PTFE. In addition, in
order to balance the oxidation reaction rate in the anode cell
126 | Clean Energy, 2023, Vol. 7, No. 1

and the reduction reaction in the cathode cell, a hole-sacrificing photocathode and the Fermi level (Ef) is lower than the Ef of the
agent (Na2SO3) is added to the electrolyte as an alternative elec- electrolyte solution. Once immersed in the electrolyte, electrons
tron donor and protective agent for the Pt anode. The photocata- flow from the electrolyte to the semiconductor to form an elec-

lytic NRR activity test was carried out at a bias potential of –0.2 V
(relative to RHE). The NH3 yield of the Au PTFE/TS photocathode
reached 18.9 µg cm–2 h–1 and the FE value was 37.8%. In addition,
DFT calculation results show that compared with Au/TS, the hy-
drogenation of N2 to generate *NNH is more favourable for Au
PTFE/TS samples, so the NH3 production rate and FE are signifi-
cantly improved. The charge-density diagram shows that a large
amount of charge transfer has occurred from PTFE to Au/TS, re-
sulting in the bonding strength of *NNH on the Au PTFE/TS sur-
face being significantly higher than that on the Au/TS surface. In
addition, because the surface of hydrophobic PTFE is inert to *H,
the HER competitive reaction on the bare part of PTFE without Au
NPs will be significantly inhibited.
Ali et al. [99] first synthesized high-density black silicon
nanowires on the surface of boron-doped silicon wafers, then
modified the silicon nanowires with gold nanoparticles (GNP) to
form GNP/bSi composite photocatalysts. The catalytic perform-
ance of the silicon nanowire-based photocatalyst was nine times
higher than that of the untreated original silicon wafer because
the silicon nanowires effectively inhibited light reflection and
enhanced light scattering and absorption. In addition, silicon
nanowires provided greater specific surface areas for anchoring
GNPs. Compared with traditional bulk photocatalytic materials,
2D structure materials significantly inhibited the recombination
of photogenerated electron–hole pairs.
3.3 Brief summary
The challenges of the photoelectrocatalysis pathway for
ammonia synthesis include problems in photocatalysis.
Photoelectrocatalysis nitrogen reduction occurs at the cathode.
Photogenerated electron holes occur on the cathode side and
the photogenerated electrons migrate to the active catalyst sur-
face site to reduce nitrogen. The photogenerated holes transfer
to the anode for oxidation under an external bias. Some re-
searchers have proposed that p-type semiconductors are more
suitable for the photocathode, so there are more restrictions on
the catalyst choice [102, 112–114]. P-type semiconductors act as a
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tric field in the semiconductor near the interface. This electric
field causes the semiconductor band to bend downward to fa-
cilitate electron transport at the photocathode–electrolyte inter-
face. Second, in the presence of electricity, the strong competitive
reaction to produce hydrogen reduces the electron selectivity of
the nitrogen reduction. Therefore, the efficiency of the photocata-
lytic nitrogen reduction improves by selecting appropriate p-type
semiconductors to promote nitrogen dissolution and diffusion,
nitrogen adsorption and activation, and carrier separation and
transmission through defect construction, morphology design,
heterojunction construction and the addition of additives [102,
112–117].
4 Biocatalytic ammonia synthesis
Nature contains nitrogen-fixing microorganisms; these catalysts
directly reduce nitrogen in the air to ammonia under ambient
temperature and pressure, and its nitrogen-fixation capacity ex-
ceeds the Haber–Bosch process by three orders of magnitude.
Organisms fix ~0.2 Gt of nitrogen, which accounts for ~48% of
surface nitrogen (the remaining 52% provided by synthetic am-
monia). Biological nitrogen fixation, in terms of both its required
conditions and its ability to fix nitrogen, greatly exceeds chemical
nitrogen fixation. Biological nitrogen fixation can be divided into
biological nitrogen-fixation bacteria and biomimetic chemical ni-
trogen fixation.
4.1 Principles of biomimetic chemical nitrogen
fixation
Biomimetic chemical nitrogen fixation is a chemical method
to simulate the function of nitrogenase in biological bodies
and prepare excellent chemical catalysts to produce am-
monia at ambient temperature and pressure. The biological
nitrogen-fixation mechanism merits study experimentally and
in theory. It provides an important basis for the chemical simu-
lation of biological nitrogen fixation. To achieve nitrogen fix-
ation, nitrogen-fixing microorganisms must have three basic

Table 3: Summary of photoelectrocatalysis NRR performance for various photocathodes

Photocathode material NH3 yield rate (μg cm−2 FE (%) Potential (VRHE) Light source Reference
h−1)

CuO nanofibers 5.3 17 0.6 1 sun with AM 1.5-G filter [102]

