Received: 29 February 2024

DOI: 10.1002/ece2.39

REVIEW
- -
Revised: 17 April 2024 Accepted: 24 April 2024

Recent advances in transition metal electrocatalysts for

effective nitrogen reduction reaction under ambient
conditions

Li An1 | Zhaoyan Zhang1 | Guohua Liu1 | Wenning Liu1 | Yajie Fu1 |

Dan Qu1 | Yichang Liu1 | Pu Hu2 | Zaicheng Sun1
1
Beijing Key Laboratory for Green Catalysis and Separation, Center of Excellence for Environmental Safety and Biological Effects, College of Chemistry
and Life Science, Beijing University of Technology, Beijing, China
2
Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Wuhan Institute of Technology, Wuhan, China

Correspondence
Zaicheng Sun and Pu Hu. Abstract
Email: [email protected] and As one of the world's largest chemical products, ammonia (NH3) plays a vital
[email protected]
role in the industry, agricultural production, and national defense. In modern
Funding information industry, NH3 is produced primarily through the high‐temperature high‐
National Key Research and Development pressure Haber–Bosch process, which consumes large amounts of energy
Program of China, Grant/Award Number:
and releases large amounts of greenhouse gases. Electrocatalytic nitrogen
2023YFB3810800; Key Project of the
National Natural Science Foundation of reduction reaction (NRR) under ambient conditions has been widely consid-
China, Grant/Award Numbers: 21801092, ered among many nitrogen fixation methods, which can be produced using
21936001; National Natural Science
Foundation of China, Grant/Award
renewable energy. However, the main challenge is to achieve both high NH3
Numbers: 22272003, 22301013; R&D yield and Faraday efficiency, which is attributed to the strong N ≡ N bond and
Program of Beijing Municipal Education serious hydrogen evolution reaction. Based on the key problems, this review
Commission, Grant/Award Number:
23JB0002; Beijing Outstanding Young discussed the transition metal (TM) catalysts, including alloys, TM oxides, TM
Scientists Program, Grant/Award sulfides, TM carbides, and strategies for tuning the electronic structure,
Number: BJJWZYJH01201910005017
regulating the morphology, and bimetallic synergistic effect on improving the
NRR performance. Moreover, this review also summarized the NH3 detection
methods and the reliable control experimental parameters in the NRR process
to obtain accurate experimental results. Finally, the challenges and future
directions of TM catalysts for NRR are considered, emphasizing the available
opportunities by following the giving principles.

KEYWORDS
NH3 detection methods, nitrogen reduction reaction, transition metal electrocatalysts

-
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2024 The Authors. EcoEnergy published by John Wiley & Sons Australia, Ltd on behalf of China Chemical Safety Association.

EcoEnergy. 2024;2:229–257. wileyonlinelibrary.com/journal/ece2 229

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- AN ET AL.

1 | INTRODUCTION adsorption and activation.20–23 It is worth noting that

nitrogenase requires hydrolysis of (adenosine triphos-
Ammonia (NH3) as a green energy supporter and alter- phate) ATP in the reduction of N2 to NH3, as well as a
native fuel is one of the world's largest chemical products, certain amount of reducing agent, a process that relies on
playing a vital role in the global economy.1,2 As an a large energy input.24 However, as far as biological
important raw material for chemical fertilizers in agri- nitrogen‐fixing enzymes are concerned, they are unable
culture, the wide application of NH3 has solved the food to meet the huge demand in the fertilizer industry sector.
security problem for most populations in the whole First, the stability of nitrogenases and molecular catalysts
world. The main pathways of NH3 include flash nitrogen remains a considerable challenge in current research, and
fixation, photocatalytic nitrogen fixation, biological ni- it is worthy of further study of the detailed reaction
trogen fixation, electrocatalytic nitrogen fixation, and mechanism. The use of renewable energy to drive elec-
industrial nitrogen fixation by the Haber–Bosch pro- trocatalytic reduction of nitrate to ammonia and other
cess.3,4 For conventional industrial applications, the chemicals is another important method for solving
production of NH3 over iron‐based catalysts requires environmental problems. The advantages that exist in
relatively harsh conditions of high pressure (150– nitrogen reduction reaction (NRR) over NOx (nitrate‐like
350 atm) and high temperature (350–550°C).5–7 However, compounds) reduction to ammonia are (1) Electro-
it consumes more than 1% of the world's total power catalytic nitrogen synthesis to ammonia is an energy‐
generation and is responsible for more than 300 million efficient process driven by electrical energy, with envi-
tons of carbon dioxide emissions annually.8 The Haber– ronmentally friendly feedstocks, H2O and N2. (2) It can
Bosch process is based on economies of scale and re- break the thermodynamic limitations of the reaction by
quires large amounts of manpower and material re- adjusting the working potential. (3) Theoretical calcula-
sources to maintain supply and demand. Ammonia tions show that electrocatalytic NRR can save up to 20%
synthesis suffers from high energy consumption and of energy compared to the Haber‐Bosch process. As for
emissions.9,10 Therefore, it is crucial to develop a sus- NOx reduction to ammonia, the side reactions generated
tainably utilized method to replace the energy‐intensive by high overpotential and the possible electrode corrosion
and polluting conventional Haber–Bosch process. Flash caused by corrosive gases generated during electrolysis
nitrogen fixation and biological nitrogen fixation are limit the catalytic activity and catalytic efficiency. (4) The
considered natural methods of nitrogen fixation.11 In the process unit is simple, flexible in operation, does not
early days of the earth, nitrogen was biologically fixed require expensive infrastructure construction, and allows
and formed nitric oxides (NO) when lightning dis- for the construction of ammonia plants in remote areas,
charges.12 NO continues to react further with oxygen with much more flexibility and adjustability than the
molecules in the atmosphere, and nitrogen oxides can Haber–Bosch process.25 (5) NRR is a process of involving
combine with water to form nitric acid and turn into six electrons. However, the direct conversion of NOx to
fertilizer in the soil. For example, nitrate ions in water ammonia involves 8‐electron and multiple proton trans-
can react with minerals in the soil to form nitrates and fer coupled processes with multiple intermediates (NO2−,
are further used as a nitrogen fertilizer for plants, which NO, NH2OH) during the reaction, making its reaction
is an essential substance. However, the efficiency of kinetically more difficult than NRR. Therefore, direct
lightning nitrogen fixation is much lower than that of conversion of nitrate to ammonia is extremely
industrial nitrogen fixation, thus it cannot be applied to challenging.26
agricultural production effectively.13–16 Electrocatalytic ammonia synthesis technology has
Biological nitrogen fixation is the process of convert- drawn much attention in the research field due to its
ing atmospheric nitrogen to organism‐available ammonia advantages of low energy consumption, controllable re-
under environmental conditions using nitrogen‐fixing action, and green environment.27–30 The most important
enzyme systems in the body. Three nitrogen‐fixing of these is the electrocatalytic NRR system which has a
enzyme systems have been identified, namely great potential to produce NH3 from nitrogen and water
molybdenum‐iron, vanadium‐iron, and iron–iron directly under ambient conditions using renewable solar
nitrogen‐fixing enzyme systems because their active and aqueous energy.31 It is expected to replace the con-
centers are composed of clusters of different metal atoms, ventional ammonia synthesis process.32,33 Therefore,
respectively.17,18 The most commonly studied nitrogen rational design of catalysts with excellent activity, high
fixation enzymes are MoFe nitrogen fixation enzymes, selectivity, and high stability for electrochemical NRR is
which are one of the main active sites for the reduction of of great research significance.34,35
N2 into immobilized NH3.19 In addition, many findings Nitrogen adsorption and activation are important
suggest that ferritin is the key active site for N2 prerequisites for NRR and have a significant influence on
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AN ET AL.
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NH3 yield.1,4,36,37 The NRR process is inhibited by the reliable detection methods will be applied to the field of
competing effects of hydrogenolysis reaction (HER) and NRR. We also discuss strategies to improve NRR perfor-
the difficulty of breaking the strong N ≡ N bonds, mance and prospects for development.
resulting in low Faraday efficiency (FE) and NH3
yields.18,38–40 NRR is a typical six‐electron hydrogenation
reaction. Meanwhile, the hydrogenolysis competition 2 | REACTION PATHWAYS AND
reaction HER is a two‐electron transfer process. The MECHANISMS OF
equilibrium potential of HER in electrolytes under full ph ELECTROCHEMICAL NRR
conditions (acidic, basic and neutral) is similar to that of
NRR as shown in Equations (1)–(4).41,42 Due to the diversity of the actual reaction pathways of
electrocatalytic NRR, elucidating the characteristics of
N2 ðgÞ þ 6Hþ ðaqÞ þ 6e− ⇌ 2NH3 ðaqÞ the various pathways would be beneficial for researchers
ð1Þ
Eo ¼ 0:148 V vs: NHE to better understand and differentiate the roles and
mechanisms of electrocatalysts in the reaction environ-
2Hþ ðaqÞ þ 2e− ⇌ H2 ðgÞ Eo ¼ 0:000 V vs: NHE ment. The existence of stable N ≡ N triple bonds requires
extremely high energy for the dissociation pathway.
ð2Þ
Therefore, suitable electrocatalysts need to be selected to
reduce the reaction activation energy and accelerate the
N2 ðgÞ þ 6H2 OðlÞ þ 6e− ⇌ 2NH3 þ 6OH− ðaqÞ
ð3Þ kinetics of the NRR reaction. The molecular structure
Eo ¼ −0:736 V vs: NHE and chemical properties of N2 determine how NRR
electrocatalysts are designed.56 The molecular orbital of
N2 is formed by hybridization of atomic orbitals of two N
2H2 OðlÞ þ 2e− ⇌ H2 ðgÞ þ 2OH− ðaqÞ atoms, which includes four bonded orbitals (σ2s, σ2px,
ð4Þ
Eo ¼ −0:828 V vs: NHE π2py, π2pz).57 This orbital feature results in extremely high
N2 bond energy (941 kJ mol−1).58 In addition, the nitro-
gen molecule has a wide energy gap (10.82 eV) between
Due to the high price of precious metal materials, it is the highest occupied molecular orbital and the lowest
necessary to consider the use of sustainable materials. unoccupied molecular orbital.59 In addition, nitrogen,
Among them, non‐noble metal materials have a high being a polar molecule, has a high ionization energy
natural abundance, are environmentally friendly, and can (15.58 eV), which further hampers electron transfer
be applied in large‐scale industrialization. Transition during electrochemical processes due to the lack of dipole
metals such as Mo, Fe, Co, Zr, and Ni as well as oxides, moments.60 (Figure 3).
carbides, and sulfides have been widely used as electro- Recently, Zhang et al.61 reported the first application
catalysts for ammonia synthesis under ambient temper- of TM oxide hydrogen storage materials for electro-
ature and pressure.43,44 catalytic NRR. The density functional theory (DFT) can
Recently, transition metal (TM) electrocatalysts have accelerate the high‐throughput screening of electro-
attracted much attention in the field of NRR due to their catalysts and thus provide a theoretical basis for the
weak adsorption of protons and effective inhibition of HER construction of electrocatalysts. Hydrogenolysis is a
to improve FE.45 TM catalysts can activate N2 through a competing reaction in the non‐reducing reaction process.
give‐and‐take electron process, and their empty orbitals Finding suitable NRR electrocatalysts that can inhibit
can accept lone pair electrons from N2. At the same time, HER and facilitate the conversion of N2 to ammonia is
TM electrocatalysts can provide their d‐orbital electrons to currently one of the most popular and challenging topics
the antibonding orbitals of N2.46–51 They can also adsorb N2 in the field of applied electrocatalysis, emphasizing the
molecules by forming TM‐N bonds, which further en- importance of the analysis of the NRR through DFT.
hances the electrocatalytic NRR activity (Figure 1).52–55 Comparing Δ G (*N2H) to the comparative analysis of ΔG
This review summarizes recent advances in the design (*H) descriptors can reveal the properties of H affinity
and development of TM electrocatalysts, including alloys, (Figure 4). Therefore, the activation of nitrogen plays a
TM oxides, TM metal sulfides, and TM carbides, for ni- crucial role in the nitrogen reduction process.
trogen reduction applications at ambient temperature and There are two widely recognized pathways for NRR,
pressure (Figure 2). Meanwhile, different NH3 yield the dissociation mechanism and the binding mechanism
detection methods and the application of multiple control (Figure 5).63 In the dissociation pathway, the triple bond of
experiments are necessary for calculating NH3 yield and nitrogen is first broken before hydrogenation, which is
FE. With the progress of technology, a set of qualified and limited by the Brønsted–Evans–Polyanyi relationship and
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232
- AN ET AL.

F I G U R E 1 Schematic illustration of transition metals with N2 binding. (A) Simplified schematic of the bonding in well‐known end‐
on‐bound transition metal N2 complexes (left) and prospective application to monovalent boron species (BRL) (right, this work).
(B) Known photodecarbonylation and ligand binding chemistry of tri‐ (i and iii) and dicoordinate (ii) borylene species.52 Reproduced with
permission. Copyright 2018, Science.

has only the enzymatic pathway. In the distal pathway, the

proton‐electron pair first hydrogenates the N atom in N2
away from the active site and produces NH3, and then
hydrogenates another N atom and produces NH3. In the
alternating pathway, the proton–electron pair alternates
between the two N atoms in N2 and produces NH3. The
enzymatic pathway has a similar alternating hydrogena-
tion pattern. During the reaction process, the adsorption
conformation of intermediates generally changes contin-
uously, therefore, the actual NRR process may involve
multiple pathways mentioned above.62

F I G U R E 2 A systematic summary of NRR electrocatalyst.

