Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Current progress of electrocatalysts for ammonia synthesis

through the electrochemical nitrogen reduction reaction under
ambient conditions

Authors: Anmin Liu, Yanan Yang, Xuefeng Ren, Qidong Zhao,

Mengfan Gao, Weixin Guan, Fanning Meng, Liguo Gao,
Qiyue Yang, Tingli Ma, and Xingyou Liang

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To be cited as: ChemSusChem 10.1002/cssc.202000487

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01/2020
ChemSusChem 10.1002/cssc.202000487

Current progress of electrocatalysts for ammonia synthesis

through the electrochemical nitrogen reduction reaction under

ambient conditions

Anmin Liu 1, a,*, Yanan Yang 1, a, Xuefeng Ren d,*, Qidong Zhao a, Mengfan Gao a,

Accepted Manuscript
Weixin Guan a, Fanning Meng a, Liguo Gao a, Qiyue Yang a, Xingyou Liang a, Tingli

Ma b, c, *

a
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian

University of Technology, China.

E-mail: [email protected], [email protected]

b
Department of Materials Science and Engineering, China Jiliang University,

Hangzhou, 310018, China.

c
Graduate School of Life Science and Systems Engineering, Kyushu Institute of

Technology, 2-4 Hibikino, Wakamatsu, Kitakyushu, Fukuoka 808-0196, Japan.

E-mail: [email protected]
d
School of Ocean Science and Technology, Dalian University of Technology, Panjin,

124221, China.

E-mail: [email protected]

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ChemSusChem 10.1002/cssc.202000487

Abstract

Ammonia (NH3), one of the most important chemicals and carbon-free energy

carriers, is mainly produced by the traditional Haber-Bosh process operated at high-

pressure and high-temperature with massive amounts of energy consumption and CO2

emission. Alternatively, electrocatalytic nitrogen reduction reaction (NRR) to

synthesize NH3 under ambient conditions using renewable energy has recently attracted

Accepted Manuscript
significant attention. However, the competing hydrogen evolution reaction (HER)

significantly reduces the Faradaic efficiency (FE) and NH3 production rate of the

electrocatalytic ammonia synthesis process. The design of high-performance

electrocatalysts with the suppression of the HER for N2 reduction to NH3 under ambient

condition is a crucial consideration for the development of electrocatalytic NH3

synthesis with high FE and NH3 production rate. Five kinds of recently developed

electrocatalysts classified by their chemical compositions are summarized, with a

particular emphasis on the relationship between their optimal electrocatalytic

conditions and NH3 production performance. Conclusions and perspectives are

provided for the future designs of high-performance electrocatalysts for electrocatalytic

NH3 production. The review can give practical guidance for the design of effective

electrocatalysts with high FE and NH3 production rates.

Keywords: Electrocatalytic ammonia synthesis; NRR; High-performance

electrocatalysts; Ambient condition

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ChemSusChem 10.1002/cssc.202000487

Introduction

NH3 is one of the most important chemicals and carbon-free energy carriers with

a worldwide annual production of ∼150 million tons and nearly 80% of the produced

ammonia are used for the fertilizer industry.1-4 With increasing demand from a booming

world population, the supply was insufficient.5-6 Although over 78% of the atmosphere

is composed of nitrogen, it exists in its chemically and biologically unusable gaseous

Accepted Manuscript
form.7 The industrial applied NH3 production technology is still the traditional Haber-

Bosch process, which can synthesize NH3 using high purity streams of nitrogen (N2)

and hydrogen (H2) at high temperatures (400-500 °C) and high pressures (200-300 atm)

in the presence of iron-based and ruthenium electrocatalysts.8-10

Operated at high temperatures and high pressures, the Haber-Bosch process

accounts for about 1.4% of the world's annual energy consumption required in heating

and pumping.11 Furthermore, the H2 with high-purity used in this process is mainly

produced by steam reforming of natural gas from fossil fuels with large amounts of

non-renewable resource consumption and greenhouse gases production.12-14 Therefore,

a green and sustainable strategy for NH3 production is urgently needed. Which is similar

to the plants and bacteria produce NH3 by nitrogen fixation using only N2 and H2O at

mild conditions with low energy consumption for millions of years according to the

following reaction in equation 1.15-19

N2 + 8H+ + 8e- + 16ATP → 2NH3 + H2 + 16ADP + 16Pi (1)

Electrocatalytic NRR is considered as the most promising approach for NH3

production from N2 and H2O at ambient conditions, which can be powered by electric

energy produced from renewable solar or wind energy.20-21 In the process of

electrochemical synthesis of NH3, the required input is N2, water, and electric energy.22

The basic equation for this process can be expressed as displayed in equation 2-4.23-24

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ChemSusChem 10.1002/cssc.202000487

Anode: 3H2O → 3/2O2 + 6H+ + 6e- (2)

Cathode: N2 + 6H+ + 6e- → 2NH3 (3)

Overall: N2 + 3H2O → 3/2O2 + 2NH3 (4)

Based on its reaction process at ambient conditions, electrocatalytic NRR is more

energy-efficient than the Haber-Bosch process.25 Furthermore, by utilizing the inherent

flexibility of the electrochemical system, the production of NH3 from electrocatalytic

Accepted Manuscript
NRR can be carried out in any one using N2 and water as raw materials26-29, as the

electrochemical cell for NRR shown in Fig. 1.30

Fig. 1 Scheme of electrochemical cell for NH3 production by electrocatalytic NRR.30

The electrochemical cell in Fig. 1 revealed that the NH3 production by

electrocatalytic NRR is easier than Haber-Bosch process for its relatively simple

equipment requirements as well as N2, water, and electric energy supply at ambient

conditions. Catalysts are the core components of electrocatalytic NRR systems, which

can prompt the dissociation of N≡N at relatively low energy barrier.31-33 Furthermore,

the existence of competing HER seriously affect the NH3 production, as the two

electron transfer HER has a more significant advantage than the six electron transfer

NRR.34-35 Therefore, screening catalysts with high activity for NRR and suppression of

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ChemSusChem 10.1002/cssc.202000487

HER is the critical factor for the development of electrocatalytic NH3 production.36-37

Considering the important roles of catalysts in electrocatalytic NRR, a summary

of them is shown in this review. Currently, five types of electrocatalysts, metals, metal

compound, carbon material supporting metal or metal compound, metal complex, and

metal-free catalysts have been reported for electrocatalytic NRR at ambient conditions,

as summarized in this review and displayed in Fig. 2.

Accepted Manuscript
Fig. 2 Reported electrocatalysts for electrocatalytic NRR at ambient conditions.

With a particular emphasis on the relationship between their optimal

electrocatalytic conditions and NH3 production performance, perspectives are provided

for the future designs of high-performance electrocatalysts for electrocatalytic NH3

production. The review can give practical guidance for the design of effective

electrocatalysts with high FE and NH3 production rate.

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ChemSusChem 10.1002/cssc.202000487

1 Metal catalyst

1.1 Pure metal catalyst

Precious metals38 and transition metals39-41 were the most widely used pure metal

electrocatalysts for NRR, with unique d-electrons (8 to 10), precious metals exert high

capability to adsorb molecules for electrochemical reaction and satisfy both adsorption

and desorption of new molecules. Moreover, with excellent chemical durability, the

Accepted Manuscript
noble metal catalysts can maintain high catalytic activity for the resistant to corrosion

and participating in the reaction between the electrodes.

Ziqiang Wang et al.42 reported a method for the rapid synthesis of a flower-like Au

catalyst within 5 s. The flower-like Au microstructure (Au flower) are assembled by

staggered nanoplates as building blocks. Under ambient conditions, Au flowers were

found to exhibit high performance for NRR in 0.1 M HCl. The NH3 yield was 25.57 μg

h-1 mg-1cat. at -0.2 V vs. RHE, the FE was 6.05%. The selectivity is 100% and has long-

term durable electrochemical ammonia production. Comparative experiments have

shown that Au flowers have a significant NRR enhancement due to the high dendritic

structures that provide rich active sites. This ultra-rapid method of preparing a high-

performance NRR active catalyst has high application value. There are many researches

on Au as catalyst, the researchers design Au into various forms to improve the catalytic

performance. For example, Xue Zhao et al.43 prepared a novel nano-gold catalyst

(Au/M-BOP) supported on a boron organic polymer by a fast and efficient method. This

material promoted the reduction of electrochemical nitrogen to NH3. At -0.2 V vs. RHE,

the highest ammonia yield and FE were 75.89 μg h-1 mg-1cat. and 10.35%, respectively.

At the same time, Au/M-BOP can work continuously for a long time, and the current

density does not decrease significantly in the cycle test. By comparison, we found that

the same element of the catalyst because of different morphology, often show different

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ChemSusChem 10.1002/cssc.202000487

catalytic performance. This result, some researchers have carried on the experiment to

confirm. Mostafa A. El-Sayed et al.30 used galvanic replacement technology to

successfully prepare Au nanocage, as shown in Fig. 3a and Fig. 3b. The authors

considered the influence of multiply parameters, such as reaction temperature, voltage,

catalyst concentration, shape on the catalytic activity, etc., and finally obtained the

process conditions with the highest ammonia yield and the highest FE. The results

Accepted Manuscript
showed that the ammonia yield and FE increase with increasing catalyst concentration

and reaction temperature. The 0.5 M LiClO4 solution was used as the electrolyte, and

pure nitrogen and water were used as the reaction materials. The maximum ammonia

yield of the hollow gold nanocage was 3.9 μg cm-2 h-1 at -0.5 V vs. RHE voltage. At a

voltage of -0.4 V vs. RHE, the hollow gold nanocage achieved a maximum FE of 30.2%.

The catalyst with higher FE content (Au nanocage) is prepared by using Ag

nanoparticles as the template. Ag, a common noble metal, has also been shown to

catalyze NRR. Wen-Yan Gao et al.44 successfully prepared Ag triangular nanoplates

(AgTPs) and used them as NRR catalysts. At -0.25 V vs. RHE, the AgTPs catalyst

achieved a FE of 25%, with an NH3 yield of 58.5 mg h-1 gAg-1, which is more efficient

than circular Ag nanoparticles. The main reason is that AgTPs with sharp edges have

more atoms anchored at sharp edges and corners. Besides, potassium cations act as a

co-catalyst to promote nitrogen reduction.

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ChemSusChem 10.1002/cssc.202000487

Accepted Manuscript
Fig. 3 a) TEM image of AuHNCs. The average edge length of the AuHNCs is 35 nm. b) Ammonia
yield rate and FE at various potentials30. c) Fabrication and structure of catalysts. a synthetic
procedure of typical Cu/PI catalyst.45
Table 1. Catalytic performance of Au catalysts with different morphologies.

No. Au shape E (V) Ammonia yield FE (%) Ref.

1 flowers -0.2 V vs. RHE 25.57 μg h-1 mg-1 6.05 42

2 nano-Au -0.2 V vs. RHE 75.89 μg h-1 mg-1 10.35 43

3 nanocage -0.4 V vs. RHE 2.35 μg cm-2 h-1 30.2 30

4 rods -0.4 V vs. RHE 0.99 μg cm-2 h-1 10.69 30

5 spheres -0.4 V vs. RHE 1.19 μg cm-2 h-1 11 30

6 cubes -0.4 V vs. RHE 1.27 μg cm-2 h-1 11.35 30

In addition to the well-known Au and Ag, Ru, Pd, Rh, Pt-based catalysts with the

highest activity in HER, and some rare metals46 can also be used for NRR. Among them,

as far as NRR is concerned, the precious metal Ru is also a hot research subject. Seoin

Back and Yousung Jung47 theoretically investigated the electrochemical NRR

mechanism to produce NH3 on the Ru catalyst. Moreover, all possible N-N dissociation

steps in the NRR, as well as traditional binding and dissociation pathways, were

evaluated. The calculated free energy map reveals that the intermediate dissociation

path requires a thermodynamic limit potential (0.71 V) close to the association path

(0.68 V). HER reduces the number of active centers on the catalyst and exerts a negative

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ChemSusChem 10.1002/cssc.202000487

impact on NRR. The high product selectivity of NH3 observed on the Ru electrode is

attributed to the difficulty in desorbing *HNH due to intense adsorption energy.

Moreover, the size of Ru nanoparticles has a certain influence on the catalytic

performance, and the study by Camila Fernández et al.48 explained this phenomenon.

The migration of H atoms from larger particles to smaller particles provides the active

center of N2 dissociative adsorption for small Ru particles. However, the release of the

Accepted Manuscript
active center is prolonged and is a determining step in the rate of reaction on small

particles. At the same time, larger Ru particles reduce the energy required for hydrogen

activation. These activated H atoms are capable of migrating along the catalytic surface

and are capable of contacting smaller adjacent Ru particles, thereby promoting

hydrogenation of the adsorbed NHx species and release of the active center. The use of

metal Ru alone in experimental research is relatively rare, but theoretical research has

laid a foundation for future experimental research. Research on other precious metals,

such as, Hui-Min Liu et al.49 first synthesized a surfactant-free ultra-thin Rh nanosheets

(RhNNs) (about 1 nm) assembly and acted as an effective electrocatalyst for NRR at

ambient temperature and pressure. The higher specific surface area and excellent

electronic structure contribute to the good catalytic activity of surfactant-free RhNNs,

and the ammonia yield is 23.88 μg h-1 mg-1cat. At the same time, RhNNs has excellent

selectivity and durability to NRR in an alkaline medium. In addition to the contribution

to high-efficiency NRR electrocatalysis. Jun Wang, et al.50 studied the efficient

electroreduction of N2 to NH3 on palladium nanoparticles in phosphate buffered saline

(PBS). At a potential of 0.1 V vs. RHE, the palladium nanoparticles have high activity

and selectivity, the yield of NH3 is about 4.5 μg h-1 mg-1Pd , and the FE is 8.2%.

Comparative experiments indicate that PBS neutral electrolyte has an effective

inhibitory effect on HER, and the NRR activity of Pd is significantly higher than other

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ChemSusChem 10.1002/cssc.202000487

catalysts such as Au and Pt. Meanwhile, DFT calculations showed that α-PdH can

activate N2 through a more favorable thermodynamic Grothuss-like hydride transfer

pathway, which reduces the energy barrier of N2 hydrogenation to *N2H while facilitate

NRR.

Because of the high price of precious metals, researchers turn to study some non-

precious metals. Non-precious metals in the NRRR, not only more research, but also

Accepted Manuscript
has a greater potential. More typically, Yun-Xiao Lin et al.45 prepared polyimide (PI) by

sol-thermal method and further polycondensed at different temperatures (300 °C /

400 °C / 600 °C) to adjust the degree of conjugation, and finally by wet impregnation

Cu nanoparticles are deposited on the surface of the nanoflower, as shown in Fig. 3c.

By adjusting the electron density of the nano-copper nanoparticles, the HER activity is

inhibited, and the NRR catalytic activity is enhanced. The electrocatalytic experiment

of the catalyst was carried out in 0.1 M KOH solution, and the LSV curve indicated the

presence of NRR activity in the catalyst. The 15N isotope labeling experiment confirmed

that Cu/PI-300 could catalyze the reduction of N2 to NH3. At a potential of -0.3 V vs.

RHE, the FE reached a maximum of 6.56%. The highest NH3 yield was 17.2 μg h-1 cm-
2
. Both experimental and density functional theory (DFT) simulated results demonstrate

that the low electron density of Cu nanoparticles plays a key role in activating N2 and

increasing NRR activity. This strategy of inducing electron depletion provides a new

path for rational design of inexpensive NRR catalysts with high selectivity and high

activity.

Mo was the most used transition metal for NRR in forms of metal, oxides, and

sulfides. Not just metal Mo, but Jakob G. Howalt and Tejs Vegge51 have shown that

(partial) oxidation and molybdenum nitride nanoclusters can be reactivated by

electrochemical reduction for ammonia production. They theoretically studied the

10

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ChemSusChem 10.1002/cssc.202000487

effect of oxygen adsorption and reduction on the NRR of Mo nanoclusters. DFT was

used to calculate the adsorption and reduction of oxygen on octahedral Mo13

nanoclusters. Under low oxygen coverage, nitrogen molecules can be adsorbed onto the

surface through an association mechanism and electrochemically ammoniated by an

association mechanism. Dashuai Yang et al.52 has achieved electrochemical reduction

of N2 on a (110) oriented Mo nanofilm. When the overpotential is 0.14 V, the highest

Accepted Manuscript
FE is 0.72%. When the applied potential is -0.49 V vs. RHE, the maximum NH3 yield

reaches 3.09×10-11 mol s-1 cm-2. Mo (110) oriented nanoparticle clusters are most

advantageous for NRR. These Mo (110) nanoclusters have higher sensitivity and

selectivity and are superior to the reported NRR water-based electrocatalysts.

1.2 Alloy catalyst

Because of the interesting synergy effect between different metals on electronic

effects and geometric effects in alloy catalyst, alloy-based catalysts may exhibit more

outstanding activity and selectivity for NRR.53 Not only electrochemical ammonia

synthesis, electrocatalytic hydrogen production, fuel cells, etc. are often used because

of the unique properties of the alloy. Examples are Pt-based alloys54-56, Pd-based alloys,

and especially Ru-based alloys. For example, Ziqiang Wang et al.57 synthesized multi-

layer PdRu porous nanostructures (PdRu BPNs) by rapid reduction method, and

experimentally studied the efficient electrochemical synthesis of ammonia on three-

dimensional bimetals. PdRu BPNs provide sufficient active sites with good electronic

effects, and the NRR activity of PdRu BPNs can be greatly enhanced by a possible

distal hydride mechanism, as shown in Fig. 4a. In an acidic solution, the NH3 yield of

PdRu BPNs is 25.92 μg h-1 mgcat-1, which is superior to the single metal Pd and Ru

nanostructures (Fig. 4b and 4c). Such synthesis method offers a feasible way to prepare

tunable porous metal nanostructure, promoting the convenience and effectiveness of

11

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ChemSusChem 10.1002/cssc.202000487

NH3 production. Alloy catalysts58-59 have good catalytic activity because of their

synergistic effect. Just like the Ru-Pt (1:1) alloy prepared by Alex Schechter5 et al., the

ammonia yield is 5.110-9g s-1 cm-2 and the FE was 13.2% under 0.123 V vs. RHE. The

high ammonia yield obtained in this experiment is due to the synergistic effect of the

alloy.

Accepted Manuscript
Fig. 4 a) Possible NRR pathway for NH3 synthesis over the PdRu BPNs. b) NH3 yield and

corresponding FE of the PdRu BPNs at the given potentials. c) NH3 yields of different catalysts

with different composition at -0.1 V57.

The results show that the Ru-based catalyst has a good NH3 yield and FE in the

synthesis of ammonia from nitrogen. In addition to Ru-based catalysts, Pd-based alloys

have been extensively studied. Fangjie Pang et al.60 designed and fabricated a

nanoporous PdCu alloy with a 3D graded interconnected pore structure by a two-step

dealloying process and used for electrocatalytic NRR with high NH3 yield at room

temperature and atmospheric pressure. The Pd3Cu1 alloy has a large surface area and a

high active site density, and a NH3 yield of 39.9 μg h-1 mg-1cat. is obtained at a potential

of -0.25 V vs. RHE. Even at a potential of -0.15 V vs. RHE, the NRR yield of the Pd3Cu1

alloy exceeded 10 μg h-1 mg-1cat. Moreover, the structural integrity of the Pd3Cu1 alloy

makes it a highly stable NRR electrocatalyst that retains 100% of its original activity

for 18 h. Fangjie Pang et al.61 prepared a Pd1Ag1 alloy with a graded pore structure by

a two-step de-alloying process. The hierarchical porous structure of the catalyst has a
12

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ChemSusChem 10.1002/cssc.202000487

large number of low coordination surface atoms, which is beneficial to improve the

catalytic activity of NRR. In 1 M KOH, the NH3 yield of the nanoporous Pd1Ag1 alloy

is up to 24.1 μg h-1 mg-1cat. In addition, the Pd1Ag1 catalyst has good NRR catalytic

stability in a 24 h electrolysis operation. In addition, some studies have shown that the

catalyst activity can be further increased by using the synergistic effect of the two

elements and loading the alloy on the support. Wenzhi Fu et al.62 successfully deposited

Accepted Manuscript
bimetallic Pd-Co alloy nanoparticles on CuO nanosheets. Due to the synergistic effect,

the bimetallic Pd-Co catalyst has higher catalytic activity than the single metal Pd-Co

catalyst. In 0.1 M KOH solution, Pd-Co/CuO nanostructured catalyst is an effective

catalyst for NRR, and the highest ammonia yield is 10.04 μg h-1 mg-1cat. with FE of

2.16%. Also, the Pd-Co/CuO catalyst also has good stability and recyclability. The

catalyst also performed well in the Suzuki-Miyaura coupling reaction compared with

single metal material at room temperature without an inert atmosphere and any toxic

solvent.

