Materials Today Physics: Tingting Wu, Wenjun Fan, Yang Zhang, Fuxiang Zhang
Materials Today Physics: Tingting Wu, Wenjun Fan, Yang Zhang, Fuxiang Zhang
Materials Today Physics: Tingting Wu, Wenjun Fan, Yang Zhang, Fuxiang Zhang
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.
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. 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
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
makes the quantitative implementation of the classical Sabatier MvK mechanism to avoid decomposition [49]. As stated above, the
principle possible. Taking the electrochemical NRR as an example, scaling relationship of different variables in a reaction can signifi-
nitrogen adsorption energies on catalysts can act as the single cantly reduce the dimensionality of calculations. However, it also
variable/descriptor of ammonia synthesis activity and a volcano- makes the catalysts design a compromise process between
type diagram of catalytic activity vs. nitrogen adsorption energy different competing factors [45,50]. The work of Montoya et al.
on different transition metal catalysts (Fig. 2a) can be obtained [45]. indicated that the electrochemical NRR performance was severely
Then, the d-band model further revealed the reason why scaling limited by the linear scaling between the energetics of *N2H and
relations exist between different variables is that the adsorption *NH2, and the use of bifunctional surfaces was considered to tune
energies of different intermediates depend linearly on the surface these two parameters independently [51]. Zhang et al. stated that
electronic structure of the catalysts. The adsorbates hybridize with the use of 2,6-lutidinium (LutHþ) could selectively stabilize *N2H
the surface d electrons of transition metal catalysts to form bonding and break the scaling relationship [52]. With the rise of single-atom
and anti-bonding states during the adsorption process. The inter- catalysts, the electrochemical NRR on transition metal single-atoms
action between adsorbates and catalysts is closely related to the anchored on different supports such as nitrogen-doped carbons
filling degree of anti-bonding states of the adsorbates, which in [53,54], graphene [55e57], carbon nitride (C3N4) [55,58], black
turn depends on the position of the d-band center of transition phosphorene [59], boron monolayer [60], graphdiyne [61], Mxenes
metal catalysts relative to the Fermi level. Generally, the higher the [62], molybdenum disulfide (MoS2) [63], and platinum disulfide
d band center relative to the highest occupied states at the Fermi (PtS2) [64] gradually becomes a computational research hotspot.
energy, the interaction becomes stronger [45,46]. The d-band Moreover, transition metal dimers or trimers are increasingly
center theory has been widely used to interpret the electrochemical considered as the candidates for electrochemical NRR benefiting
NRR results, as will be discussed later in section 2.3. from their synergetic effect between different metal atoms, possi-
Specifically, Skulason et al. theoretically evaluated the electro- bility to circumvent the scaling relations, higher metal-atom
chemical NRR on flat and stepped surfaces of transition metal loading, more flexible active sites, etc. For instance, Chen et al. re-
catalysts [47]. Results revealed that Mo, Fe, Ru, and Rh were the ported that transition metal double-atom catalysts with C2N
most active surfaces but the competition of HER would seriously (Fig. 2b) as the support (TM2-C2N) such as Mn2eC2N (Fig. 2d) are
affect the NRR performance. By contrast, early transition metals more suitable for electrochemical NRR compared with their single-
such as Ti, Zr, Sc, and Y bound nitrogen more strongly than protons atom counterparts (TM-C2N, Fig. 2c) according to the DFT calcula-
and thus a significant ammonia production was expected (Fig. 2a). tion results [65]. Guo et al. sampled both homonuclear and heter-
Subsequently, Howalt et al. investigated the electrochemical NRR onuclear metal dimers supported on 2D expanded phthalocyanine
on highly under-coordinated transition metal nanoclusters using (M2-Pc or MM0 -Pc). Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, and VTa-Pc were
DFT calculations in combination with the computational standard predicted to have strong capability to suppress HER with favorable
hydrogen electrode. The results indicated that Mo and Fe are the limiting potentials for electrochemical NRR [66]. Hu et al. investi-
most promising candidates for electrochemical NRR [48]. Abghoui gated the effects of coordination atoms (C, N, O, P, and S) on the
et al. identified VN, ZrN, NbN, and CrN as the most promising electrochemical NRR performance of bimetallic pairs supported on
mononitrides for electrochemical NRR through DFT based analysis graphene and the results indicated that carbon was the optimal
and studied their stability against poisoning and decomposition. coordination atom [67]. The work of Chen et al. revealed that
The results revealed that single-crystal surfaces were required for transition metal trimers supported on the heterostructure of
ZrN, NbN, and CrN to be stable while the rocksalt (100) facet of graphdiyne and graphene could achieve higher loading amount,
polycrystalline VN could catalyze electrochemical NRR through the 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.