3 | ELECTROCATALYSTS FOR
NRR, nitrogen reduction reaction.
THE NRR

requires a large amount of energy to break the inert cova- 3.1 | Alloy electrocatalysts for the NRR
lent N2 bond.36 In contrast, the adsorbed N2 molecules split
into N atoms and then undergo protonation to produce Metal‐alloy nanomaterials are a kind of functional ma-
NH3 in the associative pathway.64 Due to the different terial in different energy‐storing devices. Multi‐element
catalyst hydrogenation reaction sequences and adsorption alloy catalysts have significant catalytic properties
modes on the surface, the association pathways can be compared to monometallic, the electronic state of the
categorized into distal association pathways, altered asso- alloy surface, the local strain, and the effective number of
ciation pathways, and enzyme‐promoted pathways.65 The ligands on the catalytic surface change due to the syn-
association pathway is a process in which the N atoms ergistic effect between the multimetals.66 In general,
undergo a hydrogenation reaction, except that the two N bimetallic alloys have excellent properties of activity,
atoms in N2 remain bonded to each other until the first selectivity, and stability. On the one hand, the addition of
NH3 is produced. Based on the mode of bonding between cheap metals to precious metal catalysts can greatly
N2 and the active site, the association pathway can be reduce the amount of precious metals used and lower the
further categorized into terminal mode (*NN) and lateral cost of catalysts.67 On the other hand, the synergistic
mode (*NN*). Depending on the order of hydrogenation, action of the bimetal redistributes the surface charge due
the terminal mode has two ways of producing NH3, the to the different Fermi energies of the metals.68–70 The
distal pathway and the alternate pathway; the lateral mode electronic structure can be adjusted by changing the
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AN ET AL.
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FIGURE 3 Schematic diagram of N2 molecular orbital.60 Reproduced with permission. Copyright 2022, The Royal Society of
Chemistry.

F I G U R E 4 (A) ΔG(*N2H) versus ΔG(*H) plot for the examined metals. Lines show linear fits for two distinct groups of metals. Green
shaded area indicates where ΔG(*N2H) < ΔG(*H) and green labels highlight metals with where this is the case. (B) ΔG(*NO) versus ΔG
(*H) plot for the examined metals. Lines show linear fits for two distinct groups of metals. Green shaded area indicates where ΔG
(*NO) < ΔG(*H) and green labels highlight metals with where this is the case. Inset shows the ΔG(*NO) versus ΔG(*N2H) plot for
transition metals examined herein.61 Reproduced with permission. Copyright 2022, The Royal Society of Chemistry.

F I G U R E 5 Reaction pathways for the nitrogen reduction reaction by proton‐coupled electron transfer, including the dissociative
pathway, distal and alternative associative pathway, and enzymatic pathway.62 Reproduced with permission. Copyright 2022, American
Chemical Society.
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234
- AN ET AL.

elemental composition to adjust the position of the d‐ desorption to improve catalytic activity and durability75–77
band center. The electronic structure of the catalyst (Figure 7A). The nanoporous intermetallic Pd3Bi (np‐
directly determines the adsorption and activation of re- Pd3Bi) was successfully synthesized by a two‐step etching
actants and intermediates, thus directly affecting the method. The PdBi2 phase was completely converted to np‐
catalytic activity of the catalyst.71,72 Pd3Bi via the electrochemical etching process. The np‐
Intermetallic compounds (IMCs) influence the Pd3Bi electrocatalyst achieved an NH3 yield rate of
adsorption energy of NRR reaction intermediates due to 59.05 � 2.27 μg h−1 mg−1 and a FE of 21.52 � 0.71% at
their highly ordered structure and tunable electronic ef- −0.2 V versus relative hydrogen electrode (RHE) at
fects between metal atoms. Yuan et al. characterized ambient conditions, respectively. Transmission electron
theoretical perturbations to the linear scaling relations microscopy mapping (TEM) and scanning transmission
(LSRs) found on these IMCs in terms of the tether di- electron microscopy (STEM) energy dispersive spectros-
mensions and the electronic properties of the adsorption copy (STEM‐EDS) images (Figure 7B–D) showed that the
configurations of the key intermediates and discussed np‐Pd3Bi electrocatalysts were nanoporous in structure,
their impact on the electrocatalytic NRR activity. Volcano and the Pd and Bi elements were uniformly distributed in
plots were constructed through the adsorption behavior the nanoporous network. Remarkably, the NRR perfor-
of 11 NRR reaction intermediates on the (111) surfaces of mance of np‐Pd3Bi electrocatalyst achieves the highest
29 L12 IMCs to assess the catalytic activity as well as to NH3 yield and FE (Figure 7E,F) in 0.05 M H2SO4
screen possible nitrogen reduction catalysts. The study compared to the np‐PdBi2 and Pd/C electrocatalysts. No
also introduced uncertainty quantification to assess and N2H4 by‐product was detected in the experiment, which
correct the effect of LSR perturbation on the volcano di- confirmed a high selectivity of np‐Pd3Bi electrocatalyst for
agrams. Finally, the team proposes that Pd3Mo IMCs are N2 fixation and suppressed HER. At the same time, it was
the weakest catalysts for hydrogen precipitation confirmed by control experiments that the np‐Pd3Bi
competitive reactions with a low limiting potential sample had NH3 production in N2 but not in Ar. The same
(−0.31 eV) and high NRR selectivity.73 Meanwhile, Lang results were obtained for the blank control glassy carbon
et al. demonstrated the high selectivity, high efficiency, electrode. It was shown that NH3 was produced by np‐
and high stability of Ni3Mo IMCs for NRR applications Pd3Bi. DFT calculations show that intermetallic Pd3Bi
through theoretical calculations. The easier activation of has a strong synergistic effect, which lowers the reaction
the catalyst surface for N2 adsorption was attributed to energy barrier and accelerates the reaction kinetics.
the synergistic interaction between Mo and Ni atoms, Meanwhile, its improved NRR performance was attrib-
which resulted in the formation of positively charged Mo uted to the accelerated charge transfer efficiency due to
atoms on the surface.74 the continuous nanoporous structure, which facilitated
The thermodynamically strong proton adsorption on the adsorption activation of N2 and efficient dissociation
the surface of Ru‐based electrocatalysts is apt to generate of the product NH3.
a more rapid HER, which can severely limit the selective For the application of High Entropy Alloy (HEA) in
occurrence of NRR. The strong binding of N2 on its sur- NRR, Wang et al.78 prepared a HEA for NRR using a low‐
face leads to difficulties in the formation of *NNH, which temperature oil phase method. It has the advantages of
is a potential determining step and an intermediate uniform particle size and small nano‐size (≈16 nm) at
desorption process. To overcome these limitations, the atmospheric pressure and low temperature (≤250°C),79–81
researchers alloyed the metal Ru with transition metals to iron, cobalt, nickel, and cuprum. It was obvious that the
tune the proton adsorption strength as a way to lower the particle size of the RuFeCoNiCu HEA concentrated about
reaction barrier. Jung et al.56 broke the limitations of 16 nm in the oil phase (Figure 8A,B). The multi‐element
alloys previously used for NRR. This study is the first to synergistic effect of RuFeCoNiCu HEA is one of the key
use RuCu nanoparticles as efficient NRR electrocatalysts. factors to improve the NRR performance. RuFeCoNiCu
High nanoparticle (NP) densities of homogeneously HEA exhibited excellent electrocatalytic NRR perfor-
mixed refractory Ru and Cu can be achieved at the mance at ambient temperature and pressure, with an NH3
atomic scale by the carbon thermal shock method on 3D yield of 57.1 μg h−1 mg−1 and an FE of 10.16% at a voltage
cellulose/carbon nanotubes (CNTs). Meanwhile, theo- of 0.05 V versus RHE (Figure 8D).79–81 The NH3 yields and
retical calculations have shown that homogeneously FE results were also characterized by UV‐Vis, nuclear
mixed RuCu NPs can exhibit selective NRR by inhibiting magnetic resonance spectroscopy (NMR), and ion chro-
proton adsorption and strong N2 binding as well as pro- matography, demonstrating that the experimentally
moting the formation of *NNH (Figure 6A–D). introduced N2 was the main N source and played an
Recently, Tan et al. demonstrated that alloying Bi and important role in the experiments (Figure 8C). All
Pd could be beneficial for N2 activation and intermediate possible N2 adsorption sites (including apex, bridge, and
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AN ET AL.
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F I G U R E 6 DFT calculations of the NRR process on the electrocatalysts. Optimized geometries of *, *H, *N2, and *NNH on (A) Ru
(101) and (B) Ru‐Cu (101). Gray, green, blue, and white balls represent Ru, Cu, N, and H atoms, respectively. Free‐energy diagram for NRR
and H adsorption on (C) Ru (101) and (D) Ru‐Cu (101).56 Reproduced with permission. Copyright 2022, Wiley‐VCH. DFT, density
functional theory; NRR, nitrogen reduction reaction.

hollow sites) were investigated by DFT. The Co‐Cu and system, and the special molecular structure shows
Ni‐Ru couplings showed excellent surface hydrogen pre- excellent catalytic performance.83,84 Sun's group syn-
cipitation. At the same time, the t‐Fe sites are adsorbed thesized nanorod‐shaped Fe2Mo3O8/XC‐72 electro-
and activated by the surface *H, and N2 is reduced to NH3 catalysts for efficient NRR using a one‐pot synthesis
via an electrochemical reaction. The ultra‐low over- method, which was experimentally proved to be a
potential for optimal NRR performance is 0.05 V (relative promising artificial nitrogen‐fixing electrocatalyst with
to RHE). In addition, its hydrogen precipitation compet- high electrocatalytic activity, selectivity, and stability for
itive reaction is weak, the metal atoms have a strong electrochemically converting N2 to NH3 at room tem-
adsorption capacity for *H and the hydrogen atoms are perature and pressure.85 Theoretical calculations showed
trapped in the hollow sites, which increases the reaction that Fe and Mo atoms play crucial roles in activating the
energy barrier for the formation of H2 and slows down the NRR. Among them, the iron atom is the most dominant
kinetics of the reaction, inhibiting the HER. The FE can active site in the enzymatic reaction because it has the
be as high as 10.16% (Figure 8E). lowest reaction energy barrier. This study provides a
good idea to explore other TM oxides for efficient ni-
trogen fixation.
3.2 | TM oxide electrocatalysts for Recently, oxide‐loaded active metals have drawn
the NRR much attention at the forefront of catalytic reactions due
to their powerful “electronic metal–support interactions”
Metal oxides have paid close attention due to their many (EMSI), which can stabilize metal species through
advantages such as easy large‐scale synthesis, tunable electron transfer between the metal and the carrier and
activity, high stability and low energy consumption.82 modulate their electronic structure by inducing large
NRR is a typical hydrogenation reduction process, metal electronic perturbations and redistributing the charge
active centers on the oxide carrier provide an accurate density of the active site. Therefore, modulating EMSI
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236
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F I G U R E 7 (A) Schematic illustration of np‐Pd3Bi. (B) TEM of the PdBi2 phase after selective chemical etching of the Pd20Bi80 alloy.
(C) HAADF‐STEM image of np‐Pd3Bi and (D) the STEM‐EDS elemental mapping of np‐Pd3Bi. (E) The NH3 yield rates at applied potential
catalyzed by np‐Pd3Bi, np‐PdBi2, and commercial Pd/C in 0.05 M H2SO4. (F) The FE at each applied potential of np‐Pd3Bi, np‐PdBi2, and
commercial Pd/C in 0.05 M H2SO4. Scale bars: (B) 200 nm, (C) 2 nm, (D) 20 nm.77 Reproduced with permission. Copyright 2021, Wiley‐
VCH. FE, Faraday efficiency; STEM‐EDS, STEM energy dispersive spectroscopy; TEM, transmission electron microscopy.

by adjusting the metal and carrier is expected to which was 10.8 and 2.8 times higher than that of VO2
generate Lewis acid sites to make it available for NRR. (Figure 9C,D), respectively. In addition, DFT calcula-
Zhang et al.86 utilized VO2, which strongly adsorbs N2, tions showed that the activation of N ≡ N due to the
as a carrier to provide a source of N2 while avoiding presence of an electron‐deficient region in the EMSI
hydrogen precipitation reactions. The metal Mo, which between Mo and VO2, which can effectively reduce the
has high NRR activity, was introduced in the VO2 as the potential barrier of the first protonation step as shown
active site for NRR. The weakening of the adsorption in Figure 9E. This study has a wide range of applications
capacity of the catalyst for protons was attributed to the in the field of designing and developing high‐
creation of an electron‐deficient site by the electron– performance catalysts for the synthesis of NH3 by elec-
metal–carrier interaction between the carrier and mo- trochemical reduction of N2.
lybdenum metal, and, at the same time, its weakening Recently, a TM oxide (TMO) hydrogen storage mate-
lowered the reaction energy barrier for the first step of rial has been discovered. Researchers used this material
protonation, which accelerated the kinetics of the NRR for the first time in the field of electrocatalytic NRR re-
reaction and improved the catalytic reaction activity. At action. The researchers optimised and tuned the hydrogen
−0.5 V versus RHE, the average NH3 yield of Mo/VO2 and oxygen storage vacancies of the material.87 The NH3
was 190.1 μg NH3 mgcat.−1 h−1 with a FE of 32.4%, yield reached 31.6 μg h−1 mgcat.−1 at −0.1 V (relative to
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AN ET AL.
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F I G U R E 8 (A) TEM image of RuFeCoNiCu NPs. (B) Particle size distribution of RuFeCoNiCu NPs. (C) The NH3 yields for UV‐vis, IC,
and NMR. (D) NH3 yields and FEs at each given potential in 0.1 M KOH. (E) Schematic illustration of a possible mechanism to explain the
enhanced NRR activity of RuFeCoNiCu NPs at low overpotential.78 Reproduced with permission. Copyright 2021, Wiley‐VCH. NMR,
nuclear magnetic resonance spectroscopy; NPs, nanoparticles; NRR, nitrogen reduction reaction; TEM, transmission electron microscopy.

RHE). The FE was 47.7% at 0 V (relative to RHE) Yan et al. discussed the difference between the active
(Figure 10A,B). Meanwhile, the B‐TiO1.8 electrocatalyst center before and after precious metal loading and
exhibited high electrochemical stability in the 100‐h test revealed a different type of metal‐support interaction in
(Figure 10C). Meanwhile, the results of in situ Fourier Au/Fe2(MoO4)3.88 DFT calculations show that Au im-
Transform Infrared spectroscopy and electrochemical proves the catalytic performance due to the fact that with
tests showed that H in the lattice could promote N2 hy- Mo atoms it is the active center for activation of N ≡ N
drogenation with weak competition for hydrogen precip- bonds. At −0.4 V, the catalytic efficiency is increased by
itation (Figure 10D). In addition, the higher NRR 18.79% relative to RHE.89 (Figure 11E). In order to
selectivity of the material is attributed to the oxygen va- investigate whether there are interactions between the
cancies in the material that can promote the adsorption carriers and metal NPs, Fe2(MoO4)3 unloaded with C and
and activation of nitrogen. Au NPs loaded with C were also synthesized. X‐ray
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
238
- AN ET AL.