As well as single-metal catalysts, gold and silver catalysts have been studied.

Qiwen Zhang et al.63 used Ag nanowires as a template to prepare AgAu nanotubes by

electrical substitution method, and systematically studied the effect of Ag-based alloy

nanotubes on NRR catalytic activity. It was found that AgAu nanotubes with an atomic

ratio of 2:1 had the most considerable improvement in NRR catalytic activity.

Specifically, the NH3 yield and FE of Ag2Au1 nanotubes were 21.7 μg h-1 mg-1cat. and

3.8%. The theoretical calculation results show that the negative ion characteristics of

Au atoms in Ag2Au1 alloy are beneficial to the adsorption and activation of N2, thus

improving the NRR catalytic performance. Meanwhile, Ag2Au1 nanotubes exhibited

higher catalytic stability during 18 h of electrolysis. A bimetallic electrocatalyst

prepared by replacing a transition metal with one of the noble metals also enhanced the

13

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ChemSusChem 10.1002/cssc.202000487

NRR performance. Most typically, Zhong-Hua Xue et al.64 significantly increased the

FE of the catalyst by constructing Ni and Au nanoparticles. The existence of Au and Ni

metals was found by theoretical simulation methods, which promoted the adsorption

and dissociation of molecular N2 on the active center of electron-rich Au, and the FE of

N was significantly improved. In the 0.05 M H2SO4 solution, the highest NH3 yield was

7.41 μg h-1 mg-1cat. at -0.14 V vs. RHE, and the highest FE was 67.8%. Both

Accepted Manuscript
experimental and theoretical results illustrate that electron enrichment of Au

nanoparticles plays an critical role, which accept electrons from Ni nanoparticles,

facilitate the adsorption and activation of N2 molecules and produce ammonia. For the

above two studies, the design of the catalyst is more important in the catalytic NRR.

The synergistic action of the two-component alloys increases the catalytic activity.

Can the three-component alloys65 further enhance the catalytic activity? Many

researchers have explored this issue in both theoretical and experimental studies. For

example, Magdalena Zybert et al.66 proposed a new catalytic system based on cobalt.

Unsupported Cobalt Catalyst (La or Ba) and double promotion (La and Ba) were

prepared in an NH3 synthesis reaction under industrial synthesis conditions.

Characterization studies have shown that a certain structural promotion is promoted. It

improves the surface of the catalyst precursor and prevents sintering during calcination.

However, in a single promotion system (La or Ba), cockroaches are less effective. At

the same time, ruthenium has a negative effect on the reduction of cobalt oxide, but the

addition of ruthenium promoter will reduce the negative impact of La to a certain extent.

The synergistic effect of cobalt with cerium and lanthanum can increase the activity of

the catalyst in the synthesis of NH3. Furthermore, the catalytic activity of alloy catalysts

can be adjusted by controlling their composition. Magdalena Zybert et al.67 studied the

effect of cerium content (La content of 0 ~ 55.7%) and Ba (constant content, about 1.5

14

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ChemSusChem 10.1002/cssc.202000487

mmol gCo-1) on the ammonia synthesis performance of cobalt catalyst. The study found

that cerium is an effective structure promoter, and the increase of cerium content

improves the structural parameters of the catalyst precursor while reduces the

uniformity of the catalyst. However, the increase in the activity of the Co/La/Ba catalyst

is caused by an increase in the surface of the active phase. With the increase of the La

content, the specific surface area of the active phase (Co) increases, thereby increasing

Accepted Manuscript
the activity of the catalyst. The introduction of medium and large amounts of rhodium

(≥ 7.4 wt.%) significantly prolonged the time required for complete reduction of the

Co/La system studied. It can be concluded that the properties of alloy catalysts are

closely related to the kinds and proportions of elements, so the research on this kind of

catalysts should be systematic.

The electrocatalytic NRR of noble metals shows relatively high FE, especially on

Au-based catalysts, which can reach over 20% on Ag triangular nanoplates. Especially

on Au6/Ni nanoparticles in 0.05 M H2SO4 with a reaction potential of -0.14 V vs. RHE

to catalyze the conversion of N2 to NH3 to obtain a high FE of 67.8%, making Au6/Ni

nanoparticles the most promising electrocatalytic NRR catalyst. However, nanoporous

Pd3Cu1 alloy (1.22% at -0.25 V vs. RHE), Mo nanofilm (0.72% at -0.49 V vs. RHE)

and PdRu alloy (1.53% at -0.1 V vs. RHE), considering their low FE, it is not ideal

catalysts.

In general, when single metals are used as NRR electrocatalysts, precious metal

catalysts, especially Au catalysts, have higher FE and ammonia yield than non-precious

metal catalysts. In addition, the same metal catalyst is also greatly affected by

morphology, has more sharp edges and morphologies with specific surface area, can

obtain more active sites, and has stronger activity. When the alloy is used as the NRR

catalyst, similar to the single metal catalyst, the Au-based alloy catalyst has more

15

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ChemSusChem 10.1002/cssc.202000487

advantages. By comparing the activity of different alloy catalysts, it is found that Pd-

based alloy catalysts are at a disadvantage in terms of electrocatalytic NRR.

2 Metal compound catalyst

2.1 Metal sulfide catalyst

Inspired by the structure and composition of nitrogenases, a range of metal sulfides

were used as NRR electrocatalysts. These non-precious metal electrocatalysts have

Accepted Manuscript
profound values on NRR research. Mark Dorr et al.68 reports a method for synthesizing

NH3 using hydrogen sulfide as a reducing agent, newly precipitated iron sulfide as a

catalyst, and nitrogen as a raw material. The total reaction is: N2(g) + 3FeS + 3H2S(aq)

→ 3FeS2(s) + 2NH3(g). The driving force for the entire reaction is hydrogen generated

during the reaction of iron sulfide and hydrogen sulfide. However, the yield of this

method is meager, with 3 mol of iron sulfide as the raw material, and the ammonia

water yield is only 0.1% (3 mmol). Transition metal sulfides have unique band structure,

semiconductor or superconducting properties, and excellent mechanical properties for

the application in many fields. Among them, an electrocatalyst represented by MoS2

exhibits excellent NRR activity.69 Based on theoretical prediction, Ling Zhang et al.70

first studied the MoS2 catalyzed N2 reduction reaction under normal temperature and

pressure, as shown in Fig. 5a and Fig. 5b. Electrochemical tests have shown that MoS2

is an active NRR electrocatalyst with high selectivity under ambient conditions. The

catalyst has a NH3 yield of 8.08×10-11 mol s-1 cm-2 and a FE of 1.17% in a 0.1 M Na2SO4

at a potential of -0.5 V vs. RHE. Even under acidic conditions, MoS2 is still an active

substance of NRR when a strong hydrogen evolution reaction occurs. Xianghong Li et

al.71 studied the NRR performance of a multi-defective MoS2 nanocatalyst, shown in

Fig. 5c and Fig. 5d. The MoS2 nanocatalyst is an electrocatalyst with high activity,

durability and electrochemical stability. In addition, the catalyst has 100% selectivity

16

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ChemSusChem 10.1002/cssc.202000487

under ambient conditions. The NH3 yield of the catalyst was 29.28 µg h-1 mg-1cat. and

the FE was 8.34% in 0.1 M Na2SO4 electrolyte at a potential of -0.40 V vs. RHE. This

catalytic performance is much higher/better than the defect-free MoS2 nanocatalyst

(13.41 µg h-1 mg-1cat. and 2.18%). DFT calculations show that the barrier of the high-

defect MoS2 nanocatalyst (0.60 eV) is lower than the barrier of the defect-free catalyst

(0.68 eV).

Accepted Manuscript
Fig. 5 a) SEM images for MoS2/CC. b) Average NH3 yields and FEs of MoS2/CC at different

potentials.70 c) SEM image for DR MoS2 nanoflower. d) Average NH3 yields and FEs for DR

MoS2/CPE at a series of potentials71.

Luis Miguel Azofra et al.72 reported that Fe deposited on MoS2 nanosheets has

high selectivity to N2 for chemisorption. The DFT calculations show that Fe atoms

become active species when deposited on MoS2 2D sheets, mimicking FeMoco. In

addition, the catalyst is characterized by effective adsorption of N2 through Nlp →

LV(Fe) σ- donation from N2 to the Fe center and complementary d(Fe) → π*(N2) π-

back-donation, which is a spontaneous and effective process. Therefore, the material is

fixed relative to H2O or CO2 and can spontaneously and selectively capture N2. In the

process of catalytic nitrogen conversion to NH3 under normal temperature and pressure,

the limiting step is the first step H+/e- transfer, and the activation barrier is 1.02 eV. The
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ChemSusChem 10.1002/cssc.202000487

innovative works mentioned above provide some new ideas for exploring the transition

metal sulfide as high-performance NRR catalyst for the electrochemical synthesis of

NH3. At the same time, it is worth noting that the series of excellent properties of

transition metal sulfides enable them to be broadly applied in the fields of

electrochemistry and related areas. Further studies of transition metal sulfides for NRR

are urgently needed.

Accepted Manuscript
2.2 Metal oxide catalyst

Metal oxides73 are widely used in chemical researches. Metal oxides have been

widely used in the field of catalysis as a primary catalyst, a co-catalyst and a carrier.

One of an effective way to enhance catalytic performance is reducing metal oxides size

to nano-meter level. Kun Jia et al.74 reported a highly efficient NRR electrocatalyst.

Carbon-doped TiO2 nanoparticles have good selectivity. Under the condition of -0.7 V

vs. RHE, 0.1 M Na2SO4 was used as the electrolyte solution, the NH3 yield was 16.22

μg h-1 mg-1cat., and the FE was 1.84%. As a possible by-product of the NRR test,

hydrazine (N2H4) was tested by the method of Watt and Chrisp. N2H4 was not detected

at various potentials, indicating that C-TiO2 has good selectivity as an NRR

electrocatalyst. In addition, the catalyst also showed sound stability in electrolysis and

cycle tests. Rong Zhang et al.75 found that the TiO2 alloy array (TiO2/Ti) on the Ti plate

can effectively achieve N2 electrochemical conversion under ambient conditions. At a

potential of -0.7 V vs. RHE, the yield of TiO2/Ti is higher when tested in 0.1 M Na2SO4,

which is about 9.16×10-11 mol·s-1·cm-2with 2.5% of FE. This higher reduction activity

is due to the increased vacancies in the electrochemical reduction of N2 adsorption and

activation. The electrolyte was stained with p-C9H11NO indicator. The UV-visible

absorption spectrum after NRR did not detect by-product (N2H4) at all potentials,

indicating that the TiO2/Ti catalyst has good selectivity to NRR. After the cycle test, the

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ammonia yield and the FE decreased slightly, which may be related to the decay of the

electrode for a long time. The adjustment of the particle size does improve the catalytic

performance to some extent. In addition to this method, using oxide as a carrier and

supporting some precious metals is also a good way to promote NRR. For example，

Miao-Miao Shi et al.76 was successfully prepared by a simple method to prepare a noble

metal Au (Au loading of 1.542%) sub-nano clusters (≈ 0.5 nm) embedded on the surface

Accepted Manuscript
of TiO2. The application of this catalyst to electrocatalytic NRR under ambient

conditions was also studied. The results show that the NRR yield is high and the yield

is stable (NH3 yield: 21.4 µg h-1 mg-1cat., FE is 8.11%) and has good selectivity at -0.2

V (no formation of N2H4). Compared to RHE, the best effect of N2 fixation under

ambient conditions is much higher, even comparable to yield and activation energy at

elevated temperatures and/or pressures. This is mainly because the isolated noble metal

active center dispersed on the oxide support provides a clear system for promoting NRR.

Moreover, the special structure of the atomic Au cluster promotes other essential

reactions in addition to promoting NRR.

In the past few decades, nitrogen reduction studies have a wide temperature range,

but how to achieve high-efficiency ammonia synthesis under environmental conditions

remains a major problem. In recent years, many researchers have started with a variety

of different types of catalysts to find ways to synthesize ammonia under ambient

conditions. Like the Fe-based catalysts of the Haber-Bosh process, in the field of

electrocatalytic NRR, many researchers have also designed iron oxide to increase their

activity against nitrogen reduction. Jimin Kong et al.77 system studied the basic behavior

and catalytic activity of nano-γ-Fe2O3 electrochemically synthesizing NH3 at low

temperature (< 65 °C) and low pressure. The optimum reaction conditions were as

follows: in 0.1 M KOH electrolyte, the γ-Fe2O3 electrode had a FE of 1.9% and an

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ChemSusChem 10.1002/cssc.202000487

ammonia yield of 12.5 nmol h-1 mg-1 at a potential of 0.0 V vs. RHE. However, at a

negative potential, the selectivity for N2 reduction is reduced by the HER. When the γ-

Fe2O3 nanoparticles are coated on the porous carbon paper to form the MEA electrode,

a microelectrode is generated between the nano γ-Fe2O3 and the carbon. The activity of

N2 reduction is significantly increased and can be as high as 55.9 nmol h-1 mg-1. The

improvement of the catalytic utilization of γ-Fe2O3 nanoparticles on porous carbon

Accepted Manuscript
paper may be one of the reasons for improving its activity. The results of 25 h durability

test showed that the renormalization and area normalized N2 reduction activity of γ-

Fe2O3 decreased from 35.9 to 14.8 nmol h-1 mg-1 and decreased from 0.105 to 0.043

nmol h-1 cm-2act, respectively. Pure iron oxide is difficult to achieve a good catalytic

efficiency. If some other substances are added, the efficiency can be improved to a

certain extent. Qin Liu et al.78 reported that spinel Fe3O4 nanorods are a highly efficient

and durable NRR electrocatalyst on Ti mesh (Fe3O4/Ti). When 0.1 M Na2SO4 was used

as the electrolyte solution, the Fe3O4/Ti catalyst obtained a higher FE value at a potential

of -0.4 V vs. RHE. The FE is 2.6% and the NH3 yield is 5.6×10-11 mol s-1 cm-2. Moreover,

six cycles and 20 h stability test results show that this Fe3O4/Ti catalyst has strong long-

term electrochemical durability. Another example, Lin Hu et al.79 developed a Fe/Fe3O4

catalyst for electrochemical synthesis of ammonia. The catalyst was prepared by

oxidizing Fe foil in flowing O2 at 300 °C and then electrochemically reducing it at a

potential of -0.5 V vs. RHE until a steady state was reached. At a potential of -0.3 V vs.

RHE, the Fe/Fe3O4 catalyst has a FE of 8.29% in phosphate buffer, which is about 120

times that of the original iron foil. The Fe/Fe3O4 composite oxide is a high-efficiency

electrocatalyst for NRR in the environment. The NRR selectivity of Fe/Fe3O4 catalysts

is also higher than that of Fe, Fe3O4 and Fe2O3 nanoparticles. Compared with iron foil,

NRR activity is increased by 9 times, and HER is effectively inhibited, thereby

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ChemSusChem 10.1002/cssc.202000487

enhancing selectivity. At the same time, comparative studies on Fe/Fe oxide samples

prepared at different oxidation temperatures show that the NRR catalytic performance

is also related to the Fe/Fe oxide ratio. In general, when iron-based catalysts are used

to electrocatalyze the synthesis of ammonia from nitrogen, FE needs to be further

improved.

γ-Al2O3 produced by calcination of aluminum hydroxide has strong adsorption and

Accepted Manuscript
catalytic activity and can be used as adsorbent and catalyst. Camila Fernández et al.80

prepared Ru/γ-Al2O3 catalysts with different particle size distributions by wet

impregnation method, colloid method and microemulsion method. Studies have shown

that Ru-loaded nanoparticles present better catalytic properties. Under mild reaction

conditions, larger ruthenium nanoparticles can activate and transfer hydrogen atoms

more effectively in the range of 2-10 nm, releasing the active center of activated N2,

thereby promoting ammonia synthesis reaction. Moreover, with the wide distribution

of sizes, it is possible to promote good contact and cooperation between large particles

and small particles, and to obtain higher activity by using synergistic effects. It can be

seen that Al2O3 can catalyze the conversion of nitrogen into ammonia, and the addition

of Ru makes the catalytic activity of Al2O3 improved. In experimental research,

Yasunori Inoue et al.81 used a CaH2 as a reducing agent to hydrolyze a 12CaO·7Al2O3

electronic compound (HT-C12A7:e-) with high specific surface area and characterized

it, displayed in Fig. 6a. The specific surface area of the hydrothermal synthetic material

(ca. 20 m2 g-1) is higher than that of the conventional solid phase C12A7 electrical

material (SP-C12A7:e-, ca. 1 m2 g-1). Under the optimal conditions, both catalysts have

catalytic activity, but the ammonia synthesis rate of Ru/HT-C12A7:e- is twice that of

Ru/SP-C12A7:e-. The apparent activation energy with high electron density and high

specific surface area is very similar to Ru/HT-C12A7:e- and Ru/SP-C12A7:e-,

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ChemSusChem 10.1002/cssc.202000487

indicating that the electron donation ability of HT-C12A7:e- is sufficiently strong in Ru

catalyst. It can promote N2 dissociation. The high catalytic performance of Ru/HT-

C12A7:e- is attributed to its efficient electron injection into highly dispersed Ru

nanoparticles. TEM and CO chemisorption test results show that Ru nanoparticles have

higher dispersion on HT-C12A7:e- than SP-C12A7:e-, and the enhancement of

ammonia synthesis is also greater.

Accepted Manuscript
Fig. 6. a)Production of Ru/HT-C12A7:e- and its catalytic mechanism for NRR.81 b) SEM images

of SnO2/CC. c) NH3 yields and FEs of SnO2/CC with alternating 2 h cycles between N2-saturated

and Ar-saturated electrolytes at -0.7 V under ambient conditions.82 d) Illustration of the fabrication

of BVC-A and BVC-C NRR electrocatalysts83.

Iron oxide and alumina are relatively common oxides. Molybdenum oxides, like

sulfides, can be used for catalysis, but the catalytic performance is not as good as that

of molybdenum sulfides. For example, Zao Wang et al.84 found that MnO particles are

a highly active catalyst with high selectivity. In 0.1 M Na2SO4 electrolyte solution, the

ammonia yield can reach 1.11×10-10 mol s-1 cm-2 and FE is 0.1% at a potential of -0.39

V vs. RHE. In the 10 cycles of MnO/TM, the NH3 yield and FE change were negligible,

which means that the catalyst has good electrochemical and structural stability. DFT
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ChemSusChem 10.1002/cssc.202000487

calculation results show that compared with H, the adsorption energy of N on MnO

(200) surface is lower, and *N2 → *N2H is the decisive step of nitrogen reduction

reaction. Jingrui Han et al.85 experiment studied the efficiency of MoO3 nanosheets for

electrochemical synthesis of ammonia under ambient conditions. As a highly efficient

non-precious metal catalyst, it has good selectivity for electrochemical nitrogen fixation

at room temperature and pressure. The catalyst had good NRR activity in 0.1 M HCl,

Accepted Manuscript
the highest ammonia yield was 4.80×10-10 mol s-1 cm-2 (29.43 μg h-1mg-1cat.), and the

FE was 1.9%. DFT calculations show that the outermost Mo atom is the active center

for efficient adsorption of N2. In addition, the electrochemical stability test results show

that the catalyst also has high electrochemical stability and durability. In addition, as an

excellent transparent conductive material, tin oxide is also used in electrocatalysis

because of its excellent conductivity and stability. Ling Zhang et al.82 grown cubic

submicron SnO2 particles on carbon cloth (SnO2/CC) as the SEM image in Fig. 6b

showed, and the used it as an NRR electrocatalyst. SnO2/CC has a higher current

density in a saturated solution of N2, indicating that SnO2/CC has an activity of

catalyzing NRR. In 0.1 M Na2SO4 solution, electrochemical tests showed that the NH3

yield of SnO2/CC was as high as 1.47×10-10 mol s-1 cm-2 at a potential of -0.8 V vs.

