Materials Today Physics 16 (2021) 100310

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Materials Today Physics

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materials-today-physics

Electrochemical synthesis of ammonia: Progress and challenges

Tingting Wu, Wenjun Fan, Yang Zhang, Fuxiang Zhang*
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian,
116023, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Ammonia, as an essential chemical and a promising fuel, has been predominantly synthesized by the
Received 16 August 2020 Haber-Bosch process since the beginning of the 20th century. However, the harsh conditions, high energy
Received in revised form consumption, and large carbon footprint of this century-old process enforce human being to develop
22 October 2020
clean and sustainable ammonia synthesis technologies. The electrochemical synthesis of ammonia has
Accepted 30 October 2020
Available online 2 November 2020
advantages of mild operating conditions, zero emission of carbon dioxide, capability to store renewable
electricity in chemical bonds, and possibilities for distributed ammonia production. Benefiting from
these merits, the electrochemical synthesis of ammonia is expected as a promising alternative to the
Keywords:
Electrocatalysis
Haber-Bosch process and has been extensively explored. Research on the electrochemical synthesis of
Ammonia synthesis ammonia by nitrogen reduction reaction (NRR) can be principally divided into several aspects including
Nitrogen reduction the development of catalysts, innovations on the configurations of electrolytic cells, strategies to improve
Nitrogenous pollutants reduction the selectivity, and verification of ammonia synthesis results. Moreover, the electrochemical reduction of
nitrogenous pollutants has also been tried to produce ammonia. In this review, we summarize the recent
progress on these points and conclude with perspectives on challenges and future directions of elec-
trochemical ammonia synthesis.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction unsustainable Haber-Bosch process. Up to now, approaches such as

Ammonia is a key chemical widely used in modern industry and
agriculture as well as a promising carbon-free energy carrier with
high hydrogen content (17.6 wt %), high energy density (4.25 kWh/
L), and ease of storage and transportation [1e3]. The predominant
route of ammonia synthesis, Haber-Bosch process, is one of the
greatest achievements of the 20th century. However, this process
requires a pure hydrogen precursor primarily produced from
strongly endothermic steam-methane reforming. Also, it operates
at elevated temperatures (400e500
C) and pressures (10e30 MPa)
to kinetically accelerate the reaction and shift the equilibrium
favorably. As a result, it consumes 1e2% of the total energy
worldwide and releases ~420 Mt of CO2 annually [4,5]. In addition,
the large-scale and centralized Haber-Bosch plant requires huge
capital investment and results in severe regional distribution im-
balances [6]. To this end, scientists have been dedicated to devel-
oping facile ammonia synthetic methods that can be operated
under mild conditions to replace the energy-intensive and
chemical looping [7], organometallic [8], biomimetic [9], photo-
catalytic [10], and (photo)electrochemical [11] have been proposed.
Among these approaches, the electrochemical synthesis of
ammonia is emerging as a compelling alternative to the Haber-
Bosch process, benefiting from its mild operating conditions, zero
emission of carbon dioxide, capability to store renewable electricity
in chemical bonds, and possibilities for distributed ammonia
production.
During the electrochemical NRR, NRR and hydrogen evolution
reaction (HER) take place at the cathode and compete with each
other, which can be expressed as follows [11e13].
In acidic electrolytes:
N2 ðgÞ þ 6H þ þ 6 e / 2NH3 ðgÞ E0 ¼ 0:148 V vs: RHE (1)
2Hþ þ 2e / H2 ðgÞ E0 ¼ 0 V vs: SHE ðpH ¼ 0Þ (2)
In basic electrolytes:

N2 ðgÞ þ 6H2 O þ 6 e / 2NH3 ðaq:Þ þ 6OH

* Corresponding author.
E-mail address: fxzhang@dicp.ac.cn (F. Zhang).

https://doi.org/10.1016/j.mtphys.2020.100310
2542-5293/© 2020 Elsevier Ltd. All rights reserved.
T. Wu, W. Fan, Y. Zhang et al.
E0 ¼  0:736 V vs: SHE ðpH ¼ 14Þ (3)
2H2 O þ 2e / H2 ðgÞ þ 2OH E0
¼ 0:828 V vs: SHE ðpH ¼ 14Þ (4)
The challenges facing electrochemical NRR mainly come from
the following two aspects. Firstly, N2 features high bonding energy
(941 kJ mol1), large energy gap (10.8 eV), high ionization potential
(15.8 eV), negative electron affinity (1.9 eV), and ultralow solu-
bility in water (6.8  104 M, 1.01  105 Pa, 298 K), which hinders
the reduction of N2 both thermodynamically and kinetically [4,14];
Secondly, the electrochemical NRR has been plagued by low
selectivity since its emergence. The electrochemical NRR and HER
both can occur from a thermodynamic point of view and their
equilibrium potentials are close to each other. However, the elec-
trochemical NRR is a multi-step process that involves six electrons
and six protons, and has suffered from sluggish kinetics. By
contrast, the HER is a two-electron process, which is much more
kinetically preferred. Consequently, the selectivity of electro-
chemical NRR is usually very low, which means high energy
expenditure and lack of industrial competitiveness. The challenges
make the electrochemical synthesis of ammonia from nitrogen
particularly difficult and trigger research interests including the
development of catalysts [11], innovations on the configurations of
electrolytic cells [15,16], strategies to improve the selectivity [17],
and verification of ammonia formation results [18].
On the other hand, human activities add ~150 million metric
tons of N every year to nature. This significantly alters the natural N
cycle and results in deposition of undesired reactive N (NO 
3 , NO2 ,
NO2, NO, N2O, etc.) in the environment, which is known as
nitrogenous pollutants and responsible for a variety of cascading
environmental damages [1,19]. To reduce the environmental im-
pacts, removal of nitrogenous pollutants has been widely investi-
gated in the environmental field albeit with N2 as the target
product instead of NH3 [20]. Compared with N2, nitrogenous pol-
lutants are much more reactive and can be reduced more easily
from the thermodynamic viewpoint [12,21]. Considering the
extraordinary difficulty of nitrogen fixation, it seems feasible to
recycle these exhausts into valuable NH3. On this account, re-
searchers conducted investigations on electrochemical synthesis of
ammonia employing nitrate, nitrite, or NO as the feedstock
[22e24], which is emerging as a new category of electrochemical
ammonia synthesis.
The electrochemical synthesis of ammonia is developing at an
unprecedented speed, which makes the summary and update of
relevant progress especially imperative. Although several reviews
have been reported recently, they have different emphases such as
strategies for catalyst design and system optimization [11,25e31].
This review is aimed at providing a concise but comprehensive
overview on the latest progress in electrochemical synthesis of
ammonia. Firstly, we summarize the latest works on electro-
chemical nitrogen reduction to ammonia. Then, recent de-
velopments on the electrochemical nitrogenous pollutants
reduction to ammonia are briefly introduced. Finally, we point out
the opportunities and challenges in this field.
2. Electrochemical synthesis of ammonia from NRR
2.1. Mechanisms of electrochemical NRR
The catalytic reduction of nitrogen usually involves three steps:
(1) adsorption of N2 molecules onto the catalyst surface, (2) the
dissociative or associative breaking of N^N bond and
2
Materials Today Physics 16 (2021) 100310
hydrogenation, (3) desorption of the generated ammonia. It is
generally believed that the industrial Haber-Bosch process evolves
through a dissociative mechanism. Taking Fe-based catalysts as an
example, 2 to 5 Fe atoms first interact with N2 in a side-on mode
and break the N^N bond into nitrogen adatoms. HeH bonds in H2
simultaneously rupture on the catalyst surface and then react with
N adatoms to form NH3 (Fig. 1a) [32]. However, the direct broken of
the N^N bond is extremely difficult and requires a large amount of
energy. The electrochemical NRR and the catalytic process of ni-
trogenases both occur at mild conditions that don’t favor direct
N^N bond breaking. Therefore, discussions on their mechanisms
focus mainly on the associative mechanism during which the N^N
bond gradually breaks as the hydrogenation of N proceeds until an
ammonia molecule is released. The associative mechanism can be
subdivided into distal, alternating, and enzymatic pathways. For
the distal pathway, N2 adsorbs onto the surface of catalysts in an
end-on mode. The N atom remote from the adsorption site is
consecutively hydrogenated first and then hydrogenation of the
other N atom occurs (Fig. 1c) [13]. For the alternating pathway, N2
adsorbs onto the surface of catalysts in an end-on mode and then N
atoms in N2 are hydrogenated alternately (Fig. 1b). During the
enzymatic pathway, N atoms in N2 are also hydrogenated alter-
nately but N2 adsorbs onto the surface of catalysts in a side-on
mode (Fig. 1d) [33]. For electrochemical NRR, the activation of N2
is usually the rate-determining step. To break this restriction, Liu
et al. recently prepared cobalt single clusters dispersed in nitrogen-
doped carbon. They declared that the introduction of cobalt single
clusters altered the rate-determining step from N2 activation to the
barrier-less proton addition process [34].
Moreover, there are some pathways for electrochemical NRR
that don’t involve N2 adsorption on the surface of catalysts, such as
the Mars-van-Krevelen (MvK) mechanism and Li-mediated pro-
cess. It has been supposed that transition metal nitrides such as VN
can catalyze the electrochemical NRR through the MvK mechanism
during which the lattice nitrogen atoms in nitrides are hydroge-
nated to form NH3 and then the generated nitrogen vacancies are
replenished by N2 (Fig. 1e) [35]. However, it should be noted that
this view has been questioned recently [36,37]. Therefore, it re-
mains to be clarified whether catalytic processes following the MvK
mechanism have ever occurred. During the Li-mediated process, N2
first reacts with lithium metal to make lithium nitride, which can
occur spontaneously at ambient conditions. Then the lithium
nitride is protonated to form ammonia and a lithium salt. Finally,
the lithium salt is electrochemically reduced back to lithium metal
to close the cycle (Fig. 1f) [16].
To date, most of the discussions on the mechanisms of electro-
chemical NRR have been based on density functional theory (DFT)
calculations. Nevertheless, experimental studies on the mecha-
nisms of electrochemical NRR are of great importance because they
can provide direct evidence for the nitrogen reduction process,
which is helpful to clarify the principles of electrochemical NRR and
dispel doubts about the results. Considering this, Yao et al. moni-
tored the reaction intermediates of electrochemical NRR on Ru thin
film and the Rh/C catalyst employing surface-enhanced infrared-
absorption spectroscopy (SEIRAS) and/or differential electro-
chemical mass spectroscopy (DEMS) [38,39]. The results revealed
that intermediate N2Hx (0  y  2) was detected on the Ru thin film
and Rh/C catalysts. Therefore, it can be known that both the Ru thin
film and Rh/C catalyst catalyze NRR through the associative
mechanism following a two-electron transfer pathway. Addition-
ally, it is encouraging that an increasing number of works on
catalyst development are using in situ/operando characterizations
(such as operando X-ray absorption spectroscopy and in situ Raman
spectra) to investigate the mechanisms of electrochemical NRR and
validate their catalytic results [35,40e43]. However, it should be
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 1. Schematic diagrams of possible mechanisms for electrochemical NRR. (a) Dissociate pathway, (b) associate-alternating pathway, (c) associate-distal pathway, and (d)
associate-enzymatic pathway. Reprinted with permission from Ref. [33]. Copyright (2019) American Chemical Society. (e) Reactivity (right) and deactivation (left) mechanisms of
VN0.7O0.45. Reprinted with permission from Ref. [35]. (f) Li-mediated mechanism. Reprinted with permission from Ref. [16]. Copyright (2020) Nature Publishing Group.