F I G U R E 9 Electroreduction of N2 to NH3 at ambient conditions. (A) LSV curves of Mo/VO2 in 0.05 M H2SO4 saturated with Ar and N2
at a scan rate of 10 mV s−1. (B) Current density versus time curves of Mo/VO2 at different potentials. (C) NH3 yield and (D) FE of Mo/VO2
and VO2 at different potentials. (E) Density functional theory calculation for NRR. The model of DFT calculation. Spheres: red = O,
gray = V, cyan = Mo. (F) Gibbs free energy diagrams for NRR on VO2 distal pathway (black line), Mo/VO2 distal pathway (red line) Mo/
VO2 alternating pathway (blue line), the transition state energy barriers of N2 (TS1) adsorption, and H (TS2) adsorption and the first
protonation process (TS3) were calculated. (G) Gibbs free energy diagrams for the reaction of HER on Mo/VO2 and VO2 surfaces.86
Reproduced with permission. Copyright 2023, Wiley‐VCH. DFT, density functional theory; FE, Faraday efficiency; LSV, linear sweep
voltammetry; NRR, nitrogen reduction reaction.

diffraction (XRD) and Raman analyses of the diffraction uniformly distributed on Au NPs. Au NPs with a particle
peaks of Fe2(MoO4)3 were not clear, which may be due to size of ≈15 nm were successfully synthesized by using the
the low crystallinity. The diffraction peaks of Au/ tannic acid reducing agent (Figure 11C).
Fe2(MoO4)3 were more consistent with the characteristic In order to investigate whether the addition of the
peaks of Au. The diffraction peaks of Au/Fe2(MoO4)3 are metal element Au to Fe2(MoO4)3 can change the NRR
similar to the characteristic peaks of Au (Figure 11A). performance, the researchers conducted N2 adsorption
The Au NPs supported on C, on the other hand, proved to and desorption experiments and temperature desorption
be a mixture of C and metallic Au. Raman spectroscopy of N2 (N2‐TPD) studies on Au/Fe2(MoO4)3 and
demonstrated the presence of Fe and Mo elements in Fe2(MoO4)3, which showed that the adsorption strength of
both Au/Fe2(MoO4)3 and Fe2(MoO4)3 (Figure 11B). TEM N2 on Fe2(MoO4)3 was weaker than that of Au/
images of Au/Fe2(MoO4)3 show that Fe2(MoO4)3 is Fe2(MoO4)3. The adsorption strength of N2 on Fe2(MoO4)3
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
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F I G U R E 1 0 (A) NH3 yield rate and (B) FE of the B‐TiO1.8 at different potentials. (C) Time‐dependent current density curve over for
100 h at −0.1 V (vs. RHE). (D) In situ FTIR spectra from 0.0 to −0.4 V (vs. RHE) on the B‐TiO1.8 in an N2‐saturated 0.1 M Li2SO4 solution.87
Reproduced with permission. Copyright 2022, Elsevier. FE, Faraday efficiency. FTIR, Fourier Transform Infrared; RHE, relative hydrogen
electrode.

is weaker than that of Au/Fe2(MoO4)3, which implies that surface areas may promote the activation of N2 mole-
the introduction of Au can promote the adsorption and cules, which are important factors affecting the catalytic
activation of N2 on Fe2(MoO4)3 and improve the catalytic performance of the material. The Co3O4@CNT electro-
activity of Au/Fe2(MoO4)3 (Figure 11D). X‐ray photoelec- catalyst displayed more micropores and mesopores than
tron spectroscopy (XPS) of different Au loadings, including pure Co3O4 and BET surface areas are estimated
Au/Fe2(MoO4)3‐2.4%, Au/Fe2(MoO4)3‐4.7%, and Au/ to be 239.6 m2 g−1 (Figure 12A,B), exhibiting an
Fe2(MoO4)3‐9.5%, showed the strongest electron interac- excellent NRR activity (27.16 μg h−1 mg−1) and selec-
tion between Au and Fe2(MoO4)3 (Figure 11F–H). Mean- tivity (FE = 3.86% at −0.49 V vs. RHE) in 0.1 M Na2SO4
while, the electrochemical double‐layer capacitances (Cdl) (Figure 12C), which are attributed to the rich porous
of Au/Fe2(MoO4)3‐4.7% have a larger surface area with structure and large specific surface area to expose more
more exposed active sites (Figure 11I). Therefore, the active sites and sufficient reactant/ion transport
above evidence suggests that the introduction of gold can in NRR.
regulate the electronic structure and increase the specific Recently several bimetallic electrocatalysts have been
surface area of electrochemical activity, thereby increasing investigated and discovered, such as FeMoO4,94
the catalytic activity. CoFe2O4,95 and MnMoO4.93 The bimetallic electro-
Co‐based oxides are widely employed in the field of catalysts toward NRR performance are greatly improved
NRR attributed to their simple, scalable, and safe syn- compared to the single metal. Chu et al. developed an
thetic routes in order to effectively weaken their bond electrocatalyst of MnMoO4 nanorods loading on the
energy to reduce activation and accelerate reaction ki- reduced graphene oxide (MnMoO4/RGO), which exhibi-
netics.90,91 Wu's group describes Co3O4‐loaded CNTs as ted high NH3 yield (60.3 μg h−1 mg−1) and FE (14.7%) in
an excellent substrate for improving electron transport. N2‐saturated 0.5 M LiClO4 (Figure 12E,F).93 The activity
The adsorption and activation of N2 can be promoted of MnMoO4/RGO electrocatalyst is superior to almost all
through surface active sites.92 Pore size distribution and Mo and Mn‐based NRR catalysts previously reported. In
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
240
- AN ET AL.

F I G U R E 1 1 (A) XRD patterns of Au/Fe2(MoO4)3, Fe2(MoO4)3 and Au/C. (B) Raman spectra for Au/Fe2(MoO4)3 and Fe2(MoO4)3.
(C) HRTEM image of Au/Fe2(MoO4)3. (D) N2‐TPD curves for Au/Fe2(MoO4)3 and Fe2(MoO4)3. (E) FE of Au/Fe2(MoO4)3 at each applied
potential in 0.2 M Na2SO4. XPS results of (F) Au 4f, (G) Fe 2p, and (H) Mo 3d with different Au loading. (I) Charging current densities at
0.75 V Au/Fe2(MoO4)3‐2.4%, 4.7%, and 9.5%.89 Reproduced with permission. Copyright 2021, Wiley‐VCH. FE, Faraday efficiency; HRTEM,
High Resolution Transmission Electron Microscopy; XPS, X‐ray photoelectron spectroscopy; XRD, X‐ray diffraction.

order to accurately assess the NRR activity of the developed by Li et al. This was accomplished by thermal
MnMoO4/RGO electrocatalysts, linear sweep voltamme- decomposition of bismuth citrate (Figure 13A).97 When
try tests were performed in ultra‐high purity N2 gas heat‐treated in an argon atmosphere at temperatures
(99.999%) and Ar gas (99.999%) atmospheres below 700°C, Bi is converted to Bi2O3 and the organic
(Figure 12D). The experimental results showed that the ligand pyrolyzes to carbon, forming a heterogeneous
current densities obtained under nitrogen atmosphere structure of Bi2O3 NPs embedded in carbon nanosheets
conditions were higher than under argon conditions, (Figure 13B). The atom ratio of Bi0 to Bi3þ in Bi 4f
which indicated that the electrocatalysts had higher cat- spectrum increases at the range of 700–900°C. The in-
alytic activity.96 As the potential rises above −0.4 V, the crease of annealing temperature helps to construct a
yield of NH3 decreases due to the presence of the HER carbon framework to limit the metal Bi NPs with reduced
competition reaction. The elements manganese and mo- oxidation degree (Figure 13C). The NRR performance at
lybdenum provide excellent catalytic activity due to their ambient conditions was evaluated in Ar‐ or N2‐saturated
ability to activate the N2 molecule as a reactive dual 0.1 M Na2SO4. The Bi@C‐900 electrocatalyst showed the
active site. The RGO acts as a good dispersing agent to highest NH3 yield rate and FE (15.10 � 0.43% at −0.4 V
prevent the transition metals from agglomerating, and vs. RHE) among all the tested samples, which is consis-
the strong interaction between metal and carbon carrier tent with that of the Bi0/Bi3þ atomic ratios of XPS and
can significantly improve the electrical conductivity, thus XRD patterns of different heat treatment temperatures
accelerating electron transfer. DFT calculations indicate (Figure 13D). In summary, the synergistic interaction
that Mo and Mn atoms are the dual active sites that between metal oxides and carriers, and the oxidation
enhance N2 adsorption activation. A novel Bi NP struc- state modulation method are proposed to improve the
ture embedded in carbon nanosheets (Bi@C) was NRR performance at ambient conditions.
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
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F I G U R E 1 2 Co3O4@CNT and pristine Co3O4 of (A) N2 adsorption–desorption isotherms and (B) corresponding pore size distribution
curves. (C) NH3 yields and FEs at each given potential from [email protected] Reproduced with permission. Copyright 2020, Elsevier.
(D) LSV curves of MnMoO4/RGO in Ar and N2. (E) UV‐vis absorption spectra of the electrolytes stained with indophenol indicator after
charging at −0.40 V for 2 h under various conditions. (F) The obtained NH3 yields and FEs after 2 h of NRR electrolysis at various
potentials.93 Reproduced with permission. Copyright 2020, The Royal Society of Chemistry. FEs, Faraday efficiencies; LSV, linear sweep
voltammetry; NRR, nitrogen reduction reaction.

3.3 | TM sulfides electrocatalysts (MoS2) nanostructures with hydrophobic surfaces via

alkyl mercaptan modification. The hydrophobic surface
The electrocatalytic NRR reaction is a low energy of the material promotes effective three‐phase contact
consuming and sustainable method for the production of between gas‐phase N2, liquid‐phase H2O, and solid‐phase
NH3. However, competitive HER reactions in aqueous catalyst. Because mercaptans may cover the active sites,
solutions result in low NH3 yields and poor Faraday ef- the active sites decrease with increasing alkyl chains, but
ficiencies. Recently, Wang et al.98 balanced NRR activity a larger local concentration of N2 molecules can over-
and selectivity by utilizing the inverse relationship be- come the mass transfer limitations of N2 and thus inhibit
tween NRR and HER activities and the concentration of S HER. The FE and NH3 yield of the electrocatalyst arrived
vacancies (vs.) to increase NRR activity while inhibiting at 22.23% and 12.86 � 10−11 mol cm−2 s−1, respectively
HER. Targeted modulation of non‐reducing reactivity by (Figure 14B). The improved catalytic performance was
null introduction provides inspiration for catalyst attributed to the strong adsorption of N2 by the electro-
design.99 By combining DFT calculations and experi- catalyst while inhibiting HER. The experimental results
mental validation, Wu et al. demonstrated a unique combined with theoretical calculations indicate that the
synergistic strategy to change the concentration of S va- hydrophobic modification of the electrocatalyst plays a
cancies of MoS2 to enhance the NRR. The results showed very crucial role in increasing the N2 concentration and
that the enhancement of the NRR performance of MoS2‐ limiting proton adsorption (Figure 14D–I). Therefore, the
Vs was divided into two phases: (1) the enhancement of improvement in catalytic performance was attributed to
the NRR activity by adjusting the concentration of the S the reduction of HER due to the high concentration of N2
vacancy, which enhances the adsorption of N2 adsorption on the catalyst surface. This study suggests that modu-
and reduces the energy consumption of the reaction; (2) lating the wettability of the catalyst surface is an effective
within a specific concentration window, the concentra- method to improve the efficiency of the non‐reducing
tion of S vacancies can simultaneously increase the NRR reaction at this stage of the process. In addition,
selectivity, and inhibit the HER by restricting the elemental doping can regulate the charge density of the
desorption kinetics while stabilize the NRR activity. catalyst surface, while the charge density of the active site
Here, Niu et al.100 synthesized the molybdenum disulfide plays a crucial role in NRR Meanwhile, the introduction
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
242
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F I G U R E 1 3 (A) Schematic illustration of the synthesis of Bi@C electrocatalyst and effect of the annealing temperature on the
composition of as‐synthesized Bi@C samples. (B) XRD patterns and (C) Bi 4f XPS spectra of samples prepared at different annealing
temperatures. (D) NH3 yield rate and FE of different samples prepared at different annealing temperatures at −0.4 V versus RHE.97
Reproduced with permission. Copyright 2021, Wiley‐VCH. FE, Faraday efficiency; RHE, relative hydrogen electrode; XPS, X‐ray
photoelectron spectroscopy; XRD, X‐ray diffraction.

of defects promotes the adsorption and activation of N2 providing a strong guideline for the design of catalysts in
on the catalyst surface. Niu et al.100 synthesized a series of the field of NRR.7
electrocatalysts with different electron cloud densities by Inspired by the natural nitrogen fixation enzyme,101
doping MoS2 with Fe and V elements. Experimental re- Li's group constructed a S‐coordinated and Fe single‐
sults and theoretical calculations showed that Fe‐doped atom (Fe1Sx@TiO2) catalyst on mesoporous TiO2 using
MoS2 (MoS2‐Fe) electrocatalysts had lower nitrogen a lattice restriction strategy (Figure 15). It has been
adsorption and activation properties, while the highest shown that the coordination of elemental S can effec-
ammonia yield was achieved due to their easier desorp- tively modulate the electronic structure of the active sites
tion of ammonia (20.11 μg h−1 mgcat−1). The results prove on the lattice of titanium dioxide, thus enhancing the
that a better balance between the process of nitrogen adsorption and activation of N2 to NH3. This study pro-
adsorption, nitrogen activation, and ammonia desorption vides a new idea for the design and biomimetic synthesis
is required to obtain the best NRR performance, of efficient electrocatalysts in the field of NRR.
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
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F I G U R E 1 4 (A) Linear sweep voltammetry curves of different electrocatalysts. (B) NH3 field and FE of C8‐MoS2‐CP electrocatalyst.
(C) NH3 yield and FE of C8‐MoS2‐CP electrocatalyst for six cycles. (D) The optimized atomic configuration of MoS2‐CP and C8‐MoS2‐CP
electrocatalysts after adsorbed N (purple, yellow, brown, gray, and pink spheres represent Mo, S, C, N, and H). (E) The Gibbs free energy
profile of NRR on MoS2‐CP and C8‐MoS2‐CP electrocatalysts, AIMD Initially models of (F) MoS2 and (H) C3‐MoS2, AIMD finally models of
(G) MoS2 and (I) C3‐MoS2 (pink, yellow, cyan, red, blue, and white spheres represent Mo, S, C, O, N, and H).100 Reproduced with
permission. Copyright 2021, Springer. AIMD, Ab initio molecular dynamics; FE, Faraday efficiency; NRR, nitrogen reduction reaction.