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
compared with single atoms or dimers [68]. prepared nanoporous palladium hydride (np-PdH) through deal-
DFT is a workhorse of first-principles-based simulation in loying of Al80Pd20 and in situ hydrogen injection (Fig. 3a) [40].
catalysis and has been used in nearly all of the computational Isotopic deuterium labeling experiments revealed that the outmost
studies mentioned above. However, the high computational cost hydrogen atoms in np-PdH participated in the electrochemical NRR
has greatly limited its application. By contrast, machine learning is and a lattice hydrogen involved reaction pathway was proposed
the practice of building models from data, which can avoid time- (Fig. 3b). Hydrogen doping of np-PdH improved the internal elec-
consuming steps and reveal reaction processes in a short time, tron concentration and shifted the d band center towards the Fermi
thus accelerating the catalyst development [50,69]. Recently, Kim level, leading to stronger adsorption of intermediates and
et al. reported a work that used machine learning to evaluate the enhanced catalytic activity. The electrochemical NRR performance
electrochemical NRR performance on L12 intermetallic crystals and improved with the increase of hydrogen content in np-PdH. The np-
predicted that V3Ir (111), Tc3Hf (111), V3Ni (111), and Tc3Ta (111) PdH0.43 exhibited the best performance with a FE of 43.6% and an
were stable candidates that may exhibit improved catalytic per- NH3 yield rate of 20.4 mg h1 mg1 cat at 0.15 V vs. RHE in 0.1 M
formance compared with the reference Mo (110) [70]. Zafari et al. phosphate buffer solution (Fig. 3c and d). Tong et al. optimized the
investigated the electrochemical NRR performance of transition NRR catalytic activity of PdCu through a crystal phase engineering
metal single-atom catalysts anchored on B-doped graphene using strategy [78]. The prepared PdCu nanoparticles loaded on carbon
machine learning [71]. The results revealed that the chromium powder were transformed from face-centered cubic (FCC) to body-
single-atom catalyst with a CrB3C1 structure exhibited the best centered cubic (BCC) phase through annealing in Ar/H2 atmo-
performance with a minimal potential of 0.13 V and high selectivity. sphere. The NRR catalytic performance of BCC PdCu outperformed
Besides electronic structure, morphologies of the electrodes also FCC PdCu with a maximum NH3 yield rate of 35.7 mg h1 mg1 cat and a
may greatly affect the electrochemical NRR performance but few of FE of 11.5% at 0.1 V vs. RHE in 0.5 M LiCl. Surface valence band
the computational studies have taken them into account. In this spectra indicated that the transformation of PdCu from FCC to BCC
regard, Hoar et al. proposed a machine learning model (Fig. 2e, f, uplifted the d-band center towards the Fermi level, leading to
and g) to explore the morphology influence of micro/nanowire enhanced N2 adsorption and catalytic activity. DFT calculation re-
array electrodes on the performance of electrochemical NRR [72]. sults revealed that the Cu 3d band in BCC PdCu bridged the
Overall, plenty of progress has been made on the computational electron-transfer coulomb gap of Pd 4d and boosted the electronic
studies for electrochemical NRR as depicted above but there re- activities of Pd 4d for NRR. Yang et al. proposed a generalized sur-
mains many challenges to be overcome. Firstly, the improvements face chalcogenation strategy to boost the electrochemical NRR
in the accuracy of computational studies are required to avoid performance of noble-metal nanocrystals (Pt, Pd, Ru, and Rh) [79].
wrong results and misleading the development of catalyst. Sec- A series of noble metal selenide/chalcogenides were prepared, all of
ondly, the current computational studies for electrochemical NRR which exhibited enhanced performance compared with their
usually adopt simplified models with the major concern on the counterparts without selenide/chalcogenation. For RheSe nano-
electronic structure of catalysts and there is an urgent need to crystals, selenation created additional Rh3þ species on the surface
develop multi-scale approaches that incorporate the effects of and upshifted the d-band center to the Fermi level, which can
temperature, pressure, electrolytes, etc. Lastly, the advances in enhance the adsorption of N2 and inhibit the HER process. As a
computational science and development of new methods are ur- result, the RheSe nanocrystals exhibited significantly enhanced
gently needed to enable the large-scale screening of catalysts. NH3 yield rate (175 mg h1 mg1 Rh ), FE (13.3%), and stability (18 h)
compared with the pristine Rh nanocrystals.
2.3. Experimental explorations on catalyst development
2.3.2. Non-noble metal catalysts
Besides the computational research, a lot of experimental efforts Low reserves and high cost of noble metals severely restrict
have also been made. The elements used in the catalysts for elec- their application. By contrast, non-noble metals are abundant and
trochemical NRR can be divided into three groups: (1) noble metals low-cost. Moreover, nitrogenases in the nature contain non-noble
such as Au, Ru, Rh, Pd, Pt, Ag, and Ir; (2) non-noble metals such as Y, metals including Fe, Mo, and V. Therefore, plenty of studies have
Sc, Ti, Zr, V, Cr, Nb, Mo, Fe, Co, Mn, Ni, Cu, W, Re, Sn, Sb, Bi, La, Ce, and been carried out in search of efficient non-noble metal catalysts for
Dy; (3) non-metal elements such as B, C, N, O, F, P, S, Se, and Te. electrochemical NRR, as will be discussed below.