RHE. The FE of SnO2/CC was2.17% at -0.7 V vs. RHE (Fig. 6c), which is superior to

most of the reported water-based NRR electrocatalysts. The chronoamperometry results

show that the current densities at different potentials remain relatively stable, indicating

that SnO2/CC has good stability.

The d-electron layer of the metal cations in the transition metal oxide is liable to

lose or capture electrons, demonstrating a strong redox performance. Moreover, due to

its high heat resistance and anti-toxicity, as well as its sensitivity and thermal sensitivity,

it is more conducive to the regulation of catalyst performance, so it is more widely used.

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ChemSusChem 10.1002/cssc.202000487

In addition, Huitong Du et al.86 found that Cr2O3 nanofibers are highly efficient NRR

catalysts with excellent selectivity under ambient conditions. The catalyst has a higher

ammonia yield and FE in 0.1 M HCl. The highest ammonia yield was 28.13 μg h-1 mg-
1
cat., the highest FE was 8.56%. In addition, it was observed in the 6-cycle test that the

ammonia yield and the change in FE were negligible. This indicates that the catalyst

has strong electrochemical durability. Jingrui Han et al.87 researched Nb2O5 nanofiber

Accepted Manuscript
is a non-precious metal NRR electrocatalyst. The NRR catalyst catalyzes the

conversion of N2 to NH3 with higher activity and selectivity. When Nb2O5 nanofibers

were at a reversible hydrogen electrode of -0.55 V vs. RHE and 0.1 M HCl was used as

the electrolyte, the average NH3 yield was higher (43.6 µg h-1 mg-1cat.) and the highest

FE was 9.26%. In addition, the results of electrolysis and cycle tests indicate the high

stability of Nb2O5 nanofibers. Density functional theory calculations show that Nb2O5

nanofibers are considered to be an excellent electrocatalyst for artificial nitrogen

fixation at room temperature and atmospheric pressure. In addition to pure metal oxides,

Chade Lv et al.83 studied the performance of Bi4V2O11/CeO2 crystal phase hybrid (BVC-

C) and Bi4V2O11/CeO2 amorphous phase hybrid (BVC-A) as electrocatalyst for

electrochemical synthesis of ammonia as displayed in Fig. 6d. Under ambient

conditions, BVC-A has good electrocatalytic NRR performance, the average yield (NH3:

23.21 μg h-1 mg-1cat.) is higher, and the FE is 10.16%, which is better than

Bi4V2O11/CeO2 crystal phase hybrid (BVC-C). Since amorphous Bi4V2O11/CeO2 has

apparent defects, it has more active centers. At the same time, CeO2 is not only a trigger

for inducing an amorphous structure, but also a dominating fact to facilitate the

formation of an energy band alignment with Bi4V2O11 to achieve the rapid transfer of

interface charge. Therefore, the BVC-A type electrocatalyst has excellent NRR

performance. From the above studies on metal oxides, the FE is basically below 10%,

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ChemSusChem 10.1002/cssc.202000487

and finally the FE of the hybrid catalyst reaches 10.16%. From this point of view, metal

oxide catalysts need to strengthen the design of catalysts in the electrocatalytic

synthesis of ammonia to improve the catalytic performance.

2.3 Metal nitride catalyst

Younes Abghoui and Egill Skúlason88 conducted DFT calculation on a new class

of materials and studied nitrogen activation and electrochemical ammonia formation at

Accepted Manuscript
room temperature. The research mainly focus on the surface of the NaCl-type structure

(111) of transition metals such as Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Mo, HF, Ta, W, Re. The

authors explicitly considered the hydrogen production of all of these candidate

substances and eliminated the limitations of proton adsorption that only occurred on

surface nitrogen atoms. Therefore, most of these candidate materials exhibited the

ability to inhibit hydrogen production, with almost complete release of hydrogen while

metal surface proves the contrary. It was found that VN, CrN and MnN have the lowest

onset potential (from -0.8 V to -0.5 V vs. SHE) in all nitrides studied here, but NbN,

MoN and WN have relatively low onset potentials (about -1.1 V vs. SHE). Evaluation

of the possibility of catalyst decomposition and catalyst regeneration indicates that

MnN and WN are susceptible to poisoning in electrochemical media, and MnN also has

a very endothermic reaction step to adsorb N2 to the N-vacancy, and those N-vacancies

cannot be regenerated. In calculating the free energy activation barriers of the two

processes, it was found that only NbN is a promising candidate material that can

withstand the catalytic cycle and perform N2 activation and ammonia generation during

operation.

As a new type of functional material with high melting point and hardness, good

thermal stability and mechanical stability, as well as excellent corrosion resistance,

metal nitride89 has been widely used in high temperature resistance, abrasion resistance

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ChemSusChem 10.1002/cssc.202000487

and chemical corrosion resistance.90-92 The molybdenum nitride has been found to have

good capacitance characteristics and can be used for the electrode material of the

capacitor. In addition, like molybdenum sulfide research, molybdenum nitride is also

widely used for NRR at ambient conditions. Na Liu et al.93 prepared a molybdenum

nitride material in HZSM-5 by reacting ammonia with MoNx at 973 K, and MoNx was

pre-exchanged into the channel of HZSM-5. Quantitative temperature-programmed

Accepted Manuscript
oxidation measurements showed that the Mo/N ratio of MoNx species in HZSM-5 was

close to two. In the ammonia synthesis reaction, the zeolite sites occupied by

molybdenum during the solids exchange process are due to the formation of highly

dispersed molybdenum nitride (dispersion > 90%) in the zeolite. Moreover, MoNx

substances are very active in ammonia synthesis, and the catalytic activity is much more

stable than bulk Mo2N. Due to the interaction between MoNx and the charged zeolite

framework, the largest dispersed small MoNx species in ZSM-5 is more stable than

conventional bulk Mo2N to prevent oxidation. At equivalent pressure, the interaction of

the nitrogen molecules with the internal electric field of the zeolite enhances the

reaction of ammonia synthesis. Therefore, the reaction pressure is more favorable for

ammonia formation on the MoNx/ZSM-5 catalyst than for bulk Mo2N. The kinetic

measurements show that the apparent activation energy (9.8 kcal mol-1) of ammonia

synthesized on MoNx/Z is lower than the apparent activation energy (12.4 kcal mol-1)

on bulk Mo2N, and the reaction order of the reactants is also different. Qinye Li et al.94

studied the catalytic performance of molybdenum nitride (MoN2) nanosheets as

ammonia synthesis catalysts at room temperature by DFT calculation, as shown in Fig.

7a and Fig. 7b. Pure MoN2 has excellent adsorption and activation properties, but is not

an ideal catalyst in itself. It requires 1.75 eV of energy to refresh the surface after the

reaction. However, Fe doping slightly weakens the metal-nitrogen interaction and

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ChemSusChem 10.1002/cssc.202000487

improves its performance. After iron doping, ΔGmax = 0.47 eV for the RDS (N2

adsorption), indicating that Fe-doped MoN2 is a promising catalyst for electrochemical

synthesis of ammonia.

The above theoretical research on molybdenum nitride shows that molybdenum

nitride have some potential in electrocatalysis. On the basis of theoretical research, the

experimental results further prove the good catalytic performance of molybdenum

Accepted Manuscript
nitride in terms of NRR. Xiang Ren et al.95 reported a method of using a Mo2N nanorod

for artificial nitrogen fixation under acidic conditions. With 0.1 M HCl as the electrolyte

solution, a high FE of 4.5% was obtained at a potential of -0.3 V vs. RHE, and the yield

was 78.4 μg h-1 mg-1cat.. The ammonia yield of Mo2N is much higher than that of MoO2,

indicating that N element plays an important role in the reduction process. At the same

time, the DFT calculation also showed that the free energy barrier (DGH*) of NRR on

the Mo2N catalyst was significantly lower than that of MoO2, which is consistent with

the results of ammonia yield. In addition, the catalytic cycle experiments of Mo2N

catalysts show that Mo2N has good electrochemical durability under ambient conditions.

Ling Zhang et al.96 studied the use of MoN nanosheet arrays (MoN NA/CC) on carbon

cloth as high-performance NRR electrocatalysts. Under the ambient conditions,

electrochemical ammonia synthesis was carried out in 0.1 M HCl solution at a potential

of -0.3 V vs. RHE. The catalyst achieved an ammonia yield of 3.01×10-10 mo1 s-1 cm-2

and the FE of 1.15%. Catalyst cycle stability experimental results demonstrate that the

catalyst has strong electrochemical durability. Also, in the process of reducing N2, N2H4

was not detected, and therefore, the MoN nanosheet array catalyst had good selectivity.

DFT calculations revealed that MoN NA/CC catalyzed NRR by the Mars-van Krevelen

mechanism. Further, by labeling N atoms in N2 by an isotope labeling method, it was

confirmed that ammonia gas was produced by N2 reduction by detecting N atoms in

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ChemSusChem 10.1002/cssc.202000487

NH4+.

Accepted Manuscript
Fig. 7. a) Top views of MoN2 monolayer. b) N2 fixation through filling NV. (a) NH* + (H+ + e−)

→ NH2*. b) NH2* + (H+ + e-) → NV + NH3(g); c) N2(g) + NV → N2*94. c) Production rate and FE

of VN catalysts at different potentials for 1 h tests. d) Time-dependent production rate and FE at -

0.1 V and -0.2 V for 8 h tests, respectively. e) Proposed reaction pathway for nitrogen reduction on

the surface of VN0.7O0.45 via a Mars-van Krevelen mechanism and the catalyst deactivation

mechanism97.

The addition of N atoms can change the properties of the metal d-band, and the

shrinkage of the metal d-band makes the electronic structure of the metal nitride more

similar to the noble metal. The small radius of the nitrogen atom can be nested in the

gap of the crystal lattice, so the arrangement of the metal atoms is always kept tightly

packed, giving the metal nitride a high electronic conductivity. These promising

properties, combined with high corrosion resistance, make this material more reliable

as electrocatalysts with respect to metals or metal alloys. Xuan Yang et al.97 reported an

active, selective and well electrochemically stable NRR catalyst, VN nanoparticles. At

-0.1 V vs. RHE, the ammonia production rate and FE were 3.3×10-10 mol s-1 cm-2 and

6.0%, respectively, within one hour (Fig. 7c and Fig. 7d). The steady state ammonia

production rate was 1.1×10-10 mol s-1 cm-2, and the FE was 1.6%, which can be
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ChemSusChem 10.1002/cssc.202000487

15 14
maintained for 116 hours. The NRR fed with N2 produced a mixture of NH3 and
15
NH3, which demonstrates the role of surface N in catalytic conversion and indicates

that the reaction is carried out by the Mars-van Krevelen mechanism (Fig. 7e). The non-

in situ X-ray photoelectron spectroscopy of fresh catalyst and post-catalyst showed that

there are many vanadium oxides, oxynitrides and nitrides on the surface, and VN0.7O0.45

may be the key to catalyze the conversion of N2. X-ray absorption spectroscopy and

Accepted Manuscript
catalyst durability test results showed that VN0.7O0.45 was determined as the active

phase, and the conversion of VN0.7O0.45 to the VN phase resulted in catalyst deactivation.

Rong Zhang et al.98 experimentally proved that the noble metal free array (VN nano

array) is a highly efficient and stable catalyst suitable for NRR under acidic conditions.

In 0.1 M HCl, at -0.5 V vs. RHE, the ammonia yield of 8.40×10-11 mol s-1 cm-2 was

obtained, and the FE was 2.25%. This type of catalyst material also has a high

selectivity (no N2H4 formation) during the catalytic process. Not only is the selectivity

high, but the ammonia yield can also be maintained at a certain level in the stability test

of 10 cycles. Theoretical and experimental results reflect that the NRR on the catalyst

is achieved by the Mars-van Krevelen mechanism.

Based on the studies above, we cannot dent the fact that metal compound catalysts

still leaves much to be desired in terms of the FE in NRR. For metal sulfides, there is

relatively little research. However, the researches on MoS2/CC nanosheet (1.17% at -

0.5 V vs. RHE) and DR MoS2 nanoflower (-0.4 V vs. RHE at 8.34%) prove its great

application potential. Metal oxides and nitrides have been widely studied, such as, C-

TiO2 (1.84% at -0.7 V vs. RHE), γ-Fe2O3 (1.9% at 0.0 V vs. RHE), MnO/TM (0.1% at

-0.39 V vs. RHE), MoO3 (1.9% at -0.3 V vs. RHE), MoN NA/CC (1.15% at -0.3 V vs.

RHE), and Mo2N nanorod (4.5% at -0.3 V vs. RHE), where the urgent problem is the

low FE.

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Although metal compounds as catalysts barely have advantage on FE compared to

pure metal catalysts, their availability is rather attractive. Taking iron oxide (Fe/Fe3O4)

as an example, its FE is 8.29%, which is higher than that of the alloy containing the

precious metal Pd. In addition, based on the cross reference of the FE between pre- and

post- optimization of MOS2 catalyst, it is obvious that FE is greatly improved by

optimization. Besides, metal nitrides are currently controversial catalytic materials.

Accepted Manuscript
Studies have shown that some metal nitrides can decompose by themselves to produce

ammonia. Therefore, when metal nitrides are used as NRR catalysts, mechanism

research and isotope labeling detection should be carried out to further confirm that the

NH3 was produced by NRR not the decomposition of metal nitrides catalysts.

3. Carbon material supporting metal or metal compound catalysts

Most catalysts are composed of carbon materials99-101 such as graphene, reduced

graphene oxide, carbon nanotubes, heteroatom doped carbon materials, etc. Moreover,

in order to achieve better electrochemical catalytic performance, researchers also

designed series of experiments to load some metals or metal compounds on the carbon

material.102-105 Xiao-Fei Li et al.106 proposed a FeN3 embedded graphene catalyst by

DFT calculation to activate N2 and convert it to NH3 at room temperature. The results

show that the catalyst has excellent N2 immobilization activity because the FeN3 center

is highly spin-polarized, has a local magnetic moment, promotes N2 adsorption and

activates N≡N. At the same time, the synergy between graphene and FeN3 also

promotes the catalytic conversion of N2 to NH3. Although Fe is the only necessary TM

atom in nitrogenases, the TM atoms embedded in graphene-deficient Sc, V and Mn also

cause high spin polarization and are also possible active sites for N2 fixation. Ke Chu

et al.107 experimentally studied the application of graphene NiO nanodots (NiO/G)

composites in electrocatalytic NRR. NiO nanodots structure can expose more active

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ChemSusChem 10.1002/cssc.202000487

sites, thereby improving NRR performance. Moreover, the experimental results show

that with 0.1 M Na2SO4 as the electrolyte, NiO/G has an ammonia yield of 18.6 μg-1 h-
1
mg-1 and a FE of 7.8% at a potential of -0.7 V vs. RHE. At the same time, NiO/G also

has high selectivity and stability.

NiO/G catalyst has achieved better catalytic effect, but in the research on NRR

catalyst, reduced graphene oxide (rGO) is more widely used. Miao-Miao Shi et al.108

Accepted Manuscript
succeeded in the preparation of PdCu amorphous nanoclusters anchored on rGO by the

mixed reduction of graphene oxide (GO) and metal precursor. Under the environmental

conditions, the best performance of the Pd0.2Cu0.8/rGO composite catalyst at the

potential of -0.2 V vs. RHE is 2.80 µg h-1 mg-1cat.. The Pd0.2Cu0.8/rGO composite catalyst

has a synergistic effect on NRR and exhibits much higher electrocatalytic performance

than a single metal (especially a noble metal). Xiaoxue Zhang et al.109 experimentally

studied a TiO2 nanoparticle-reduced graphene oxide mixture (TiO2-rGO), which

showed good catalytic activity in NRR. In 0.1 M Na2SO4, TiO2-rGO achieved a high

FE of 3.3% and an ammonia yield of 15.13 μg h-1 mg-1cat. at -0.90 V vs. RHE. At the

same time, the catalyst exhibited higher electrochemical stability in the cycle test. Hong

Huang et al.110studied the electrocatalytic performance of Mn3O4 nanoparticles and

reduced graphene oxide (Mn3O4@rGO) composites in NRR. The experimental results

show that Mn3O4@rGO has excellent selectivity and electrochemical stability. In 0.1

M Na2SO4 solution, at -0.85 V vs. RHE, this catalyst showed an NH3 yield of 17.4 μg

h-1 mg-1cat. and a FE of 3.52%. At the same time, DFT calculations show that the (112)

plane of Mn3O4 has excellent NRR activity. Fan Wang et al.111demonstrated that CuO

nanoparticle-supported reduced graphene oxide (CuO/rGO) materials have superior

NRR catalytic properties. In 0.1 M Na2SO4 electrolyte, the NH3 yield of CuO/rGO was

1.8×10-10 mol s-1 cm-2 at a potential of -0.75 V vs. RHE, and the FE was 3.9%, far better

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ChemSusChem 10.1002/cssc.202000487

than bare CuO or rGO. At the same time, long-term stability tests and cycle test results

show that CuO/rGO also has excellent catalytic and structural stability. Xianghong Li

et al.112 reported a high-performance catalyst for NRR—MoS2 nanosheet-reduced

graphene oxide blend (MoS2-rGO). In 0.1 M LiClO4, the catalyst had a FE of 4.58%

and a NH3 yield of 24.82 μg h-1 mg-1cat. at -0.45 V vs. RHE. Hongtao Xie et al.113

successfully prepared CeO2 nanoparticle-reduced graphene oxide nanocomposites

Accepted Manuscript
(CeO2-rGO) by simple hydrothermal method and used it as a catalyst for NRR to study

the activity, selectivity and stability of the catalyst. In 0.1 M Na2SO4, CeO2-rGO gave

a FE of 4.78% and an NH3 yield of 16.98 μg h-1 mg-1cat. at a potential of -0.7 V vs. RHE.

The Fe2O3 nanoparticle-supported reduced graphene oxide (Fe2O3-rGO) prepared by

Jian Li et al.114 is a highly efficient NRR electrocatalyst. In 0.5 M LiClO4, Fe2O3-rGO

gave an NH3 yield of 22.13 μg h-1 mg-1cat. at -0.50 V vs. RHE, while a FE of 5.89% was

obtained at -0.40 V vs. RHE. Ke Chu et al.115 reported the high efficiency NRR

performance of reduced graphene oxide and SnO2 quantum dot (SnO2/rGO) composites.

In 0.1 M Na2SO4, SnO2/rGO obtained an NH3 yield of 25.6 μg h-1 mg-1 and a FE of 7.1%

at -0.5 V vs. RHE. The experimental and DFT calculations show that the ultra-small

SnO2 quantum dots distributed uniformly on rGO are effective N2 adsorption sites.

SnO2 quantum dots and rGO can improve the conductivity and promote the occurrence

of NRR by reducing the energy barrier of *N2 → *N2H. The Cr2O3 nanoparticle-

reduced Graphene Oxide prepared by Li Xia et al.116 showed good electrocatalytic

activity and stability in 0.1 M HCl. The highest NH3 yield was 33.3 μg h-1 mg-1cat. at -

0.7 V vs. RHE, and the highest FE was 7.33% at -0.6 V vs. RHE.

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Table 2 Summary of catalytic performance of reduced graphene oxide supported metal oxide

catalysts

No. Catalysts E(V) Ammonia yield FE (%) Ref.