For TM sulfides, researchers can design electro- 51.7 μg h−1 mg−1 and an FE of 12.8% at −0.3 V versus
catalysts containing Fe, Mo and S cofactors in the field of RHE in 0.5 M LiClO4 (Figure 16E). Studies have shown
biological nitrogen fixation. Among them, MoS2 plays an that the larger the cation size (Kþ > Naþ > Liþ), the
important role due to its excellent catalytic activity in the lower the FE and NH3 yield, which may be the fact that
HER field.102–104 The change in charge distribution near the counterion layer can limit the contact with water
the active center of the catalyst is due to the presence of molecules on the electrode surface. Flaky MoS3 has not
abundant sulfur vacancies. The energy band structure only connected porous nanostructures but also disor-
and electronic structure of MoS2 are affected. Therefore, dered molecular chain‐like structures (Figure 15A). The
it will adsorb and activate N2 to a larger extent, which crystalline MoS2 can be obtained by annealing amor-
ultimately improves the performance of NRR. However, phous MoS3 in Ar atmosphere at 600°C for 3 h
MoS2 has a certain catalytic activity toward HER.105 The (Figure 16B). The high‐resolution XPS data of S 2p
MoS3 is another important molybdenum sulfide material spectra in 2H‐MoS2 showed fitted S 2p3/2 (162.3 eV) and S
because of its good electrical conductivity and high S 2p1/2 (163.5 eV) (Figure 16C), which have an obvious
concentration.106 According to Chu et al., the MoS3 ma- difference from the S 2p spectra of MoS3. In addition,
terial can be used as an efficient and stable electrocatalyst during the transformation of amorphous MoS3 to crys-
for NRR.107 It showed an excellent NH3 yield of talline MoS2, the electron paramagnetic resonance (EPR)
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
244
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F I G U R E 1 5 (A) DFT‐calculated optimized free energy pathways for NRR on FeS2O2, FeS1O3, FeS1O2 and FeO3 coordination
configurations, respectively. (B) Possible reaction mechanisms of nitrogen adsorption and reduction on FeS2O2 active sites of Fe1Sx@TiO2.
(C) Charge difference of nitrogen adsorption state on FeS2O2 active sites (yellow and blue represents the increase and decrease of electrons,
respectively. The surface value is 0.005 e Å−3). (D) N2 adsorption on FeS2O2 active sites.101 Reproduced with permission. Copyright 2022,
Wiley‐VCH. DFT, density functional theory; NRR, nitrogen reduction reaction.

spectra show that the intensity of the EPR signal of MoS2 In addition, the presence of NH3 was not detected by UV‐
is much weaker than that of MoS3, which suggests that a visible analysis of the original C cloth of the argon satu-
high concentration of S vacancies exists in MoS3 rated solution (Figure 16G).14,113,114 The definite and reli-
(Figure 16D). Because of the strong electron‐donating able detection method and control experiment obtained an
effect, the vacancies can transfer electrons to the 2p* NH3 yield of 41.3 mg h−1 mg−1 at −0.5 V versus RHE and a
antibonding orbitals of the N2 molecule, thus promoting FE of 20.8% at −0.4 V versus RHE. After 20 h electrolysis on
the adsorption and activation of N2. DFT showed that the a multifunctional electrode material (carbon cloth) (CC),
S vacancies in MoS3 have a low reaction energy barrier in the current density hardly changed, indicating that the
the NRR, and inhibit the competitive reaction of electrocatalyst has good catalytic stability. The Mo‐SnS2‐Vs
hydrogen precipitation on the surface.108 electrocatalyst can further induce hydrogenation as highly
On the basis of catalyst vacancies, doping of hetero- active catalytic sites, which significantly decreases the
atoms is also an important method to adjust the electronic energy barrier. This important factor promotes and facili-
structure of sulfides to improve catalytic activity. The tates N2 adsorption, activation, and hydrogenation to
synergistic effect between heteroatom doping and va- improve NRR performance.
cancies can significantly improve the NRR perfor- Chu's group also reported FeMo3S4 nanorods by two‐
mance.111,112 Chu et al. synthesized Mo‐doped SnS2 (Mo‐ step hydrothermal and one‐step calcination. It increases
SnS2) nanosheets loaded on C cloth using a one‐step sol- FE and NH3 yields to 19.2% and 65.3 μg h−1 mg−1 at −0.3 V
vothermal method.109 Mo‐SnS2 nanosheets have a large (RHE).110 The NRR selectivity and catalytic activity were
number of sulfur vacancies (vs.), and with the doping of Mo improved due to the exposed iron sites on the catalyst
elements, Mo/Vs induces large electron cloud densities surface that hindered HER production. The TEM image
that can be transferred to the antibonding orbitals of N2, (Figure 16H) showed FeMo3S4 nanorods are between 20
thereby weakening the N ≡ N bond to make it easier to and 50 nm in diameter and it has bright lattice fringes for
dissociate.52 The authors accurately test ammonia pro- better crystallinity. DFT calculations have shown that
duction through UV‐vis analysis, 1H NMR, and IC tech- adsorption of N2 occurred at low‐coordinate Fe3c atoms
nique. The standard curve used to detect ammonia rather than high‐coordinate Mo8c atoms, and the electro-
production is within a reasonable error range (Figure 16F). catalytic NRR mechanism on the FeMo3S4 nanorods has
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
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F I G U R E 1 6 (A) Schematic of the disordered structure of MoS3. (B) Schematic of amorphous MoS3 to crystalline MoS2. (C) XPS S 2p
spectra of MoS2 and MoS3. (D) EPR spectra of MoS2 and MoS3. (E) Corresponding NH3 yields and FEs.108 Reproduced with permission.
Copyright 2021, Elsevier. (F) IC spectra of Mo‐SnS2/CC at −0.5 V versus RHE (inset), and the determined NH4 þ concentration of the
calibration curve. (G) The corresponding NH3 yields and FEs of Mo‐SnS2/CC.109 Reproduced with permission. Copyright 2020, Royal Society
of Chemistry. (H) TEM image of FeMo3S4 nanorods. (I) Schematic of the distal and alternating NRR pathways on Fe3c and (J) Gibbs free
energy diagrams of NRR pathways on Fe3c.110 Reproduced with permission. Copyright 2020, American Chemical Society. EPR, electron
paramagnetic resonance; FEs, Faraday efficiencies; NRR, nitrogen reduction reaction; RHE, relative hydrogen electrode; TEM, transmission
electron microscopy; XPS, X‐ray photoelectron spectroscopy.

been identified to follow the associative alternating 3.4 | TM carbides electrocatalysts

pathway (Figure 16I,J). Thermodynamically, the FeMo3S4
(100) surface of NRR revealed that the alternating pathway In the field of electrocatalytic NRR, the development of
(*NHNH → *NHNH2 → *NH2NH2) can less release 1.23 eV TM carbide electrocatalysts with low overpotentials, high
less energy than the distal pathway (*NNH2 → *NHNH2 → selectivity and fast reaction kinetics is a significant
*NH). The limiting reaction potential for FeMo3S4 (0.72 V) challenge. In this study, the prospects of various two‐
is smaller than molybdenum carbide (Mo2C) (0.92 V),37 dimensional (2D) ordered transition bimetallic carbons
MnO (1.88 V),115 and MoO3 (2.25 V).107 It demonstrated (MXenes) as NRR electrocatalysts were predicted based
that *N2H formation exerted the primary reduction barrier on DFT calculations (Figure 17). The results show that
for the whole NRR process.105,116 In general, biological the basal plane of Mo2Nb2C3 MXene possesses the most
nitrogen fixation is based on electrocatalysts containing prominent catalytic activity, and at the same time can
sulfide cofactors. The active sites on the surface of the effectively inhibit the hydrogen precipitation reaction
nanorods of the catalysts due to their special morphology with an overpotential of only 0.48 V. This study has
and structure give them excellent catalytic activity. This broadened the application area of 2D materials as NRR
work offers many new possibilities for the search of bio- electrocatalysts by guiding the TM carbide catalysts
logically favorable compounds of many kinds. through theoretical calculations.117
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246
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for adsorption and activation of N2, which makes it

easier for N2 to diffuse to the catalyst surface. Never-
theless, Mo2C/C has high HER activity and leads to low
selectivity, especially at high potentials. The adsorption
energy of *N2/*H is linearly correlated for individual
active components, which leads to poor NRR activ-
ity.122,124,125 Wang et al. reported that Mo single atoms
and Mo2C NPs (MoSAs‐Mo2C/N‐doped carbon nano-
F I G U R E 1 7 Summary of 18 ordered double‐transition metal
tubes [NCNTs]) assembled on NCNTs gave an NH3
MXenes in this work. Brown, purple, and green balls represent
the C, M0 , and M″ atoms, respectively.117 Reproduced with
yield of 16.1 μg h−1 cm−2 at −0.25 V versus RHE. It is
permission. Copyright 2023, American Chemical Society. shown that the enhanced NRR activity and increased
selectivity is due to the synergistic effect of MoSAs and
Recently reported on two‐dimensional metal carbides Mo2C bound to the same NCNTs (Figure 18J). More-
and nitrides (MXenes) as NRR catalysts. It was shown that over, the FE of the MoSAs‐Mo2C/NCNTs electrocatalyst
the presence of Ti active site sites in the edge sites of the is raised to twofold and sevenfold of the Mo2C/NCNTs
nanosheets and Ti3C2OH promotes the adsorption and and Mo SAs/NCNTs, respectively.120 Theoretical calcu-
activation of N2 due to the presence of internal electron lations showed that the MoNC2 monoatomic catalysts
transfer and improves the catalytic activity of the reac- (SAC) and Mo2C (101) electrocatalysts exhibited
tion.117,118 Gabriele Centi et al. showed that nanostructural different hydrogen precipitation activities and NRR
modification from two‐dimensional (nanosheets) to three‐ selectivity (Figure 18I). Isotopic labeling experiment was
dimensional type of nanostructures can form exposed Ti‐ applied to trace the N real origin.126 1H NMR spectra
OH sites, thus facilitating N2 adsorption and activa- showed a distinguished doublet for 15 NH4 þ (J‐coupling:
tion.118,119 Specifically, they synthesized Ti3C2 MXene ~72 Hz) and a triplet for 14 NH4 þ (J‐coupling: ~52 Hz)
nanosheets (MNSs) by etching Ti3AlC2 in the first step, and after electrolysis using 15N2 or 14N2 as feeding gas
then treated them in 6 M KOH under argon for 72 h. High (Figure 18L). Therefore, the NMR results provided
Resolution Transmission Electron Microscopy images further proof that the NH3 detected was produced dur-
showed that the nanoribbons had a diameter of about ing the catalyst process. Meanwhile, after six cycles, the
16 nm (Figure 18A–D). The corresponding XRD patterns MoSAs‐Mo2C electrocatalyst had strong electrochemical
and XPS results confirmed that the peak (104) of Ti3AlC2 stability due to the existence of this unique structure
disappeared, and the (002) reflection of MXene in passing (Figure 18K). The synergistic effect of multiple active
from Ti3AlC2 to Ti3C2 MNSs.119 The (002) reflection shifts sites significantly reduces the reaction activation energy
further broaden when the Ti3C2 MNSs are further pyro- barrier, thereby accelerating the reaction kinetics.
lyzed in KOH solution and the content of O significantly Due to the synergistic interactions between the
increased, which indicated that a lot of OH groups are in metals, Fe‐Mo is more favorable for the polarization and
the nanoribbon edges (Figure 18E,F). The highest NH3 activation of N2 molecules, thus lowering the activation
yield was observed for NMR compared to Ti3AlC2 and energy barrier (*N2H) in the NRR process and acceler-
Ti3C2 MNS. The NH3 yield of Ti3C2 MNS reached ating the reaction kinetics. Inspired by the Mo‐Fe sites in
16.1 μg h−1 cm−2 at −0.25 V versus RHE, while the FE was biological enzymes, Peng's study reported that the
highest at 7.1% at −0.20 V versus RHE (Figure 18G). The Mo3Fe3C electrocatalyst possessed excellent NRR activity,
NH3 yield of the three samples and the amount of oxygen with FE values as high as 27.0% at 0.05 V versus RHE.
on the surface (atomic%) had a linear relationship Four Mo‐Fe carbide NRR electrocatalysts were prepared
(Figure 18H). Due to the large amount of ‐OH in Ti3C2 using solvothermal and acid treatment (Figure 19A).12
MXene, the exposed Ti‐O sites in NMR provide a large The MoFeC‐1 electrocatalyst showed a high FE of 43.6%,
number of active sites for N2 adsorption and activation, but the lowest NH3 yield was achieved when the potential
which further improves the NRR reaction activity.118,121 was set at 0.05 V. The NRR electrocatalyst was found to
In order to explore efficient NRR electrocatalysts, the have a high FE of 0.5 V (Figure 19B). It is obvious that the
researchers also conducted an in‐depth study of Mo element is not very active in the NRR, with an FE of
Mo2C.37,122,123 The structure of Mo2C embedded in up to 2% (Figure 19C), which excludes the influence of
carbon nanosheets (Mo2C/C) synthesized by Wang et al. the metal Mo and its small amount of surface oxides
showed a higher NH3 yield of 11.3 μg h−1 mg−1 at a (MoOx) in the catalysts tested. In order to investigate the
lower overpotential.37 Due to the smaller particle size of electron transfer process in the reaction of these catalysts,
Mo2C/C nanocatalysts, more active sites are provided The Fourier transform alternating current voltammetry
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
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F I G U R E 1 8 (A) SEM image and (B) cross‐sectional TEM image of Ti3C2 MNSs. (C) SEM image and (D) HRTEM image of Ti3C2
NMRs. (E) XRD patterns of Ti3C2 NMRs, Ti3C2 MNSs, and pristine Ti3AlC2. (F) XPS spectra of Ti3C2 NMRs, Ti3C2 MNSs, and pristine
Ti3AlC2. (G) NH3 formation rate and FE at −0.5 V versus RHE. (H) Relationship between NH3 formation rate at −0.5 V versus RHE and at%
of oxygen.119 Reproduced with permission. Copyright 2020, Wiley‐VCH. (I) Gibbs free energy change MoNC2 SAC or the Mo2C (101)
surface. (J) Average NH3 yield rate and FE of MoSAs‐Mo2C/NCNTs in N2 saturated electrolyte. (K) Stability test of NH3 yield rate at
−0.25 V versus RHE. (L) 1H NMR spectra of the electrode after 12 h for MoSAs‐Mo2C/NCNTs.120 Reproduced with permission. Copyright
2020, Wiley‐VCH. FE, Faraday efficiency; HRTEM, High Resolution Transmission Electron Microscopy; MNSs, MXene nanosheets;
NCNTs, N‐doped carbon nanotubes; NMR, nuclear magnetic resonance spectroscopy; RHE, relative hydrogen electrode; SAC, monoatomic
catalysts; SEM, scanning electron microscope; TEM, transmission electron microscopy; XPS, X‐ray photoelectron spectroscopy; XRD, X‐ray
diffraction.