paid attention that the dominance of HER during the electro- research due to its capabilities of free energy calculations, kinetic
chemical NRR may interfere with the results of these in situ/oper- analysis, and catalyst design [44]. In this section, we summarize the
ando characterizations [4]. principles and progress in computational research on electro-
chemical NRR.
At the early stage of the 20th century, the French chemist
2.2. Computational studies on electrochemical NRR
Sabatier proposed that the optimal catalyst should bind atoms or
molecules moderately because too weak binding makes the acti-
As mentioned above, the reduction of nitrogen is of great diffi-
vation process difficult while too strong binding results in
culty. Catalysts can change the reaction pathway, lower the energy
poisoning of the catalysts [45]. This principle provided a qualitative
barrier, and thus accelerate the rate of electrochemical NRR. It is
criterion of the optimal catalyst but lacked predictive power
precisely because of this that the development of high-
because it was not clear which quantity should be used to represent
performance catalysts will always be the key to make break-
the “bond strength” between the intermediate and the catalyst.
throughs in electrochemical NRR. For the entire field of catalysis,
Afterwards, it turned out that scaling relations exist universally in
the development of catalysts was once completely dependent on
the adsorption energies of different intermediates/transient states
experimental research and conducted in an empirical manner. In
that determine the reaction rate, which means that the associated
the past decades, the advances in the fields of computation and
variables can be reduced to one [46]. The generality of the scaling
modelling gradually changed this situation. Nowadays, computa-
relation significantly reduces the dimensionality of calculations and
tional catalysis has become a valuable companion of experimental
3
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

makes the quantitative implementation of the classical Sabatier
principle possible. Taking the electrochemical NRR as an example,
nitrogen adsorption energies on catalysts can act as the single
variable/descriptor of ammonia synthesis activity and a volcano-
type diagram of catalytic activity vs. nitrogen adsorption energy
on different transition metal catalysts (Fig. 2a) can be obtained [45].
Then, the d-band model further revealed the reason why scaling
relations exist between different variables is that the adsorption
energies of different intermediates depend linearly on the surface
electronic structure of the catalysts. The adsorbates hybridize with
the surface d electrons of transition metal catalysts to form bonding
and anti-bonding states during the adsorption process. The inter-
action between adsorbates and catalysts is closely related to the
filling degree of anti-bonding states of the adsorbates, which in
turn depends on the position of the d-band center of transition
metal catalysts relative to the Fermi level. Generally, the higher the
d band center relative to the highest occupied states at the Fermi
energy, the interaction becomes stronger [45,46]. The d-band
center theory has been widely used to interpret the electrochemical
NRR results, as will be discussed later in section 2.3.
Specifically, Skulason et al. theoretically evaluated the electro-
chemical NRR on flat and stepped surfaces of transition metal
catalysts [47]. Results revealed that Mo, Fe, Ru, and Rh were the
most active surfaces but the competition of HER would seriously
affect the NRR performance. By contrast, early transition metals
such as Ti, Zr, Sc, and Y bound nitrogen more strongly than protons
and thus a significant ammonia production was expected (Fig. 2a).
Subsequently, Howalt et al. investigated the electrochemical NRR
on highly under-coordinated transition metal nanoclusters using
DFT calculations in combination with the computational standard
hydrogen electrode. The results indicated that Mo and Fe are the
most promising candidates for electrochemical NRR [48]. Abghoui
et al. identified VN, ZrN, NbN, and CrN as the most promising
mononitrides for electrochemical NRR through DFT based analysis
and studied their stability against poisoning and decomposition.
The results revealed that single-crystal surfaces were required for
ZrN, NbN, and CrN to be stable while the rocksalt (100) facet of
polycrystalline VN could catalyze electrochemical NRR through the
MvK mechanism to avoid decomposition [49]. As stated above, the
scaling relationship of different variables in a reaction can signifi-
cantly reduce the dimensionality of calculations. However, it also
makes the catalysts design a compromise process between
different competing factors [45,50]. The work of Montoya et al.
indicated that the electrochemical NRR performance was severely
limited by the linear scaling between the energetics of *N2H and
*NH2, and the use of bifunctional surfaces was considered to tune
these two parameters independently [51]. Zhang et al. stated that
the use of 2,6-lutidinium (LutHþ) could selectively stabilize *N2H
and break the scaling relationship [52]. With the rise of single-atom
catalysts, the electrochemical NRR on transition metal single-atoms
anchored on different supports such as nitrogen-doped carbons
[53,54], graphene [55e57], carbon nitride (C3N4) [55,58], black
phosphorene [59], boron monolayer [60], graphdiyne [61], Mxenes
[62], molybdenum disulfide (MoS2) [63], and platinum disulfide
(PtS2) [64] gradually becomes a computational research hotspot.
Moreover, transition metal dimers or trimers are increasingly
considered as the candidates for electrochemical NRR benefiting
from their synergetic effect between different metal atoms, possi-
bility to circumvent the scaling relations, higher metal-atom
loading, more flexible active sites, etc. For instance, Chen et al. re-
ported that transition metal double-atom catalysts with C2N
(Fig. 2b) as the support (TM2-C2N) such as Mn2eC2N (Fig. 2d) are
more suitable for electrochemical NRR compared with their single-
atom counterparts (TM-C2N, Fig. 2c) according to the DFT calcula-
tion results [65]. Guo et al. sampled both homonuclear and heter-
onuclear metal dimers supported on 2D expanded phthalocyanine
(M2-Pc or MM0 -Pc). Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, and VTa-Pc were
predicted to have strong capability to suppress HER with favorable
limiting potentials for electrochemical NRR [66]. Hu et al. investi-
gated the effects of coordination atoms (C, N, O, P, and S) on the
electrochemical NRR performance of bimetallic pairs supported on
graphene and the results indicated that carbon was the optimal
coordination atom [67]. The work of Chen et al. revealed that
transition metal trimers supported on the heterostructure of
graphdiyne and graphene could achieve higher loading amount,
improved dynamic stability, and better catalytic performance

Fig. 2. (a) Volcano diagrams of electrochemical NRR on stepped (red) and flat (black) transition metal surfaces through a Heyrovsky type reaction with (dashed lines) and without
(solid lines) H-bonds effect. The grey-shaded area represents that the surface of catalysts will likely be covered with H-adatoms. Reprinted with permission from Refs. [47].
Copyright (2012) The Royal Society of Chemistry. (b) Structure of C2N, (c) single transition metal atoms supported on C2N, and (d) double transition metal atoms supported on C2N.
The yellow and red shadows denote electron loss and accumulation, respectively. The grey, blue, and purple balls represent C, N, and Mn atoms, respectively. Reprinted with
permission from Ref. [65]. Copyright (2018) Wiley-VCH. Microkinetic model including (e) measures of efficacy, (f) models for electrochemical NRR and HER, and (g) electrode
geometry definitions. Reprinted with permission from Ref. [72]. Copyright (2020) American Chemical Society.