These elements can derive many sorts of catalysts for electro- Inspired by the nitrogenase MoFe protein, researchers have
chemical NRR, including metals, metal alloys, transition metal developed many kinds of Mo-based catalysts for electrochemical
carbides, nitrides, oxides, and sulfides, carbon materials, black and NRR such as Mo thin films [80], MoS2 [81], Mo2C [82], and single Mo
red phosphorous, Mxene, covalent organic frameworks (COF), C3N4, atoms [83]. For MoS2, Mo atoms in the basal plane are blocked by S
etc. Herein, the catalysts are classified (noble metal catalysts, non- atoms on both sides and thus only Mo atoms in the edge plane act
noble metal catalysts, and metal-free catalysts) and summarized to as active sites for electrochemical NRR. To expose more molybde-
shed light on the development tendency of catalysts for electro- num atoms and activate the basal plane of MoS2-x, Zhang et al.
chemical NRR. Considering that a number of the early reported recently fabricated Co-doped MoS2-x polycrystalline nanosheets
catalysts have been reviewed for many times, we give priorities to with abundant S vacancies (Vs) on carbon cloth substrate [84].
the latest and representative ones. Through Co doping, the S/Mo ratio decreased markedly, indicating
a substantial increase of S vacancies in Co-doped MoS2-x. For the
2.3.1. Noble metal catalysts undoped MoS2-x, N2 adsorbed to the center of Vs and interacted
Although the membership is not well-defined, it is generally with three Mo atoms (Fig. 4a), resulting in a reaction energy barrier
supposed that noble metals include silver, gold, and platinum of 1.62 eV. After Co doping, the adsorbed N2 bound to one Mo atom
group metals (Ru, Rh, Pd, Os, Ir, and Pt). As a whole, there are plenty (Fig. 4b) and the reaction energy barrier reduced to 0.94 eV, leading
of investigations on Au, Ru, Rh, and Pd while reports on Ag, Os, Ir, to enhanced NRR performance. In this work, Co atoms exist as an
and Pt are sporadic for electrochemical NRR [73e77]. Due to the interior dopant for MoS2. By contrast, Li et al. conjugated single
high cost of noble metals, it is necessary to take atomic utilization atomic Fe protrusions onto the surface of MoS2 (Fig. 4c, d, and e)
into account. Therefore, single-atoms, nanostructures, and alloys and made use of the high curvature of this structure to induce
are the most investigated noble metal catalysts. Recently, Xu et al. interfacial polarization field between the single-atomic Fe
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
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- Fe could improve the electrical activity of SnO2, leading to
larization field can drive the injection of electrons from Fe into the outstanding activity for both NRR and NOR. An NH3 yield rate of
antibonding orbitals of N2 and make the splitting of N2 easier. The 82.7 mg h1 mg1cat and a FE of 20.4% were achieved for NRR while a
electrochemical NRR performance of the prepared catalysts was NO3 yield rate of 42.9 mg h
1
mg1
cat and a FE of 0.84% were obtained
tested in a flow cell using gas diffusion electrodes (GDEs) and ul- for NOR. In the reported Fe single atoms immobilized onto carbon
trahigh performance (NH3 yield rate: 97.5 ± 6 mg h1 cm2, FE: materials, Fe usually coordinates with N or C atoms. To enrich the
31.6% ± 2%) that exceeded all of the reported MoS2 based catalysts types of coordination atoms for Fe single atoms and obtain high
was obtained for SACs-MoS2-Fe-2.0 with 2 at.% of Fe loading. electrochemical NRR performance, Zhang et al. prepared a Fe
Iron-base catalyst is another research hotspot and a variety of single-atom catalyst anchored onto lignocellulose-derived carbon
iron-base catalysts such as the SACs-MoS2-Fe-2.0 depicted above through a Fe-(OeC2)4 coordination configuration, and an NH3 yield
[43], Fe3O4 [85], a-Fe@Fe3O4 [86], FeOOH [87], FeeNeC [88], and rate of 32.1 mg h1 mg1cat and a FE of 29.3% were obtained [91].
FeSx [89] have been reported. Recently, Zhang et al. prepared a Ja- Reports on Cu based catalysts for electrochemical NRR are
nus FeeSnO2 catalyst for bifunctional N2 fixation, i.e. NRR and N2 relatively few perhaps because of its weak N2 adsorption and high
oxidation reaction (NOR) [90]. Lattice-doped Fe and single-atom Fe activity towards nitrogenous pollutants reduction. Recently, Lin
anchored by oxygen vacancies coexisted in FeeSnO2. Computa- et al. prepared Cu-based catalysts for electrochemical NRR by
tional and experimental results revealed that the Fe single atoms tuning the electronic structure of Cu [92]. Copper nanoparticles
anchored on SnO2 played as the active sites while the lattice-doped were loaded onto semi-conductive polyimide nanoflowers (Fig. 4f)
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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 and ordered atomic hybridization. Computational results revealed
contact at the interface and electron-deficient copper particles. that the single-metal ReS2 adopted a distal pathway with N2
According to the DFT calculation results, the electron deficiency of adsorbed in the end-on mode. By contrast, N2 bound with both Re
Cu nanoparticles enhanced the polarization of N2 and reduced the and Mn simultaneously for the Re2MnS6 nanosheets, leading to
Gibbs free energy change of NRR. Also, OH tends to adsorb onto more favorable N2 adsorption and 6.6 times higher catalytic
electron-deficient Cu nanoparticles, which can retard the HER activity.
process in alkaline electrolytes. As a result, the Cu/PI-300 catalyst, As depicted above, early transition metal surfaces such as Sc, Y,
in which Cu nanoparticles have the most pronounced electron Ti, and Zr were expected to exhibit significant NH3 yield rate owing
deficiency, exhibited the best NRR performance with an NH3 yield to their stronger binding towards N-adatoms than H-adatoms [47].