108
1 Pd0.2Cu0.8/rGO -0.2 V vs. RHE 2.80 µg h-1 mg-1cat. ---

2 TiO2-rGO -0.90 V vs. RHE 15.13 μg h−1 mg−1cat. 3.3 109

3 Mn3O4@rGO -0.85 V vs. RHE 17.4 μg h−1 mg−1cat. 3.52 110

4 CuO/rGO -0.75 V vs. RHE 1.8×10-10 mol s-1 cm-2 3.9 111

Accepted Manuscript
5 MoS2-rGO -0.45 V vs. RHE 24.82 μg h−1 mg−1cat. 4.58 112

6 CeO2-rGO -0.70 V vs. RHE 16.98 μg h−1 mg−1cat. 4.78 113

5.89

7 Fe2O3-rGO -0.50 V vs. RHE 22.13 μg h-1 mg-1cat. -0.40 V vs. 114

RHE

8 SnO2/rGO -0.50 V vs. RHE 25.6 μg h-1 mg-1 7.1 115

7.33

9 Cr2O3-rGO -0.70 V vs. RHE 33.3 μg h−1 mg−1cat. -0.60 V vs. 116

RHE

From the data in Table 2, it can be seen that materials with noble metal or alloy

support tend to obtain lower optimal potentials, while more researched metal oxide-

supported rGO materials have less optimal potentials. Not only that, there is no higher

breakthrough in the FE of the catalytic process. Carbon nanotubes are also carbon

materials that are often used as carriers. E.g, Shiming Chen et al.117 used Fe2O3

supported on carbon nanotubes (Fe2O3-CNTs) as an electrocatalyst for NRR and studied

its catalytic activity. The ammonia yield obtained with the noble metal (Ru/C) was

obtained at an applied potential of -2.0 V vs. Ag/AgCl (the ammonia yield of the catalyst

was 2.2×10-3 g m-2 h-1), and the total FE was as high as 95.1%. The catalyst has good

electrochemical stability and can be used for at least 60 hours. The data also indicate

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ChemSusChem 10.1002/cssc.202000487

that the electrocatalytic synthesis of active sites in NH3 may be associated with specific

carbon sites formed at the interface between Fe2O3 and CNTs. Xiaoyang Cui et al.118

proved that the o-Fe2O3/CNT catalyst could improve the ammonia yield and FE of

nitrogen reduction under ambient conditions. Electrochemical test with 0.10 M KOH

as the electrolyte, under the potential of -0.9 V vs. Ag/AgCl, with hematite abundant in

oxygen vacancies as catalyst, can improve the performance of NRR. The average yield

Accepted Manuscript
of NH3 was 0.46 μg h-1 cm-2 and the FE was 6.04%. The chronoamperometry results

showed that the highest ammonia yield and FE were obtained after the first 1 hour test,

which were 1.45 μg h-1 cm-2 and 8.28%, respectively. And with increasing time,

ammonia yield and FE can be maintained at a certain level. Conseuqently, we can draw

a justifiable conclusion that the catalyst has better durability. Similar to carbon

nanotubes, carbon nanofibers are often studied in electrocatalysis. The TiC/C nanofiber

(TiC/C NF) prepared by Guangsen Yu et al.119 is an effective one-dimensional NRR

electrocatalyst. In 0.1 M HCl, the NH3 yield of TiC/C NF was 14.1 μg-1 h-1 mg-1 and

the FE was 5.8% at -0.5 V vs. RHE. DFT calculation shows that the TiC nanocrystallites

in TiC/C NF have strong N2 affinity, which is beneficial to the fracture and

hydrogenation of N≡N. At the same time, carbon nanofibers can provide sufficient

conductivity and a larger specific surface area to facilitate the adsorption of N2.

Guangsen Yu et al.120 prepared a Cr3C2 nanoparticle-supported carbon nanofiber

composite (Cr3C2@CNF) and used it as a catalyst for the conversion of N2 to NH3. In

0.1 M HCl, at -0.3 V vs. RHE, Cr3C2@CNF achieved the highest NH3 yield of 23.9 μg-
1
h-1 mg-1 and the FE of 8.6%. Moreover, long-term test results show that the catalyst

has good electrochemical stability.

Porous carbon materials possess controlled pore structure and surface chemistry,

carbon-based nanomaterials are widely used in catalysts or catalyst carriers in the

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ChemSusChem 10.1002/cssc.202000487

chemical studies due to their excellent properties and modification possibility. Among

multiply modification strategies, nitrogen doping is a feasible method for the

enhancement of physical and chemical properties of carbon materials11,121. Zhe Chen et

al.122 studied the catalytic properties of a series of single metal atoms supported on

graphite carbonitride (g-C3N4) by DFT calculation. For five single-atom (Ti, Co, Mo,

W and Pt) supported g-C3N4 catalysts, the Gibbs free energy change is less than (or

Accepted Manuscript
equal to) Ru (001). In particular, a single tungsten (W) atom anchored on g-C3N4

(W@g-C3N4) has the highest catalytic activity for NRR through the association

pathway, has a limiting potential of -0.35 V, and inhibits HER. The high NRR activity

and selectivity of W@g-C3N4 is attributed to its inherent properties, such as greater spin

torque, conductivity and moderate adsorption strength at W atoms. Based on the density

functional theory calculation, Lifu Zhang et al.123 studied the catalytic performance of

different metal-loaded gt-C3N4 materials as electrocatalysts for NRR. The calculation

results show that the limit potential of Mo/gt-C3N4 is -0.82 V when N2 is adsorbed,

which is smaller than other metals. The best catalyst for adsorbing N2. In the case of

adsorption of N2, the limiting potential of V/gt-C3N4 is -0.79 V, which is superior to

other materials and may be a promising electrochemical NRR material. Chongyi Ling124,

et al. calculations investigated the catalytic performance of single-metal atoms (Cu, Pd,

Pt and Mo) supported on N-doped carbon as NRR catalysts. Studies have found that

the active coordination effect study shows that the active site is composed of a single

Mo atom coordinated by one N atom and two C atoms (Mo1-N1C2) has the highest

catalytic performance. Mo1-N1C2 can catalyze NRR through an enzymatic mechanism

with an ultra-low potential of only 0.24 V. Most importantly, the NH3 produced can be

removed quickly at 0.47 eV. The metal nature of Mo1-N1C2 also ensures the efficiency

of electron transfer. At the same time, the strong coupling with N2, the low overpotential

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ChemSusChem 10.1002/cssc.202000487

of NRR, the excellent removal of NH3 and good electrical conductivity make Mo1-N1C2

an efficient and durable NRR catalyst. The above theoretical research shows that the

nitrogen-doped carbon catalyst possesses extensive specific surface area and a large

number of pore structures, which can effectively promote the adsorption and mass

transfer rate during the catalytic reaction. With metal loaded, the metal nanoparticles

can be uniformly dispersed on the surface of the nitrogen-doped carbon materials, ultra-

Accepted Manuscript
fine state due to the presence of nitrogen in the carbon material125. Therefore, the

catalytically active component can be maximized, thereby increasing the activity.

From this, it can be seen that loading some metals or metal compounds on a

nitrogen-doped carbon material can improve the catalytic activity. Such as, Xiaoqian

Wang et al.126 synthesized an atom-dispersed AU1 catalyst and applied it to the

electrochemical synthesis of ammonia under ambient conditions. It was found that NH3

can be electrochemically generated directly from N2 and H2 using AU1 catalyst, and its

energy utilization rate is 4.02 mmol kJ-1. The AU1 catalyst achieved 11.1% FE and the

NH3 yield was 1.305 μg h-1 mgAu-1. In addition, the DFT calculation results show that

AU1/C3N4 and Au NPs/C3N4 have alternating hydrogenation mechanisms, thus

increasing the FE of NH3 formation on AU1/C3N4. Although the Haber-Bosch process

is likely to dominate the synthesis of industrial NH3 for a long time, this study provides

a more energy-efficient method of ammonia synthesis. Qing Qin et al.127 introduces a

stable Au single site on an N-doped porous and highly oxidized ("precious metal")

carbon catalyst (NDPC). The introduction of Au monoatomic leads to the generation of

active reactive sites. As a result, the AuSAs-NDPCs catalyst exhibits excellent NRR

properties. The AuSAs-NDPCs catalyst had a FE of 12.3% and an ammonia yield of

2.32 µg h-1 cm-2 at a potential of -0.2 V vs. RHE. In addition, there were no significant

fluctuations in FE and NH3 yield in the six catalytic cycle tests, indicating the catalyst

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ChemSusChem 10.1002/cssc.202000487

can function steadily. The addition of precious metal (Au) improves the FE, and the

addition of Ru makes the improvement of FE even more significant. Zhigang Geng et

al.128 experimentally studied the N2 electrochemical reduction performance of Ru

monoatomic/nitrogen-doped carbon (Ru SAs/N-C) materials. At a potential of -0.2 V

vs. RHE, the FE of Ru SAs/N-C was 29.6%, and the NH3 yield was 120.9 μg h-1 mg-
1
cat., an order of magnitude higher than the highest ever. As discussed in Table 2, the

Accepted Manuscript
addition of precious metals can often lead to lower optimal potentials. In addition, noble

metal-supported nitrogen-doped carbon materials have also achieved good catalytic

activity in catalytic reactions.

Metal-organic framework (MOF) are materials that have been studied a lot in the

past ten years. Not only do they have many excellent characteristics, but also the

nitrogen-doped carbon materials obtained after high temperature calcination have great

development prospects. Shijian Luo et al.129 investigated the electrocatalytic

performance of MOF-derived nitrogen-doped carbon/Co3O4 nanocomposites

(Co3O4@NCs) in nitrogen reduction (Fig. 8b). The core-shell structure of the catalyst

can further improve the electrochemical activity of NH3, and the synergistic effect of

Co3O4 and nitrogen-doped carbon materials as well as the oxygen vacancies of Co3O4

can also promote the activity of NRR. In 0.05 M H2SO4, an ammonia yield of 42.58 μg

h-1 mg-1cat. and a FE of 8.5% were obtained at a potential of -0.2 V vs RHE. The results

of isotope labeling experiments showed that the NH3 produced in the experiment is

from the N2 introduced in the reaction. The above experimental results show that

Co3O4@NCs has good activity and excellent selectivity on NRR. Ying Wang et al.130

designed and prepared a noble metal-free Fe-N/C-carbon nanotube (Fe-N/C-CNT)

catalyst from metal-organic framework and carbon nanotube-based composites with

built-in Fe-N3 activity, as shown in Fig. 8a. The catalyst exhibited strong NRR activity.

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ChemSusChem 10.1002/cssc.202000487

The 0.1 M KOH aqueous medium was used as the electrolyte. Under the potential of -

0.2 V vs. RHE, the ammonia yield was 34.83 μg·h-1·mg-1cat., and the FE was 9.28%.

The experimental results and theoretical calculations prove that the built-in Fe-N3

species is the main catalytic active center of NRR, which effectively increases the NRR

activity. It can be found that this type of material can obtain a lower optimal potential

without precious metals, and that FE is higher than some metal compounds. In addition,

Accepted Manuscript
this type of material also has a surprising breakthrough in FE. Ximing Qu et al.131

prepared an oxygen-containing molybdenum carbide (O-MoC@NC-800) embedded in

a nitrogen-doped carbon layer by a simple polymerization reaction and a carbothermal

reduction route, shown in Fig. 8c. With 0.1 M HCl and 0.5 M Li2SO4 as the electrolyte,

the NH3 yield of 22.5 μg·h-1·mg-1cat. was obtained at a potential of -0.35 V vs. RHE, and

the FE was as high as 25.1%. The excellent NRR activity of O-MoC@NC-800 may be

attributed to the electron transfer process between O-containing MoC and nitrogen-

doped graphite carbon shell, which effectively inhibits HER and increases the FE of

NRR. Moreover, O-MoC@NC-800 does not produce enthalpy during the potential

reaction, along with high selectivity and electrochemical stability. Moreover, when this

material is supported with precious metals, FE even reaches 44%, even if the optimal

potential becomes higher. Yijie Yang et al.132 studied the application of nanoporous

gold (NPG) embedded ZIF-8 composites in NRR. The high catalytic active center

density NPG core and hydrophobic ZIF-8 shell in NPG@ZIF-8 material can effectively

improve the catalytic performance of NRR. At a potential of -0.8 V vs. RHE, the highest

ammonia yield was 28.7 ± 0.9 μg h-1 cm-2, with a maximum FE of 44% at -0.6 V vs.

RHE. Moreover, the composite catalyst has high electrochemical stability and 98%

selectivity.

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ChemSusChem 10.1002/cssc.202000487

Accepted Manuscript
Fig. 8. a) Scheme of the synthesis of Fe-N/C-CNTs. Characterization of the morphology and

structure of Fe-N/C-CNT catalysts.130 b) ZIF67-derived core-shell Co3O4@NCs electrocatalyst

for. 129 c) Carbon shells-coated O-doped Molybdenum Carbide nanoparticles electrocatalysts. 131

From the above summary, the choice of carbon materials exerts a profound impact

on catalytic activity. In general, heteroatom-doped carbon materials, especially N-

doped carbon materials, are better than graphene, carbon nanotubes and other materials,

indicating that heteroatom doping can indeed improve catalytic performance to some

extent. The N-doped carbon material obtained by high-temperature sintering has more

defects, leading to more active sites and stronger catalytic activity. In addition, for

supported metals or metal compounds, precious metal-supported materials tend to

achieve relatively higher FE due to their high performance for electrocatalytic NRR.

4 Metal complex catalyst

MOF, also known as porous coordination polymers, are crystalline porous

materials formed by metal ions or clusters and organic ligands self-assembled by

coordination bonds under certain conditions133-134. These materials possess large

specific surface area, adjustable pore size and shape, controllable chemical

modification, making them widely used in the fields of catalysis, gas adsorption as well

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ChemSusChem 10.1002/cssc.202000487

as energy conversion and storage. The MOF-derived materials have good development

prospects in catalysis, and MOF also has applications in catalysis. E.g, Fengxiang Yin

et al.135 prepared MOF(Fe), MOF(Co) and MOF(Cu) by hydrothermal method and

characterized the catalyst prepared. The characterization results show that the

experimentally prepared MOFs catalyst has a good porous structure and a large specific

surface area. In addition, with nitrogen and water as the reaction materials, MOFs

Accepted Manuscript
catalysts presented good catalytic activity at 1.2 V and 90 °C. Among them, MOF (Fe)

is the most excellent, and the ammonia generation rate and current efficiency are

2.12×10-9 mol s-1 cm-2 and 1.43%, respectively. Despite air and water served as raw

materials, the ammonia formation rate and CE of MOF (Fe) were 1.52×10-9 mol s-1 cm-
2
and 0.88%, respectively, at 1.2 V and 90 °C (specific data as shown in Table 3). The

result of this experiment shows that the non-precious metal catalyst also has significant

catalytic activity for electrochemical ammonia synthesis under low temperature and

normal pressure. Although MOF has many excellent characteristics, without any

treatment, it will have low catalytic performance due to its poor conductivity.

Table 3. Catalytic performance of MOF(Fe), MOF(Co) and MOF(Cu).

No. Catalysts Raw materials T/E Ammonia yield FE(%)

1 MOF (Fe) N2，H2O 90 ℃ / 1.2 V 2.12×10-9 mol s-1 cm-2 1.43

2 MOF(Co) N2，H2O 90 ℃ / 1.2 V 1.64×10-9 mol s-1 cm-2 1.06

3 MOF(Cu) N2，H2O 90 ℃ / 1.2 V 1.24×10-9 mol s-1 cm-2 0.96

4 MOF (Fe) Air，H2O 90 ℃ / 1.2 V 1.52×10-9 mol s-1 cm-2 0.88

At present, most of the ammonia-producing materials of such complexes136-137 are

in the stage of theoretical calculation, and few experimental progresses have been made.

The new trinuclear bisphosphine (PNP) type ligand metal complex is one of the feasible

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ChemSusChem 10.1002/cssc.202000487

materials to convert dinitrogen to ammonia under mild reaction conditions. Shogo

Kuriyama et al.138 designed a novel cobalt diazo complex with an anionic PNP type

clamp ligand, which is an effective catalyst for NRR under mild reaction conditions.

The catalyst, when used for nitrogen fixation, can produce up to 15.9 equivalents of

ammonia and 1.0 equivalent of hydrazine based on the amount of catalyst (17.9

equivalents of fixed nitrogen atoms). Kazuya Arashiba et al.139 prepared a molybdenum-

Accepted Manuscript
nitrogen complex ( [Mo(N)Cl(PPP)]BArF4) containing tridentate triphosphine as a

ligand and used it in the environment. A catalyst for the catalytic reduction of N2 to

ammonia under conditions. The complex can produce up to 63 equivalents of ammonia

based on Mo atoms. Moreover, the catalytic activity of the complex is more than 5 times

higher than that of the original reaction system using [Mo(N2)2(PNP)]2(μ-N2) catalyst.

Shogo Kuriyama et al.140 was synthesized by a reduction of the corresponding

molybdenum trichloride complexes at 1 atm of N2 to synthesize a series of dinitrogen-

bridged dimolybdenum-dinitrogen complexes with 4-methoxy substituted PNP-clamp

ligands. Theoretical studies have shown that by introducing an electron-donating group

on the pyridine ring of the PNP-clamping ligand to enhance the catalytic activity, the

introduction of the electron-donating group accelerates the protonation step in the first

protonation process involved in the catalytic reaction. At the same time, a complex

having a 4-methoxy-substituted PNP-clamping ligand is an effective catalyst which

produces 26 equivalents of ammonia per Mo atom based on the catalyst and 52

equivalents of ammonia, as well as H2. The time course of the catalytic reaction

indicates that the rate of formation of NH3 and H2 depends on the nature of the

substituent on the PNP-clamping ligand of the complex. The nature of the substituents

on the PNP-clamp ligand in the complex not only substantially affects the electronic

and electrochemical properties, but also affects the catalytic properties of the formation

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ChemSusChem 10.1002/cssc.202000487

of ammonia and H2. Shogo Kuriyama et al.141 has synthesized a series of super-

nucleophilic complexes containing near substituents by reducing the corresponding

molybdenum-based molybdenum. The complex introduces ferrocene as a redox active

moiety into the pyridine ring of the PNP clamp ligand in an N2 environment at 1 atm,

increasing the catalytic activity for formation, and the ammonia is separated from the

molecule up to 45 equivalents (based on the catalyst has 22 equivalents of ammonia per

Accepted Manuscript
Mo atom). The results of the time profile reaction indicate that the presence of units in

the catalyst increases the rate of ammonia formation. Electrochemical tests and

theoretical studies have shown that the interaction between Fe atoms and Mo atoms in

the catalyst may play an important role in obtaining higher catalytic activity. Theoretical

studies have shown that the presence of an active nitrous acid reductant increases the

rate of the reduction step in the ammonia catalysis process during the catalytic ammonia

reaction. The intramolecular electron transfer from the Fe atom of ferrocene to the

active site of the Mo atom in the complex apparently accelerated the catalytic reduction

step. Based on the existing experimental and theoretical studies, Hiromasa Tanaka142 et

al. proposed a new reaction pathway, on the basis of the stoichiometry and catalytic

formation of ammonia from N2 under environmental conditions, and conducted the

study of clamped ligands by DFT calculation. Catalytic behavior of diazo-bridged

dimolybdenum complexes. The NRR of the complex has an ammonia content of up to

twenty-three equivalents based on catalyst production. Comparison of the di- and

mono-molybdenum systems indicates that the dinitro-bridged di-molybdenum complex

core structure plays a key role in the N2 protonation in the catalytic cycle. There is a

synergistic effect between the two molybdenum linked to the bridging dinitrogen ligand,

which supplies electrons by bridging the dinitrogen ligand to the active site of the other

molybdenum, thereby activating the terminal dinitride to accept protons.

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Table 4. Catalytic performance of the complex.

No. Catalysts Benchmark Ref.