Cu2O film 7.2 20 0.4 1 sun with AM 1.5-G filter [102]
Ag/Ni–MOF/Cu2O 4.64 24.3 0.5 1 sun with AM 1.5-G filter [103]
Cu2S/In2S3 17.7 29.4 −0.6 1 sun with AM 1.5-G filter [104]
NV‐g‐C3N5/BiOBr 29.4 (μg mgcat−1 h−1) 11 −0.2 A solar simulator with a [105]
cutoff filter (λ ≥ 420 nm)
p‐BiVO4 ~1.9 16.2 −0.1 A 300-W xenon lamp (100 [106]
MW cm−2)
MoS2/TiO2 24.1 65.52 −0.2 A 300-W xenon lamp [107]
with AM 1.5-G filter
MoSe2/g‐C3N4 131.2 28.91 −0.3 A 300-W xenon lamp [108]
with AM 15-G filter
Au NPs/BSi/Cr ~1.3 N/A N/A A 300-W xenon lamp [109]
with 2 sun
Ag NPs/BSi ~47.3 ~55.05 −0.2 A 300-W xenon lamp [110]
with AM 1.5-G filter
Black phosphorus 102.4 (μg mgcat−1 h−1) 23.3 −0.4 A 300-W xenon lamp [111]
with AM 1.5-G filter
127 | Clean Energy, 2023, Vol. 7, No. 1
­ onditions: (i) nitrogenase; (ii) MgATP2–; (iii) electron donors such
c nitrogenase is the photosynthesis of nitrogen-fixing bacteria in
as reduced ferredoxin, reduced flavin redoxin or anthropogenic
Na2S2O4, to provide electrons for N2 reduction (where ATP is ad-
enosine triphosphate) [118].
Nitrogenase is a complex system comprising two proteins:
MoFe and Fe [119]. Some organisms do not contain Mo, VFe
nitrogenase or FeFe nitrogenase, though they have the same cata-
lytic effect as MoFe, but are less active. The MoFe protein contains
two metallic clusters: an M-cluster [7Fe–9S-Mo-C high citrate],
also known as the FeMo cofactor, which provides the active site
for N2 bonding and reduction [120]; and the P-cluster [8Fe–7S],
transferring electrons to the MoFe protein. The Fe protein [4Fe–4S]
provides the MoFe protein with the needed electrons [121].
The reduction of N2 to NH3 often includes H2 generation under
the catalytic action of nitrogenase and the energy provided by
ATP hydrolysis. Howard and Rees reviewed three types of electron
transfer that occurred during N2 reduction catalysed by nitrogenase
[122]. These include: (i) electron carriers (such as ferredoxin and
flavin redox proteins in the organism, dithionite outside the or-
ganism) donate electrons to the Fe protein and the Fe protein under-
goes reduction; (ii) the energy provided by the hydrolysis of two
equivalent ATP facilitates electron transfer from the Fe protein to
the MoFe protein. The conjugates of MgATP and the Fe protein bind
to the MoFe protein, ATP hydrolyses to form ADP, ADP binds to the
Fe protein, then separates from the MoFe protein; (3) the electron
is transferred to the active site of the MoFe protein and reduces N2.
For more than two decades, Lowe and Thorneley conducted a lot of
research on the kinetics of nitrogenase catalysis and summarized
and put forward the kinetic model of nitrogenase function, namely
Lowe–Thorneley (LT) [123]. LT nitrogenase function gives the energy
conversion of each intermediate during catalysis. Among them, the
bonding and hydrolysis of MgATP with Fe protein promoted electron
migration from Fe protein to MoFe protein. Release of the Fe protein
is the rate-determining step after electron transfer.
During nitrogenase catalysis, the MoFe protein reduces the
proton to H2, while N2 binds to the catalytic intermediate to form
a complex. The reduction of one N2 into NH3 forms one H2. The
system needs to complete the transfer of eight electrons and the
participation of 16 MgATP, so the nitrogen-fixation reaction stoi-
chiometry formula is:
+ -
(9) N2 + 8H + 16MgATP + 8e → 2NH3 + H2 + 16MgADP + 16Pi
where ADP is adenosine diphosphate and Pi is inorganic phos-
phate [122].
FeMo cofactor is the catalytic activity centre of nitrogenase and
is composed of two nicking cubane-type atom clusters (MoFe3S3
and Fe4S3), connected by three disulfide bonds and a high citric
acid molecule is covalently connected to a Mo atom, with a cen-
tral carbon atom [124–130].
For biological nitrogen fixation, Fe is the active site for N2 com-
plexation on FeMo cofactors as well as reduction. The experi-
mental evidence supporting Fe as the active centre comes from
the interaction between CO and nitrogenase. Rees et al. resolved
the crystal structure of MoFe protein inhibited by CO at 1.50-Å
resolution. CO molecules bridge with Fe2 and Fe6 in FeMo cofac-
tors by replacing coordinated sulphur atoms, suggesting that Fe
actively reduces N2 [122].
4.2 Biomimetic chemical nitrogen-fixation
catalyst
Nitrogenase does not require the direct involvement of light to
achieve biological nitrogen fixation. But the energy source of
symbiotic plants. In the simulation of nitrogen fixation, the use
of direct light-driven nitrogen fixation has always been the focus
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of attention.
Brown et al. prepared MoFe protein–CdS nanorod hybrid mater-
ials as photocatalysts for nitrogen fixation [132]. Since the band
gap of CdS is only 2.4 eV, visible light excites CdS and transfers
photogenerated electrons to nitrogenase MoFe proteins, and uses