response signals of the MoFeC‐1 and Mo2C electro- and the nitrogen real sources. NH3 is a kind of polar
catalysts in N2 saturated atmosphere were stronger than molecule, easily soluble in water (482 g L−1 at 24°C).151 It
that of Ar atmosphere, while the MoFeC‐1 electrocatalyst is well known that the yield of ammonia gas during the
had a significant response signal before 0.05 V, indicating electrochemical synthesis of ammonia at ambient tem-
that MoFeC‐1 was more active than Mo2C NRR. Mean- perature and pressure is very small, typically with
while, MoFeC‐2 has a more negative potential, which experimental yields in the range of 10–1000 nmol and
indicates that MoFeC‐1 requires less energy to activate ammonia is ubiquitous in the laboratory environment,
nitrogen (Figure 19D). Therefore, an increase in iron being a common contaminant in chemicals and espe-
content can attenuate the HER competition reaction and cially in gases. As a volatile gas, it also tends to accu-
promote nitrogen reduction at the same time. mulate over time on the surfaces of common glassware
Based on the results discussed above, the NRR activ- or in aqueous solutions. In areas of impaired air quality,
ities of different electrocatalysts under ambient condi- where atmospheric ammonia levels can reach much
tions are presented in Table 1. higher levels, the source of ammonia in the air is also a
significant influence on experimental accuracy. The re-
sults of ammonia concentration are easily affected by
3.5 | Different ammonia detections nitrogen‐containing impurities in the raw gas, electro-
lyzer, proton exchange membrane, electrolyte, elec-
The NH3 yield and FE are the important indexes to trodes, catalysts, glassware, consumables used in the
evaluate the performance of NRR in an electrochemical experiment, and even human respiratory gas, which can
cell, depending on the accurate quantification of NH3 lead to false‐positive results. To avoid the introduction of
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248
- AN ET AL.

F I G U R E 1 9 (A) Schematic illustration of Mo3Fe3C. (B) FEs and (C) NH3 yield of Mo3Fe3C on different samples. (D) The sixth
harmonic of FTACV in different atmospheres.12 Reproduced with permission. Copyright 2019, Elsevier. FEs, Faraday efficiencies; FTACV,
Fourier‐transform alternating current voltammetry.

such errors, on the one hand, try to avoid the use of reduced to ammonia. For example, for the purification of
nitrogen‐containing materials in the selection process of raw gas, sulfuric acid can be used as an adsorbent to
electrolysis tanks, electrolytes, catalysts, etc. in the elec- remove NH3 impurities in the raw gas; soluble nitrogen‐
trode system. At the same time, the experimental oper- containing impurities such as nitrites, nitrates, and ni-
ation is standardized to avoid the introduction of trogen dioxide can be removed by water washing; for
nitrogen‐containing impurities in the experimental pro- some poorly water‐soluble oxides of nitrogen, selective
cess. On the other hand, necessary purification measures catalytic reduction can be used to remove impurities and
should be taken to avoid impurities in the device system. then sulfuric acid can be used for washing to remove the
Oxidized forms of nitrogen (NOx) including anions in excess NH3.152 If there are nitrogen impurities in the
chemicals and solvents, as well as nitrogen oxides in the electrolyte solution or electrodes, the impurities can be
supply gas are also difficult to exclude as they are easily removed by high‐temperature treatment or washing with
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AN ET AL.
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TABLE 1 A summary of the representative experimental studies on N2 electroreduction and NH3 formation using electrocatalysts.

NH3 yield Potential (V)

Category Electrocatalysts Electrolyte (μg h−1 mg−1) versus RHE FE (%) Refs

Alloy Pd3Bi 0.05 M 59.05 � 2.27 −0.2 21.52 77

H2SO4
Au1Co1/GO 0.5 M K2SO4 25.92 −0.2 22.3 127
Pd0.2Cu0.8/RGO 0.1 M KOH 2.80 −0.2 4.5 128
RhCu‐BUNNs 0.1 M KOH 95.06 −0.2 1.5 129
PdCuIr 0.1 M 13.43 −0.3 5.29 130
Na2SO4
3D amorphous BiNi 0.1 M 17.50 −0.6 13.80 131
Na2SO4
FeTe2/RGO 0.5 M 39.2 −0.5 18.1 132
LiClO4
PtMo‐6 cluster 0.1 M KOH 65.3 −0.15 14.37 133
3D CoFeB@ rGO 0.05 M 35 −0.2 31.6 134
H2SO4
Transition metal Au/TiO2 0.1 M HCl 21.4 −0.2 8.11 135
oxides
B‐TiO1.8 0.1 M 31.6 −0.1 47.7 87
Li2SO4
Au/Fe2(MoO4)3 0.2 M 7.61 −0.4 18.79 89
Na2SO4
Au‐Fe3O4 0.1 M KOH 21.42 −0.2 10.54 136
MnMoO4/RGO 0.5 M 60.3 −0.4 14.7 93
LiClO4 (−0.3 V)
FeMoO4 0.5 M 45.8 −0.5 13.2 94
LiClO4 (−0.3 V)
FeOOH nanorods 0.5 M 23.32 −0.7 6.7 50
LiClO4
CeO2 0.1 M 27.5 −0.3 17.2 137
Na2SO4
MoO3 nanosheets 0.1 M HCl 29.43 −0.5 1.9 138
MoO2@MoO3 0.05 M 60.9 −0.35 23.8 139
H2SO4
Ti‐Bi2WO6 0.1 M HCl 23.14 −0.2 11.44 140
Transition metal Fe3S4 0.1 M HCl 75.4 −0.5 6.45 141
sulfides
MoS2 with Li‐S 0.1 M 43.4 −0.2 9.81 142
interactions Li2SO4
FeS@MoS2/CFC 0.1 M 6.34 −0.5 2.96 143
Na2SO4
FeMo3S4 nanorods 0.5 M 65.3 −0.3 19.2 110
LiClO4
Mo‐SnS2/CC 0.5 M 41.3 −0.5 20.8 109
LiClO4 (−0.4 V)
Bi2S3‐x/Ti3C2Tx 0.5 M 68.3 −0.6 22.5 144
LiClO4 (−0.4 V)
NiCo2S4@MnO2 0.1 M KOH 57.31 −0.2 22.55 145

(Continues)
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T A B L E 1 (Continued)

NH3 yield Potential (V)

Category Electrocatalysts Electrolyte (μg h−1 mg−1) versus RHE FE (%) Refs

Transition metal Mo2C/C 0.5 M 11.3 −0.3 7.8 146

carbides Li2SO4
Mo3Fe3C 0.1 M 1.23 −0.05 27.0 12
Li2SO4
Mo‐Co/NC 0.1 M 1.52 −0.1 13.5 147
Na2SO4
Cobalt/nitrogen‐doped 0.1 M KOH 5.1 −0.4 7.8 148
carbon
Mo/Mo2C/MoC 0.1 M 20.4 −0.3 18.9 149
Na2SO4
Co2N/graphdiyne 0.1 M HCl 219.3 −0.2 58.6 150
Abbreviations: FE, Faraday efficiency; RHE, relative hydrogen electrode.

KOH solution, etc. For the proton exchange membranes, The ion‐selective electrode method has the advantage
such as the Nafion membrane, in addition to the neces- of a lower detection limit and a larger detection range
sary decontamination and activation processes such as (5 � 10−7 or 3 � 10−6 mol L−1). Due to the pH decreasing,
immersion in H2O2 and H2SO4 solution, the pretreated dissolved ammonia is converted to ammonium ions
membrane can be further ultrasonicated in ultrapure during the measurement process.
water and dilute sulfuric acid solution. To eliminate Correspondingly, to obtain accurate results, this
mixed nitrogenous impurities, the membrane can be method requires more reaction time when detecting
ultrasonicated in a solution of ultrapure water and dilute lower concentrations and seals the electrolyte during the
sulphuric acid. While taking effective measures to elim- test to prevent ammonia contamination, leading to a high
inate nitrogen‐containing impurities in the electro- cost and needing complex instrumentation.157
chemical system, attention should be paid to avoiding the In recent years, NRR has developed rapidly and has
generation of new pollutants in the decontamination great prospects for development. However, the yield of
process. In order to ensure the accuracy of the ammonia NH3 remains to be further promoted and hopes to exclude
content test results, isotope experiments or blank exper- nitrogen contaminations of nitrates, nitrites, nitrogen ox-
iments are also generally required to exclude the influ- ides, and so on.158,159 NH3 is easily adsorbed by various
ence of nitrogen‐containing impurities.126 Therefore, substances and causes air pollution.160 For example, elec-
avoidance of nitrogen contaminants and NH3 products is trolyte,161 ion‐exchange membranes,162 human respira-
essential to accurately evaluate the activity of the elec- tion, and latex glove soaking, can lead to an increase in
trocatalyst. The concentration of NH3 in aqueous solu- ammonia levels.163 So, this reagent must be stored, used,
tions can be measured by various methods. Currently, and disposed of according to the relevant regulations.
the most commonly used methods for the determination In order to have accurate and reliable test results, the
of NH3 in aqueous solutions are the indophenol blue raw 14N2 is purified by dilute sulfuric acid solution and the
method, NH3 ion selective electrode method, Nessler's electrochemical cell needs to be cleaned repeatedly with
reagent method, as well as IC and 1H NMR.153,154 N2H4 ultrapure water before use. The nitrite/nitrate can be
is a common by‐product in NRR and is usually deter- effectively absorbed and eliminated by the aqueous solu-
mined using the Watts and Crisp methods. However, tion. In addition, the electrocatalysts should be carried out
these detection methods have limitations and different in controlled experiments under Ar and N2 saturation to
detection methods must be used under different condi- eliminate pollution of electrochemical batteries and gas
tions. The pH of the reaction solvent and the presence of from NH3 in the environment.151,164 Isotope tracing
organic compounds and certain metal ions may interfere studies with 15N2 are required to verify that NH3 is reduced
with the quantitative detection of NH3. Therefore, it is by N2 when calculating NH3 yield and FE. It should be
advisable to use different assays under different testing noted that the NH3 produced in the control experiment
conditions to ensure the truthfulness and accuracy of the needs to be deducted from the total NH3 measured to make
results.155,156 the results more convincing and reliable.165,166
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AN ET AL.
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FIGURE 20 Schematic illustration of the prospects for the electrocatalytic nitrogen reduction reaction.