138
1 17.9 equiv / N
(R=tBu)

139
2 63 equiv / Mo

Accepted Manuscript
140
3 26 equiv / Mo
(R=MeO)

141
4 22 equiv / Mo
(R=Fe)

142
5 12 equiv / Mo

137
6 4.6 equiv / Fe

143
7 84 ± 8 equiv / Fe

144
8 64 equiv / Fe

(E = B)

144
9 47 equiv / Fe

(E = C)

144
10 4.4 equiv / Fe

(E = Si)

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Iron has a certain relationship with biological nitrogen fixation145-147. Therefore,

many researchers have designed and studied the application of iron-based complexes

in the reduction of nitrogen148. Matthew J. Chalkley et al.143 studied the catalytic

performance of P3BFe catalyzed NRR. The NH3 yield of the P3BFe catalytic system is

as high as 72% under standard substrate loading, and the number of conversions of the

synthetic molecular Fe catalyst (84 ± 8 equivalents of NH3 per Fe) is relatively high by

Accepted Manuscript
reloading additional substrates at low temperatures. Theoretical and experimental

studies have shown that the catalytic conversion of P3BFe+ to N2-NH3 is lower than that

of the original combination of weaker reducing agent (Cp*2Co) and acid

([Ph2NH2][OTf] (close to 100 kcal/mol). Some researchers have confirmed the high

ammonia synthesis activity of P3BFe by comparing three other similar complexes.

Trevor J. Del Castillo et al.144 found that the Fe-N2 complexes of tetradentate P3E ligands

(P3EFe; E = B, C) catalyst (Fig. 9a) has a higher NH3 yield when sufficient acid and

reducing agent are added. P3BFe produces 64 equiv NH3/Fe, P3CFe produces 47 equiv

NH3/Fe. Moreover, these catalysts are very stable and can remain active after repeated

reloading. There are other iron complexes, for example, Katarzyna Grube et al.149

explored a Fe complex for N2 reduction, shown in Fig. 9b. It was found through

research that the cooperation between three Fe atoms is the key to N≡N bond splitting.

The cleavage of the N≡N bond can occur when at least three low-cost Fe atoms are

close to the N2 molecule, and the N≡N cut does not occur when only two Fe atoms can

approach N2. Moreover, the size of the alkali metal cation can tailor the number of Fe

atoms close to N2 to control the three iron atoms to cooperatively cut N≡N. Or, Jonathan

Rittle and Jonas C. Peters150 directly protonated Fe=NNH2+ by Fe-N2 complex (Fig. 9c).

Fe=NNH2+ has redox activity. At the hotter temperature, Fe=NNH2+ is converted to the

strontium iron complex Fe-NH2NH2+, and Fe-NH2NH2+ can release NH3.

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From the specific data summarized in Table 4, we can find that in the Mo-centric

complex, [Mo(N)Cl(PPP)]BArF4 has the best ammonia synthesis performance, which

can reach 63 equiv / Mo. Among Fe-centered complexes, P3BFe has the best ammonia

synthesis performance, which can reach 84 ± 8 equiv / Fe. In general, the complex with

Mo as the center atom is slightly lower than that of Fe.

Accepted Manuscript
Fig. 9 a) Fe-N2 complexes of tetradentate P3E ligands (E = B, C) for N2 reduction.144b) Molecular

Fe system for N2 reduction using different alkali metals as reductants.149 c) Fe-N2 complex

generates Hydrazine and Ammonia via Fe═NNH2 for N2 reduction.150

Sulfur-rich iron-molybdenum clusters (FeMoco) are co-factors for nitrogenases

and are important active sites for biological nitrogen fixation. Nitrogenase can be

directly fixed under nitrogen under ambient conditions, which is a key entry point for

electrocatalytic synthesis of ammonia at ambient conditions. Therefore, the structure

and function of the synthetic diiron amide complexes containing thio ligands to

simulate nitrogenases have become one of the research hotspots. Yang Li et al.151

designed and synthesized a thio bridged diferric acid complex [Cp*Fe(μ-η2:η4-

bdt)FeCp*]. This complex is very effective in stabilizing nitrogen-containing donors,

partly because of the binding flexibility of the ligand. This can be demonstrated by the

existence of a series of two iron NxHy species. The DFT calculation shows that the first

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ChemSusChem 10.1002/cssc.202000487

reduction protonation occurs on the non-bridged NH2 of the N2H3- ligand. After the first

NH3 is released, the resulting NH2 bridged complex is converted into the NH2 bridged

complex by the second reduction protonation. These results provide valid evidence for

the nitrogen-fixing diiron mechanism and indicate that N2H2, N2H3-and NH2- are likely

to be produced during the N2 reduction process. In addition, a reduction route different

from the alternating and long-distance mechanisms has been proposed. HN=NH →

Accepted Manuscript
HN-NH2 → NH(+NH3) → NH2 → NH3. Based on kinetic and spectral studies, Ilija

Čorić et al.152 proposed iron complexes coordinated to sulfur and carbon atoms in

FeMoco. At rest, each iron center has three bonds of sulfur and one carbon atom. Upon

reduction, an Fe-S bond is destroyed and combined with N2. After N2 is combined, the

bond energy of the N-N bond is weakened. Therefore, it is considered that the sulfur-

rich iron position in FeMoco is suitable for the activation of N2, thereby further

improving the efficiency of electrochemical ammonia synthesis. The above two studies

on simulated nitrogenase complexes have theoretically confirmed the performance of

this complex in the synthesis of ammonia, laying a theoretical foundation for future

complexes in the direction of ammonia synthesis.

Above studies showed that the metal complex catalysts are potential ones for NRR

for its large specific surface area, adjustable pore size and shape with low cost. However,

the catalytic activity should be further improved, especially the FE should be improved

to meet the demand of practical application.

5 Metal-free catalyst

Benefiting from the high specific surface area, large pore volume, and the

tunability of structures and compositions, MOFs are promising self-success templates

and precursors for the preparation of various carbon-based nanomaterials. Compared

with other carbon-based catalysts, MOF-derived carbon-based nanomaterials have

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ChemSusChem 10.1002/cssc.202000487

great advantages in terms of regulatable morphology and graded porosity, as well as are

easily functionalized with other heteroatoms and metal/metal oxides.153 Those

favorable merits set a solid foundation for the rapid development of MOF pyrolyzed

carbon-based nanomaterials and offer many new opportunities for efficient catalysis.

Wu Gang et al.154 used ZIF-8 precursor as raw material and pyrolyzed in N2 stream for

1 h at 1100 °C to prepare MOF-derived nitrogen-doped nanoporous carbon catalyst.

Accepted Manuscript
The effects of electrolyte acidity and alkalinity on NRR were investigated by using 0.1

M KOH solution and 0.1 M HCl as electrolytes at room temperature and pressure. The

results show that the ammonia yield in the 0.1 M HCl electrolyte is much less than that

of the 0.1 M KOH electrolyte, and this phenomenon is more pronounced at elevated

temperatures. The catalyst also maintained good stability in the 18-h continuity test.

The results of the best process conditions show that at 60 °C, -0.3 V vs. RHE voltage,

the highest FE is 10.2%, and the highest ammonia yield is 7.3×10-6 mol cm-2 h-1. In

addition, the authors also studied the effect of Fe doping on the catalytic activity. The

results show that the Fe doping strategy will reduce the catalytic activity of the catalyst.

In addition to MOF, there is also a covalent organic framework (COF). Although the

preparation process of COF is more complicated, higher FE can be obtained on the

electrocatalytic synthesis of ammonia. For example, Sisi Liu et al.115 theoretically and

experimentally studied the application of electrochemically excitated COF covalent

organic frameworks supported by conductive nitrogen-doped carbon nanosheet (Eex-

COF/NC) in electrocatalytic N2 reduction. Under electrochemical conditions, the

covalent organic skeleton formed by the combination of boron sites and nitrogen-

containing species has stronger N2 affinity, and the catalyst has significant reactivity.

The experimental results show that Eex-COF/NC can achieve a FE of 45.43%.

Nitrogen doping can effectively improve the physical and chemical properties of

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ChemSusChem 10.1002/cssc.202000487

carbon materials. Just like metal-supported porous carbon catalysts, the introduction of

defects into nitrogen-doped carbon materials can significantly improve NRR

performance. Chen Gang et al.155 proposed an electrocatalyst for modifying metal-free

PCN using engineering nitrogen vacancy defects for ammonia synthesis under ambient

conditions (Fig. 10a). The authors chose metal-free polymer carbon nitride (PCN) as

the model matrix to introduce nitrogen vacancy (NV) defects. In order to control the

Accepted Manuscript
introduction of NV, polymer carbon nitride obtained by polycondensation of melamine

is further heated in an argon atmosphere. A series of PCN-introduced NV catalysts are

represented as PCN-NVx (x represents the time to re-calcinate in Ar). Because of the

high nitrogen content and layered structure of PCN, and the introduction of more NV

as an active site. Therefore, the most excellent PCN-NV4 catalyst ammonia yield can

reach 8.09 μg h-1 mg-1, and FE is 11.59%. The ammonia yield was increased by more

than 10 times compared with PCN at the absence of NV. Yanming Liu et al.156 achieves

electrochemical synthesis of ammonia from N2 by N-doped porous carbon (NPC). NPC

has high activity for ammonia synthesis, and the highest ammonia production rate is

1.40 mmol g-1 h-1 at a potential of -0.9 V vs. RHE. DFT calculations show that pyridine

N and pyrrole N are the active sites for ammonia synthesis, and their contents are very

important for N2 chemisorption and N≡N cleavage. Moreover, the preferred route for

ammonia synthesis is *N≡N → *NH=NH → *NH2-NH2 → 2NH3.

Besides nitrogen doping of carbon, boron can also be doped with carbon. 157-159 In

the periodic table of elements, the boron element is adjacent to the carbon element, and

the number of outermost electrons of the atom is one less than the latter, making it an

ideal doping atom for carbon materials. Shuang Ji et al.160 explored the potential of

several Bint-doped C2N layers for NRR by DFT calculation, and proposed that the Bint-

doped C2N layer is a metal-free catalyst with high-efficiency N2 reduction. DFT

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ChemSusChem 10.1002/cssc.202000487

calculations show that the Bint-doped C2N layer can effectively adsorb and activate N2

through the “acceptance-donation” process. Because of its significant positive charge

and magnetic moment on the Bint dopant, it has extremely high catalytic activity and

selectivity for NRR. The NRR is preferably carried out by an enzymatic mechanism

with a limiting potential of -0.15 V. In addition, the Bint-doped C2N layer has similar

binding energy and formation energy to the experimentally available S-doping, as well

Accepted Manuscript
as high thermodynamic stability, thus possessing great promise for experimental

synthesis. Ch Venkata Surya Kumar and Venkatesan Subramanian161 used DFT

calculation to study the catalytic reduction performance of boron nitride-based metal-

free catalysts. DFT calculations found that boron nitrite of boron nitride nanotubes is

the active site for nitrogen activation. Reaction energetics shows that NRR can occur

containing multipath reaction. In addition, as a feasible path under environmental

conditions, remote association mechanism is more advantageous than alternative

mechanism. The first protonation of activated nitrogen, the rate determining step of the

reaction, is endothermic, and other steps are inherently exothermic. It can be noted from

the energy science that helium is the main by-product of NRR, and the desorption of

helium requires more energy. According to the theoretical research results of many

researchers, we can find that boron doped or boron nitride and other substances have

catalytic capabilities. So when boron and boron nitride are used in experimental

research, what is the catalytic performance? Xiaoxue Zhang et al.162 used boron

nanosheets (BNS) as NRR electrocatalysts, as shown in Fig. 10c. In 0.1 M Na2SO4

solution, BNS obtained an NH3 yield of 13.22 μg h-1 mg-1cat. and a FE of 4.04% at -0.80

V vs. RHE. At the same time, both cyclic testing and long-term testing results show that

BNS has strong electrochemical durability. The hexagonal boron nitride nanosheet (h-

BNNS) prepared by Ya Zhang et al.163 has unsaturated boron at the edge to activate the

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ChemSusChem 10.1002/cssc.202000487

N2 molecule and reduce the energy barrier forming NH3, thereby having excellent N2

reducing activity. In 0.1 M HCl solution, the h-BNNS catalyst presented the highest

NH3 yield and FE of 22.4 μg h-1 mg-1cat. and 4.7% at -0.75 V vs. RHE, respectively.

Boron and boron nitride have certain properties in electrocatalytic NRR, but FE is not

high.

Based on one of the problems of low FE of boron or boron nitride, it is presumed

Accepted Manuscript
to be due to its poor conductivity. Therefore, many researchers have begun to design

doped boron elements on carbon materials such as graphene in order to improve FE.

Xiaomin Yu et al.164 experiment proved that boron-doped graphene (BG) was an

effective metal-free N2 reduction electrocatalyst (Fig. 10b). BG was obtained by

thermal annealing of graphene oxide and boric acid. BG showed significant N2

activation enhancement compared with the monoatomic layer (G) of undoped graphite.

The DFT calculation reveals the catalytic activity of different boron-doped carbon

structures, where the NRR energy barrier of the BC3 structure is the lowest. At a doping

level of 6.2%, the NH3 yield of BG was 9.8 μg.h-1.cm-2 and the highest FE was 10.8%

at -0.5 V vs. HER. Combined with experimental observations and theoretical studies,

G-like BC3 bonds play a role in N2 adsorption and ammonia formation in several types

of boron-doped carbon structures (i.e., BC3, BC2O, BCO2). Chen Chen et al.165 prepared

a metal-free catalyst, Graphene with bonded B and N (BNG-B), by pyrolysis of organic

precursors, and studied the nitrogen reduction properties of the materials by theory and

experiment. The carbon atoms near the doped B-N pair are the active centers of the

NRR. Moreover, the experimental results show that at a potential of -0.3 V vs. RHE,

the NH3 yield and the FE are 7.75 μg h-1 mg-1cat. and 13.79%, respectively. The above

research shows that the combination of carbon material and boron element does

significantly improve FE. In addition, there is a B4C substance, which is not only high

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ChemSusChem 10.1002/cssc.202000487

in strength and strong in chemical stability, but also easy to manufacture and low in

cost. Weibin Qiu et al.166 studied B4C nanosheets as metal-free catalysts for catalytic

reduction of NRR under ambient conditions. The B4C/CPE catalyst exhibited good

NRR activity in NRR. With 0.1 M HCl as the electrolyte, the catalyst can achieve a

high ammonia yield of 26.57 µg h-1 mg-1cat. at a potential of -0.75 V vs. RHE, and the

highest FE is 15.95%. At the same time, it also has high electrochemical stability and

Accepted Manuscript
excellent selectivity. The DFT calculations show that the *NH2-*NH2 → *NH2-*NH3

reaction is a rate limiting step.

Fig. 10. a) Electrocatalytic NRR on PCN-NV4 at ambient conditions.155 b) Boron-doped graphene

for electrocatalytic N2 reduction.164 c) 2D Boron nanosheet for electrocatalytic N2 reduction.162 d)

Tannic acid modified reduced graphene oxide for electrocatalytic N2 reduction.167

When the catalyst is doped with heteroatoms, in addition to the above two
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ChemSusChem 10.1002/cssc.202000487

elements, the S is often the element that is often cited. Ye Tian et al.168 reported a metal-

free NRR catalyst - N, S co-doped graphene (NSG). The electrochemical test of NSG

was carried out in 0.1 M HCl, and the highest NH3 yield and FE were obtained at -0.6

V vs. RHE, which were 7.7 μg h-1 mg-1cat. and 5.8%, respectively. The combination of

DFT calculations and experiments shows that N, S co-doping can produce more defects

as active sites, which is beneficial to NRR. Hongyu Chen et al.169 experimentally

Accepted Manuscript
studied the catalytic performance of sulfur-graphene nanohybrids on electrocatalytic

reduction of N2 to NH3. In 0.5 M LiClO4, the electrocatalyst presented an NH3 yield of

28.56 μg h-1 mg-1cat. and a high FE of 7.07% at a potential of -0.85 V vs. RHE. It is

worth noting that the catalyst exhibited good electrochemical stability in both long-term

electrolysis tests and cycle tests. There seems to be no major breakthrough in sulfur

doping for enhancing catalytic activity and improving FE. E.g, Li Xia et al.170

successfully prepared S-doped carbon nanospheres (S-CNS) and used them as catalysts

for the reduction of N2 to NH3 under ambient conditions. The excellent performance of

the catalyst was as follows: in 0.1 M Na2SO4 electrolyte, the S-CNS achieved an

ammonia yield of 19.07 μg h-1 mg-1cat. and a FE of 7.47% at a potential of -0.7 V vs

RHE. Moreover, the catalyst also exhibits high stability, and the current density remains

substantially constant over a reaction time of up to 24 h. Although FE does not have a

surprising performance, Li Xia et al.171 used a sulfur-doped graphene (SG) catalyst in

0.1M HCl, the highest FE was 11.5% at -0.5 V vs. RHE, which was much higher than

that of undoped sulfur. The highest NH3 production of S-G was 27.3 μg h-1 mg-1cat.

when the potential of -0.6 V vs. RHE. The DFT calculation combined with experimental

results demonstrated that the carbon atom near the sulfur atom is the active site of NRR

on S-G.

In addition to the above B, N, S heteroatom-doped carbon materials172-174, there

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ChemSusChem 10.1002/cssc.202000487

are also some F element and O element doped carbon materials, but the activity is

relatively low. Jinxiu Zhao et al.175 successfully synthesized defect-rich fluorographene

nanosheets (d-FG) and used them as NRR electrocatalysts. In 0.1 M Na2SO4, the NH3

yield of d-FG was 9.3 μg h-1 mg-1cat. and the FE was 4.2% at a potential of -0.7 V vs.

RHE. Yanyan Song et al.167 used surface modification of reduced graphene oxide (TA-

rGO) with tannic acid to obtain an NH3 yield of 17.02 μg h-1 mg-1cat. at -0.75 V vs. RHE

Accepted Manuscript
in 0.5 M LiClO4, and the FE was 4.83%. For specific data, see Fig. 10d. Jiayin Chen et

al.176 prepared metal-free NRR electrocatalysts - Oxygen-doped porous carbon

nanosheets (O-CNS) have good selectivity and stability in NRR. In 0.1 M HCl solution,

O-CNS obtained an NH3 yield of 18.03 μg h-1 mg-1cat. at -0.55 V vs. RHE, and the

highest FE obtained at -0.45 V vs. RHE was 10.3%. Ting Wang et al.177 performed an

electrochemical test of oxygen-doped graphene (O-G) obtained from sodium gluconate

in 0.1 M HCl. The results showed that the highest NH3 yield of O-G was 21.3 μg h-1

mg-1cat. at -0.55 V vs. RHE, and the highest FE was 12.6% at -0.45 V vs. RHE.

Compared with the above metal-free catalyst, the catalytic performance of a single

non-metal catalyst is relatively poor and it is not easy to improve. For example, pure

carbon cloth (CC), Wenyi Li et al.178 performed a simple heat treatment of commercial

CC in air at 450 °C, resulting in a large number of defects. CC-450 with a large

number of defects has excellent NRR activity compared with the original CC. In 0.1 M

Na2SO4 + 0.02 M H2SO4, the NH3 yield of CC-450 was 2.59×10-10 mol cm-2 s-1 at -0.3

V vs. RHE, and the FE was 6.92%. In addition, Lili Zhang et al.179 has experimentally

proved that black phosphorus nanosheets (FL-BP NSs) can be used as effective non-

metallic catalysts for electrochemical nitrogen fixation. The maximum ammonia yield

of the catalyst under ambient conditions can reach 31.37 μg h-1 mg-1cat. DFT

calculations show that the zigzag and diff-zigzag edges of FL-BP NSs are the active

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ChemSusChem 10.1002/cssc.202000487

centers of nitrogen adsorption and N≡N triple bond activation, which can reduce N2 to

NH3 by alternating hydrogenation pathways. Isotope tracing experiments show that N2

is a source of electrochemically synthesized ammonia.

The activity of carbon materials is relatively stable, e.g., NSG (5.8% at -0.6 V vs.

RHE), d-FG (4.2% at -0.7 V vs. RHE), TA-rGO (4.83% at -0.75 V vs. RHE), CC-450

(6.92% at -0.3 V vs. RHE), and can basically be maintained at about 5%. The catalytic

Accepted Manuscript
performance of B and N-doped carbon materials will be truly improved, e.g., BG (12.7%

at -0.60 V vs. RHE), BP (5.8% at -0.6 V vs. RHE), BNG-B (13.79% at -0.3 V vs. RHE),

B4C/CPE (15.95% at -0.75 V vs. RHE), maintaining above 10%. Although the Eex-

COF/NC material mentioned in the article has a complicated preparation process, it has

achieved a high FE of 45.43%. The main reason is that the material is abundant in B-N

bonds, which deforms the covalent organic framework crystal plane, strengthens the

adsorption of N2, and is conducive to the occurrence of NRR. We believe that B-N

bonds may have more potential for NRR than C-N and B-C bonds.