4
T. Wu, W. Fan, Y. Zhang et al.
compared with single atoms or dimers [68].
DFT is a workhorse of first-principles-based simulation in
catalysis and has been used in nearly all of the computational
studies mentioned above. However, the high computational cost
has greatly limited its application. By contrast, machine learning is
the practice of building models from data, which can avoid time-
consuming steps and reveal reaction processes in a short time,
thus accelerating the catalyst development [50,69]. Recently, Kim
et al. reported a work that used machine learning to evaluate the
electrochemical NRR performance on L12 intermetallic crystals and
predicted that V3Ir (111), Tc3Hf (111), V3Ni (111), and Tc3Ta (111)
were stable candidates that may exhibit improved catalytic per-
formance compared with the reference Mo (110) [70]. Zafari et al.
investigated the electrochemical NRR performance of transition
metal single-atom catalysts anchored on B-doped graphene using
machine learning [71]. The results revealed that the chromium
single-atom catalyst with a CrB3C1 structure exhibited the best
performance with a minimal potential of 0.13 V and high selectivity.
Besides electronic structure, morphologies of the electrodes also
may greatly affect the electrochemical NRR performance but few of
the computational studies have taken them into account. In this
regard, Hoar et al. proposed a machine learning model (Fig. 2e, f,
and g) to explore the morphology influence of micro/nanowire
array electrodes on the performance of electrochemical NRR [72].
Overall, plenty of progress has been made on the computational
studies for electrochemical NRR as depicted above but there re-
mains many challenges to be overcome. Firstly, the improvements
in the accuracy of computational studies are required to avoid
wrong results and misleading the development of catalyst. Sec-
ondly, the current computational studies for electrochemical NRR
usually adopt simplified models with the major concern on the
electronic structure of catalysts and there is an urgent need to
develop multi-scale approaches that incorporate the effects of
temperature, pressure, electrolytes, etc. Lastly, the advances in
computational science and development of new methods are ur-
gently needed to enable the large-scale screening of catalysts.
2.3. Experimental explorations on catalyst development
Besides the computational research, a lot of experimental efforts
have also been made. The elements used in the catalysts for elec-
trochemical NRR can be divided into three groups: (1) noble metals
such as Au, Ru, Rh, Pd, Pt, Ag, and Ir; (2) non-noble metals such as Y,
Sc, Ti, Zr, V, Cr, Nb, Mo, Fe, Co, Mn, Ni, Cu, W, Re, Sn, Sb, Bi, La, Ce, and
Dy; (3) non-metal elements such as B, C, N, O, F, P, S, Se, and Te.
These elements can derive many sorts of catalysts for electro-
chemical NRR, including metals, metal alloys, transition metal
carbides, nitrides, oxides, and sulfides, carbon materials, black and
red phosphorous, Mxene, covalent organic frameworks (COF), C3N4,
etc. Herein, the catalysts are classified (noble metal catalysts, non-
noble metal catalysts, and metal-free catalysts) and summarized to
shed light on the development tendency of catalysts for electro-
chemical NRR. Considering that a number of the early reported
catalysts have been reviewed for many times, we give priorities to
the latest and representative ones.
2.3.1. Noble metal catalysts
Although the membership is not well-defined, it is generally
supposed that noble metals include silver, gold, and platinum
group metals (Ru, Rh, Pd, Os, Ir, and Pt). As a whole, there are plenty
of investigations on Au, Ru, Rh, and Pd while reports on Ag, Os, Ir,
and Pt are sporadic for electrochemical NRR [73e77]. Due to the
high cost of noble metals, it is necessary to take atomic utilization
into account. Therefore, single-atoms, nanostructures, and alloys
are the most investigated noble metal catalysts. Recently, Xu et al.
5
Materials Today Physics 16 (2021) 100310
prepared nanoporous palladium hydride (np-PdH) through deal-
loying of Al80Pd20 and in situ hydrogen injection (Fig. 3a) [40].
Isotopic deuterium labeling experiments revealed that the outmost
hydrogen atoms in np-PdH participated in the electrochemical NRR
and a lattice hydrogen involved reaction pathway was proposed
(Fig. 3b). Hydrogen doping of np-PdH improved the internal elec-
tron concentration and shifted the d band center towards the Fermi
level, leading to stronger adsorption of intermediates and
enhanced catalytic activity. The electrochemical NRR performance
improved with the increase of hydrogen content in np-PdH. The np-
PdH0.43 exhibited the best performance with a FE of 43.6% and an
NH3 yield rate of 20.4 mg h1 mg1 cat at 0.15 V vs. RHE in 0.1 M
phosphate buffer solution (Fig. 3c and d). Tong et al. optimized the
NRR catalytic activity of PdCu through a crystal phase engineering
strategy [78]. The prepared PdCu nanoparticles loaded on carbon
powder were transformed from face-centered cubic (FCC) to body-
centered cubic (BCC) phase through annealing in Ar/H2 atmo-
sphere. The NRR catalytic performance of BCC PdCu outperformed
FCC PdCu with a maximum NH3 yield rate of 35.7 mg h1 mg1 cat and a
FE of 11.5% at 0.1 V vs. RHE in 0.5 M LiCl. Surface valence band
spectra indicated that the transformation of PdCu from FCC to BCC
uplifted the d-band center towards the Fermi level, leading to
enhanced N2 adsorption and catalytic activity. DFT calculation re-
sults revealed that the Cu 3d band in BCC PdCu bridged the
electron-transfer coulomb gap of Pd 4d and boosted the electronic
activities of Pd 4d for NRR. Yang et al. proposed a generalized sur-
face chalcogenation strategy to boost the electrochemical NRR
performance of noble-metal nanocrystals (Pt, Pd, Ru, and Rh) [79].
A series of noble metal selenide/chalcogenides were prepared, all of
which exhibited enhanced performance compared with their
counterparts without selenide/chalcogenation. For RheSe nano-
crystals, selenation created additional Rh3þ species on the surface
and upshifted the d-band center to the Fermi level, which can
enhance the adsorption of N2 and inhibit the HER process. As a
result, the RheSe nanocrystals exhibited significantly enhanced
NH3 yield rate (175 mg h1 mg1 Rh ), FE (13.3%), and stability (18 h)
compared with the pristine Rh nanocrystals.
2.3.2. Non-noble metal catalysts
Low reserves and high cost of noble metals severely restrict
their application. By contrast, non-noble metals are abundant and
low-cost. Moreover, nitrogenases in the nature contain non-noble
metals including Fe, Mo, and V. Therefore, plenty of studies have
been carried out in search of efficient non-noble metal catalysts for
electrochemical NRR, as will be discussed below.
Inspired by the nitrogenase MoFe protein, researchers have
developed many kinds of Mo-based catalysts for electrochemical
NRR such as Mo thin films [80], MoS2 [81], Mo2C [82], and single Mo
atoms [83]. For MoS2, Mo atoms in the basal plane are blocked by S
atoms on both sides and thus only Mo atoms in the edge plane act
as active sites for electrochemical NRR. To expose more molybde-
num atoms and activate the basal plane of MoS2-x, Zhang et al.
recently fabricated Co-doped MoS2-x polycrystalline nanosheets
with abundant S vacancies (Vs) on carbon cloth substrate [84].
Through Co doping, the S/Mo ratio decreased markedly, indicating
a substantial increase of S vacancies in Co-doped MoS2-x. For the
undoped MoS2-x, N2 adsorbed to the center of Vs and interacted
with three Mo atoms (Fig. 4a), resulting in a reaction energy barrier
of 1.62 eV. After Co doping, the adsorbed N2 bound to one Mo atom
(Fig. 4b) and the reaction energy barrier reduced to 0.94 eV, leading
to enhanced NRR performance. In this work, Co atoms exist as an
interior dopant for MoS2. By contrast, Li et al. conjugated single
atomic Fe protrusions onto the surface of MoS2 (Fig. 4c, d, and e)
and made use of the high curvature of this structure to induce
interfacial polarization field between the single-atomic Fe
T. Wu, W. Fan, Y. Zhang et al.
Fig. 3. (a) Preparation process of np-PdH. (b) Lattice hydrogen involved reaction pathway proposed for electrochemical NRR on np-PdH. (c) Ammonia yield rate and (d) FE of
electrochemical NRR on np-Pd and np-PdH0.43 at different potentials. Reprinted with permission from Ref. [40]. Copyright (2020) Wiley-VCH.
protrusions and N2 molecules [43]. The generated interfacial po-
larization field can drive the injection of electrons from Fe into the
antibonding orbitals of N2 and make the splitting of N2 easier. The
electrochemical NRR performance of the prepared catalysts was
tested in a flow cell using gas diffusion electrodes (GDEs) and ul-
trahigh performance (NH3 yield rate: 97.5 ± 6 mg h1 cm2, FE:
31.6% ± 2%) that exceeded all of the reported MoS2 based catalysts
was obtained for SACs-MoS2-Fe-2.0 with 2 at.% of Fe loading.
Iron-base catalyst is another research hotspot and a variety of
iron-base catalysts such as the SACs-MoS2-Fe-2.0 depicted above
[43], Fe3O4 [85], a-Fe@Fe3O4 [86], FeOOH [87], FeeNeC [88], and
FeSx [89] have been reported. Recently, Zhang et al. prepared a Ja-
nus FeeSnO2 catalyst for bifunctional N2 fixation, i.e. NRR and N2
oxidation reaction (NOR) [90]. Lattice-doped Fe and single-atom Fe
anchored by oxygen vacancies coexisted in FeeSnO2. Computa-
tional and experimental results revealed that the Fe single atoms
anchored on SnO2 played as the active sites while the lattice-doped
6
Materials Today Physics 16 (2021) 100310
Fe could improve the electrical activity of SnO2, leading to
outstanding activity for both NRR and NOR. An NH3 yield rate of
82.7 mg h1 mg1cat and a FE of 20.4% were achieved for NRR while a
NO3 yield rate of 42.9 mg h
1
mg1
cat and a FE of 0.84% were obtained
for NOR. In the reported Fe single atoms immobilized onto carbon
materials, Fe usually coordinates with N or C atoms. To enrich the
types of coordination atoms for Fe single atoms and obtain high
electrochemical NRR performance, Zhang et al. prepared a Fe
single-atom catalyst anchored onto lignocellulose-derived carbon
through a Fe-(OeC2)4 coordination configuration, and an NH3 yield
rate of 32.1 mg h1 mg1cat and a FE of 29.3% were obtained [91].
Reports on Cu based catalysts for electrochemical NRR are
relatively few perhaps because of its weak N2 adsorption and high
activity towards nitrogenous pollutants reduction. Recently, Lin
et al. prepared Cu-based catalysts for electrochemical NRR by
tuning the electronic structure of Cu [92]. Copper nanoparticles
were loaded onto semi-conductive polyimide nanoflowers (Fig. 4f)
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 4. DFT results of the interaction between N2 molecules and S (yellow spheres) vacancies (VS) on (a) undoped MoS2-x and (b) Co-doped MoS2-x. For MoS2-x, one N2 molecule
(light blue spheres) binds with three Mo atoms (dark blue spheres) near the VS. After Co doping, N2 binds to one of the Mo atoms near the VS. Reprinted with permission from
Ref. [84]. Copyright (2019) American Chemical Society. Schematic views of SACs-MoS2-Fe-Y: (c) side-view, (d) top-view, and (e) perspective-view. Reprinted with permission from
Ref. [43]. Copyright (2020) Elsevier B.V. (f) Preparation process of a typical Cu/PI catalyst. Reprinted with permission from Ref. [92]. Copyright (2019) Nature Publishing Group.