rate of 12.4 mg h1 cm2 (loading amount: 5 mg cm2) and a FE of Recently, Liu et al. prepared single-atom Y and Sc catalysts sup-
6.56% at 0.4 V vs. RHE in 0.1 M KOH. Moreover, Zang et al. pre- ported on nitrogen doped carbon (Fig. 5a) by a solid synthesis
pared copper single-atoms supported on nitrogen doped carbon for method and employed them as the catalysts for electrochemical
electrochemical NRR, which exhibited high performance in both NRR and CO2 reduction [96]. It was deduced that the Y and Sc atoms
acidic and alkaline electrolytes [93]. were stabilized on the carbon defects by coordinating with six
Rhenium has also been used in catalysts for electrochemical carbon and nitrogen atoms. Both the single-atom Y and Sc catalysts
NRR recently. Lai et al. reported that low-valence Fe doping and rich could catalyze the electrochemical NRR and they exhibited similar
Se vacancies could upshift the d-band center of ReS2 and ReSe2 activities with a maximum NH3 yield rate about 20 mg cm2 h1 and
towards Fermi level, respectively, and facilitate both the electro- the highest FE around 12% (Fig. 5bee). In early transition metals
chemical NRR and HER [94,95]. To suppress HER and improve the and their compounds, TiO2 is the most widely investigated and
FE of NRR, the authors adopted a hydrophobic strategy, which will applied due to its superior properties. It has been proved that Ti3þ
be discussed in section 2.5. Fu et al. introduced Mn into ReS2 and defect states around oxygen vacancies are pivotal for electro-
prepared orderly atomic-hybridized Re2MnS6 alloy with morphol- chemical NRR [97,98]. In this context, various metal heteroatoms
ogies of ultrathin nanosheets for electrochemical NRR [42]. A large such as Zr4þ, Fe, and mixed-valent Cu have been doped into TiO2 to
number of valence electrons transferred from Re to Mn, leading to induce Ti3þ and enhance NRR performance [99e101]. Moreover, Liu
strong e-e Coulomb interaction, semimetal states of Mn-3d orbitals, et al. employed a lithium-reduction strategy to generate oxygen
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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- for electrochemical NRR. To enhance the electrochemical NRR
low bulk density and ultrahigh porosity for electrochemical NRR performance of Ti3C2Tx Mxene, a variety of strategies such as size
[102]. Qin et al. acted oppositely and anionic carbon atoms were reduction to generate more edge planes, in situ growing oxygen-
doped into TiO2 by occupying the oxygen vacancies and forming vacancy-rich TiO2, surface hydroxyl modification, and ironing out
TieC bonds in their work [103]. The authors declared that (O)eTieC inactive terminals have been proposed [104e107].
bonds in C-TixOy/C could largely enhance the activation and Main group metals have also been used in catalysts for elec-
reduction of N2 compared with unoccupied oxygen vacancies. Be- trochemical NRR [108,109]. Recently, Liu et al. prepared Sb/SbPO4
sides TiO2, Ti3C2Tx Mxene is another kind of Ti containing catalysts loaded on phosphorus-doped carbon (PC) to catalyze the electro-
for electrochemical NRR. Ti3C2Tx Mxene prepared by HF etching of chemical NRR [110]. SbPO4 and P-doped carbon both were the
Ti3AlC2 MAX has a lamellate T-Ti-C-Ti-C-Ti-T sandwich structure active sites for NRR whereas metallic Sb was covered by SbPO4 and
(T ¼ F, OH, O) [104]. The Ti atoms in Ti3C2Tx Mxene are blocked by didn’t take part in the catalytic process. The valence state of Sb in
inactive functional groups, resulting in inadequate catalytic activity SbPO4 became slightly higher and SbPO4 underwent amorphization
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
and partial dissolution during the NRR tests. In 0.1 M HCl, the Recently, Liu et al. reported boron-rich COFs coated on conductive
average ammonia yield rate decreased observably during a dura- nitrogen-doped carbon nanosheets (COF-NC) for electrochemical
bility test of 24 h. In 0.1 M Na2SO4, the PC/Sb/SbPO4 catalyst NRR [41]. The prepared COF-NC can be excited by potentiostatic
exhibited better NRR performance with the maximum FE of 34% electrolyzing, forming Eex-COF/NC. During the excitation, boron
at 0.1 V vs. RHE and the highest NH3 yield rate of 23 mg h1 mg1
cat atoms in COF-NC adsorb nitrogenous species by forming BeN
at 0.3 V vs. RHE. bonds. The formation of BeN bonds leads to structure distortion
of COF from crystalline to amorphous phase, which can further
2.3.3. Metal-free catalysts enhance the adsorption of N2 onto COF. The Eex-COF/NC exhibited a
Compared with metal catalysts, metal-free catalysts possess FE of 45.43% and an NH3 yield rate of 12.53 mg h1 mg1 at 0.2 V
many merits such as low-cost, environmental friendliness, and free vs. RHE in 0.1 M KOH.
from poisoning. Therefore, research and development of metal-free The performance of all catalysts introduced in Section 2.3 has
catalysts are of both scientific importance and economic interest. been verified by isotopic 15N labeling experiments. However, most
Currently, the reported metal-free catalysts for electrochemical of the 15N labeling experiments are single-point and qualitative,
NRR mainly include carbon-based catalysts, phosphorous-based which are not rigorous enough. Even if assuming all of the reported
catalysts, nonmetallic compounds, etc. results are reliable, it is supposed that little substantial progress has
For carbon-based materials, doping is the most widely used been made on the catalyst development for electrochemical NRR.