4 | CONCLUSIONS AND PERSPECTIVE and agriculture. Developing electrochemical nitrogen

fixation technology to replace industrial ammonia
It is expected that NH3 produced using electrochemical synthesis is a challenging and profound economic
synthesis at ambient temperature and pressure will strategy. Also, the TM electrocatalysts exhibit excel-
replace the traditional industrial synthesis of NH3. lent electrochemical properties in the field of NRR.
Although the existing NRR systems have been developed ② Reasonable design and development of high‐efficiency
rapidly, they are still in the initial stage and face the electrocatalysts. The electronic structure of the cata-
problems of low solubility, difficult adsorption and acti- lyst can be adjusted by catalyst surface modification,
vation of N2, and HER side reaction, which needs to be morphology adjustment, elemental alloying, and
solved urgently. Intrinsic activity, selectivity, and dura- carrier–metal interactions to add active sites to the
bility are important indicators for assessing the apparent catalyst. It can improve the apparent and intrinsic
or intrinsic activity of non‐reducing catalysts. To further activity of the electrocatalysts to obtain excellent
explore new probabilities in this area, this review aims to selectivity and catalytic activity. On the other hand,
provide the latest overview of the recent development of the rational design of electrolyte is also crucial for
TM catalysts (especially alloy, TM oxides, TM sulfides, HER inhibition. The use of polar non‐boiling solvents
and TM carbides) for electrocatalytic NRR effectively can significantly reduce the proton concentration and
enhancing the NH3 yield and FE. In order to achieve adjust the adsorption of nitrogen on the surface of the
widely accepted electrochemically accurate detection, the TM catalyst. Compared with a single metal, composite
following points need to be noted: metal materials have a lower activation energy barrier,
which has great potential in NRR. Weak changes in
① It is well known that nitrogen fixation can be catego- the surface structure and composition of bimetallic
rized into artificial nitrogen fixation and natural ni- composites can have a particularly large impact on
trogen fixation. In many ways, biological nitrogen electrocatalytic performance. Therefore, the combi-
fixation is an efficient and environmentally friendly nation of theoretical calculations and experiments
way of fixing nitrogen to meet the daily nutritional could be used to develop and design better
needs of organisms on earth. The TM contained in electrocatalysts.
nitrogenase is an important reference and guide for ③ The presence of nitrogen pollutants is of critical
the synthesis of NRR catalysts. The industrial syn- importance for the detection of ammonia. On the
thesis of NH3 of the Haber–Bosch process in the in- one hand, researchers should develop more
dustrial revolution has been developed relatively advanced and diverse ammonia detection methods.
mature and has occupied a key position in industry In particular, isotopic NMR tests should be further
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
252
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carried out on nitrogen‐containing raw materials and DA T A A V A I L A B I LI TY S TA TE M E NT

nitrogen‐containing catalysts to determine the true Data sharing is not applicable to this article as no new
source of the nitrogen. On the other hand, testers data were created or analyzed in this study.
should consider and avoid the pollution of nitrogen
pollutants in electrocatalytic experiments as far as OR C I D
possible. In the current research situation, theoret- Zaicheng Sun https://orcid.org/0000-0002-7059-3177
ical calculations and some in situ characterization
techniques such as in situ TEM, in situ XPS and in R E F E R E NC E S
situ synchrotron radiation are still needed to give 1. Shipman MA, Symes MD. Recent progress towards the
some theoretical and structural guidance for the electrosynthesis of ammonia from sustainable resources.
rational design of electrocatalysts. This places more Catal Today. 2017;286(15):57‐68.
2. Zhu D, Zhang L, Ruther RE, Hamers RJ. Photo‐illuminated
stringent requirements on the study of the adsorp-
diamond as a solid‐state source of solvated electrons in wa-
tion state of the reactants, the changes in the cata-
ter for nitrogen reduction. Nat Mater. 2013;12(9):836‐841.
lyst, and the accurate quantitative detection of the 3. Roux Y, Duboc C, Gennari M. Molecular catalysts for N2
products. With the help of various detection and reduction: state of the art, mechanism, and challenges.
characterization methods, real and reliable results of ChemPhysChem. 2017;18(19):2606‐2617.
nitrogen fixation over TM electrocatalysts can be 4. Suryanto BHR, Kang CSM, Wang D, et al. Rational electrode‐
obtained (Figure 20). electrolyte design for efficient ammonia electrosynthesis un-
der ambient conditions. ACS Energy Lett. 2018;3(6):1219‐1224.
5. Guo C, Ran J, Vasileff A, Qiao S‐Z. Rational design of elec-
In summary, electrocatalytic NRR has made a great
trocatalysts and photo(electro)catalysts for nitrogen reduc-
breakthrough under ambient conditions and has pro- tion to ammonia (NH3) under ambient conditions. Energy
vided huge potential for the future development of NRR. Environ Sci. 2018;11(1):45‐56.
With the continuous development of science and tech- 6. Song P, Wang H, Kang L, Ran B, Song H, Wang R. Electro-
nology, we are looking forward to solving these diffi- chemical nitrogen reduction to ammonia at ambient condi-
culties ultimately and improving the conversion tions on nitrogen and phosphorus co‐doped porous carbon.
efficiency of the electrocatalytic synthesis of ammonia. Chem Commun. 2019;55(5):687‐690.
7. Niu L, Wang D, Xu K, et al. Tuning the performance of ni-
trogen reduction reaction by balancing the reactivity of N2
A UT HOR CO N T R I BU T I O N S
and the desorption of NH3. Nano Res. 2021;14(11):4093‐4099.
Li An: Data curation; writing ‐ original draft; writing ‐ 8. Guo X, Du H, Qu F, Li J. Recent progress in electrocatalytic
review & editing. Zhaoyan Zhang: Conceptualization; nitrogen reduction. J Mater Chem A. 2019;7(8):3531‐3543.
methodology; software; investigation; formal analysis; 9. Giddey S, Badwal SPS, Munnings C, Dolan M. Ammonia as a
writing ‐ original draft. Guohua Liu: Visualization; renewable energy transportation media. ACS Sustainable
investigation. Wenning Liu: Resources; supervision. Chem Eng. 2017;5(11):10231‐10239.
Yajie Fu: Software; validation. Dan Qu: Visualization; 10. Wang S, Ichihara F, Pang H, Chen H, Ye J. Nitrogen fixation
reaction derived from nanostructured catalytic materials. Adv
editing. Yichang Liu: Supervision. Pu Hu: Writing ‐
Funct Mater. 2018;28(50):1803309.
review & editing. Zaicheng Sun: Conceptualization;
11. Niu L, An L, Wang X, Sun Z. Effect on electrochemical
funding acquisition; resources; supervision; writing ‐ re- reduction of nitrogen to ammonia under ambient conditions:
view & editing. challenges and opportunities for chemical fuels. J Energy
Chem. 2021;61:304‐318.
A CK N OWL ED GM EN T S 12. Qin B, Li Y, Zhang Q, Yang G, Liang H, Peng F. Understanding
of nitrogen fixation electro catalyzed by molybdenum‐iron
This work was financially supported by the National Key
carbide through the experiment and theory. Nano Energy.
R&D Program of China (2023YFB3810800), the Key
2020;68:104374.
Project of the National Natural Science Foundation of 13. Liang J, Li Z, Zhang L, et al. Advances in ammonia electro-
China (21936001 and 21801092), the National Natural synthesis from ambient nitrate/nitrite reduction. Chem.
Science Foundation of China (No. 22272003 and 2023;9(7):1768‐1827.
22301013), R&D Program of Beijing Municipal Education 14. Liu Q, Lin Y, Gu S, et al. Enhanced N2‐to‐NH3 conversion
Commission (23JB0002), Beijing Outstanding Young efficiency on Cu3P nanoribbon electrocatalyst. Nano Res.
Scientists Program (BJJWZYJH01201910005017). These 2022;15(8):7134‐7138.
15. Liu Q, Xu T, Luo Y, et al. Recent advances in strategies for
funding agencies are acknowledged.
highly selective electrocatalytic N2 reduction toward ambient
NH3 synthesis. Curr Opin Electrochem. 2021;29:100766.
C ON F L IC T OF I N T E R EST ST AT E M E NT 16. Mushtaq MA, Kumar A, Liu W, et al. A metal coordination
The authors declare no conflicts of interest. number determined catalytic performance in manganese
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
- 253

borides for ambient electrolysis of nitrogen to ammonia. Adv enhanced conversion efficiency. ACS Catal. 2020;10(12):
Mater. 2024:36(21):2313086. 6870‐6899.
17. Foster SL, Bakovic SIP, Duda RD, et al. Catalysts for nitrogen 35. Lv X‐W, Weng C‐C, Yuan Z‐Y. Ambient ammonia electro-
reduction to ammonia. Nat Catal. 2018;1(7):490‐500. synthesis: current status, challenges, and perspectives.
18. Montoya JH, Tsai C, Vojvodic A, Nrskov JK. The challenge of ChemSusChem. 2020;13(12):3061‐3078.
electrochemical ammonia synthesis: a new perspective on the 36. Skúlason E, Bligaard T, Gudmundsdóttir S, et al. A theo-
role of nitrogen scaling relations. ChemSusChem. 2015;8(13): retical evaluation of possible transition metal electro‐
2180‐2186. catalysts for N2 reduction. Phys Chem Chem Phys.
19. Hoffman BM, Lukoyanov D, Yang Z‐Y, Dean DR, Seefeldt 2012;14(3):1235‐1245.
LC. Mechanism of nitrogen fixation by nitrogenase: the next 37. Cheng H, Ding L‐X, Chen G‐F, Zhang L, Xue J, Wang H.
stage. Chem Rev. 2014;114(8):4041‐4062. Molybdenum carbide nanodots enable efficient electro-
20. Keable SM, Zadvornyy OA, Johnson LE, et al. Structural catalytic nitrogen fixation under ambient conditions. Adv
characterization of the P1þ intermediate state of the P‐cluster Mater. 2018;30(46):e1803694.
of nitrogenase. J Biol Chem. 2018;293(25):9629‐9635. 38. Zhang X, Wang J, Jin H, Wang S, Song W. Bioinspired su-
21. Zhao J, Chen Z. Single Mo atom supported on defective bo- pramolecular lubricating hydrogel induced by shear force. J
ron nitride monolayer as an efficient electrocatalyst for ni- Am Chem Soc. 2018;140(9):3186‐3189.
trogen fixation: a computational study. J Am Chem Soc. 39. Falcone M, Barluzzi L, Andrez J, et al. The role of bridging li-
2017;139(36):12480‐12487. gands in dinitrogen reduction and functionalization by ura-
22. Liu C, Li Q, Wu C, et al. Single‐boron catalysts for nitrogen nium multimetallic complexes. Nat Chem. 2019;11(2):154‐160.
reduction reaction. J Am Chem Soc. 2019;141(7):2884‐2888. 40. Pool JA, Lobkovsky E, Chirik PJ. Hydrogenation and cleav-
23. Li X‐F, Li Q‐K, Cheng J, et al. Conversion of dinitrogen to age of dinitrogen to ammonia with a zirconium complex.
ammonia by FeN3‐embedded graphene. J Am Chem Soc. Nature. 2004;427(6974):527‐530.
2016;138(28):8706‐8709. 41. Deng J, Iñiguez JA, Liu C. Electrocatalytic nitrogen reduction
24. Milton RD, Abdellaoui S, Khadka N, et al. Nitrogenase bio- at low temperature. Joule. 2018;2(5):846‐856.
electrocatalysis: heterogeneous ammonia and hydrogen pro- 42. van der Ham CJM, Koper MTM, Hetterscheid DGH. Chal-
duction by MoFe protein. Energy Environ Sci. 2016;9(8): lenges in reduction of dinitrogen by proton and electron
2550‐2554. transfer. Chem Soc Rev. 2014;43(15):5183‐5191.
25. Mou T, Long J, Frauenheim T, Xiao J. Advances in electro- 43. Ouyang L, Liang J, Luo Y, et al. Recent advances in elec-
chemical ammonia synthesis beyond the use of nitrogen gas trocatalytic ammonia synthesis. Chin J Catal. 2023;50:6‐44.
as a source. Chempluschem. 2021;86(8):1211‐1224. 44. Zhang H, Wang H, Cao X, et al. Unveiling cutting‐edge de-
26. Gao W, Xie K, Xie J, et al. Alloying of Cu with Ru enabling velopments in electrocatalytic nitrate‐to‐ammonia conver-
the relay catalysis for reduction of nitrate to ammonia. Adv sion. Adv Mater. 2024;36(16):2312746.
Mater. 2023;35(19):2202952. 45. Zheng Y, Jiao Y, Zhu Y, et al. Hydrogen evolution by a metal‐
27. Wang L, Xia M, Wang H, et al. Greening ammonia toward free electrocatalyst. Nat Commun. 2014;5(1):3783.
the solar ammonia refinery. Joule. 2018;2(6):1055‐1074. 46. Zhang Y, Qiu W, Ma Y, et al. High‐performance electro-
28. Liu Y, Chen S, Xie Q, Yu H. Efficient electrochemical hydrogenation of N2 to NH3 catalyzed by multishelled hollow
reduction of carbon dioxide to acetate on nitrogen‐doped Cr2O3 microspheres under ambient conditions. ACS Catal.
nanodiamond. J Am Chem Soc. 2015;137(36):11631‐11636. 2018;8(9):8540‐8544.
29. Meng F, Zhong H, Bao D, Yan J, Zhang X. In situ coupling of 47. Qin Q, Zhao Y, Schmallegger M, et al. Enhanced electro-
strung Co4N and intertwined N‐C fibers toward free‐standing catalytic N2 reduction via partial anion substitution in tita-
bifunctional cathode for robust, efficient, and flexible Zn‐air nium oxide‐carbon composites. Angew Chem Int Ed.
batteries. J Am Chem Soc. 2016;138(32):10226‐10231. 2019;58(37):13101‐13106.
30. Zhong H, Wang J, Meng F, Zhang X. In situ activating 48. Li C, Ma D, Mou S, et al. Porous LaFeO3 nanofiber with
ubiquitous rust towards low‐cost, efficient, free‐standing, and oxygen vacancies as an efficient electrocatalyst for N2 con-
recoverable oxygen evolution electrodes. Angew Chem Int Ed. version to NH3 under ambient conditions. J Energy Chem.
2016;55(34):9937‐9941. 2020;50:402‐408.
31. Zhong X, Yuan E, Yang F, et al. Optimizing oxygen vacancies 49. Xu T, Ma D, Li C, et al. Ambient electrochemical NH3 syn-
through grain boundary engineering to enhance electro- thesis from N2 and water enabled by ZrO2 nanoparticles.
catalytic nitrogen reduction. Proc Natl Acad Sci USA. 2023; Chem Commun. 2020;56(25):3673‐3676.
120(40):e2306673120. 50. Zhu X, Liu Z, Wang H, et al. Boosting electrocatalytic N2
32. Banerjee A, Yuhas BD, Margulies EA, et al. Photochemical reduction to NH3 on β‐FeOOH by fluorine doping. Chem
nitrogen conversion to ammonia in ambient conditions with Commun. 2019;55(27):3987‐3990.
FeMoS‐chalcogels. J Am Chem Soc. 2015;137(5):2030‐2034. 51. Li L, Chen G, Shao Z, Huang H. Progress on smart integrated
33. Chen X, Zhang X, Li Y‐H, et al. Transition metal doping systems of seawater purification and electrolysis. Energy
BiOBr nanosheets with oxygen vacancy and exposed {102} Environ Sci. 2023;16(11):4994‐5002.
facets for visible light nitrogen fixation. Appl Catal B Environ. 52. Légaré M‐A, Bélanger‐Chabot G, Dewhurst RD, et al. Nitrogen
2021;281:119516. fixation and reduction at boron. Science. 2018;359(6378):896.
34. Shi L, Yin Y, Wang S, Sun H. Rational catalyst design for N2 53. Dahcheh F, Martin D, Stephan DW, Bertrand G. Synthesis
reduction under ambient conditions: strategies toward and reactivity of a CAAC‐aminoborylene adduct: a hetero‐
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
254
- AN ET AL.