which can attract electrons from copper, leading to rectifying
contact at the interface and electron-deficient copper particles.
According to the DFT calculation results, the electron deficiency of
Cu nanoparticles enhanced the polarization of N2 and reduced the
Gibbs free energy change of NRR. Also, OH tends to adsorb onto
electron-deficient Cu nanoparticles, which can retard the HER
process in alkaline electrolytes. As a result, the Cu/PI-300 catalyst,
in which Cu nanoparticles have the most pronounced electron
deficiency, exhibited the best NRR performance with an NH3 yield
rate of 12.4 mg h1 cm2 (loading amount: 5 mg cm2) and a FE of
6.56% at 0.4 V vs. RHE in 0.1 M KOH. Moreover, Zang et al. pre-
pared copper single-atoms supported on nitrogen doped carbon for
electrochemical NRR, which exhibited high performance in both
acidic and alkaline electrolytes [93].
Rhenium has also been used in catalysts for electrochemical
NRR recently. Lai et al. reported that low-valence Fe doping and rich
Se vacancies could upshift the d-band center of ReS2 and ReSe2
towards Fermi level, respectively, and facilitate both the electro-
chemical NRR and HER [94,95]. To suppress HER and improve the
FE of NRR, the authors adopted a hydrophobic strategy, which will
be discussed in section 2.5. Fu et al. introduced Mn into ReS2 and
prepared orderly atomic-hybridized Re2MnS6 alloy with morphol-
ogies of ultrathin nanosheets for electrochemical NRR [42]. A large
number of valence electrons transferred from Re to Mn, leading to
strong e-e Coulomb interaction, semimetal states of Mn-3d orbitals,
and ordered atomic hybridization. Computational results revealed
that the single-metal ReS2 adopted a distal pathway with N2
adsorbed in the end-on mode. By contrast, N2 bound with both Re
and Mn simultaneously for the Re2MnS6 nanosheets, leading to
more favorable N2 adsorption and 6.6 times higher catalytic
activity.
As depicted above, early transition metal surfaces such as Sc, Y,
Ti, and Zr were expected to exhibit significant NH3 yield rate owing
to their stronger binding towards N-adatoms than H-adatoms [47].
Recently, Liu et al. prepared single-atom Y and Sc catalysts sup-
ported on nitrogen doped carbon (Fig. 5a) by a solid synthesis
method and employed them as the catalysts for electrochemical
NRR and CO2 reduction [96]. It was deduced that the Y and Sc atoms
were stabilized on the carbon defects by coordinating with six
carbon and nitrogen atoms. Both the single-atom Y and Sc catalysts
could catalyze the electrochemical NRR and they exhibited similar
activities with a maximum NH3 yield rate about 20 mg cm2 h1 and
the highest FE around 12% (Fig. 5bee). In early transition metals
and their compounds, TiO2 is the most widely investigated and
applied due to its superior properties. It has been proved that Ti3þ
defect states around oxygen vacancies are pivotal for electro-
chemical NRR [97,98]. In this context, various metal heteroatoms
such as Zr4þ, Fe, and mixed-valent Cu have been doped into TiO2 to
induce Ti3þ and enhance NRR performance [99e101]. Moreover, Liu
et al. employed a lithium-reduction strategy to generate oxygen

7
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 5. (a) High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) images of Y1/NC. (b, c) Ammonia yield rate at different potentials on Y1/NC and
Sc1/NC, respectively. (d) FE of Y1/NC and Sc1/NC at different potentials. (e) I-t curves of Y1/NC and Sc1/NC during a durability test of 12 h (Bottom) and changes in ammonia yield rate
and faradaic before and after the durability test (Top). Reprinted with permission from Ref. [96]. Copyright (2020) American Chemical Society.

vacancies in self-supported TiO2 nanofibrous aerogels with ultra-
low bulk density and ultrahigh porosity for electrochemical NRR
[102]. Qin et al. acted oppositely and anionic carbon atoms were
doped into TiO2 by occupying the oxygen vacancies and forming
TieC bonds in their work [103]. The authors declared that (O)eTieC
bonds in C-TixOy/C could largely enhance the activation and
reduction of N2 compared with unoccupied oxygen vacancies. Be-
sides TiO2, Ti3C2Tx Mxene is another kind of Ti containing catalysts
for electrochemical NRR. Ti3C2Tx Mxene prepared by HF etching of
Ti3AlC2 MAX has a lamellate T-Ti-C-Ti-C-Ti-T sandwich structure
(T ¼ F, OH, O) [104]. The Ti atoms in Ti3C2Tx Mxene are blocked by
inactive functional groups, resulting in inadequate catalytic activity
for electrochemical NRR. To enhance the electrochemical NRR
performance of Ti3C2Tx Mxene, a variety of strategies such as size
reduction to generate more edge planes, in situ growing oxygen-
vacancy-rich TiO2, surface hydroxyl modification, and ironing out
inactive terminals have been proposed [104e107].
Main group metals have also been used in catalysts for elec-
trochemical NRR [108,109]. Recently, Liu et al. prepared Sb/SbPO4
loaded on phosphorus-doped carbon (PC) to catalyze the electro-
chemical NRR [110]. SbPO4 and P-doped carbon both were the
active sites for NRR whereas metallic Sb was covered by SbPO4 and
didn’t take part in the catalytic process. The valence state of Sb in
SbPO4 became slightly higher and SbPO4 underwent amorphization

8
T. Wu, W. Fan, Y. Zhang et al.
and partial dissolution during the NRR tests. In 0.1 M HCl, the
average ammonia yield rate decreased observably during a dura-
bility test of 24 h. In 0.1 M Na2SO4, the PC/Sb/SbPO4 catalyst
exhibited better NRR performance with the maximum FE of 34%
at 0.1 V vs. RHE and the highest NH3 yield rate of 23 mg h1 mg1
cat
at 0.3 V vs. RHE.
2.3.3. Metal-free catalysts
Compared with metal catalysts, metal-free catalysts possess
many merits such as low-cost, environmental friendliness, and free
from poisoning. Therefore, research and development of metal-free
catalysts are of both scientific importance and economic interest.
Currently, the reported metal-free catalysts for electrochemical
NRR mainly include carbon-based catalysts, phosphorous-based
catalysts, nonmetallic compounds, etc.
For carbon-based materials, doping is the most widely used
strategy to tune the electronic structure and improve the catalytic
activity. Liu et al. prepared F-doped porous carbon derived from
UiO-66 metal-organic-frameworks (MOF) as the catalyst for elec-
trochemical NRR (Fig. 6aed) [111]. Because electronegativity of
fluorine (3.98) is much higher than that of carbon (2.55), the
introduction of F atoms created Lewis acid sites on the neighbor
carbon atoms. These Lewis acid sites not only can facilitate the
binding and dissociation of N2 but also can keep the protons away,
which simultaneously enhanced the activity and selectivity of
electrochemical NRR. Moreover, UIO-66 derived carbon has high
Brunauer-Emmett-Teller (BET) surface area (1024.8 m2 g1), lead-
ing to more exposed active sites. Due to the above advantages, the
F-doped carbon exhibited an NH3 yield rate up to 197.7 mg h1
mg1cat. with a high FE of 54.8% in 0.05 M H2SO4 (Fig. 6e and f). Yang
et al. investigated the NRR performance of chalcogen/oxygen-group
element doped carbon prepared by vapor doping of MOF derived
nanoporous carbon [112]. DFT calculations revealed that S, Se, and
Te doping created net negative charges on their adjacent carbon
atoms, which could enhance N2 adsorption on the charge enriched
carbon atoms. Moreover, the spin moment of the active carbon
atoms increased dramatically after doping, which was beneficial to
the first step of the hydrogenation process. Among the hetero-
atoms, Te doping led to the best NRR performance with an NH3
production rate of 1.91 mg h1 cm2 and a FE of 4.67%. It is note-
worthy that the charges created on carbon atoms adjacent to het-
eroatoms in the above two works are opposite with each other, and
a consensus remains to be reached on the working principles of
charges.
Black phosphorous is an allotrope of phosphorous and has been
expected to be an ideal catalyst for electrochemical NRR because its
valence-electron structure is similar to that of nitrogen and may be
beneficial to N2 chemisorption. Zhang et al. prepared few-layer
black phosphorous nanosheets (FL-BP NSs) as the catalyst for NRR
[113]. DFT results revealed that the zigzag and diff-zigzag types of
edges of FL-BP NSs are active sites for NRR. To obtain larger surface
area and more active sites for electrochemical NRR, Liu et al.
downsized black phosphorous to quantum dots (BP QDs), which
were further stably confined on black tin oxide (SnO2-x) nanotubes
to avoid agglomeration [114]. BP QDs and SnO2-x can synergistically
catalyze NRR, leading to an NH3 an yield rate of 48.87 mg h1 mg1 cat
and a FE of 14.6%. Besides black phosphorous, few-layer triclinic
crystalline red phosphorous nanoribbons (cRP NRs) have also been
used to catalyze electrochemical NRR [115]. Theoretical calculation
results revealed that N2 bound with two P atoms between the two
coupled five atom rings (the building unit of cRP) but a distal
pathway that usually applies to the end-on N2 adsorption mode
was assumed for electrochemical NRR on cRP NRs.
Nonmetallic compounds such as B4C and C3N4 have also been
reported as the catalysts for electrochemical NRR [116,117].
9
Materials Today Physics 16 (2021) 100310
Recently, Liu et al. reported boron-rich COFs coated on conductive
nitrogen-doped carbon nanosheets (COF-NC) for electrochemical
NRR [41]. The prepared COF-NC can be excited by potentiostatic
electrolyzing, forming Eex-COF/NC. During the excitation, boron
atoms in COF-NC adsorb nitrogenous species by forming BeN
bonds. The formation of BeN bonds leads to structure distortion
of COF from crystalline to amorphous phase, which can further
enhance the adsorption of N2 onto COF. The Eex-COF/NC exhibited a
FE of 45.43% and an NH3 yield rate of 12.53 mg h1 mg1 at 0.2 V
vs. RHE in 0.1 M KOH.
The performance of all catalysts introduced in Section 2.3 has
been verified by isotopic 15N labeling experiments. However, most
of the 15N labeling experiments are single-point and qualitative,
which are not rigorous enough. Even if assuming all of the reported
results are reliable, it is supposed that little substantial progress has
been made on the catalyst development for electrochemical NRR.
As shown in Fig. 7, the ammonia yield rate of all the recently
published representative catalysts is several orders of magnitude
lower than the value required for application (9.3
107 mol cm2 s1, ~57 mg h1 cm2, FE > 90%) [118]. Many kinds of
strategies such as defect engineering (vacancies, heteroatom
doping, and edge engineering), structural manipulation (single-
atom sites and morphological regulation), crystallographic tailoring
(crystal facet control and amorphous engineering), and interface
regulation are available for catalyst design, as summarized in some
recently published reviews [11,29,119e121]. Unfortunately, these
strategies have not brought the electrochemical NRR to an appli-
cable level. Some suggestions on the further design of catalysts for
electrochemical NRR are provided as follows: Firstly, elemental
compositions are important for the electronic structure of catalysts.
Up to now, more than thirty kinds of elements have been involved
in the electrocatalysts for NRR. In general, elements on the top or
left side of the volcano diagrams (Fig. 2a) seem more promising due
to their higher nitrogen adsorption energies and worthy of further
studies. Secondly, the more efficient implementation of a certain
design strategy mentioned above, integration of multi-strategies, or
development of new strategies may be helpful for the design of
better catalysts. In this context, the development of approaches
that can realize the controllable preparation and precise regulation
of catalysts becomes urgent. Besides the electronic structure which
is closely related to the intrinsic activity, the physical structure,
conductivity, stability, and cost of catalysts should also be paid
more attention. Finally, catalyst design should be combined with
the improvements on the electrolytic cells, regulation of local re-
action environments, etc. to make significant improvements on the
performance of electrochemical NRR.
2.4. Innovations on the configurations of electrolytic cells
The electrolytic cells used in electrochemical NRR mainly
include back-to-back cell, polymer electrolyte membrane (PEM)-
type cell, flow cell, H-type cell, and single chamber cell [13,43]. In a
back-to-back cell, the porous cathodic gas diffusion electrode (GDE)
and anode catalyst are pressed onto the two sides of a piece of ion-
exchange membrane, respectively. By contrast, the PEM-type cell is
consisted of one GDE as the cathode while liquid electrolyte, the
counter electrode, and the reference electrode are placed in the
anodic chamber. The use of liquid electrolyte is not only convenient
for adding a reference electrode but also can ensure the wetting of
the membrane to reduce the conductivity loss. Different with the
back-to-back cell and PEM-type cell that don’t contain liquid
electrolyte in the cathodic chamber, the flow cell contains catholyte
that flows between the cathodic GDE and the ion-exchange
membrane while the anode can either use a GDE or not [43,122].
The presence of flow catholyte is beneficial to controlling the
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 6. (a) Scanning electron microscope (SEM) image, (b) transmission electron microscope (TEM) image, (c) high-resolution TEM image, (d) HAADF-STEM image, and corre-
sponding energy-dispersive X-ray spectroscopy (EDS) elemental mapping results of F-doped porous carbon. (e) Ammonia yield rate and (f) FE of F-doped porous carbon and pristine
carbon at different potentials. Reprinted with permission from Refs. [111]. Copyright (2020) Wiley-VCH.