strategy to tune the electronic structure and improve the catalytic As shown in Fig. 7, the ammonia yield rate of all the recently
activity. Liu et al. prepared F-doped porous carbon derived from published representative catalysts is several orders of magnitude
UiO-66 metal-organic-frameworks (MOF) as the catalyst for elec- lower than the value required for application (9.3
trochemical NRR (Fig. 6aed) [111]. Because electronegativity of 107 mol cm2 s1, ~57 mg h1 cm2, FE > 90%) [118]. Many kinds of
fluorine (3.98) is much higher than that of carbon (2.55), the strategies such as defect engineering (vacancies, heteroatom
introduction of F atoms created Lewis acid sites on the neighbor doping, and edge engineering), structural manipulation (single-
carbon atoms. These Lewis acid sites not only can facilitate the atom sites and morphological regulation), crystallographic tailoring
binding and dissociation of N2 but also can keep the protons away, (crystal facet control and amorphous engineering), and interface
which simultaneously enhanced the activity and selectivity of regulation are available for catalyst design, as summarized in some
electrochemical NRR. Moreover, UIO-66 derived carbon has high recently published reviews [11,29,119e121]. Unfortunately, these
Brunauer-Emmett-Teller (BET) surface area (1024.8 m2 g1), lead- strategies have not brought the electrochemical NRR to an appli-
ing to more exposed active sites. Due to the above advantages, the cable level. Some suggestions on the further design of catalysts for
F-doped carbon exhibited an NH3 yield rate up to 197.7 mg h1 electrochemical NRR are provided as follows: Firstly, elemental
mg1cat. with a high FE of 54.8% in 0.05 M H2SO4 (Fig. 6e and f). Yang compositions are important for the electronic structure of catalysts.
et al. investigated the NRR performance of chalcogen/oxygen-group Up to now, more than thirty kinds of elements have been involved
element doped carbon prepared by vapor doping of MOF derived in the electrocatalysts for NRR. In general, elements on the top or
nanoporous carbon [112]. DFT calculations revealed that S, Se, and left side of the volcano diagrams (Fig. 2a) seem more promising due
Te doping created net negative charges on their adjacent carbon to their higher nitrogen adsorption energies and worthy of further
atoms, which could enhance N2 adsorption on the charge enriched studies. Secondly, the more efficient implementation of a certain
carbon atoms. Moreover, the spin moment of the active carbon design strategy mentioned above, integration of multi-strategies, or
atoms increased dramatically after doping, which was beneficial to development of new strategies may be helpful for the design of
the first step of the hydrogenation process. Among the hetero- better catalysts. In this context, the development of approaches
atoms, Te doping led to the best NRR performance with an NH3 that can realize the controllable preparation and precise regulation
production rate of 1.91 mg h1 cm2 and a FE of 4.67%. It is note- of catalysts becomes urgent. Besides the electronic structure which
worthy that the charges created on carbon atoms adjacent to het- is closely related to the intrinsic activity, the physical structure,
eroatoms in the above two works are opposite with each other, and conductivity, stability, and cost of catalysts should also be paid
a consensus remains to be reached on the working principles of more attention. Finally, catalyst design should be combined with
charges. the improvements on the electrolytic cells, regulation of local re-
Black phosphorous is an allotrope of phosphorous and has been action environments, etc. to make significant improvements on the
expected to be an ideal catalyst for electrochemical NRR because its performance of electrochemical NRR.
valence-electron structure is similar to that of nitrogen and may be
beneficial to N2 chemisorption. Zhang et al. prepared few-layer 2.4. Innovations on the configurations of electrolytic cells
black phosphorous nanosheets (FL-BP NSs) as the catalyst for NRR
[113]. DFT results revealed that the zigzag and diff-zigzag types of The electrolytic cells used in electrochemical NRR mainly
edges of FL-BP NSs are active sites for NRR. To obtain larger surface include back-to-back cell, polymer electrolyte membrane (PEM)-
area and more active sites for electrochemical NRR, Liu et al. type cell, flow cell, H-type cell, and single chamber cell [13,43]. In a
downsized black phosphorous to quantum dots (BP QDs), which back-to-back cell, the porous cathodic gas diffusion electrode (GDE)
were further stably confined on black tin oxide (SnO2-x) nanotubes and anode catalyst are pressed onto the two sides of a piece of ion-
to avoid agglomeration [114]. BP QDs and SnO2-x can synergistically exchange membrane, respectively. By contrast, the PEM-type cell is
catalyze NRR, leading to an NH3 an yield rate of 48.87 mg h1 mg1 cat consisted of one GDE as the cathode while liquid electrolyte, the
and a FE of 14.6%. Besides black phosphorous, few-layer triclinic counter electrode, and the reference electrode are placed in the
crystalline red phosphorous nanoribbons (cRP NRs) have also been anodic chamber. The use of liquid electrolyte is not only convenient
used to catalyze electrochemical NRR [115]. Theoretical calculation for adding a reference electrode but also can ensure the wetting of
results revealed that N2 bound with two P atoms between the two the membrane to reduce the conductivity loss. Different with the
coupled five atom rings (the building unit of cRP) but a distal back-to-back cell and PEM-type cell that don’t contain liquid
pathway that usually applies to the end-on N2 adsorption mode electrolyte in the cathodic chamber, the flow cell contains catholyte
was assumed for electrochemical NRR on cRP NRs. that flows between the cathodic GDE and the ion-exchange
Nonmetallic compounds such as B4C and C3N4 have also been membrane while the anode can either use a GDE or not [43,122].