allene or an organoboron isoelectronic with singlet carbenes. 72. Liu Z, Tee SY, Guan G, Han M‐Y. Atomically substitutional
Angew Chem Int Ed. 2014;53(48):13159‐13163. engineering of transition metal dichalcogenide layers for
54. Edel K, Krieg M, Grote D, Bettinger HF. Photoreactions of enhancing tailored properties and superior applications.
phenylborylene with dinitrogen and carbon monoxide. J Am Nano‐Micro Lett. 2024;16(1):95.
Chem Soc. 2017;139(42):15151‐15159. 73. Zhou J, Chen X, Guo M, Hu W, Huang B, Yuan D. Enhanced
55. Wu TT, Fan WJ, Zhang Y, Zhang FX. Electrochemical syn- catalytic activity of bimetallic ordered catalysts for nitrogen
thesis of ammonia: progress and challenges. Mater Today reduction reaction by perturbation of scaling relations. ACS
Phys. 2021;16:100310. Catal. 2023;13(4):2190‐2201.
56. Kim C, Song J‐Y, Choi C, et al. Atomic‐scale homogeneous 74. Zhou HY, Qu YB, Fan YC, et al. Multi‐site intermetallic
Ru‐Cu alloy nanoparticles for highly efficient electrocatalytic Ni3Mo effectively boosts selective ammonia synthesis. Appl
nitrogen reduction. Adv Mater. 2022;34(40):2205270. Catal B Environ. 2023;339:123133.
57. Pang Y, Su C, Jia G, Xu L, Shao Z. Emerging two‐dimensional 75. Lee Y, Kim SJ, Kim YJ, et al. Oxidation‐resistant titanium
nanomaterials for electrochemical nitrogen reduction. Chem carbide MXene films. J Mater Chem A. 2020;8(2):573‐581.
Soc Rev. 2021;50(22):12744‐12787. 76. Nierengarten J, Houk KN, Ding K. Front cover: a journey of a
58. Xia X, Li B, Liu S, Tang B. Recent advances and challenges in thousand miles begins with a single step (Chem. Eur. J. 67/
2D metal‐free electrocatalysts for N2 fixation. Front Chem. 2020). Chem Eur J. 2020;26(67):15339.
2020;8:437. 77. Wang X, Luo M, Lan J, Peng M, Tan Y. Nanoporous inter-
59. Ren Y, Yu C, Tan X, et al. Strategies to activate inert nitrogen metallic Pd3Bi for efficient electrochemical nitrogen reduc-
molecules for efficient ammonia electrosynthesis: current tion. Adv Mater. 2021;33(18):2007733.
status, challenges, and perspectives. Energy Environ Sci. 78. Zhang D, Zhao H, Wu X, et al. Multi‐site electrocatalysts
2022;15(7):2776‐2805. boost pH‐universal nitrogen reduction by high‐entropy al-
60. Yang J‐H, Peng M, Zhai D‐D, et al. Fixation of N2 into value‐ loys. Adv Funct Mater. 2021;31(9):2006939.
added organic chemicals. ACS Catal. 2022;12(5):2898‐2906. 79. Geng Z, Liu Y, Kong X, et al. N2 electrochemical reduction:
61. Carro P, Choi J, MacFarlane DR, Simonov AN, Doña‐ achieving a record‐high yield rate of 120.9 μg NH3 mgcat.‐1 h‐1
Rodríguez JM, Azofra LM. Competition between metal‐ for N2 electrochemical reduction over Ru single‐atom cata-
catalysed electroreduction of dinitrogen, protons, and ni- lysts (Adv. Mater. 40/2018). Adv Mater. 2018;30(40):1870301.
trogen oxides: a DFT perspective. Catal Sci Technol. 80. Wang XX, Cullen DA, Pan YT, et al. Nitrogen‐coordinated
2022;12(9):2856‐2864. single cobalt atom catalysts for oxygen reduction in proton
62. Ball B, Das P, Sarkar P. Molybdenum atom‐mediated exchange membrane fuel cells. Adv Mater. 2018;30(11):
salphen‐based covalent organic framework as a promising 1706758.
electrocatalyst for the nitrogen reduction reaction: a first‐ 81. Ji S, Chen Y, Zhao S, et al. Atomically dispersed ruthenium
principles study. J Phys Chem C. 2021;125(47):26061‐26072. species inside metal‐organic frameworks: combining the high
63. Cui X, Tang C, Zhang Q. A review of electrocatalytic reduc- activity of atomic sites and the molecular sieving effect of
tion of dinitrogen to ammonia under ambient conditions. MOFs. Angew Chem Int Ed. 2019;58(13):4271‐4275.
Adv Energy Mater. 2018;8(22):1800369. 82. Chu K, Liu Y‐p, Li Y‐b, Zhang H, Tian Y. Efficient electro-
64. Kim M‐C, Nam H, Choi J, et al. Hydrogen bonding‐mediated catalytic N2 reduction on CoO quantum dots. J Mater Chem
enhancement of bioinspired electrochemical nitrogen reduc- A. 2019;7(9):4389‐4394.
tion on Cu2‐xS catalysts. ACS Catal. 2020;10(18):10316‐10802. 83. Gu H, Li J, Niu X, et al. Symmetry‐breaking p‐block anti-
65. Lv S‐Y, Huang C‐X, Li G, Yang L‐M. Electrocatalytic mech- mony single atoms trigger N‐bridged titanium sites for elec-
anism of N2 reduction reaction by single‐atom catalyst rect- trocatalytic nitrogen reduction with high efficiency. ACS
angular TM‐TCNQ monolayers. ACS Appl Mater Interfaces. Nano. 2023;17(21):21838‐21849.
2021;13(25):29641‐29653. 84. Li S, Zhou Y, Li K, et al. Electrosynthesis of ammonia with
66. Wang XX, Swihart MT, Wu G. Achievements, challenges and high selectivity and high rates via engineering of the solid‐
perspectives on cathode catalysts in proton exchange mem- electrolyte interphase. Joule. 2022;6(9):2083‐2101.
brane fuel cells for transportation. Nat Catal. 2019;2(7): 85. Liu G, Niu L, Ma Z, et al. Fe2Mo3O8/XC‐72 electrocatalyst for
578‐589. enhanced electrocatalytic nitrogen reduction reaction under
67. Xin Y, Li S, Qian Y, et al. High‐entropy alloys as a platform ambient conditions. Nano Res. 2022;15(7):5940‐5945.
for catalysis: progress, challenges, and opportunities. ACS 86. Xie M, Dai F, Guo H, et al. Improving electrocatalytic ni-
Catal. 2020;10(19):11280‐11306. trogen reduction selectivity and yield by suppressing
68. Xin H, Vojvodic A, Voss J, Nørskov JK, Abild‐Pedersen F. hydrogen evolution reaction via electronic metal‐support
Effects of d‐band shape on the surface reactivity of transition‐ interaction. Adv Energy Mater. 2023;13(21):2203032.
metal alloys. Phys Rev B. 2014;89(11):115114. 87. Sun Y, Han Y, Zhang X, et al. TiO1.8 with lattice H for
69. Ding Z‐B, Wu F, Wang Y‐C, Jiang H. Theoretical studies of effective electrocatalytic nitrogen fixation. Appl Catal B En-
the work functions of Pd‐based bimetallic surfaces. J Chem viron. 2022;319:121933.
Phys. 2015;142(21):214706. 88. Li S‐J, Bao D, Shi M‐M, Wulan B‐R, Yan J‐M, Jiang Q.
70. Long R, Li Y, Liu Y, et al. Isolation of Cu toms in Pd lattice: Amorphizing of Au nanoparticles by CeOx‐RGO hybrid sup-
forming highly selective sites for photocatalytic conversion of port towards highly efficient electrocatalyst for N2 reduction
CO2 to CH4. J Am Chem Soc. 2017;139(12):4486‐4492. under ambient conditions. Adv Mater. 2017;29(33):1700001.
71. Zhang A, Liang Y, Zhang H, Geng Z, Zeng J. Doping regu- 89. Yao J, Zhou Y, Yan J‐M, Jiang Q. Regulating Fe2(MoO4)3 by
lation in transition metal compounds for electrocatalysis. Au nanoparticles for efficient N2 electroreduction under
Chem Soc Rev. 2021;50(17):9817‐9844. ambient conditions. Adv Energy Mater. 2021;11(14):2003701.
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
- 255

90. Liu Z, Hu J, Gao F, Cao H, Zhou Q, Wang X. Biodegradable and 107. Chu K, Nan H, Li Q, Guo Y, Tian Y, Liu W. Amorphous MoS3
resilient poly (propylene carbonate) based foam from high enriched with sulfur vacancies for efficient electrocatalytic
pressure CO2 foaming. Polym Degrad Stabil. 2019;165:12‐19. nitrogen reduction. J Energy Chem. 2021;53:132‐138.
91. Wang X, Li M, Chang Z, Yang Y, Wu Y, Liu X. 108. Chu K, Liu Y‐p, Cheng Y‐h, Li Q‐q. Synergistic boron‐
Co3O4@MWCNT nanocable as cathode with superior elec- dopants and boron‐induced oxygen vacancies in MnO2
trochemical performance for supercapacitors. ACS Appl nanosheets to promote electrocatalytic nitrogen reduction. J
Mater Interfaces. 2015;7(4):2280‐2285. Mater Chem A. 2020;8(10):5200‐5208.
92. Wen J, Chang H, Huang T, et al. A simple synthesis of 109. Chu K, Wang J, Liu Y‐p, Li Q‐q, Guo Y‐l. Mo‐doped SnS2
Co3O4@CNT to boost electrochemical nitrogen fixation. with enriched S‐vacancies for highly efficient electrocatalytic
Electrochim Acta. 2021;367:137421. N2 reduction: the critical role of the Mo‐Sn‐Sn trimer. J Mater
93. Liu Y, Luo Y, Li Q, Wang J, Chu K. Bimetallic MnMoO4 with Chem A. 2020;8(15):7117‐7124.
dual‐active‐centers for highly efficient electrochemical N2 110. Wang J, Nan H, Tian Y, Chu K. FeMo3S4 for efficient nitrogen
fixation. Chem Commun. 2020;56(70):10227‐10230. reduction reaction. ACS Sustainable Chem Eng. 2020;8(20):
94. Chu K, Li Q‐Q, Cheng Y‐H, Liu Y‐P. Efficient electrocatalytic 7536‐7750.
nitrogen fixation on FeMoO4 nanorods. ACS Appl Mater In- 111. Cao N, Chen Z, Zang K, et al. Doping strain induced bi‐Ti3þ
terfaces. 2020;12(10):11789‐11796. pairs for efficient N2 activation and electrocatalytic fixation.
95. Ahmed MI, Chen S, Ren W, Chen X, Zhao C. Synergistic Nat Commun. 2019;10:2877.
bimetallic CoFe2O4 clusters supported on graphene for 112. Wu T, Zhu X, Xing Z, et al. Greatly improving electro-
ambient electrocatalytic reduction of nitrogen to ammonia. chemical N2 reduction over TiO2 nanoparticles by iron
Chem Commun. 2019;55(81):12184‐12187. doping. Angew Chem Int Ed. 2019;58(51):18449‐18453.
96. Qin M, Li X, Gan G, et al. Boosting electrocatalytic nitrogen 113. Li C, Yu J, Yang L, et al. Spinel LiMn2O4 nanofiber: an effi-
fixation with Co‐N3 site‐decorated porous carbon. ACS Sus- cient electrocatalyst for N2 reduction to NH3 under ambient
tainable Chem Eng. 2020;8(35):13430‐13439. conditions. Inorg Chem. 2019;58(15):9597‐9601.
97. Wan Y, Zhou H, Zheng M, et al. Oxidation state modulation 114. Yu J, Li C, Li B, et al. A perovskite La2Ti2O7 nanosheet as an
of bismuth for efficient electrocatalytic nitrogen reduction to efficient electrocatalyst for artificial N2 fixation to NH3 in
ammonia. Adv Funct Mater. 2021;31(30):2100300. acidic media. Chem Commun. 2019;55:6401‐6404.
98. Fei H, Liu R, Wang J, et al. Targeted modulation of competitive 115. Wang Z, Gong F, Zhang L, et al. Electrocatalytic hydroge-
active sites toward nitrogen fixation via sulfur vacancy engi- nation of N2 to NH3 by MnO: experimental and theoretical
neering over MoS2. Adv Funct Mater. 2023;33(36):2302501. investigations. Adv Sci. 2019;6(1):1801182.
99. Fei H, Liu R, Wang J, et al. Unveiling the competitive 116. Chu K, Liu Y‐p, Li Y‐b, Guo Y‐l, Tian Y, Zhang H. Multi‐
behavior by the orientated regulation of S‐vacancy over functional Mo‐doping in MnO2 nanoflowers toward effi-
MoS2 for highly effective N2 fixation. Chem Eng J. cient and robust electrocatalytic nitrogen fixation. Appl Catal
2023;476:146895. B Environ. 2020;264:118525.
100. Niu L, Liu Z, Liu G, et al. Surface hydrophobic modification 117. Zhao R, Chen Y, Xiang H, et al. Two‐dimensional ordered
enhanced catalytic performance of electrochemical nitrogen double‐transition metal carbides for the electrochemical ni-
reduction reaction. Nano Res. 2022;15(5):3886‐3893. trogen reduction reaction. ACS Appl Mater Interfaces.
101. Chen J, Kang Y, Zhang W, et al. Lattice‐confined single‐atom 2023;15(5):6797‐6806.
Fe1Sx on mesoporous TiO2 for boosting ambient electro- 118. Wei H, Jiang Q, Ampelli C, et al. Enhancing N2 fixation ac-
catalytic N2 reduction reaction. Angew Chem Int Ed. tivity by converting Ti3C2 MXenes nanosheets to nano-
2022;61(27):e202203022. ribbons. ChemSusChem. 2020;13(21):5614‐5619.
102. Hou Y, Laursen AB, Zhang J, et al. Layered nanojunctions for 119. Qiu W, Xie X‐Y, Qiu J, et al. High‐performance artificial ni-
hydrogen‐evolution catalysis. Angew Chem Int Ed. trogen fixation at ambient conditions using a metal‐free
2013;52(13):3621‐3625. electrocatalyst. Nat Commun. 2018;9(1):3485.
103. Hu S, Chen X, Li Q, Zhao Y, Mao W. Effect of sulfur vacancies 120. Ma Y, Yang T, Zou H, et al. Synergizing Mo single atoms and
on the nitrogen photofixation performance of ternary metal Mo2C nanoparticles on CNTs synchronizes selectivity and
sulfide photocatalysts. Catal Sci Technol. 2016;6(15): activity of electrocatalytic N2 reduction to ammonia. Adv
5884‐5890. Mater. 2020;32(33):2002177.
104. Kyriakou V, Garagounis I, Vasileiou E, Vourros A, Stoukides 121. Xia J, Yang S‐Z, Wang B, et al. Boosting electrosynthesis of
M. Progress in the electrochemical synthesis of ammonia. ammonia on surface‐engineered MXene Ti3C2. Nano Energy.
Catal Today. 2017;286:2‐13. 2020;72:104681.
105. Zhang L, Ji X, Ren X, et al. Electrochemical ammonia synthesis 122. Li Q, Qiu S, He L, Zhang X, Sun C. Impact of H‐termination on
via nitrogen reduction reaction on a MoS2 catalyst: theoretical the nitrogen reduction reaction of molybdenum carbide as an
and experimental studies. Adv Mater. 2018;30(28):1800191. electrochemical catalyst. Phys Chem Chem Phys. 2018;20:
106. Ye H, Wang L, Deng S, et al. Amorphous MoS3 infiltrated 23338‐23343.
with carbon nanotubes as an advanced anode material of 123. Ren X, Zhao J, Wei Q, et al. High‐performance N2‐to‐NH3
sodium‐ion batteries with large gravimetric, areal, and volu- conversion electrocatalyzed by Mo2C nanorod. ACS Cent Sci.
metric capacities. Adv Energy Mater. 2017;7(5):1601602. 2019;5(1):116‐121.
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
256
- AN ET AL.