Conclusion and perspectives

NH3 is one of the most important chemicals and carbon-free energy carriers,

traditional production relies on the Haber-Bosch process operated at high temperatures

(400-500 °C) and high pressures (200-300 atm) is energy intensive with significant CO2

emission. Synthesizing NH3 via electrochemical NRR at ambient conditions is an

interesting and urgently needed method. Significant research efforts have been devoted

to NH3 synthesis via electrochemical NRR, including different designs of reactors,

electrolytes, and electrocatalysts. In this review, the author summarized various

catalysts that can be used for electrochemical NRR at ambient conditions. These

catalysts were categorized into metal catalyst including pure metal catalyst and alloy

catalyst, metal compound catalyst of metal sulfide catalyst, metal oxide catalyst, and

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ChemSusChem 10.1002/cssc.202000487

metal nitride catalyst, metal supported nitrogen-doped carbon catalyst, metal complex

catalyst, as well as metal-free catalyst.

When single metals are used as NRR electrocatalysts, precious metal catalysts,

especially Au catalysts, have higher FE and ammonia yield than non-precious metal

catalysts. In addition, the same metal catalyst is also greatly affected by morphology,

has more sharp edges and morphologies with specific surface area, can obtain more

Accepted Manuscript
active sites, and has stronger activity. When the alloy is used as the NRR catalyst,

similar to the single metal catalyst, the Au-based alloy catalyst has more advantages.

By comparing the activity of different alloy catalysts, it is found that Pd-based alloy

catalysts are at a disadvantage in terms of electrocatalytic NRR.

With relatively little researches, the studies on MoS2/CC nanosheet and DR MoS2

nanoflower proved its great application potential. Metal oxides and nitrides have been

widely studied, however, the urgent problem of the low FE is still unsolved.

Although metal compounds as catalysts barely have advantage on FE compared to

pure metal catalysts, their availability is rather attractive. Taking iron oxide (Fe/Fe3O4)

as an example, its FE is 8.29%, which is higher than that of the alloy containing the

precious metal Pd. In addition, based on the cross reference of the FE between pre- and

post- optimization of MOS2 catalyst, it is obvious that FE is greatly improved by

optimization. Besides, metal nitrides are currently controversial catalytic materials.

Studies have shown that some metal nitrides can decompose by themselves to produce

ammonia. When metal nitrides are used as NRR catalysts, mechanism research and

isotope labeling detection should be carried out to further confirm that the NH3 was

produced by NRR not the decomposition of metal nitrides catalysts.

The choice of carbon materials exerts a profound impact on catalytic activity. In

general, heteroatom-doped carbon materials, especially N-doped carbon materials, are

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ChemSusChem 10.1002/cssc.202000487

better than graphene, carbon nanotubes and other materials, indicating that heteroatom

doping can indeed improve catalytic performance to some extent. The N-doped carbon

material obtained by high-temperature sintering has more defects, leading to more

active sites and stronger catalytic activity. In addition, for supported metals or metal

compounds, precious metal-supported materials tend to achieve relatively higher FE

due to their high performance for electrocatalytic NRR.

Accepted Manuscript
The metal complex catalysts are potential ones for NRR for its large specific

surface area, adjustable pore size and shape with low cost. However, the catalytic

activity should be further improved, especially the FE should be improved to meet the

demand of practical application.

The activity of carbon materials is relatively stable, e.g., NSG, d-FG, TA-rGO,

CC-450, and can basically be maintained at about 5%. The catalytic performance of B

and N-doped carbon materials will be truly improved, e.g., BG, BP, BNG-B, B4C/CPE,

maintaining above 10%. Although the Eex-COF/NC material mentioned in the article

has a complicated preparation process, it has achieved a high FE of 45.43%. The main

reason is that the material is abundant in B-N bonds, which deforms the covalent

organic framework crystal plane, strengthens the adsorption of N2, and is conducive to

the occurrence of NRR. We believe that B-N bonds may have more potential for NRR

than C-N and B-C bonds.

Despite substantial research, key challenges remain unsolved in finding efficient

catalysts for practical NRR applications. Most of the current studied catalysts show low

FE and productivity of the electrocatalytic ammonia synthesis as the standard reduction

potential (0 V vs. SHE) for the HER is comparable to that for the NRR (0.057 V vs.

SHE). The design of low-cost high-performance NRR catalysts with the suppression of

the HER is the vital consideration for development of electrocatalytic ammonia

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ChemSusChem 10.1002/cssc.202000487

synthesis with high FE and productivity.

The application of high-efficiency theoretical studies give us opportunity for

design and preparation of high performance catalysts with high catalytic activity and

selectivity for NH3 and intense suppression of HER to significantly improve the FE and

productivity of target NH3. Moreover, the combination of experimental and theoretical

studies can give the exact mechanism of N2 to NH3 on as-prepared catalysts, which is

Accepted Manuscript
helpful to further improve the performance of the catalysts.

Design of effective catalysts with lower overpotential, high FE, and NH3

production rate in technology and characterization of materials combined with

continuous theoretical investigation, high-performance catalysts will be developed to

overcome the problems of insufficient catalyst activity, NH3 production rate, low FE

and poor stability.

Acknowledgements

Supports of the National Natural Science Foundation of China (21902021,

21908017, 51972293, 51772039, and 21703027), the Joint Research Fund Liaoning-

Shenyang National Laboratory for Materials Science (20180510020), the Fundamental

Research Funds for the Central Universities (DUT18LK15, DUT18LK21, and

DUT20LK46), and Supercomputing Center of Dalian University of Technology for this

work are gratefully acknowledged.

Competing interests

The authors declare no competing interests.

References

1. Zhou, F.; Azofra, L. M.; Ali, M.; Kar, M.; Simonov, A. N.; McDonnell-Worth, C.; Sun, C.; Zhang,
X.; MacFarlane, D. R., Electro-synthesis of ammonia from nitrogen at ambient temperature and pressure
57

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

in ionic liquids. Energy & Environmental Science 2017, 10 (12), 2516-2520.

2. Guo, W.; Zhang, K.; Liang, Z.; Zou, R.; Xu, Q., Electrochemical nitrogen fixation and utilization:
theories, advanced catalyst materials and system design. Chem Soc Rev 2019, 48 (24), 5658-5716.
3. Guo, C.; Ran, J.; Vasileff, A.; Qiao, S.-Z., Rational design of electrocatalysts and
photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy &
Environmental Science 2018, 11 (1), 45-56.
4. Wang, J.; Chen, S.; Li, Z.; Li, G.; Liu, X., Recent Advances in Electrochemical Synthesis of
Ammonia through Nitrogen Reduction under Ambient Conditions. ChemElectroChem 2020, 7 (5), 1067-
1079.
5. Manjunatha, R.; Schechter, A., Electrochemical synthesis of ammonia using ruthenium–platinum

Accepted Manuscript
alloy at ambient pressure and low temperature. Electrochem. Commun. 2018, 90, 96-100.
6. Chen, J. G.; Crooks, R. M.; Seefeldt, L. C.; Bren, K. L.; Bullock, R. M.; Darensbourg, M. Y.;
Holland, P. L.; Hoffman, B.; Janik, M. J.; Jones, A. K.; Kanatzidis, M. G.; King, P.; Lancaster, K. M.;
Lymar, S. V.; Pfromm, P.; Schneider, W. F.; Schrock, R. R., Beyond fossil fuel-driven nitrogen
transformations. Science 2018, 360 (6391).
7. Erisman, J. W.; Sutton, M. A.; Galloway, J.; Klimont, Z.; Winiwarter, W., How a century of
ammonia synthesis changed the world. Nature Geoscience 2008, 1, 636.
8. Suryanto, B. H. R.; Du, H.-L.; Wang, D.; Chen, J.; Simonov, A. N.; MacFarlane, D. R., Challenges
and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nature Catalysis 2019, 2 (4),
290-296.
9. Deng, J.; Iñiguez, J. A.; Liu, C., Electrocatalytic Nitrogen Reduction at Low Temperature. Joule
2018, 2 (5), 846-856.
10. Kitano, M.; Kanbara, S.; Inoue, Y.; Kuganathan, N.; Sushko, P. V.; Yokoyama, T.; Hara, M.; Hosono,
H., Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in
ammonia synthesis. Nature communications 2015, 6 (1), 6731.
11. Roux, Y.; Duboc, C.; Gennari, M., Molecular Catalysts for N2 Reduction: State of the Art,
Mechanism, and Challenges. Chemphyschem 2017, 18 (19), 2606-2617.
12. Acar, C.; Dincer, I., Comparative assessment of hydrogen production methods from renewable and
non-renewable sources. International Journal of Hydrogen Energy 2014, 39 (1), 1-12.
13. Yin, J.; Fan, Q.; Li, Y.; Cheng, F.; Zhou, P.; Xi, P.; Sun, S., Ni–C–N Nanosheets as Catalyst for
Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2016, 138 (44), 14546-14549.
14. Chen, G. F.; Ren, S.; Zhang, L.; Cheng, H.; Luo, Y.; Zhu, K.; Ding, L. X.; Wang, H., Advances in
Electrocatalytic N2 Reduction—Strategies to Tackle the Selectivity Challenge. Small Methods 2018, 3
(6), 1800337.
15. Tang, C.; Qiao, S. Z., How to explore ambient electrocatalytic nitrogen reduction reliably and
insightfully. Chem Soc Rev 2019, 48 (12), 3166-3180.
16. Hoffman, B. M.; Lukoyanov, D.; Yang, Z. Y.; Dean, D. R.; Seefeldt, L. C., Mechanism of nitrogen
fixation by nitrogenase: the next stage. Chem Rev 2014, 114 (8), 4041-62.
17. Foster, S. L.; Bakovic, S. I. P.; Duda, R. D.; Maheshwari, S.; Milton, R. D.; Minteer, S. D.; Janik,
M. J.; Renner, J. N.; Greenlee, L. F., Catalysts for nitrogen reduction to ammonia. Nature Catalysis 2018,
1 (7), 490-500.
18. Kyriakou, V.; Garagounis, I.; Vasileiou, E.; Vourros, A.; Stoukides, M., Progress in the
Electrochemical Synthesis of Ammonia. Catalysis Today 2017, 286, 2-13.
19. Danyal, K.; Rasmussen, A. J.; Keable, S. M.; Inglet, B. S.; Shaw, S.; Zadvornyy, O. A.; Duval, S.;

58

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

Dean, D. R.; Raugei, S.; Peters, J. W.; Seefeldt, L. C., Fe Protein-Independent Substrate Reduction by
Nitrogenase MoFe Protein Variants. Biochemistry 2015, 54 (15), 2456-2462.
20. Bao, D.; Zhang, Q.; Meng, F.-L.; Zhong, H.-X.; Shi, M.-M.; Zhang, Y.; Yan, J.-M.; Jiang, Q.; Zhang,
X.-B., Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and
Renewable Energy Storage Using N2/NH3 Cycle. Advanced Materials 2017, 29 (3), 1604799.
21. Soloveichik, G., Electrochemical synthesis of ammonia as a potential alternative to the Haber–
Bosch process. Nature Catalysis 2019, 2 (5), 377-380.
22. Julie N. Renner, L. F. G., Andrew M. Herring, Katherine E. Ayers, Electrochemical Synthesis of
Ammonia: A Low Pressure, Low Temperature Approach. The Electrochemical Society Interface 2018,
24 (2), 51-57.

Accepted Manuscript
23. Chang, C.-C.; Li, S.-R.; Chou, H.-L.; Lee, Y.-C.; Patil, S.; Lin, Y.-S.; Chang, C.-C.; Chang, Y. J.;
Wang, D.-Y., Photoactive Earth-Abundant Iron Pyrite Catalysts for Electrocatalytic Nitrogen Reduction
Reaction. Small 2019, 15 (49), 1904723.
24. Yu, J.; Li, J.; Zhu, X.; Zhang, X.; Jia, K.; Kong, W.; Wei, P.; Chen, H.; Shi, X.; Asiri, A. M.; Li, Q.;
Sun, X., Structured Polyaniline: An Efficient and Durable Electrocatalyst for the Nitrogen Reduction
Reaction in Acidic Media. ChemElectroChem 2019, 6 (8), 2215-2218.
25. Chaliha, C.; Kalita, E., Electrocatalytic Nitrogen (N2) Reduction. In Sustainable Ammonia
Production, Inamuddin; Boddula, R.; Asiri, A. M., Eds. Springer International Publishing: Cham, 2020;
pp 107-122.
26. Chu, S.; Majumdar, A., Opportunities and challenges for a sustainable energy future. Nature 2012,
488 (7411), 294-303.
27. Lan, R.; Irvine, J. T.; Tao, S., Synthesis of ammonia directly from air and water at ambient
temperature and pressure. Sci Rep 2013, 3, 1145.
28. Rong Lan, K. A. A., Ibrahim A. Amar, Shanwen Tao, Synthesis of ammonia directly from wet air
at intermediate temperature. App. Catal. B: Environ. 2014, 152 (153), 212-217.
29. Wang, Q.; Lei, Y.; Wang, D.; Li, Y., Defect engineering in earth-abundant electrocatalysts for CO2
and N2 reduction. Energy & Environmental Science 2019, 12 (6), 1730-1750.
30. Nazemi, M.; Panikkanvalappil, S. R.; El-Sayed, M. A., Enhancing the rate of electrochemical
nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold
nanocages. Nano Energy 2018, 49, 316-323.
31. Jia, H. P.; Quadrelli, E. A., Mechanistic aspects of dinitrogen cleavage and hydrogenation to
produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and
dihydrogen. Chem Soc Rev 2014, 43 (2), 547-64.
32. Luo, Y.; Chen, G.-F.; Ding, L.; Chen, X.; Ding, L.-X.; Wang, H., Efficient Electrocatalytic N2
Fixation with MXene under Ambient Conditions. Joule 2019, 3 (1), 279-289.
33. Hou, J.; Yang, M.; Zhang, J., Recent advances of catalysts, electrolytes and electrode engineering
for Nitrogen reduction reaction at ambient conditions. Nanoscale 2020.
34. Tao, H.; Choi, C.; Ding, L.-X.; Jiang, Z.; Han, Z.; Jia, M.; Fan, Q.; Gao, Y.; Wang, H.; Robertson,
A. W.; Hong, S.; Jung, Y.; Liu, S.; Sun, Z., Nitrogen Fixation by Ru Single-Atom Electrocatalytic
Reduction. Chem 2019, 5 (1), 204-214.
35. Shipman, M. A.; Symes, M. D., Recent progress towards the electrosynthesis of ammonia from
sustainable resources. Catalysis Today 2017, 286, 57-68.
36. Liu, J.; Zhu, D.; Zheng, Y.; Vasileff, A.; Qiao, S.-Z., Self-Supported Earth-Abundant Nanoarrays as
Efficient and Robust Electrocatalysts for Energy-Related Reactions. ACS Catalysis 2018, 8 (7), 6707-

59

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

6732.
37. Wan, Y.; Xu, J.; Lv, R., Heterogeneous electrocatalysts design for nitrogen reduction reaction under
ambient conditions. Materials Today 2019, 27, 69-90.
38. 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.
39. Mukherjee, S.; Yang, X.; Shan, W.; Samarakoon, W.; Karakalos, S.; Cullen, D. A.; More, K.; Wang,
M.; Feng, Z.; Wang, G.; Wu, G., Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction
toward Electrochemical Ammonia Synthesis Using N2 and H2O. Small Methods 2020, n/a (n/a),
1900821.

Accepted Manuscript
40. Guo, C.; Liu, X.; Gao, L.; Kuang, X.; Ren, X.; Ma, X.; Zhao, M.; Yang, H.; Sun, X.; Wei, Q., Fe-
doped Ni2P nanosheets with porous structure for electroreduction of nitrogen to ammonia under ambient
conditions. Applied Catalysis B: Environmental 2020, 263, 118296.
41. Arif, M.; Yasin, G.; Luo, L.; Ye, W.; Mushtaq, M. A.; Fang, X.; Xiang, X.; Ji, S.; Yan, D.,
Hierarchical hollow nanotubes of NiFeV-layered double hydroxides@CoVP heterostructures towards
efficient, pH-universal electrocatalytical nitrogen reduction reaction to ammonia. Applied Catalysis B:
Environmental 2020, 265, 118559.
42. Wang, Z.; Li, Y.; Yu, H.; Xu, Y.; Xue, H.; Li, X.; Wang, H.; Wang, L., Ambient Electrochemical
Synthesis of Ammonia from Nitrogen and Water Catalyzed by Flower-Like Gold Microstructures.
ChemSusChem 2018, 11 (19), 3480-3485.
43. Zhao, X.; Yao, C.; Chen, H.; Fu, Y.; Xiang, C.; He, S.; Zhou, X.; Zhang, H., In situ nano Au triggered
by a metal boron organic polymer: efficient electrochemical N2 fixation to NH3 under ambient conditions.
Journal of Materials Chemistry A 2019, 7 (36), 20945-20951.
44. Gao, W. Y.; Hao, Y. C.; Su, X.; Chen, L. W.; Bu, T. A.; Zhang, N.; Yu, Z. L.; Zhu, Z.; Yin, A. X.,
Morphology-dependent electrocatalytic nitrogen reduction on Ag triangular nanoplates. Chem Commun
(Camb) 2019, 55 (72), 10705-10708.
45. Lin, Y. X.; Zhang, S. N.; Xue, Z. H.; Zhang, J. J.; Su, H.; Zhao, T. J.; Zhai, G. Y.; Li, X. H.; Antonietti,
M.; Chen, J. S., Boosting selective nitrogen reduction to ammonia on electron-deficient copper
nanoparticles. Nat Commun 2019, 10 (1), 4380.
46. Hao, Q.; Liu, C.; Jia, G.; Wang, Y.; Arandiyan, H.; Wei, W.; Ni, B.-J., Catalytic reduction of nitrogen
to produce ammonia by bismuth-based catalysts: state of the art and future prospects. Materials Horizons
2020.
47. Back, S.; Jung, Y., On the mechanism of electrochemical ammonia synthesis on the Ru catalyst.
Physical chemistry chemical physics : PCCP 2016, 18 (13), 9161-6.
48. Fernández, C.; Pezzotta, C.; Gaigneaux, E. M.; Bion, N.; Duprez, D.; Ruiz, P., Disclosing the
synergistic mechanism in the catalytic activity of different-sized Ru nanoparticles for ammonia synthesis
at mild reaction conditions. Catalysis Today 2015, 251, 88-95.
49. Hui-Min Liu, S.-H. H., Ying-Ying Zhu, Xin-Long Tian, Bao Yu Xia ,Yu Chen, Surfactant-free
atomically ultrathin rhodium nanosheet nanoassemblies for efficient nitrogen electroreduction. J. Mater.
Chem. A 2018, 6, 3211–3217.
50. Wang, J.; Yu, L.; Hu, L.; Chen, G.; Xin, H.; Feng, X., Ambient ammonia synthesis via palladium-
catalyzed electrohydrogenation of dinitrogen at low overpotential. Nature communications 2018, 9 (1),
1795.
51. Howalt, J. G.; Vegge, T., The role of oxygen and water on molybdenum nanoclusters for electro

60

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

catalytic ammonia production. Beilstein J Nanotechnol 2014, 5, 111-20.