reaction environment but may accelerate the flooding of GEDs. For
an H-type cell, the anodic and the cathodic chambers are both filled
with liquid electrolytes and separated by a piece of ion-exchange
membrane. The membrane can help to balance the ionic charge
while preventing the transport of products to the anodic chamber.
The reference electrode is located at the cathodic chamber and thus
the potential of the working electrode can be measured more
accurately compared with the PEM-type cell. In a single-chamber
cell, the cathode, anode, and reference electrode are all placed in
a single chamber filled with liquid electrolyte. Due to the absence of
a membrane in the single-chamber cell, the produced ammonia
may be reoxidized at the anode. The performance of electro-
chemical NRR not only depends on the activity of catalysts but also
on the cell configurations. Therefore, the improvements on cell

10
T. Wu, W. Fan, Y. Zhang et al.
Fig. 7. An electrochemical NRR performance map of the recently reported represen-
tative catalysts.
configurations are of great importance. Nonetheless, most of the
reported works for electrochemical NRR use H-type cells and ef-
forts put into this direction are relatively few. In this section, we
will introduce two works that have made innovations on the con-
figurations of electrolytic cells for electrochemical NRR.
Recently, Kyriakou et al. proposed an electrochemical Haber-
Bosch process by building an ingenious BaZrO3-based protonic
ceramic membrane reactor (PCMR) operated at atmospheric pres-
sure and temperature of 550
Ce650
C (Fig. 8a) [15]. At the anode
of the PCMR, steam-methane reforming (SMR) and water-gas shift
(WGS) reaction occurred on the nickel catalyst to generate H2. The
produced H2 can be converted into protons upon closing the circuit
which then transferred through the protonic ceramic membrane to
the cathodic compartment. The rapid extraction of protons from
the anode chamber and dominance of WGS reaction led to a
considerable increase of CH4 conversion and a CO2 selectivity over
95%, which maximized the hydrogen yield. Over the VN-Fe cathode,
NRR occurred, and an NH3 yield rate of 68 mmol h1 m2 and a FE
of 5.5% were obtained at the cell voltage of 0.63 V and temperature
of 600
C. The PCMR was further assembled with a protonic ceramic
fuel cell (PCFC) into an electrochemical Haber-Bosch (EHB) plant to
recover part of the electricity consumed in PCMR and separate ni-
trogen from the air by consuming the by-product hydrogen. FE is
critical for the energy consumption of the EHB plant. Only at fara-
daic efficiencies above 35%, less energy consumption and CO2
emissions compared with an industrial plant may be achieved,
which emphasizes the importance of the cathodic electrode per-
formance. Methane is necessary for the low-voltage operation and
stability of the EHB. If only steam was fed into the EHB, it would
require a ~1.0 V higher operation voltage and thus much more
energy according to theoretical calculations. Moreover, the nickel
catalyst at the anode is prone to oxidation at high steam concen-
trations in the absence of methane. The authors proposed that
methane could be derived from biogas and solid carbonaceous
biofuels rather than natural gas to minimize the carbon footprint.
Although the faradaic efficiency needs to be further improved, the
EBH plant reported in this work is highly integrated and holds
promise for application in remote areas. It should be noted that this
work conducted control experiments under Ar/H2 but lacked
rigorous 15N labeling experiments, which compromises the reli-
ability of the results. As mentioned above, the electrochemical NRR
performance of nitrides at ambient conditions has been questioned
11
Materials Today Physics 16 (2021) 100310
[36,37]. It was proposed that the situation under high-temperature
conditions was different and the N-vacancies generated on VN
could be replenished by N atoms derived from N2 dissociation in
this work as has been observed in the Co3Mo3N system [123,124].
Nonetheless, this statement would be more convictive if it was
verified by rigorous 15N labeling experiments.
The lithium-mediated approach is an electrochemical NRR
process that usually uses non-aqueous electrolytes and features
both high ammonia yield rate and FE. Its mechanism can be
referred to the section 2.1. The lithium-mediated approach is usu-
ally operated in batch mode during which formation and hydro-
genation of Li3N run separately and obviously this approach would
be more attractive if it could be operated continuously under
ambient conditions. In fact, an early work has carried out related
research despite not exhaustive [125]. Recently, Lazouski et al.
investigated the mechanism of continuous lithium-mediated
approach in tetrahydrofuran (THF) based electrolyte [126]. They
found that the whole reaction was limited by N2 transport at high
current densities and the anodic reaction probably involved THF
oxidation, which impeded the practical application of this method.
To overcome these drawbacks, the authors proposed to employ
GDEs to break the transport limitation (Fig. 8b) and use hydrogen
oxidation reaction (HOR) as renewable anode chemistry [16]. It is
well known that GDEs can effectively shorten the N2 diffusion
distance and facilitate the contact between gas and liquid. How-
ever, most of the GDEs use hydrophobic carbon fiber substrate to
control wetting and would be rapidly flooded in non-aqueous
electrolytes due to the lipophilicity of carbon fibers. Therefore,
they are unfavorable for the lithium-mediated approach using
organic electrolytes. To solve this problem, the authors chose
stainless steel cloth (SSC) as the GDE substrate and applied pressure
across the cloth. By doing this, the gas and liquid were effectively
separated and GDE-like behavior was achieved in non-aqueous
solvents.
Firstly, half-cell reactions of HOR and NRR were investigated in
3-compartment cells with only GDEs at the working sides,
respectively. For HOR, platinum electrodeposited on SSC (Pt/SSC)
was used to oxidize H2 and a current density of 25 mA cm2 with
near-unity FE was achieved. For NRR, SSC with Li plated in situ was
used to react with N2 and then the produced Li3N reacted with
ethanol forming ammonia. An NH3 yield rate of about
30 nmol cm2 s1 and a FE of near 46% were achieved. After effi-
cient chemistries were obtained independently on both the anode
and the cathode, an electrochemical Haber-Bosch reactor was
demonstrated by coupling the two reactions (Fig. 8c). The GDEs
reported by this work can be applied to NaeN2 batteries and AleN2
batteries that likewise suffer from discontinuous operation for ni-
trogen fixation [127,128], and also has broad application prospects
in other organic electrosynthetic fields. However, the energy effi-
ciency of this system is extremely low (ranging from 1.4 to 2.8%)
due to the energy loss coming from the large electrolyte resistance
and needs to be improved.
2.5. Strategies to improve the selectivity
In general, the selectivity of electrochemical NRR can be
improved from two aspects: tuning the local reaction environment
and catalyst design. In 2016, Singh et al. analyzed the challenge of
selectivity facing electrochemical NRR through a qualitative model,
which laid the foundation for improving the selectivity of electro-
chemical NRR by adjusting the local reaction environment [129].
Firstly, the coverages of H and N2 on the surfaces of catalysts were
investigated by simple Langmuir isotherms. Results revealed that
the adsorption of H would inevitably dominate during the elec-
trochemical NRR although this situation may be slightly improved
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 8. (a) Schematic diagram of the electrochemical Haber-Bosch cell that integrates hydrogen production and purification with electrochemical synthesis of ammonia. Reprinted
with permission from Ref. [15]. Copyright (2020) Elsevier B.V. (b) Schematic illustration of the gas diffusion electrode (GDE) using stainless steel (SSC) mesh and a non-zero pressure
to prevent substantial capillary action and catalyst flooding. (c) Demonstration of the electrochemical Haber-Bosch reactor using SSC-based GDEs at both electrodes. Reprinted with
permission from Ref. [16]. Copyright (2020) Nature Publishing Group.

on the most reactive catalysts. In this case, the rate of ammonia and near the catalyst surface, respectively. ~c is the concentration of
hydrogen production can be expressed as below: electrons when the electron transfer rate is limiting. Capital K’s are
the equilibrium constants while the small k’s denote rate constants.
KN From the Eqs. (5) and (6), it can be seen that the rN is zeroth
rN zkN ~c (5)
KH N2 order in the electron and proton concentrations while rH is first
order in both. Therefore, lowering the accessibility of protons and
rH zkH ~cþ ~c (6) electrons was supposed to be capable of increasing the ammonia
selectivity. The transportation of electrons is difficult to control
where ~cN2 and ~cþ represent the concentrations of N2 and protons during the electrochemical NRR but limiting the access of protons is