light to replace ATP hydrolysis and drive nitrogenase catalysis.
Under visible light, the CdS–MoFe protein biohybrid synthesizes
NH3 at a rate of 15 nmol mg –1 min–1, comparable to NH3 synthesis
by nitrogenase in nature. Kanatzidis et al. simulated the inter-
action of nitrogenase FeMo and Fe co-groups in the protein [133].
They confined artificially simulated FeMo (NBu4)3 [Mo2Fe6S8 (SPh)
3
Cl6] and Fe (Ph4P)2 [Fe4S4Cl4] to polymer networks, individually or
simultaneously, to mimic nitrogenase structurally and function-
ally. They found that gels composed of iron (Ph4P)2[Fe4S4Cl] had
better nitrogen-fixation efficiencies at room temperature, pres-
sure and light. This indicated that Fe can also be used as an active
site for N2 reduction in the absence of Mo.
4.3 Brief summary
Currently, nitrogen-fixation efficiencies of photocatalysts are still
relatively low and not enough is known about the mechanistic
pathway. The reliabilities of some results are also questionable
due to the ubiquity of NH4 + pollution in the atmosphere. Isotope
calibration data are missing. Therefore, it is urgent to establish a
standardized characterization system for photocatalytic nitrogen
fixation.
5 Conclusions
Traditional ammonia syntheses suffer from high energy con-
sumption and serious pollution. Scientists are exploring more
green ways to produce ammonia to ‘disconnect’ it from fossil
fuels and carbon emissions. Developing a high-efficiency, low-
energy, green-ammonia synthetic process at room temperature
and pressure is critical. Photosynthesis or electrochemistry uses
H2O and N2 as raw materials, which produce ammonia at ambient
temperature and pressure using sunlight and/or electricity, and
has received extensive attention. However, the production rate
and efficiency are not up to the actual requirements. Nitrogenase
ammonia-synthesis technology has the advantages of high elec-
tronic efficiency and low energy consumption, but low reaction
rates limit improvements. In addition, the stability and recycling
of the catalyst also pose significant challenges.
The main problem facing ammonia synthesis at ambient tem-
perature and pressure is a low production rate of NH3 that is well
below commercial requirements (9.3 × 10–7 mol cm–2 s–1). In add-
ition, NRR catalyst stability is another key issue. According to the
US Department of Energy’s ARPA-erefuel program, the perform-
ance targets required for electrocatalytic NRR commercialization
are an ammonia-production rate of 10–6 mol s–1 cm–2 at a current
density of 300 mA cm–2 and a FE of 90%. Moreover, the catalyst
must have high stability; this requires a catalytic efficiency de-
crease of <0.3% after 1000 h of electrolysis [13]. Geng et al. re-
ported a record-high activity for N2 electrochemical reduction
over Ru single atoms distributed on nitrogen-doped carbon (Ru
SAs/N–C) [120].
There are challenges and opportunities in future catalyst
studies:
 Research progress in green synthesis of ammonia as hydrogen-storage carrier under ‘hydrogen 2.0 economy’ |
(i) Design catalysts by coupling multiple strategies.
Combining strategies jointly/cooperatively optimizes the
binding energies of reactants and key intermediates, and
maximizes active site exposure while inhibiting HER.
Multiple strategies have been explored to minimize the
occurrence of HER, from both a catalyst and an electro-
lyte perspective. Nonetheless, selectivity remains quite
low in aqueous-solution-based NRR, typically ≤15%. On
the other hand, strategies to suppress the competing HER
have demonstrated the potential to achieve FEs of 35%,
and even >60% [121].
(ii) Combining in situ representations, theoretical calculations
and predictions (machine-learning models). The develop-
ment of in situ technologies helps establish more effective
theoretical models and deepens the understanding of re-
action pathways, degradation modes and structure–prop-
erty relationships of specific materials, and further guides
new catalyst design directions.
(iii) Establish standards and protocols for accurate, reliable
and reproducible NRR measurements. The impurity com-
position of nitrogen used requires clear specifications.
The N2 feed gas and the chemical medium required in the
reaction require purification to exclude exogenous nitro-
gen contaminants (NH3, nitrate/nitrite and nitrous oxide)
prior to NRR. In addition, 15N2 isotope labelling experi-
ments should be carried out to confirm the actual reduc-
tion of N2.
Under the ‘hydrogen 2.0 economy’, as a highly concerned
hydrogen-storage material, ammonia provides a potentially ef-
ficient and zero-emission energy storage and conversion path
through the mutual conversion of ammonia and hydrogen.
Acknowledgments
Funding was provided by National Energy Group Project
xST930022006C.
Conflict of interest statement
None declared.
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