reported as the catalysts for electrochemical NRR [116,117]. The presence of flow catholyte is beneficial to controlling the
9
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 accurately compared with the PEM-type cell. In a single-chamber
an H-type cell, the anodic and the cathodic chambers are both filled cell, the cathode, anode, and reference electrode are all placed in
with liquid electrolytes and separated by a piece of ion-exchange a single chamber filled with liquid electrolyte. Due to the absence of
membrane. The membrane can help to balance the ionic charge a membrane in the single-chamber cell, the produced ammonia
while preventing the transport of products to the anodic chamber. may be reoxidized at the anode. The performance of electro-
The reference electrode is located at the cathodic chamber and thus chemical NRR not only depends on the activity of catalysts but also
the potential of the working electrode can be measured more on the cell configurations. Therefore, the improvements on cell
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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. Materials Today Physics 16 (2021) 100310
feasible and can be achieved in many ways. Besides limiting the NRR by incorporating Liþ into the poly (N-ethyl-benzene-1,2,4,5-
accessibility of protons and electrons to suppress HER, it can be tetracarboxylic diimide) (PEBCD) catalyst [135]. For PEBCD, the
known from Eq. (5) that improving the solubility of N2 also can oxygen atoms are the best active sites for HER. When a negative
improve the ammonia selectivity. Up to now, most of the strategies potential was applied, Liþ associated with the O atoms in PEBCD
and methods proposed in this work have been validated by ex- and occupied part of the active sites for HER, leading to sluggish
periments, as will be discussed below. kinetics and higher barrier energy for HER. Wang et al. prepared
The regulation of the type, pH and concentration of electrolytes single Fe atoms supported on carbon nanosheets (FeeNeC) as the
is one of the approaches to limiting the accessibility of protons and catalyst of electrochemical NRR [136]. Fe single atoms in FeeNeC
has been widely implemented in experimental studies. For bore positive charges which greatly facilitated the adsorption of N2
instance, Zhou et al. used ionic liquids with high N2 solubility and and increased the energy barriers for protons adsorption. The
ppm-level water as the electrolyte [130]. The high N2 solubility in adsorption of N2 onto the Fe single atoms was an exothermic pro-
ionic liquids facilitated the electrochemical NRR while the limited cess and the released energy contributed to overcoming the energy
amount of proton source significantly suppressed the HER. As a barriers of the following hydrogenation. As a result, the onset po-
result, the FE can reach 60%. Wang et al. reported that the neutral tential of electrochemical NRR positively shifted to 0.193 V vs. RHE,
phosphate buffer solution (PBS) could effectively inhibit HER. and a FE of 56.55% was achieved at 0 V vs. RHE. Sim et al. modified
Compared with that in 0.1 M NaOH and 0.05 M H2SO4, the ammonia the electronic structure of Pt nanospheres deposited on the Au
yield rate doubled and the FE increased from below 0.1% to 2.4% in electrode by ZIF-71 coating. Electrons were transferred from Pt to
neutral 0.1 M PBS electrolyte [77]. Counterions (cations for the ZIF via Pt/AueN coordination, which not only lowered the d-band
cathode) can also influence the performance of electrochemical center of Pt thus weakening the H adsorption but also generated
NRR. The work of Song et al. revealed that the ammonia yield rate electron-deficient catalytic sites with strong N2 affinity. Moreover,
(Fig. 9a) and FE (Fig. 9b) of electrochemical NRR on N-doped carbon the nanoporous and superhydrophobic ZIF layer can concentrate N2
nanospikes were in the order of Liþ > Naþ > Kþ in electrolytes with and limit protons availability. Owing to the above reasons, a FE of
different counterions, which may be because Liþ can interact with >44% was achieved [137]. In addition to these examples, Co single
N2 and the electric field in the Stern layer becomes stronger as the clusters supported on nitrogen-doped carbon (Section 2.1), surface
counterion becomes smaller [131]. selenated Rh nanocrystals (Section 2.3.1), and fluorine-doped car-
Tuning the surface wettability of the electrode is another way to bon (Section 2.3.3) mentioned above all can effectively suppress
limiting the accessibility of protons. Hydrophobic protection layers HER and improve the FE of electrochemical NRR.