52. Yang, D.; Chen, T.; Wang, Z., Electrochemical reduction of aqueous nitrogen (N2) at a low
overpotential on (110)-oriented Mo nanofilm. J. Mater. Chem. A 2017, 5 (36), 18967-18971.
53. Liu, Y.; Huang, L.; Zhu, X.; Fang, Y.; Dong, S., Coupling Cu with Au for enhanced electrocatalytic
activity of nitrogen reduction reaction. Nanoscale 2020, 12 (3), 1811-1816.
54. Liu, L.; Pippel, E.; Scholz, R.; Go¨sele, U., Nanoporous Pt-Co Alloy Nanowires: Fabrication,
Characterization, and Electrocatalytic Properties. Nano Letters 2009, 9, 4352-4358.
55. Zhang, W.; Yang, J.; Lu, X., Tailoring Galvanic Replacement Reaction for the Preparation of Pt/Ag
Bimetallic Hollow Nanostructures with Controlled Number of Voids. ACS Nano 2012, 6, 7397-7405.
56. Li, H.-H.; Fu, Q.-Q.; Xu, L.; Ma, S.-Y.; Zheng, Y.-R.; Liu, X.-J.; Yu, S.-H., Highly crystalline PtCu

Accepted Manuscript
nanotubes with three dimensional molecular accessible and restructured surface for efficient catalysis.
Energy & Environmental Science 2017, 10 (8), 1751-1756.
57. Wang, Z.; Li, C.; Deng, K.; Xu, Y.; Xue, H.; Li, X.; Wang, L.; Wang, H., Ambient Nitrogen
Reduction to Ammonia Electrocatalyzed by Bimetallic PdRu Porous Nanostructures. ACS Sustainable
Chemistry & Engineering 2019, 7 (2), 2400-2405.
58. Kugler, K.; Luhn, M.; Schramm, J. A.; Rahimi, K.; Wessling, M., Galvanic deposition of Rh and
Ru on randomly structured Ti felts for the electrochemical NH3 synthesis. Physical chemistry chemical
physics : PCCP 2015, 17 (5), 3768-82.
59. Ma, X. L.; Liu, J. C.; Xiao, H.; Li, J., Surface Single-Cluster Catalyst for N2-to-NH3 Thermal
Conversion. J Am Chem Soc 2018, 140 (1), 46-49.
60. Pang, F.; Wang, Z.; Zhang, K.; He, J.; Zhang, W.; Guo, C.; Ding, Y., Bimodal nanoporous Pd3Cu1
alloy with restrained hydrogen evolution for stable and high yield electrochemical nitrogen reduction.
Nano Energy 2019, 58, 834-841.
61. Pang, F.; Wang, F.; Yang, L.; Wang, Z.; Zhang, W., Hierarchical nanoporous Pd1Ag1 alloy enables
efficient electrocatalytic nitrogen reduction under ambient conditions. Chem Commun (Camb) 2019, 55
(68), 10108-10111.
62. Fu, W.; Cao, Y.; Feng, Q.; Smith, W. R.; Dong, P.; Ye, M.; Shen, J., Pd-Co nanoalloys nested on
CuO nanosheets for efficient electrocatalytic N2 reduction and room-temperature Suzuki-Miyaura
coupling reaction. Nanoscale 2019, 11 (3), 1379-1385.
63. Zhang, Q.; Shen, Y.; Hou, Y.; Yang, L.; Chen, B.; Lei, Z.; Zhang, W., Composition-dependent
electrochemical activity of Ag-based alloy nanotubes for efficient nitrogen reduction under ambient
conditions. Electrochimica Acta 2019, 321, 134691.
64. Xue, Z. H.; Zhang, S. N.; Lin, Y. X.; Su, H.; Zhai, G. Y.; Han, J. T.; Yu, Q. Y.; Li, X. H.; Antonietti,
M.; Chen, J. S., Electrochemical Reduction of N2 into NH3 by Donor-Acceptor Couples of Ni and Au
Nanoparticles with a 67.8% Faradaic Efficiency. J Am Chem Soc 2019, 141 (38), 14976-14980.
65. Gong, Y.; Wu, J.; Kitano, M.; Wang, J.; Ye, T.-N.; Li, J.; Kobayashi, Y.; Kishida, K.; Abe, H.; Niwa,
Y.; Yang, H.; Tada, T.; Hosono, H., Ternary intermetallic LaCoSi as a catalyst for N2 activation. Nature
Catalysis 2018, 1 (3), 178-185.
66. Zybert, M.; Karasińska, M.; Truszkiewicz, E.; Mierzwa, B.; Raróg-Pilecka, W., Properties and
activity of the cobalt catalysts for NH3 synthesis obtained by co-precipitation – the effect of lanthanum
addition. Polish Journal of Chemical Technology 2015, 17 (1), 138-143.
67. Zybert, M.; Tarka, A.; Mierzwa, B.; Kępiński, L.; Raróg-Pilecka, W., Promotion effect of lanthanum
on the Co/La/Ba ammonia synthesis catalysts—the influence of lanthanum content. Applied Catalysis A:
General 2016, 515, 16-24.

61

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

68. Dorr, M.; Kassbohrer, J.; Grunert, R.; Kreisel, G.; Brand, W. A.; Werner, R. A.; Geilmann, H.; Apfel,
C.; Robl, C.; Weigand, W., A possible prebiotic formation of ammonia from dinitrogen on iron sulfide
surfaces. Angewandte Chemie 2003, 42 (13), 1540-3.
69. Zhang, H.; Cui, C.; Luo, Z., MoS2-Supported Fe2 Clusters Catalyzing Nitrogen Reduction Reaction
to Produce Ammonia. The Journal of Physical Chemistry C 2020.
70. Zhang, L.; Ji, X.; Ren, X.; Ma, Y.; Shi, X.; Tian, Z.; Asiri, A. M.; Chen, L.; Tang, B.; Sun, X.,
Electrochemical Ammonia Synthesis via Nitrogen Reduction Reaction on a MoS2 Catalyst: Theoretical
and Experimental Studies. Adv Mater 2018, 30 (28), e1800191.
71. Li, X.; Li, T.; Ma, Y.; Wei, Q.; Qiu, W.; Guo, H.; Shi, X.; Zhang, P.; Asiri, A. M.; Chen, L.; Tang,
B.; Sun, X., Boosted Electrocatalytic N2 Reduction to NH3 by Defect-Rich MoS2 Nanoflower. Advanced

Accepted Manuscript
Energy Materials 2018, 8 (30), 1801357.
72. Azofra, L. M.; Sun, C.; Cavallo, L.; MacFarlane, D. R., Feasibility of N2 Binding and Reduction to
Ammonia on Fe Deposited MoS2 2D Sheets: A DFT Study. Chemistry – A European Journal 2017, 23,
8275-8279.
73. Höskuldsson, Á. B.; Abghoui, Y.; Gunnarsdóttir, A. B.; Skúlason, E., Computational Screening of
Rutile Oxides for Electrochemical Ammonia Formation. ACS Sustainable Chemistry & Engineering
2017, 5 (11), 10327-10333.
74. Jia, K.; Wang, Y.; Pan, Q.; Zhong, B.; Luo, Y.; Cui, G.; Guo, X.; Sun, X., Enabling the
electrocatalytic fixation of N2 to NH3 by C-doped TiO2 nanoparticles under ambient conditions.
Nanoscale Advances 2019, 1, 961-964.
75. Zhang, R.; Ren, X.; Shi, X.; Xie, F.; Zheng, B.; Guo, X.; Sun, X., Enabling Effective Electrocatalytic
N2 Conversion to NH3 by the TiO2 Nanosheets Array under Ambient Conditions. ACS Appl Mater
Interfaces 2018, 10 (34), 28251-28255.
76. Shi, M. M.; Bao, D.; Wulan, B. R.; Li, Y. H.; Zhang, Y. F.; Yan, J. M.; Jiang, Q., Au Sub-
Nanoclusters on TiO2 toward Highly Efficient and Selective Electrocatalyst for N2 Conversion to NH3
at Ambient Conditions. Adv Mater 2017, 29 (17), e1606550.
77. Jimin Kong, A. L., Changwon Yoon, Jong Hyun Jang, Hyung Chul Ham, Jonghee Han, Sukwoo
Nam, Dokyoon Kim, Yung-Eun Sung, Jungkyu Choi and Hyun S. Park, Electrochemical Synthesis of
NH3 at Low Temperature and Atmospheric Pressure Using a γ-Fe2O3 Catalyst. ACS Sustainable
Chemistry & Engineering 2017, 5, 10986-10995.
78. Liu, Q.; Zhang, X.; Zhang, B.; Luo, Y.; Cui, G.; Xie, F.; Sun, X., Ambient N2 fixation to NH3
electrocatalyzed by a spinel Fe3O4 nanorod. Nanoscale 2018, 10 (30), 14386-14389.
79. Hu, L.; Khaniya, A.; Wang, J.; Chen, G.; Kaden, W. E.; Feng, X., Ambient Electrochemical
Ammonia Synthesis with High Selectivity on Fe/Fe Oxide Catalyst. ACS Catalysis 2018, 8 (10), 9312-
9319.
80. Fernández, C.; Sassoye, C.; Debecker, D. P.; Sanchez, C.; Ruiz, P., Effect of the size and distribution
of supported Ru nanoparticles on their activity in ammonia synthesis under mild reaction conditions.
Applied Catalysis A: General 2014, 474, 194-202.
81. Inoue, Y.; Kitano, M.; Kim, S.-W.; Yokoyama, T.; Hara, M.; Hosono, H., Highly Dispersed Ru on
Electride [Ca24Al28O64]4+(e–)4 as a Catalyst for Ammonia Synthesis. ACS Catalysis 2014, 4 (2), 674-680.
82. Zhang, L.; Ren, X.; Luo, Y.; Shi, X.; Asiri, A. M.; Li, T.; Sun, X., Ambient NH3 synthesis via
electrochemical reduction of N2 over cubic sub-micron SnO2 particles. Chem Commun (Camb) 2018, 54
(92), 12966-12969.
83. Lv, C.; Yan, C.; Chen, G.; Ding, Y.; Sun, J.; Zhou, Y.; Yu, G., An Amorphous Noble-Metal-Free

62

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions. Angewandte Chemie 2018, 57
(21), 6073-6076.
84. Wang, Z.; Gong, F.; Zhang, L.; Wang, R.; Ji, L.; Liu, Q.; Luo, Y.; Guo, H.; Li, Y.; Gao, P.; Shi, X.;
Li, B.; Tang, B.; Sun, X., Electrocatalytic Hydrogenation of N2 to NH3 by MnO: Experimental and
Theoretical Investigations. Adv Sci (Weinh) 2019, 6 (1), 1801182.
85. Jingrui Han, X. J., Xiang Ren, Guanwei Cui, Lei Li, Fengyu Xie, Hui Wang, Baihai Li and Xuping
Sun, MoO3 nanosheets for efficient electrocatalytic N2 fixation to NH3. J. Mater. Chem. A 2018, 6,
12974–12977.
86. Du, H.; Guo, X.; Kong, R. M.; Qu, F., Cr2O3 nanofiber: a high-performance electrocatalyst toward
artificial N2 fixation to NH3 under ambient conditions. Chem Commun (Camb) 2018, 54 (91), 12848-

Accepted Manuscript
12851.
87. Han, J.; Liu, Z.; Ma, Y.; Cui, G.; Xie, F.; Wang, F.; Wu, Y.; Gao, S.; Xu, Y.; Sun, X., Ambient N2
fixation to NH3 at ambient conditions: Using Nb2O5 nanofiber as a high-performance electrocatalyst.
Nano Energy 2018, 52, 264-270.
88. Abghoui, Y.; Skúlason, E., Electrochemical synthesis of ammonia via Mars-van Krevelen
mechanism on the (111) facets of group III–VII transition metal mononitrides. Catalysis Today 2017,
286, 78-84.
89. Zeinalipour-Yazdi, C. D.; Hargreaves, J. S. J.; Catlow, C. R. A., Nitrogen Activation in a Mars–van
Krevelen Mechanism for Ammonia Synthesis on Co3Mo3N. J. Phys. Chem. C 2015, 119 (51), 28368-
28376.
90. Liu, A.; Gao, M.; Ren, X.; Meng, F.; Yang, Y.; Yang, Q.; Guan, W.; Gao, L.; Liang, X.; Ma, T., Two-
Dimensional Ru@MXene Catalyst for Highly Selective Ambient Electrocatalytic Nitrogen Reduction.
Nanoscale 2020.
91. Yu, L.-l.; Qin, J.-z.; Zhao, W.-j.; Zhang, Z.-g.; Ke, J.; Liu, B.-j., Advances in Two-Dimensional
MXenes for Nitrogen Electrocatalytic Reduction to Ammonia. International Journal of Photoenergy
2020, 2020, 1-11.
92. Sun, J.; Kong, W.; Jin, Z.; Han, Y.; Ma, L.; Ding, X.; Niu, Y.; Xu, Y., Recent advances of MXene as
promising catalysts for electrochemical nitrogen reduction reaction. Chinese Chemical Letters 2020.
93. Liu, N.; Nie, L.; Xue, N.; Dong, H.; Peng, L.; Guo, X.; Ding, W., Catalytic Ammonia Synthesis
over Mo Nitride/ZSM-5. ChemCatChem 2010, 2 (2), 167-174.
94. Li, Q.; He, L.; Sun, C.; Zhang, X., Computational Study of MoN2 Monolayer as Electrochemical
Catalysts for Nitrogen Reduction. J. Phys. Chem. C 2017, 121 (49), 27563-27568.
95. Ren, X.; Cui, G.; Chen, L.; Xie, F.; Wei, Q.; Tian, Z.; Sun, X., Electrochemical N2 fixation to NH3
under ambient conditions: Mo2N nanorod as a highly efficient and selective catalyst. Chem Commun
(Camb) 2018, 54 (61), 8474-8477.
96. Zhang, L.; Ji, X.; Ren, X.; Luo, Y.; Shi, X.; Asiri, A. M.; Zheng, B.; Sun, X., Efficient
Electrochemical N2 Reduction to NH3 on MoN Nanosheets Array under Ambient Conditions. ACS
Sustainable Chemistry & Engineering 2018, 6 (8), 9550-9554.
97. Yang, X.; Nash, J.; Anibal, J.; Dunwell, M.; Kattel, S.; Stavitski, E.; Attenkofer, K.; Chen, J. G.;
Yan, Y.; Xu, B., Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium
Nitride Nanoparticles. J Am Chem Soc 2018, 140 (41), 13387-13391.
98. Zhang, R.; Zhang, Y.; Ren, X.; Cui, G.; Asiri, A. M.; Zheng, B.; Sun, X., High-Efficiency
Electrosynthesis of Ammonia with High Selectivity under Ambient Conditions Enabled by VN
Nanosheet Array. ACS Sustainable Chemistry & Engineering 2018, 6 (8), 9545-9549.

63

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

99. Wu, X.; Wang, Z.; Han, Y.; Zhang, D.; Wang, M.; Li, H.; Zhao, H.; Pan, Y.; Lai, J.; Wang, L.,
Chemically coupled NiCoS/C nanocages as efficient electrocatalysts for nitrogen reduction reactions.
Journal of Materials Chemistry A 2020, 8 (2), 543-547.
100. Zhou, Y.; Yu, X.; Sun, F.; Zhang, J., MoP supported on reduced graphene oxide for high
performance electrochemical nitrogen reduction. Dalton Transactions 2020, 49 (4), 988-992.
101. Xie, J.; Dong, H.; Cao, X.; Li, Y., Computational insights into nitrogen reduction reaction catalyzed
by transition metal doped graphene: Comparative investigations. Materials Chemistry and Physics 2020,
243, 122622.
102. He, X.; Yin, F.; Yuan, S.; Liu, N.; Huang, X., Hybrid Spinel Oxides/N-Doped Reduced Graphene
Oxide as Highly-Active Bifunctional Electrocatalysts for Oxygen Reduction/Evolution Reactions.

Accepted Manuscript
ChemElectroChem 2016, 3 (7), 1107-1115.
103. Wen, C.; Gao, X.; Huang, T.; Wu, X.; Xu, L.; Yu, J.; Zhang, H.; Zhang, Z.; Han, J.; Ren, H., Reduced
graphene oxide supported chromium oxide hybrid as high efficient catalyst for oxygen reduction reaction.
International Journal of Hydrogen Energy 2016, 41 (26), 11099-11107.
104. Zhu, J.; Jiang, Y.; Lu, Z.; Zhao, C.; Xie, L.; Chen, L.; Duan, J., Single-crystal Cr2O3 nanoplates with
differing crystalinities, derived from trinuclear complexes and embedded in a carbon matrix, as an
electrode material for supercapacitors. J Colloid Interface Sci 2017, 498, 351-363.
105. Wang, S.; Liao, L.; Shi, Z.; Xiao, J.; Gao, Q.; Zhang, Y.; Liu, B.; Tang, Y., Mo2C/Reduced-
Graphene-Oxide Nanocomposite: An Efficient Electrocatalyst for the Hydrogen Evolution Reaction.
ChemElectroChem 2016, 3 (12), 2110-2115.
106. Li, X. F.; Li, Q. K.; Cheng, J.; Liu, L.; Yan, Q.; Wu, Y.; Zhang, X. H.; Wang, Z. Y.; Qiu, Q.; Luo,
Y., Conversion of Dinitrogen to Ammonia by FeN3-Embedded Graphene. J Am Chem Soc 2016, 138
(28), 8706-9.
107. Chu, K.; Liu, Y.-p.; Wang, J.; Zhang, H., NiO Nanodots on Graphene for Efficient Electrochemical
N2 Reduction to NH3. ACS Applied Energy Materials 2019, 2 (3), 2288-2295.
108. Shi, M.-M.; Bao, D.; Li, S.-J.; Wulan, B.-R.; Yan, J.-M.; Jiang, Q., Anchoring PdCu Amorphous
Nanocluster on Graphene for Electrochemical Reduction of N2 to NH3 under Ambient Conditions in
Aqueous Solution. Advanced Energy Materials 2018, 8 (21), 1800124.
109. Zhang, X.; Liu, Q.; Shi, X.; Asiri, A. M.; Luo, Y.; Sun, X.; Li, T., TiO2 nanoparticles–reduced
graphene oxide hybrid: an efficient and durable electrocatalyst toward artificial N2 fixation to NH3 under
ambient conditions. Journal of Materials Chemistry A 2018, 6 (36), 17303-17306.
110. Huang, H.; Gong, F.; Wang, Y.; Wang, H.; Wu, X.; Lu, W.; Zhao, R.; Chen, H.; Shi, X.; Asiri, A.
M.; Li, T.; Liu, Q.; Sun, X., Mn3O4 nanoparticles@reduced graphene oxide composite: An efficient
electrocatalyst for artificial N2 fixation to NH3 at ambient conditions. Nano Research 2019, 12 (5), 1093-
1098.
111. Wang, F.; Liu, Y. p.; Zhang, H.; Chu, K., CuO/Graphene Nanocomposite for Nitrogen Reduction
Reaction. ChemCatChem 2019, 11 (5), 1441-1447.
112. Li, X.; Ren, X.; Liu, X.; Zhao, J.; Sun, X.; Zhang, Y.; Kuang, X.; Yan, T.; Wei, Q.; Wu, D., A MoS2
nanosheet–reduced graphene oxide hybrid: an efficient electrocatalyst for electrocatalytic N2 reduction
to NH3 under ambient conditions. Journal of Materials Chemistry A 2019, 7 (6), 2524-2528.
113. Xie, H.; Geng, Q.; Li, X.; Wang, T.; Luo, Y.; Alshehri, A. A.; Alzahrani, K. A.; Li, B.; Wang, Z.;
Mao, J., Ceria-reduced graphene oxide nanocomposite as an efficient electrocatalyst towards artificial
N2 conversion to NH3 under ambient conditions. Chem Commun (Camb) 2019, 55 (72), 10717-10720.
114. Li, J.; Zhu, X.; Wang, T.; Luo, Y.; Sun, X., An Fe2O3 nanoparticle-reduced graphene oxide

64

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

composite for ambient electrocatalytic N2 reduction to NH3. Inorganic Chemistry Frontiers 2019, 6 (10),
2682-2685.
115. Chu, K.; Liu, Y. P.; Li, Y. B.; Wang, J.; Zhang, H., Electronically Coupled SnO2 Quantum Dots and
Graphene for Efficient Nitrogen Reduction Reaction. ACS Appl Mater Interfaces 2019, 11 (35), 31806-
31815.
116. Xia, L.; Li, B.; Zhang, Y.; Zhang, R.; Ji, L.; Chen, H.; Cui, G.; Zheng, H.; Sun, X.; Xie, F.; Liu, Q.,
Cr2O3 Nanoparticle-Reduced Graphene Oxide Hybrid: A Highly Active Electrocatalyst for N2 Reduction
at Ambient Conditions. Inorg Chem 2019, 58 (4), 2257-2260.
117. Chen, S.; Perathoner, S.; Ampelli, C.; Mebrahtu, C.; Su, D.; Centi, G., Electrocatalytic Synthesis of
Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-