12
T. Wu, W. Fan, Y. Zhang et al.
feasible and can be achieved in many ways. Besides limiting the
accessibility of protons and electrons to suppress HER, it can be
known from Eq. (5) that improving the solubility of N2 also can
improve the ammonia selectivity. Up to now, most of the strategies
and methods proposed in this work have been validated by ex-
periments, as will be discussed below.
The regulation of the type, pH and concentration of electrolytes
is one of the approaches to limiting the accessibility of protons and
has been widely implemented in experimental studies. For
instance, Zhou et al. used ionic liquids with high N2 solubility and
ppm-level water as the electrolyte [130]. The high N2 solubility in
ionic liquids facilitated the electrochemical NRR while the limited
amount of proton source significantly suppressed the HER. As a
result, the FE can reach 60%. Wang et al. reported that the neutral
phosphate buffer solution (PBS) could effectively inhibit HER.
Compared with that in 0.1 M NaOH and 0.05 M H2SO4, the ammonia
yield rate doubled and the FE increased from below 0.1% to 2.4% in
neutral 0.1 M PBS electrolyte [77]. Counterions (cations for the
cathode) can also influence the performance of electrochemical
NRR. The work of Song et al. revealed that the ammonia yield rate
(Fig. 9a) and FE (Fig. 9b) of electrochemical NRR on N-doped carbon
nanospikes were in the order of Liþ > Naþ > Kþ in electrolytes with
different counterions, which may be because Liþ can interact with
N2 and the electric field in the Stern layer becomes stronger as the
counterion becomes smaller [131].
Tuning the surface wettability of the electrode is another way to
limiting the accessibility of protons. Hydrophobic protection layers
can hinder the transfer of protons while allowing N2 transportation.
Lee et al. coated the AueAg bimetallic electrocatalyst with super-
hydrophobic zeolitic imidazolate framework-71 (ZIF-71) to repel
water and accumulate N2, which significantly suppressed HER and
facilitated the electrochemical NRR. With tetrahydrofuran (THF)
solution containing LiCF3SO3 and ~1 vol % ethanol as the electrolyte,
ammonia yield rate and FE of the obtained electrode are more than
4-fold and 2-fold superior to the AueAg catalyst without ZIF-71
coating, respectively [132]. On this basis, Koh et al. further modi-
fied the surface of ZIF-71 with hydrophobic oleylamine (OAm) and
used butanol as the molecular filler, which can regulate water
accessibility at the catalyst surface and suppress water electrolysis.
As a result, water was changed from a hinderance to a promoter for
electrochemical NRR and FE of this system can reach >18% with the
presence of 0.1% water as the proton source in the electrolyte [133].
Ahmed et al. modified the Ru nanocrystals anchored on reduced
graphene oxide (Ru/rGO) with dodecanethiol, which can form a
hydrophobic self-assembled monolayer (SAM) on Ru surfaces by
RueS linkage. The RueS linkage can modify the electronic structure
of Ru nanocrystals while the hydrophobic SAM can limit the
transfer of protons, leading to improved FEs of electrochemical NRR
[134]. Cheng et al. reported that the FE of electrochemical NRR
showed a fivefold enhancement by substituting the pristine hy-
drophilic carbon cloth substrate with a hydrophobic one and
increasing pH from 2 to 3 (Fig. 9c), but the NH3 yield rate decreased
from 11.3 mg h1 mg1 Mo2C to 8.2 mg h
1
mg1
Mo2C [82]. Lai et al.
sandwiched selenium vacancy-rich ReSe2 loaded on carbonized
bacterial cellulose nanofibers (Vr-ReSe2@CBC) between two pieces
of hydrophobic CBC nanofibers via a layer by layer process to
restrict contact between the catalyst and the aqueous electrolyte,
which enabled the FE to increase from 10.2% for pristine Vr-
ReSe2@CBC to 42.5%. However, the NH3 yield rate also exhibited a
drop from 41.9 mg h1 cm2 to 28.3 mg h1 cm2 [94]. The latter two
cases indicate that excessive suppression of HER to improve the FE
may sacrifice a portion of the ammonia yield rate.
The suppression of HER and improvement in the selectivity of
electrochemical NRR can also be achieved through rational catalyst
design. For instance, Chen et al. improved the FE of electrochemical
13
Materials Today Physics 16 (2021) 100310
NRR by incorporating Liþ into the poly (N-ethyl-benzene-1,2,4,5-
tetracarboxylic diimide) (PEBCD) catalyst [135]. For PEBCD, the
oxygen atoms are the best active sites for HER. When a negative
potential was applied, Liþ associated with the O atoms in PEBCD
and occupied part of the active sites for HER, leading to sluggish
kinetics and higher barrier energy for HER. Wang et al. prepared
single Fe atoms supported on carbon nanosheets (FeeNeC) as the
catalyst of electrochemical NRR [136]. Fe single atoms in FeeNeC
bore positive charges which greatly facilitated the adsorption of N2
and increased the energy barriers for protons adsorption. The
adsorption of N2 onto the Fe single atoms was an exothermic pro-
cess and the released energy contributed to overcoming the energy
barriers of the following hydrogenation. As a result, the onset po-
tential of electrochemical NRR positively shifted to 0.193 V vs. RHE,
and a FE of 56.55% was achieved at 0 V vs. RHE. Sim et al. modified
the electronic structure of Pt nanospheres deposited on the Au
electrode by ZIF-71 coating. Electrons were transferred from Pt to
ZIF via Pt/AueN coordination, which not only lowered the d-band
center of Pt thus weakening the H adsorption but also generated
electron-deficient catalytic sites with strong N2 affinity. Moreover,
the nanoporous and superhydrophobic ZIF layer can concentrate N2
and limit protons availability. Owing to the above reasons, a FE of
>44% was achieved [137]. In addition to these examples, Co single
clusters supported on nitrogen-doped carbon (Section 2.1), surface
selenated Rh nanocrystals (Section 2.3.1), and fluorine-doped car-
bon (Section 2.3.3) mentioned above all can effectively suppress
HER and improve the FE of electrochemical NRR.
Besides the strategies mentioned above, hybrid electrolytic
systems also hold great promise to improve the FE of electro-
chemical NRR. As depicted in section 2.1 and 2.4, the lithium-
mediated approach can be viewed as a hybrid system combining
chemical reactions and electricity during which the activation and
hydrogenation of N become easy and high selectivity can usually be
achieved. Hawtof et al. demonstrated a hybrid plasma electrolytic
system without any catalysts, which exhibited a record-high FE
(nearly 100%) at low currents [14]. In this work, the gaseous plasma
cathode generated solvated electrons at the plasma-water inter-
face, which could reduce protons to hydrogen radicals. Then, the
hydrogen radicals further reduced N2 to ammonia. It was inferred
that N2 in the plasma was vibrationally excited and reacted with
water to form an intermediate with much higher solubility than N2,
which enhanced NH3 formation kinetically. Nevertheless, this sys-
tem still suffers from low energy efficiency although high FE was
achieved because a voltage of ~500 V was applied to induce the
plasma. Cheng et al. applied a significantly lower pressure than the
Haber-Bosch process on the electrochemical NRR system [138].
Because the reaction of nitrogen and water to NHþ 4 is a volume-
decreased process whereas hydrogen evolution is a volume-
increased reaction, applying pressure is beneficial to the forma-
tion of NHþ 4 and the inhibition of hydrogen evolution, leading to
improved selectivity towards NRR. On the other hand, the applied
pressure can improve the solubility of nitrogen, promote nitrogen
mass transfer to the electrode, and thus enhance the electro-
chemical NRR (Fig. 9d). Benefiting from the above advantages, the
FE of the electrochemical NRR system using Fe3Mo3C/C composite
nanosheets as the catalyst increased notably from 0.26% at ambient
conditions to 14.7% when a 0.7 MPa pressure was applied. Besides,
the potentials at which the highest ammonia yield rate and FE were
achieved shifted positively with the increase of applied pressure.
2.6. Verification of ammonia synthesis results
The current ammonia yield rate of electrochemical NRR is so low
that doubts about the results are rife. These doubts mainly arise
from two aspects: Firstly, ammonia is ubiquitous in the air, human
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 9. Comparison of the ammonia yield rate (a) and FE (b) of the N-doped carbon nanospikes in electrolytes containing Liþ, Naþ, and Kþ. Reprinted with permission from Ref. [131].
Copyright (2018) AAAS. (c) Mechanisms of electrochemical NRR with abundant and scarce protons in the electrolyte. Reprinted with permission from Refs. [82]. Copyright (2018)
Wiley-VCH. (d) Diffusion and adsorption of N2 molecules and water on a catalyst surface under the pressure of 0.1 MPa (Top) and 0.7 MPa (Bottom). Reprinted with permission from
Ref. [138]. Copyright (2019) Wiley-VCH.

breath, ion-exchange membranes, etc., which can easily dissolve
into the electrolytes and the off-gas absorber; Secondly, other
reactive N species may exist in the reagents, electrodes, nitrogen
gas, etc. and their reduction is more favorable than N2, thus
resulting in more indiscernible false-positive results. Based on
these concerns, the researchers have carried out works mainly in
three directions, i.e. ferreting out possible contaminants, setting
protocols for tests, and revaluation of the reported works.
To ensure the reliability of electrochemical NRR results, Green-
lee et al. discussed the control experiments conducted in the low-
temperature NRR field and proposed a rigorous set of control ex-
periments including a series of steps [139]. Firstly, the catalysts
should be tested in the Ar and N2 bubbled electrolytes without
electrochemistry, respectively, to eliminate the contamination of
ammonia from the environment, gas and electrochemical cell.
Then, electrochemical tests in the Ar and N2 bubbled electrolyte
should be tested, respectively. After the catalytic performance of
the catalysts is identified under Ar control testing, it should be
further verified using quantitative isotopic (15N) experiments. They
also stressed that the control experiments should be conducted for