124. Liu X, Jiao Y, Zheng Y, Jaroniec M, Qiao S‐Z. Building up a 140. Wang H, Zhang C, Liu B, et al. Tuning surface potential
picture of the electrocatalytic nitrogen reduction activity of polarization to enhance N2 affinity for ammonia electrosyn-
transition metal single‐atom catalysts. J Am Chem Soc. thesis. Adv Mater. 2024:2401032.
2019;141(24):9664‐9672. 141. Zhao X, Lan X, Yu D, Fu H, Liu Z, Mu T. Deep eutectic‐
125. Sun T, Xu L, Wang D, Li Y. Metal organic frameworks solvothermal synthesis of nanostructured Fe3S4 for electro-
derived single atom catalysts for electrocatalytic energy chemical N2 fixation under ambient conditions. Chem Com-
conversion. Nano Res. 2019;12(9):2067‐2080. mun. 2018;54(92):13010‐13013.
126. Andersen SZ, Čolić V, Yang S, et al. A rigorous electro- 142. Liu Y, Han M, Xiong Q, et al. Dramatically enhanced
chemical ammonia synthesis protocol with quantitative ambient ammonia electrosynthesis performance by in‐
isotope measurements. Nature. 2019;570(7762):504‐508. operando created Li‐S interactions on MoS2 electrocatalyst.
127. Wang Q, Zheng G, Hao S, et al. Au1Co1 alloy supported on Adv Energy Mater. 2019;9(14):1803935.
graphene oxide with enhanced performance for ambient 143. Guo Y, Yao Z, Timmer BJJ, et al. Boosting nitrogen reduc-
electrolysis of nitrogen to ammonia. ACS Sustainable Chem tion reaction by bio‐inspired FeMoS containing hybrid
Eng. 2020;8(1):44‐49. electrocatalyst over a wide pH range. Nano Energy.
128. Deng K, Xu Y, Xue H, Li X, Wang L, Wang H. Ambient ni- 2019;62:282‐288.
trogen reduction to ammonia electrocatalyzed by bimetallic 144. Luo Y, Shen P, Li X, Guo Y, Chu K. Sulfur‐deficient Bi2S3‐x
PdRu porous nanostructures. ACS Sustainable Chem Eng. synergistically coupling Ti3C2Tx‐MXene for boosting electro-
2019;7(2):2400‐2405. catalytic N2 reduction. Nano Res. 2022;15(5):3991‐3999.
129. Bai J, Huang H, Li F‐M, et al. Glycerol oxidation assisted 145. Mushtaq MA, Kumar A, Yasin G, et al. Multivalent sulfur
electrocatalytic nitrogen reduction: ammonia and glyceralde- vacancy‐rich NiCo2S4@MnO2 urchin‐like heterostructures
hyde co‐production on bimetallic RhCu ultrathin nanoflake for ambient electrochemical N2 reduction to NH3. Small.
nanoaggregates. J Mater Chem A. 2019;7(37):21149‐21156. 2024;2310431.
130. Kumar RD, Wang Z, Li C, et al. Trimetallic PdCuIr with long‐ 146. Cheng H, Ding LX, Chen GF, Zhang L, Xue J, Wang H. Ni-
spined sea‐urchin‐like morphology for ambient electro- trogen reduction reaction: molybdenum carbide nanodots
reduction of nitrogen to ammonia. J Mater Chem A. 2019;7: enable efficient electrocatalytic nitrogen fixation under
3190‐3196. ambient conditions. Adv Mater. 2018;30(46):1803694.
131. Fang Z, Wu P, Qian Y, Yu G. Gel‐derived amorphous 147. Zhang Y, Hu J, Zhang C, et al. Bimetallic Mo‐Co nano-
bismuth‐nickel alloy promotes electrocatalytic nitrogen fixa- particles anchored on nitrogen‐doped carbon for enhanced
tion via optimizing nitrogen adsorption and activation. electrochemical nitrogen fixation. J Mater Chem A.
Angew Chem Int Ed. 2021;60(8):4275‐4281. 2020;8(18):9091‐9098.
132. Guo Y, Cheng Y, Li Q, Chu K. FeTe2 as an earth‐abundant 148. Gao Y, Han Z, Hong S, et al. ZIF‐67‐derived cobalt/nitrogen‐
metal telluride catalyst for electrocatalytic nitrogen fixation. doped carbon composites for efficient electrocatalytic N2
J Energy Chem. 2021;56:259‐263. reduction. ACS Appl Energy Mater. 2019;2(8):6071‐6077.
133. Guo X, Li XY, Li YC, et al. Molecule template method for 149. Liu Y, Zhu X, Zhang Q, et al. Engineering Mo/Mo2C/MoC
precise synthesis of Mo‐based alloy clusters and electro- hetero‐interfaces for enhanced electrocatalytic nitrogen
catalytic nitrogen reduction on partially reduced PtMo alloy reduction. J Mater Chem A. 2020;8(18):8920‐8926.
oxide cluster. Nano Energy. 2020;78:105211. 150. Fang Y, Xue Y, Li Y, et al. Graphdiyne interface engineering:
134. Arif M, Kumar A, Asim Mushtaq M, et al. Edge‐hosted CoFeB highly active and selective ammonia synthesis. Angew Chem
active sites with graphene nanosheets for highly selective ni- Int Ed. 2020;59(31):13021‐13027.
trogen reduction reaction towards ambient ammonia synthe- 151. Greenlee LF, Renner JN, Foster SL. The use of controls for
sis. Chem Eng J. 2023;473:145368. consistent and accurate measurements of electrocatalytic
135. Shi MM, Bao D, Wulan BR, et al. Au sub‐nanoclusters on ammonia synthesis from dinitrogen. ACS Catal. 2018;8(9):
TiO2 toward highly efficient and selective electrocatalyst for 7820‐7827.
N2 conversion to NH3 at ambient conditions. Adv Mater. 152. Shan W, Liu F, He H, Shi X, Zhang C. The remarkable
2017;29(17):1606550. improvement of a Ce‐Ti based catalyst for NOx abatement,
136. Zhang J, Ji Y, Wang P, Shao Q, Li Y, Huang X. Adsorbing and prepared by a homogeneous precipitation method. Chem-
activating N2 on heterogeneous Au‐Fe3O4 nanoparticles for CatChem. 2011;3(8):1286‐1289.
N2 fixation. Adv Funct Mater. 2020;30(4):1906579. 153. Qing G, Ghazfar R, Jackowski ST, et al. Recent advances and
137. Xiang X, Wang Z, Shi X, Fan M, Sun X. Ammonia synthesis challenges of electrocatalytic N2 reduction to ammonia.
from electrocatalytic N2 reduction under ambient conditions Chem Rev. 2020;120(12):5437‐5516.
by Fe2O3 nanorods. ChemCatChem. 2018;10(20):4530‐4535. 154. Zhou L, Boyd CE. Comparison of Nessler, phenate, salicylate
138. Han J, Ji X, Ren X, et al. MoO3 nanosheets for efficient elec- and ion selective electrode procedures for determination of
trocatalytic N2 fixation to NH3. J Mater Chem A. 2018;6(27): total ammonia nitrogen in aquaculture. Aquaculture. 2016;
12974‐12977. 450:187‐193.
139. Tan H, Ji Q, Wang C, et al. Asymmetrical π back‐donation of 155. Duan GY, Ren Y, Tang Y, et al. Improving the reliability and
hetero‐dicationic Mo4þ‐Mo6þ pairs for enhanced electro- accuracy of ammonia quantification in electro‐and photo-
chemical nitrogen reduction. Nano Res. 2022;15(4):3010‐3016. chemical synthesis. ChemSusChem. 2020;13(1):88‐96.
 28359399, 2024, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/ece2.39, Wiley Online Library on [08/01/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
AN ET AL.
- 257

She received her Master's degree in Physical Chem-

156. Zhao Y, Shi R, Bian X, et al. Ammonia detection methods in
istry from Beijing University of Technology in 2012
photocatalytic and electrocatalytic experiments: how to
improve the reliability of NH3 production rates? Adv Sci. and her PhD degree from Peking University in 2016.
2019;6(8):1802109. Her main research interest is focused on electro-
157. Yang Y, Zhang W, Tan X, Jiang K, Zhai S, Li Z. Atomic‐level catalysis of proton exchange membrane fuel cells and
reactive sites for electrocatalytic nitrogen reduction to other materials applied in energy storage devices.
ammonia under ambient conditions. Coord Chem Rev. 2023; Email: [email protected].
489:215196.
158. Du H‐L, Gengenbach TR, Hodgetts R, MacFarlane DR, Simo-
Pu Hu earned his PhD in Chemical Engineering from
nov AN. Critical assessment of the electrocatalytic activity of
vanadium and niobium nitrides toward dinitrogen reduction
the Qingdao Institute of Bioenergy and Bioprocess
to ammonia. ACS Sustainable Chem Eng. 2019;(7):6839‐6850. Technology, CAS in 2016. Following this, he pursued
159. Kibsgaard J, Nørskov JK, Chorkendorff I. The difficulty of postdoctoral research positions at the University of
proving electrochemical ammonia synthesis. ACS Energy Houston and the University of Florida in the USA. He
Lett. 2019;4(12):2986‐2988. is currently a professor at Wuhan Institute of Tech-
160. Sun J, Chen A, Guan J, et al. Interpretable machine learning‐ nology, focusing his research on developing advanced
assisted high‐throughput screening for understanding NRR
materials for energy storage and conversion, contrib-
electrocatalyst performance modulation between active center
uting to the progress of sustainable energy
and C‐N coordination. Energy Environ Mater. 2023;0:e12693.
161. Li L, Tang C, Yao D, Zheng Y, Qiao S‐Z. Electrochemical ni- technologies.
trogen reduction: identification and elimination of contami-
nation in electrolyte. ACS Energy Lett. 2019;4(9):2111‐2116. Zaicheng Sun received his PhD degree in Chemistry
162. Tang C, Qiao S‐Z. How to explore ambient electrocatalytic from Changchun Institute of Applied Chemistry,
nitrogen reduction reliably and insightfully. Chem Soc Rev. CAS. After that, he started to work as an AvH
2019;48(12):3166‐3180. research fellow at Marburg University in Germany.
163. Chen G‐F, Ren S, Zhang L, et al. Advances in electrocatalytic
Followed by a research associate position at UW,
N2 reduction‐strategies to tackle the selectivity challenge.
Udel, and UNM. He took the professor position at
Small Methods. 2019;3(6):1800337.
164. Nielander AC, McEnaney JM, Schwalbe JA, et al. A versatile Changchun Institute of Optics, Fine Mechanics and
method for ammonia detection in a range of relevant elec- Physics, CAS in 2010. He is currently a professor in
trolytes via direct nuclear magnetic resonance techniques. the Department of Chemistry and Biology, Beijing
ACS Catal. 2019;9(7):5797‐5802. University of Technology. His research focuses on the
165. Suryanto BHR, Du H‐L, Wang D, Chen J, Simonov AN, rational design of photocatalysts with high charge
MacFarlane DR. Challenges and prospects in the catalysis of separation efficiency and fluorescent carbon dots with
electroreduction of nitrogen to ammonia. Nat Catal.
tunable emission and their applications.
2019;2(4):290‐296.
166. Yao Y, Zhu S, Wang H, Li H, Shao M. A spectroscopic study on
the nitrogen electrochemical reduction reaction on gold and
platinum surfaces. J Am Chem Soc. 2018;140(4):1496‐1501.
How to cite this article: An L, Zhang Z, Liu G,
et al. Recent advances in transition metal
AU TH OR B IO G R A P HI ES electrocatalysts for effective nitrogen reduction
reaction under ambient conditions. EcoEnergy.
Li An has been an associate professor of chemistry at 2024;2(2):229‐257. https://doi.org/10.1002/ece2.39
Beijing University of Technology, China, since 2019.