Accepted Manuscript
Nanotube-Based Electrocatalyst. Angew Chem Int Ed Engl 2017, 56 (10), 2699-2703.
118. Cui, X.; Tang, C.; Liu, X. M.; Wang, C.; Ma, W.; Zhang, Q., Highly Selective Electrochemical
Reduction of Dinitrogen to Ammonia at Ambient Temperature and Pressure over Iron Oxide Catalysts.
Chemistry 2018, 24 (69), 18494-18501.
119. Yu, G.; Guo, H.; Kong, W.; Wang, T.; Luo, Y.; Shi, X.; Asiri, Abdullah M.; Li, T.; Sun, X.,
Electrospun TiC/C nanofibers for ambient electrocatalytic N2 reduction. Journal of Materials Chemistry
A 2019, 7 (34), 19657-19661.
120. Yu, G.; Guo, H.; Liu, S.; Chen, L.; Alshehri, A. A.; Alzahrani, K. A.; Hao, F.; Li, T., Cr 3C2
Nanoparticle-Embedded Carbon Nanofiber for Artificial Synthesis of NH3 through N2 Fixation under
Ambient Conditions. ACS Appl Mater Interfaces 2019, 11 (39), 35764-35769.
121. Zhang, Z.; Yao, K.; Cong, L.; Yu, Z.; Qu, L.; Huang, W., Facile synthesis of a Ru-dispersed N-
doped carbon framework catalyst for electrochemical nitrogen reduction. Catalysis Science &
Technology 2020.
122. Chen, Z.; Zhao, J.; Cabrera, C. R.; Chen, Z., Computational Screening of Efficient Single‐Atom
Catalysts Based on Graphitic Carbon Nitride (g‐C3N4) for Nitrogen Electroreduction. Small Methods
2018, 3 (6), 1800368.
123. Zhang, L.; Zhao, W.; Zhang, W.; Chen, J.; Hu, Z., gt-C3N4 coordinated single atom as an efficient
electrocatalyst for nitrogen reduction reaction. Nano Research 2019, 12 (5), 1181-1186.
124. Ling, C.; Bai, X.; Ouyang, Y.; Du, A.; Wang, J., Single Molybdenum Atom Anchored on N-Doped
Carbon as a Promising Electrocatalyst for Nitrogen Reduction into Ammonia at Ambient Conditions. J.
Phys. Chem. C 2018, 122 (29), 16842-16847.
125. Zheng, Y.; Liu, J.; Liang, J.; Jaroniec, M.; Qiao, S. Z., Graphitic carbon nitride materials:
controllable synthesis and applications in fuel cells and photocatalysis. Energy & Environmental Science
2012, 5 (5), 6717.
126. Wang, X.; Wang, W.; Qiao, M.; Wu, G.; Chen, W.; Yuan, T.; Xu, Q.; Chen, M.; Zhang, Y.; Wang,
X.; Wang, J.; Ge, J.; Hong, X.; Li, Y.; Wu, Y.; Li, Y., Atomically dispersed Au1 catalyst towards efficient
electrochemical synthesis of ammonia. Sci Bull 2018, 63 (19), 1246-1253.
127. Qin, Q.; Heil, T.; Antonietti, M.; Oschatz, M., Single‐Site Gold Catalysts on Hierarchical N‐Doped
Porous Noble Carbon for Enhanced Electrochemical Reduction of Nitrogen. Small Methods 2018, 2 (12),
1800202.
128. Geng, Z.; Liu, Y.; Kong, X.; Li, P.; Li, K.; Liu, Z.; Du, J.; Shu, M.; Si, R.; Zeng, J., Achieving a
Record-High Yield Rate of 120.9 μgNH3 mgcat.-1 h-1 for N2 Electrochemical Reduction over Ru Single-
Atom Catalysts. Adv Mater 2018, 30, e1803498.
129. Luo, S.; Li, X.; Zhang, B.; Luo, Z.; Luo, M., MOF-Derived Co3O4@NC with Core-Shell Structures

65

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

for N2 Electrochemical Reduction under Ambient Conditions. ACS Appl Mater Interfaces 2019, 11 (30),
26891-26897.
130. Wang, Y.; Cui, X.; Zhao, J.; Jia, G.; Gu, L.; Zhang, Q.; Meng, L.; Shi, Z.; Zheng, L.; Wang, C.;
Zhang, Z.; Zheng, W., Rational Design of Fe–N/C Hybrid for Enhanced Nitrogen Reduction
Electrocatalysis under Ambient Conditions in Aqueous Solution. ACS Catalysis 2018, 9 (1), 336-344.
131. Qu, X.; Shen, L.; Mao, Y.; Lin, J.; Li, Y.; Li, G.; Zhang, Y.; Jiang, Y.; Sun, S., Facile Preparation of
Carbon Shells-Coated O-Doped Molybdenum Carbide Nanoparticles as High Selective Electrocatalysts
for Nitrogen Reduction Reaction under Ambient Conditions. ACS Appl Mater Interfaces 2019, 11 (35),
31869-31877.
132. Yang, Y.; Wang, S. Q.; Wen, H.; Ye, T.; Chen, J.; Li, C. P.; Du, M., Nanoporous Gold Embedded

Accepted Manuscript
ZIF Composite for Enhanced Electrochemical Nitrogen Fixation. Angew Chem Int Ed Engl 2019, 58 (43),
15362-15366.
133. Jiao, L.; Wang, Y.; Jiang, H. L.; Xu, Q., Metal-Organic Frameworks as Platforms for Catalytic
Applications. Adv Mater 2018, 30 (37), e1703663.
134. Wang, Y.; Li, Q.; Shi, W.; Cheng, P., The application of metal-organic frameworks in
electrocatalytic nitrogen reduction. Chinese Chemical Letters 2020.
135. Zhao, X.; Yin, F.; Liu, N.; Li, G.; Fan, T.; Chen, B., Highly efficient metal–organic-framework
catalysts for electrochemical synthesis of ammonia from N2 (air) and water at low temperature and
ambient pressure. J. Mater. Sci. 2017, 52 (17), 10175-10185.
136. Del Castillo, T. J.; Thompson, N. B.; Suess, D. L.; Ung, G.; Peters, J. C., Evaluating molecular
cobalt complexes for the conversion of N2 to NH3. Inorganic chemistry 2015, 54 (19), 9256-62.
137. Creutz, S. E.; Peters, J. C., Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-
atom anchor. J Am Chem Soc 2014, 136 (3), 1105-15.
138. Kuriyama, S.; Arashiba, K.; Tanaka, H.; Matsuo, Y.; Nakajima, K.; Yoshizawa, K.; Nishibayashi,
Y., Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen
Complexes Bearing Anionic PNP Pincer Ligands. Angewandte Chemie 2016, 55 (46), 14291-14295.
139. Arashiba, K.; Kinoshita, E.; Kuriyama, S.; Eizawa, A.; Nakajima, K.; Tanaka, H.; Yoshizawa, K.;
Nishibayashi, Y., Catalytic reduction of dinitrogen to ammonia by use of molybdenum-nitride complexes
bearing a tridentate triphosphine as catalysts. J Am Chem Soc 2015, 137 (17), 5666-9.
140. Kuriyama, S.; Arashiba, K.; Nakajima, K.; Tanaka, H.; Kamaru, N.; Yoshizawa, K.; Nishibayashi,
Y., Catalytic formation of ammonia from molecular dinitrogen by use of dinitrogen-bridged
dimolybdenum-dinitrogen complexes bearing PNP-pincer ligands: remarkable effect of substituent at
PNP-pincer ligand. J Am Chem Soc 2014, 136 (27), 9719-31.
141. Kuriyama, S.; Arashiba, K.; Nakajima, K.; Tanaka, H.; Yoshizawa, K.; Nishibayashi, Y., Nitrogen
fixation catalyzed by ferrocene-substituted dinitrogen-bridged dimolybdenum-dinitrogen complexes:
unique behavior of ferrocene moiety as redox active site. Chem Sci 2015, 6 (7), 3940-3951.
142. Tanaka, H.; Arashiba, K.; Kuriyama, S.; Sasada, A.; Nakajima, K.; Yoshizawa, K.; Nishibayashi, Y.,
Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards
catalytic formation of ammonia. Nature communications 2014, 5, 3737.
143. Chalkley, M. J.; Del Castillo, T. J.; Matson, B. D.; Roddy, J. P.; Peters, J. C., Catalytic N2-to-NH3
Conversion by Fe at Lower Driving Force: A Proposed Role for Metallocene-Mediated PCET. ACS Cent
Sci 2017, 3 (3), 217-223.
144. Del Castillo, T. J.; Thompson, N. B.; Peters, J. C., A Synthetic Single-Site Fe Nitrogenase: High
Turnover, Freeze-Quench 57Fe Mossbauer Data, and a Hydride Resting State. J Am Chem Soc 2016, 138

66

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

(16), 5341-50.
145. Kuriyama, S.; Arashiba, K.; Nakajima, K.; Matsuo, Y.; Tanaka, H.; Ishii, K.; Yoshizawa, K.;
Nishibayashi, Y., Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen
complexes bearing pincer ligand. Nat Commun 2016, 7, 12181.
146. Tanabe, Y.; Nishibayashi, Y., Catalytic Dinitrogen Fixation to Form Ammonia at Ambient Reaction
Conditions Using Transition Metal-Dinitrogen Complexes. Chem Rec 2016, 16 (3), 1549-77.
147. Tanaka, H.; Nishibayashi, Y.; Yoshizawa, K., Interplay between Theory and Experiment for
Ammonia Synthesis Catalyzed by Transition Metal Complexes. Acc Chem Res 2016, 49 (5), 987-95.
148. Hazari, N., Homogeneous iron complexes for the conversion of dinitrogen into ammonia and
hydrazine. Chem Soc Rev 2010, 39 (11), 4044-56.

Accepted Manuscript
149. Grubel, K.; Brennessel, W. W.; Mercado, B. Q.; Holland, P. L., Alkali metal control over N-N
cleavage in iron complexes. J Am Chem Soc 2014, 136 (48), 16807-16.
150. Rittle, J.; Peters, J. C., An Fe-N2 Complex That Generates Hydrazine and Ammonia via Fe =NNH2 :
Demonstrating a Hybrid Distal-to-Alternating Pathway for N2 Reduction. J Am Chem Soc 2016, 138 (12),
4243-8.
151. Li, Y.; Li, Y.; Wang, B.; Luo, Y.; Yang, D.; Tong, P.; Zhao, J.; Luo, L.; Zhou, Y.; Chen, S.; Cheng,
F.; Qu, J., Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic. Nat
Chem 2013, 5 (4), 320-6.
152. Coric, I.; Mercado, B. Q.; Bill, E.; Vinyard, D. J.; Holland, P. L., Binding of dinitrogen to an iron-
sulfur-carbon site. Nature 2015, 526 (7571), 96-9.
153. Kui Shen, X. C., Junying Chen, and Yingwei Li, Development of MOF-Derived Carbon-Based
Nanomaterials for Efficient Catalysis. ACS Catalysis 2016, 6, 5887-5903.
154. Mukherjee, S.; Cullen, D. A.; Karakalos, S.; Liu, K.; Zhang, H.; Zhao, S.; Xu, H.; More, K. L.;
Wang, G.; Wu, G., Metal-organic framework-derived nitrogen-doped highly disordered carbon for
electrochemical ammonia synthesis using N2 and H2O in alkaline electrolytes. Nano Energy 2018, 48,
217-226.
155. Lv, C.; Qian, Y.; Yan, C.; Ding, Y.; Liu, Y.; Chen, G.; Yu, G., Defect Engineering Metal-Free
Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions.
Angewandte Chemie 2018, 57 (32), 10246-10250.
156. Yanming Liu, Y. S., Xie Quan, Xinfei Fan,Shuo Chen, Hongtao Yu, Huimin Zhao, Yaobin Zhang,
and Jijun Zhao, Facile Ammonia Synthesis from Electrocatalytic N2 Reduction under Ambient
Conditions on NDoped Porous Carbon. ACS Catalysis 2018, 8, 1186-1191.
157. Zhu, X.; Wu, T.; Ji, L.; Li, C.; Wang, T.; Wen, S.; Gao, S.; Shi, X.; Luo, Y.; Peng, Q.; Sun, X.,
Ambient electrohydrogenation of N2 for NH3 synthesis on non-metal boron phosphide nanoparticles: the
critical role of P in boosting the catalytic activity. Journal of Materials Chemistry A 2019, 7 (27), 16117-
16121.
158. Xiao, S.; Luo, F.; Hu, H.; Yang, Z., Boron and nitrogen dual-doped carbon nanospheres for efficient
electrochemical reduction of N2 to NH3. Chemical Communications 2020, 56 (3), 446-449.
159. Ren, J.-T.; Wan, C.-Y.; Pei, T.-Y.; Lv, X.-W.; Yuan, Z.-Y., Promotion of electrocatalytic nitrogen
reduction reaction on N-doped porous carbon with secondary heteroatoms. Applied Catalysis B:
Environmental 2020, 266, 118633.
160. Ji, S.; Wang, Z.; Zhao, J., A boron-interstitial doped C2N layer as a metal-free electrocatalyst for N2
fixation: a computational study. Journal of Materials Chemistry A 2019, 7, 2392-2399.
161. Kumar, C. V. S.; Subramanian, V., Can boron antisites of BNNTs be an efficient metal-free catalyst

67

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

for nitrogen fixation? - A DFT investigation. Physical chemistry chemical physics : PCCP 2017, 19 (23),
15377-15387.
162. Zhang, X.; Wu, T.; Wang, H.; Zhao, R.; Chen, H.; Wang, T.; Wei, P.; Luo, Y.; Zhang, Y.; Sun, X.,
Boron Nanosheet: An Elemental Two-Dimensional (2D) Material for Ambient Electrocatalytic N2-to-
NH3 Fixation in Neutral Media. ACS Catalysis 2019, 9 (5), 4609-4615.
163. Zhang, Y.; Du, H.; Ma, Y.; Ji, L.; Guo, H.; Tian, Z.; Chen, H.; Huang, H.; Cui, G.; Asiri, A. M.; Qu,
F.; Chen, L.; Sun, X., Hexagonal boron nitride nanosheet for effective ambient N2 fixation to NH3. Nano
Research 2019, 12 (4), 919-924.
164. Yu, X.; Han, P.; Wei, Z.; Huang, L.; Gu, Z.; Peng, S.; Ma, J.; Zheng, G., Boron-Doped Graphene
for Electrocatalytic N2 Reduction. Joule 2018, 2 (8), 1610-1622.

Accepted Manuscript
165. Jiao, J.; Lin, R.; Liu, S.; Cheong, W. C.; Zhang, C.; Chen, Z.; Pan, Y.; Tang, J.; Wu, K.; Hung, S. F.;
Chen, H. M.; Zheng, L.; Lu, Q.; Yang, X.; Xu, B.; Xiao, H.; Li, J.; Wang, D.; Peng, Q.; Chen, C.; Li, Y.,
Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical
reduction of CO2. Nat Chem 2019, 11 (3), 222-228.
166. Qiu, W.; Xie, X. Y.; Qiu, J.; Fang, W. H.; Liang, R.; Ren, X.; Ji, X.; Cui, G.; Asiri, A. M.; Cui, G.;
Tang, B.; Sun, X., High-performance artificial nitrogen fixation at ambient conditions using a metal-free
electrocatalyst. Nature communications 2018, 9 (1), 3485.
167. Song, Y.; Wang, T.; Sun, J.; Wang, Z.; Luo, Y.; Zhang, L.; Ye, H.; Sun, X., Enhanced
Electrochemical N2 Reduction to NH3 on Reduced Graphene Oxide by Tannic Acid Modification. ACS
Sustainable Chemistry & Engineering 2019, 7 (17), 14368-14372.
168. Tian, Y.; Xu, D.; Chu, K.; Wei, Z.; Liu, W., Metal-free N, S co-doped graphene for efficient and
durable nitrogen reduction reaction. Journal of Materials Science 2019, 54 (12), 9088-9097.
169. Chen, H.; Zhu, X.; Huang, H.; Wang, H.; Wang, T.; Zhao, R.; Zheng, H.; Asiri, A. M.; Luo, Y.; Sun,
X., Sulfur dots-graphene nanohybrid: a metal-free electrocatalyst for efficient N2-to-NH3 fixation under
ambient conditions. Chem Commun (Camb) 2019, 55 (21), 3152-3155.
170. Xia, L.; Wu, X.; Wang, Y.; Niu, Z.; Liu, Q.; Li, T.; Shi, X.; Asiri, A. M.; Sun, X., S‐Doped Carbon
Nanospheres: An Efficient Electrocatalyst toward Artificial N2 Fixation to NH3. Small Methods 2018, 3
(6), 1800251.
171. Xia, L.; Yang, J.; Wang, H.; Zhao, R.; Chen, H.; Fang, W.; Asiri, A. M.; Xie, F.; Cui, G.; Sun, X.,
Sulfur-doped graphene for efficient electrocatalytic N2-to-NH3 fixation. Chem Commun (Camb) 2019,
55 (23), 3371-3374.
172. Chu, K.; Li, Q.-q.; Liu, Y.-p.; Wang, J.; Cheng, Y.-h., Filling the nitrogen vacancies with sulphur
dopants in graphitic C3N4 for efficient and robust electrocatalytic nitrogen reduction. Applied Catalysis
B: Environmental 2020, 267, 118693.
173. Li, H.; Yang, L.; Wang, Z.; Jin, P.; Zhao, J.; Chen, Z., N-heterocyclic carbene as a promising metal-
free electrocatalyst with high-efficiency for nitrogen reduction to ammonia. Journal of Energy Chemistry
2020, 46, 78-86.
174. Yuan, L.-P.; Wu, Z.-Y.; Jiang, W.-J.; Tang, T.; Niu, S.; Hu, J.-S., Phosphorus-doping activates carbon
nanotubes for efficient electroreduction of nitrogen to ammonia. Nano Research 2020.
175. Zhao, J.; Yang, J.; Ji, L.; Wang, H.; Chen, H.; Niu, Z.; Liu, Q.; Li, T.; Cui, G.; Sun, X., Defect-rich
fluorographene nanosheets for artificial N2 fixation under ambient conditions. Chemical
Communications 2019, 55 (29), 4266-4269.
176. Chen, J.; Huang, H.; Xia, L.; Xie, H.; Ji, L.; Wei, P.; Zhao, R.; Chen, H.; Asiri, A. M.; Sun, X.,
Oxygen‐Doped Porous Carbon Nanosheet for Efficient N2 Fixation to NH3 at Ambient Conditions.

68

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.202000487

ChemistrySelect 2019, 4 (12), 3547-3550.

177. Wang, T.; Xia, L.; Yang, J. J.; Wang, H.; Fang, W. H.; Chen, H.; Tang, D.; Asiri, A. M.; Luo, Y.; Cui,
G.; Sun, X., Electrocatalytic N2-to-NH3 conversion using oxygen-doped graphene: experimental and
theoretical studies. Chem Commun (Camb) 2019, 55 (52), 7502-7505.
178. Li, W.; Wu, T.; Zhang, S.; Liu, Y.; Zhao, C.; Liu, G.; Wang, G.; Zhang, H.; Zhao, H., Nitrogen-free
commercial carbon cloth with rich defects for electrocatalytic ammonia synthesis under ambient
conditions. Chem Commun (Camb) 2018, 54 (79), 11188-11191.
179. Zhang, L.; Ding, L. X.; Chen, G. F.; Yang, X.; Wang, H., Ammonia Synthesis Under Ambient
Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets.
Angew Chem Int Ed Engl 2019, 58 (9), 2612-2616.

Accepted Manuscript

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