can hinder the transfer of protons while allowing N2 transportation. Besides the strategies mentioned above, hybrid electrolytic
Lee et al. coated the AueAg bimetallic electrocatalyst with super- systems also hold great promise to improve the FE of electro-
hydrophobic zeolitic imidazolate framework-71 (ZIF-71) to repel chemical NRR. As depicted in section 2.1 and 2.4, the lithium-
water and accumulate N2, which significantly suppressed HER and mediated approach can be viewed as a hybrid system combining
facilitated the electrochemical NRR. With tetrahydrofuran (THF) chemical reactions and electricity during which the activation and
solution containing LiCF3SO3 and ~1 vol % ethanol as the electrolyte, hydrogenation of N become easy and high selectivity can usually be
ammonia yield rate and FE of the obtained electrode are more than achieved. Hawtof et al. demonstrated a hybrid plasma electrolytic
4-fold and 2-fold superior to the AueAg catalyst without ZIF-71 system without any catalysts, which exhibited a record-high FE
coating, respectively [132]. On this basis, Koh et al. further modi- (nearly 100%) at low currents [14]. In this work, the gaseous plasma
fied the surface of ZIF-71 with hydrophobic oleylamine (OAm) and cathode generated solvated electrons at the plasma-water inter-
used butanol as the molecular filler, which can regulate water face, which could reduce protons to hydrogen radicals. Then, the
accessibility at the catalyst surface and suppress water electrolysis. hydrogen radicals further reduced N2 to ammonia. It was inferred
As a result, water was changed from a hinderance to a promoter for that N2 in the plasma was vibrationally excited and reacted with
electrochemical NRR and FE of this system can reach >18% with the water to form an intermediate with much higher solubility than N2,
presence of 0.1% water as the proton source in the electrolyte [133]. which enhanced NH3 formation kinetically. Nevertheless, this sys-
Ahmed et al. modified the Ru nanocrystals anchored on reduced tem still suffers from low energy efficiency although high FE was
graphene oxide (Ru/rGO) with dodecanethiol, which can form a achieved because a voltage of ~500 V was applied to induce the
hydrophobic self-assembled monolayer (SAM) on Ru surfaces by plasma. Cheng et al. applied a significantly lower pressure than the
RueS linkage. The RueS linkage can modify the electronic structure Haber-Bosch process on the electrochemical NRR system [138].
of Ru nanocrystals while the hydrophobic SAM can limit the Because the reaction of nitrogen and water to NHþ 4 is a volume-
transfer of protons, leading to improved FEs of electrochemical NRR decreased process whereas hydrogen evolution is a volume-
[134]. Cheng et al. reported that the FE of electrochemical NRR increased reaction, applying pressure is beneficial to the forma-
showed a fivefold enhancement by substituting the pristine hy- tion of NHþ 4 and the inhibition of hydrogen evolution, leading to
drophilic carbon cloth substrate with a hydrophobic one and improved selectivity towards NRR. On the other hand, the applied
increasing pH from 2 to 3 (Fig. 9c), but the NH3 yield rate decreased pressure can improve the solubility of nitrogen, promote nitrogen
from 11.3 mg h1 mg1 Mo2C to 8.2 mg h
1
mg1
Mo2C [82]. Lai et al. mass transfer to the electrode, and thus enhance the electro-
sandwiched selenium vacancy-rich ReSe2 loaded on carbonized chemical NRR (Fig. 9d). Benefiting from the above advantages, the
bacterial cellulose nanofibers (Vr-ReSe2@CBC) between two pieces FE of the electrochemical NRR system using Fe3Mo3C/C composite
of hydrophobic CBC nanofibers via a layer by layer process to nanosheets as the catalyst increased notably from 0.26% at ambient
restrict contact between the catalyst and the aqueous electrolyte, conditions to 14.7% when a 0.7 MPa pressure was applied. Besides,
which enabled the FE to increase from 10.2% for pristine Vr- the potentials at which the highest ammonia yield rate and FE were
ReSe2@CBC to 42.5%. However, the NH3 yield rate also exhibited a achieved shifted positively with the increase of applied pressure.
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 2.6. Verification of ammonia synthesis results
may sacrifice a portion of the ammonia yield rate.
The suppression of HER and improvement in the selectivity of The current ammonia yield rate of electrochemical NRR is so low
electrochemical NRR can also be achieved through rational catalyst that doubts about the results are rife. These doubts mainly arise
design. For instance, Chen et al. improved the FE of electrochemical from two aspects: Firstly, ammonia is ubiquitous in the air, human
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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 temperature NRR field and proposed a rigorous set of control ex-
into the electrolytes and the off-gas absorber; Secondly, other periments including a series of steps [139]. Firstly, the catalysts
reactive N species may exist in the reagents, electrodes, nitrogen should be tested in the Ar and N2 bubbled electrolytes without
gas, etc. and their reduction is more favorable than N2, thus electrochemistry, respectively, to eliminate the contamination of
resulting in more indiscernible false-positive results. Based on ammonia from the environment, gas and electrochemical cell.