14
T. Wu, W. Fan, Y. Zhang et al.
each test and the ammonia produced in the control experiments
should be subtracted from the measured ammonia when calcu-
lating NH3 yield rate and FE. Chen et al. reported that standing of
the solution, human respiration, and latex glove soaking all could
result in an increase in the amount of ammonia in 0.01 M HCl [17].
Li et al. found that some brands of Li2SO4 contain trace amount of
nitrate and nitrite which can result in false-positives during the
screening of catalysts [140]. Hanifpour et al. reported that signifi-
cant amount of ammonia was accumulated in the Nafion mem-
branes after the commonly practiced pretreatment methods. To
avoid this, the authors proposed a new pretreatment method that
includes additional processes of sufficient expansion before storage
and short sonication prior to use compared with the commonly
used one [141]. Licht et al. retracted their paper that use nanoscale
Fe2O3 as the catalyst for electrochemical NRR in molten hydroxide
suspensions and stated that the ammonia detected may come from
the reduction of trace NO x impurities in the catalyst [142,143].
Andersen et al. demonstrated that ammonia and labile NOx may
exist in the 15N gas. Therefore, false-positive ammonia synthesis
results may be obtained even if isotopic 15N labeling experiments
were conducted [18]. To eliminate the interference of the impu-
rities in 15N gas, additional purification such as by a Cu impurity
trap was recommended to remove the contaminants. Moreover, a
Fig. 10. Flow diagram of steps recommended for electrochemical NRR tests. Reprinted with permission from Ref. [18]. Copyright (2019) Nature Publishing Group.
15
Materials Today Physics 16 (2021) 100310
rigorous protocol was given for the benchmarking of electro-
chemical NRR (Fig. 10). Following this protocol, the authors suc-
cessfully reproduced the lithium-mediated ammonia synthesis
results while no ammonia was detected when Ru, Re, and Rh were
used as the catalysts for electrochemical NRR in aqueous electro-
lyte. However, it should be noted that precious metal foils were
used as the working electrodes and catalysts in this work. Kibs-
gaard et al. further stressed that the amount of produced ammonia
should be quantitatively confirmed by isotopic 15N labeling exper-
iments at multiple points. They also pointed out that there is a large
discrepancy between the DFT calculations and experimental results
in some works [144]. Compared with protocols on control experi-
ments, standardization of experimental parameters is equally
important. Tang et al. made detailed experimental suggestions on
how to explore ambient electrochemical NRR reliably and insight-
fully [145].
Considering that there are many interference factors during
electrochemical NRR and it is highly inclined to false-positive re-
sults, the inspection or reevaluation of reported results is beneficial
to the development of this field and should be encouraged. As
mentioned above, it has been reported that transition metal ni-
trides could catalyze electrochemical NRR through the MvK
mechanism both theoretically and experimentally [35,49,146e149].
T. Wu, W. Fan, Y. Zhang et al.
However, recent works revealed that all of the rock salt cubic VN,
NbN, tetragonal Nb4N5, and Mo2N were inactive to the electro-
chemical NRR and some of them may undergo decomposition to
release lattice nitrogen during the catalytic process [36,37]. Hao
et al. reported high electrochemical NRR performance for both
bismuth nanocrystals and bulk particles [150]. Recently, Choi et al.
attempted to synthesis Bi nanocrystals by following the method in
the work of Hao et al. but coarse Bi aggregates rather than finely
dispersed nanocrystals were obtained. They successfully synthe-
sized bismuth bulk nanoparticles similar to those reported by Hao
et al. Furthermore, they investigated the electrochemical NRR
performance of the bismuth bulk nanoparticles and commercial Au
nanoparticles loaded on carbon black. Results revealed that the two
kinds of catalysts had no activity towards electrochemical NRR but
both could catalyze the reduction of ionic/gaseous NOx contami-
nants [151]. This work cast doubts on the reliability of works on
electrochemical NRR using Au and Bi-based catalysts. McPherson
et al. attempted to confirm the results of electrochemical NRR in the
molten LiCleKCleLi3N salt. It is generally considered that the
electrochemical NRR in molten salts permits the direct reduction of
N2 to N3 and can achieve both high NH3 yield rate and FE. Among
the various molten salts, chloride molten salts containing Li3N is
supposed to be the most promising because it has been believed
that its high solubility towards Li3N can facilitate the conversion of
N2 to N3 [152]. However, McPherson et al. discovered that Li3N can
directly react with H2, resulting in non-faradaic formation of NH3
and FE exceeded 100%. To avoid this problem, the authors
employed LiH to replace Li3N and declared that a truly catalytic
path to ammonia formation was possible in the LiCleKCleLiH
molten salt. A peak NH3 yield rate of 2.4  108 mol cm2 s1 and a
maximum FE of 4.2% were obtained for the LiCleKCleLiH molten
salt system [153]. Nonetheless, it is subject to be further clarified
whether LiH directly reacted with N2 in this work because LiH can
react with N2 to generate Li3N and NH3 at elevated temperatures.
3. Electrochemical recycling of nitrogenous pollutants into
ammonia
As shown in Table 1, the reduction of nitrate to ammonium ions
is a reaction that involves eight electrons and ten protons. It is more
thermodynamically preferred compared with NRR and HER (Eqs.
(1)e(4)), and can usually achieve high NH3 yield rate and FE. Given
the ease of nitrogenous pollutants reduction and the great difficulty
in electrochemical NRR, researchers have attempted to electro-
chemically recycle nitrogenous pollutants into value-added
ammonia.
It is generally considered that the main challenge in the elec-
trochemical reduction of nitrogenous pollutants to ammonia lies in
the diversity of products. The oxidation state of N varies from þ5
to 3 and stable nitrogenous species exist for all oxidation states in
this range. Taking nitrate as an example, a variety of intermediates
Table 1
Reactions related to the reduction of nitrogenous pollutants to ammonia and cor-
responding standard equilibrium potentials [21].
Reactions E0/V vs. NHE
NO þ þ 8e / NH þ þ 3H O
3 þ 10H 4 2 0.875
NO
3 þ 2H þ þ 2e / NO þ H O
2 2 0.835
NO
3 þ 4H
þ þ 3e / NOðgÞ þ 2H O
2 0.958
2NO3 þ 10H þ þ 8e / N OðgÞ þ 5H O
2 2 1.116
2NO3 þ 12H
þ þ 10e / N ðgÞ þ 6H O
2 2 1.246
NO
3 þ 8H
þ þ 6e / NH OH þ þ 2H O
3 2 0.727
NOðgÞ þ 6Hþ þ 5e / NH4þ þ H2 O 0.836
þ þ 6e / NH þ þ 2H O
NO
2 þ 8H 4 2 0.897
Materials Today Physics 16 (2021) 100310
or byproducts such as nitrite, NO, N2O, N2, etc. may be generated
during its reduction to NH3 (Table 1 and Fig. 11) [30,154]. Among
the products, N2 and NH3 are the most preferred because of their
higher thermodynamic stability [21]. NO is supposed to be the
divergence center towards N2 or NHþ 4 . As shown in Fig. 11, the
adsorbed NO (NO*) is reduced to adsorbed atomic N* and then N* is
hydrogenated to form NHþ 4 during the electrochemical reduction of
nitrate to ammonia. The reduction of nitrate to N2 follows the
Vooys-Koper mechanism (the NO*/N2O*/N2 pathway in Fig. 11)
while the combination of two N* to form N^N was not favorable.
For the Vooys-Koper mechanism, one dissolved NO reacts with an
adsorbed NO* to form HN2O2. The HN2O2 is unstable and can be
easily reduced to N2O and then N2 [20]. Duca et al. proposed that
the ability to dissociate NO was the prerequisite for the nitrite
reduction to ammonia [155]. The interaction between NO and the
surfaces of the optimum catalyst for nitrite reduction to ammonia
should be strong enough to dissociate the NeO bond but not too
strong to avoid poisoning of catalysts, i.e., follow the Sabatier
principle. The results revealed that Rh and Ru could meet the re-
quirements and had decent selectivity towards ammonia. More-
over, copper is also an excellent catalyst for the reduction of nitrate
to ammonia despite its weak NO adsorption, which may be because
that the prolonged generation of NO may hinder its desorption rate
and compel it to be further reduced to ammonia [20].
Nitrogenous pollutants with lower N valence states are in-
termediates of nitrate reduction to ammonia. Therefore, in-
vestigations on nitrate reduction are of significant importance for
the electrochemical reduction of nitrogenous pollutants. Wang
et al. proposed that the reduction of nitrate could be used as a
method to produce ammonia [22]. In this work, Co3O4 nanorod
arrays supported on Ti mesh were used as the catalyst, which
achieved an NH3 selectivity of 33.6% and an NH3 yield rate of
14.5 mg h1 cm2. After that, their group prepared TiO2 nanotubes
with rich oxygen vacancies for electrochemical synthesis of
ammonia from nitrate [156]. With a concentration of 50 ppm
nitrate-N, a conversion rate of 95.2%, an NH3 selectivity of 87.1%, a
FE of 85.0%, and a yield rate of 0.045 mmol h1 mg1 (loading
amount: ~2 mg cm2) were achieved at the voltage of 1.6 V vs.
SCE. Oxygen vacancies in TiO2 can not only be filled with the oxygen
in nitrate to weaken the NeO bond but also can modulate the
interaction between intermediates and catalysts to optimize the
reaction pathway and hinder the formation of byproducts. There-
fore, the nitrate reduction performance of TiO2 with oxygen va-
cancies is much better than that without vacancies. They further
investigated the performance and activity origin of copper-based
catalysts for electrochemical nitrate reduction to ammonia [157].
The reduction process induced the structure evolution of initial CuO
nanowire arrays (NWAs) to Cu/Cu2O NWAs. An electron transfer
from Cu2O to Cu occurred at the interface of Cu/Cu2O, which led to
an increased electron density of Cu, thus facilitating the formation
of intermediates *NOH and suppressing the HER. In 0.5 M Na2SO4
with 200 ppm nitrate-N, the FE, nitrate conversion rate, NH3
selectivity, and yield rate of Cu/Cu2O NWAs can reach 95.8%, 97.0%,
81.2%, and 0.2449 mmol h1 cm2, respectively. Wang et al. elec-
trochemically deposited dendritic CueNi alloys on different sub-
strates for electrochemical nitrate reduction to ammonia [158]. The
introduction of Ni positively shifted the d-band center of Cu to-
wards the Fermi level and modulated the intermediate adsorption.
(7)
(8) With the increasing amount of Ni in CueNi alloys, a volcano-type
(9) relationship was seen between the nitrate adsorption energy and
(10) the experimental nitrate reduction overpotential. Cu50Ni50 was
(11)
located at the top of the volcano plots and had the optimal inter-
(12)
mediate adsorption. As a result, Cu50Ni50 exhibited the best elec-
(13)
trochemical nitrate reduction performance among CueNi alloys
(14)
with different compositions, including a 0.12 V upshift of the half-
16
T. Wu, W. Fan, Y. Zhang et al.
Fig. 11. (a) Direct mechanism of electrochemical reduction of nitrate to different products on transition metal (TM) catalysts. Hydrogen atoms are not shown to highlight N species.
The orange, yellow, and blue arrows represent nitrate adsorption, dissociation/formation of intermediates, and desorption of products, respectively. (bed) Representative con-
figurations of adsorbates NO3*, NO2*, and N2O* on a stepped TM surface. (eef) Representative transition-state configurations for NO3* and NO2* dissociation. The yellow line
signifies bond breaking. (bef) Cyan ball: transition metal, Red ball: oxygen, blue ball: nitrogen. Reprinted with permission from Refs. [154]. Copyright (2019) American Chemical
Society.
wave potential and a 6-fold increase in intrinsic nitrate reduction
activity compared with pure Cu. Fu et al. adopted a strategy of
crystal facet engineering and prepared copper nanosheets enclosed
with (111) facets. Compared with copper nanocubes covered by
(110) facets and irregular nanoparticles, the copper nanosheets
exhibited lower HER activity and higher activity towards nitrate
reduction to ammonia [159]. Chen et al. incorporated copper into
crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) to
form a copper-molecular solid catalyst for electrochemical reduc-
tion of nitrate to ammonia [160]. The PTCDA substrate can facilitate
the conduction of electrons and protons while the uniformly
distributed copper has stronger adsorption for nitrate and lower
activity toward HER compared with other screened metals. The
catalyst with moderate amount of copper doping (OeCuePTCDA)
exhibited the best performance with an NH3 yield rate of
436 ± 85 mg h1 cm2 and a FE of 85.9% at the potential of 0.4 V vs.
RHE. Li et al. designed Ru/oxygen-doped-Ru core/shell nanoclusters
with a diameter of ~2 nm to catalyze the reduction of nitrate
(Fig. 12aec) [161]. The tensile strain effect, induced by the core-
shell structure, effectively prohibited the dimerization of
hydrogen adatoms to form hydrogen, leading to their desorption
from the catalyst and formation of hydrogen radicals ($H). The
presence of $H significantly ameliorated the hydrogenation process
of nitrate reduction, which is rate-limiting in nitrate reduction.
Benefiting from this, high FEs in a wide potential range and an
ultrahigh NH3 yield rate of 1.17 ± 0.04 mmol h1 cm2 were ob-
tained for 12% strained Ru/oxygen-doped-Ru core/shell nano-
clusters (Ru-ST-12), which outcompeted most of the reported
catalysts (electrolyte: 1 M KOH þ 1 M KNO3, Fig. 12e, f, and h).
Moreover, the Ru-ST-12 catalyst exhibited excellent stability
without decay during 100 periods of 1 h running at 0.2 V vs. RHE
(Fig. 12g).
Compared with nitrate, nitrite and NO can be reduced more
easily and have also been used to synthesize ammonia. Wang et al.
17
Materials Today Physics 16 (2021) 100310
prepared MnO2 nanoarrays supported on Ti mesh (MnO2 NA/TM)
for nitrite detection and reduction [23]. Wide detection range, low
detection limit, and high response sensitivity were obtained when
MnO2 NA/TM was used as a nitrite sensor and a transformation
efficiency of 6% was achieved when MnO2 NA/TM catalyzed nitrite
reduction to ammonia. Long et al. investigated the electrochemical
reduction of exhaust NO into ammonia [24]. DFT calculations
revealed that copper was the most active transition metal catalyst
for NO reduction. Experiments with commercial copper foam as the
catalyst were conducted to validate the theoretical prediction. A
record-high NH3 yield rate of 517.1 mmol cm2 h1, a FE of 93.7%,
and stable electrochemical performance of 100 h were achieved.
At present, studies on electrochemical synthesis of ammonia
from nitrogenous pollutants are much fewer compared with elec-
trochemical NRR. The standard equilibrium potentials of nitroge-
nous pollutants reduction to ammonia are more positive than that
of electrochemical NRR but its optimum working potentials are not
necessarily higher than that of electrochemical NRR. The partial
current density for nitrogenous reduction to ammonia can reach
hundreds of milliampere which is several orders of magnitude
higher than that of the electrochemical NRR. Thus, the performance
of electrochemical nitrogenous reduction to ammonia has an
overwhelming advantage over that of electrochemical NRR (Fig. 13).
However, it converts reactive N species into ammonia instead of
fixing inert nitrogen from the atmosphere. Therefore, the electro-
chemical nitrogenous reduction to ammonia is supposed as a
supplement to the nitrogen fixation technologies to prevent the
loss of the laboriously fixed nitrogen. Moreover, there are many
issues to be addressed for this technology. Firstly, the deep reason
why the ammonia production predominates over other products
such as N2 on the reported catalysts is important to defining the
research directions to advanced catalysts but remains unclear.
Secondly, it has been reported that the catalysts for electrochemical
nitrogenous pollutants reduction such as copper are susceptible to
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310

Fig. 12. (a) TEM image, (b, c) abbreviation-corrected HAADF-STEM image, and (d) EELS elemental map of 12% strained Ru/oxygen-doped-Ru core/shell nanoclusters (Ru-ST-12). (e)
FE (FENH3) and (f) partial current density for nitrate reduction to ammonia (JNH3) on Ru-ST-12, Ru-ST-5, and Ru-ST-0.6 at different potentials. (g) JNH3 and FENH3 of nitrate reduction
on Ru-ST-12 during a durability test of 100 h at 0.2 V vs. RHE. (h) Comparison of the performance of Ru-ST-12 for electrochemical nitrate reduction to ammonia with those
previously reported catalysts. Reprinted with permission from Ref. [161]. Copyright (2020) American Chemical Society.

oxidative dissolution and surface leaching but most of the recently
reported works have ignored this problem. Thirdly, synthetic
electrolytes with high concentrations were utilized in most of the
reported works while the low concentration and complex compo-
sition of nitrogenous pollutants in real world may compromise the
performance of nitrogenous pollutants reduction.
4. Summary and outlook
In this review, we summarized the recent progress in the elec-
trochemical synthesis of ammonia through NRR or nitrogenous
pollutants reduction. On the whole, a lot of attempts and significant
progress have been made, but the electrochemical synthesis of
ammonia is still in the infancy stage with great challenges
remained to be addressed.
As for the electrochemical NRR to ammonia, the NH3 yield rate
and FE fall far below the commercially viable targets released by the
U. S. Department of Energy (a current density of 300 mA cm2 with
a FE of 90% and energy efficiency of 60%) [162]. Basically, the in-
vestigations on electrochemical NRR suffer from the lack of
systematicity, and activities of many of the developed catalysts are
at a not entirely convincing level. Accordingly, continuous efforts
should be made with proposals given as follows. First of all, only
reliable results can aid the screening of catalysts and promote the
progress of electrochemical NRR, so the control experiments should
be as rigorous as possible to rule out false-positive results caused by
the ubiquitous contaminants. The authors should reexamine their
results and respond to the doubts on their works in time and
objectively, which can help eliminate errors and maintain
authenticity to ensure the healthy and rapid development of this
field. Secondly, the catalysts should be designed more accurately
and systematically to make breakthroughs in both the activity and
selectivity. It has been proposed theoretically that the circumvent
of scaling relationships can lead to a leap of the electrochemical
NRR performance but specific methods to achieve this aim remain
to be implemented. In situ advanced characterizations should be
further developed and employed to provide insights into the cat-
alytic process and set up correlation between structure and per-
formance. Moreover, theoretical calculations such as the high-
throughput machine learning can significantly accelerate the

18
T. Wu, W. Fan, Y. Zhang et al.
Fig. 13. Comparison between the performance of electrochemical NRR and nitrate
reduction to ammonia.
catalyst screening. Thirdly, the low solubility of N2 severally affects
the electrochemical NRR performance, so extended efforts should
be put into breaking the diffusion limit of N2. In this regard, elec-
trolytic cells that employ GDEs are promising because the GDEs can
shorten the diffusion distance of N2 and facilitate the contact be-
tween the N2 gas and electrolytes, thus achieving high ammonia
partial current densities. Last but not the least, hybrid systems in-
tegrated electricity with other driving forces such as pressure,
elevated temperature, chemical reactions, and plasma may hold the
promise to bring the electrochemical NRR to a competitive level
relative to the Haber-Bosch process. The applied pressure can
change the chemical equilibrium and improve the solubility of N2
while elevated temperatures can accelerate the kinetically sluggish
NRR. Taking advantage of the reaction between Li and N2 makes the
broken of N^N which is usually the rate-determining step of
electrochemical NRR become a spontaneous process, leading to the
relatively high performance of the Li-mediated approach. Although
the detailed mechanism of the plasma electrolytic system is un-
clear, it was supposed that solvated electrons and hydrogen radicals
were generated, and N2 in the plasma was vibrationally excited,
which may significantly lower the energy barriers and enhance the
efficiency of NRR.
As for the electrochemical synthesis of ammonia from nitroge-
nous pollutants, the studies are relatively few and there are a lot of
works to be done although some reported catalysts exhibited
excellent performance. Firstly, the detailed mechanisms of elec-
trochemical nitrogenous pollutants reduction are unclear and
remain to be elucidated through both computational studies and in
situ characterization techniques to guide the design of high-
performance catalysts. Secondly, the development of more
advanced catalysts is the constant theme in the field of catalysis,
which is also applicable to the electrochemical synthesis of
ammonia from nitrogenous pollutants. It seems not that difficult to
achieve high NH3 yield rates and FEs for some catalysts while more
attention should be paid to lowering the overpotential of reactions
and improving the stability of catalysts. Thirdly, it is highly
encouraged to evaluate the performance of catalysts using real
wastes containing nitrogenous pollutants, which can help to better
understand the feasibility of this technology and promote its
application.
Finally, we would like to point out that the research and
development of most technologies such as the Haber-Bosch process
have undergone long-term explorations. We believe the challenges
19
Materials Today Physics 16 (2021) 100310
facing the electrochemical synthesis of ammonia will be resolved
gradually through unremitting efforts, thus opening an era of green
and sustainable ammonia synthesis.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
We sincerely thank the financial support from the National
Natural Science Foundation of China (21633009, 21925206,
21902159), China Postdoctoral Science Foundation (2018M641724),
Dalian National Laboratory for Clean Energy (DNL) Cooperation
Fund, Chinese Academy of Sciences (DNL 201913), International
Partnership Program of Chinese Academy of Sciences
(121421KYSB20190025), the DICP foundation of innovative
research (DICP I201927), and Dalian Institute of Chemical Physics
(DCLS201701). F. Zhang thanks the support from Liaoning Revital-
ization Talents Program (XLYC1807241).
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