these concerns, the researchers have carried out works mainly in Then, electrochemical tests in the Ar and N2 bubbled electrolyte
three directions, i.e. ferreting out possible contaminants, setting should be tested, respectively. After the catalytic performance of
protocols for tests, and revaluation of the reported works. the catalysts is identified under Ar control testing, it should be
To ensure the reliability of electrochemical NRR results, Green- further verified using quantitative isotopic (15N) experiments. They
lee et al. discussed the control experiments conducted in the low- also stressed that the control experiments should be conducted for
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
each test and the ammonia produced in the control experiments rigorous protocol was given for the benchmarking of electro-
should be subtracted from the measured ammonia when calcu- chemical NRR (Fig. 10). Following this protocol, the authors suc-
lating NH3 yield rate and FE. Chen et al. reported that standing of cessfully reproduced the lithium-mediated ammonia synthesis
the solution, human respiration, and latex glove soaking all could results while no ammonia was detected when Ru, Re, and Rh were
result in an increase in the amount of ammonia in 0.01 M HCl [17]. used as the catalysts for electrochemical NRR in aqueous electro-
Li et al. found that some brands of Li2SO4 contain trace amount of lyte. However, it should be noted that precious metal foils were
nitrate and nitrite which can result in false-positives during the used as the working electrodes and catalysts in this work. Kibs-
screening of catalysts [140]. Hanifpour et al. reported that signifi- gaard et al. further stressed that the amount of produced ammonia
cant amount of ammonia was accumulated in the Nafion mem- should be quantitatively confirmed by isotopic 15N labeling exper-
branes after the commonly practiced pretreatment methods. To iments at multiple points. They also pointed out that there is a large
avoid this, the authors proposed a new pretreatment method that discrepancy between the DFT calculations and experimental results
includes additional processes of sufficient expansion before storage in some works [144]. Compared with protocols on control experi-
and short sonication prior to use compared with the commonly ments, standardization of experimental parameters is equally
used one [141]. Licht et al. retracted their paper that use nanoscale important. Tang et al. made detailed experimental suggestions on
Fe2O3 as the catalyst for electrochemical NRR in molten hydroxide how to explore ambient electrochemical NRR reliably and insight-
suspensions and stated that the ammonia detected may come from fully [145].
the reduction of trace NO x impurities in the catalyst [142,143]. Considering that there are many interference factors during
Andersen et al. demonstrated that ammonia and labile NOx may electrochemical NRR and it is highly inclined to false-positive re-
exist in the 15N gas. Therefore, false-positive ammonia synthesis sults, the inspection or reevaluation of reported results is beneficial
results may be obtained even if isotopic 15N labeling experiments to the development of this field and should be encouraged. As
were conducted [18]. To eliminate the interference of the impu- mentioned above, it has been reported that transition metal ni-
rities in 15N gas, additional purification such as by a Cu impurity trides could catalyze electrochemical NRR through the MvK
trap was recommended to remove the contaminants. Moreover, a mechanism both theoretically and experimentally [35,49,146e149].
Fig. 10. Flow diagram of steps recommended for electrochemical NRR tests. Reprinted with permission from Ref. [18]. Copyright (2019) Nature Publishing Group.
15
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
However, recent works revealed that all of the rock salt cubic VN, or byproducts such as nitrite, NO, N2O, N2, etc. may be generated
NbN, tetragonal Nb4N5, and Mo2N were inactive to the electro- during its reduction to NH3 (Table 1 and Fig. 11) [30,154]. Among
chemical NRR and some of them may undergo decomposition to the products, N2 and NH3 are the most preferred because of their
release lattice nitrogen during the catalytic process [36,37]. Hao higher thermodynamic stability [21]. NO is supposed to be the
et al. reported high electrochemical NRR performance for both divergence center towards N2 or NHþ 4 . As shown in Fig. 11, the
bismuth nanocrystals and bulk particles [150]. Recently, Choi et al. adsorbed NO (NO*) is reduced to adsorbed atomic N* and then N* is
attempted to synthesis Bi nanocrystals by following the method in hydrogenated to form NHþ 4 during the electrochemical reduction of
the work of Hao et al. but coarse Bi aggregates rather than finely nitrate to ammonia. The reduction of nitrate to N2 follows the
dispersed nanocrystals were obtained. They successfully synthe- Vooys-Koper mechanism (the NO*/N2O*/N2 pathway in Fig. 11)
sized bismuth bulk nanoparticles similar to those reported by Hao while the combination of two N* to form N^N was not favorable.
et al. Furthermore, they investigated the electrochemical NRR For the Vooys-Koper mechanism, one dissolved NO reacts with an
performance of the bismuth bulk nanoparticles and commercial Au adsorbed NO* to form HN2O2. The HN2O2 is unstable and can be
nanoparticles loaded on carbon black. Results revealed that the two easily reduced to N2O and then N2 [20]. Duca et al. proposed that
kinds of catalysts had no activity towards electrochemical NRR but the ability to dissociate NO was the prerequisite for the nitrite
both could catalyze the reduction of ionic/gaseous NOx contami- reduction to ammonia [155]. The interaction between NO and the
nants [151]. This work cast doubts on the reliability of works on surfaces of the optimum catalyst for nitrite reduction to ammonia
electrochemical NRR using Au and Bi-based catalysts. McPherson should be strong enough to dissociate the NeO bond but not too
et al. attempted to confirm the results of electrochemical NRR in the strong to avoid poisoning of catalysts, i.e., follow the Sabatier
molten LiCleKCleLi3N salt. It is generally considered that the principle. The results revealed that Rh and Ru could meet the re-
electrochemical NRR in molten salts permits the direct reduction of quirements and had decent selectivity towards ammonia. More-
N2 to N3 and can achieve both high NH3 yield rate and FE. Among over, copper is also an excellent catalyst for the reduction of nitrate
the various molten salts, chloride molten salts containing Li3N is to ammonia despite its weak NO adsorption, which may be because
supposed to be the most promising because it has been believed that the prolonged generation of NO may hinder its desorption rate
that its high solubility towards Li3N can facilitate the conversion of and compel it to be further reduced to ammonia [20].
N2 to N3 [152]. However, McPherson et al. discovered that Li3N can Nitrogenous pollutants with lower N valence states are in-
directly react with H2, resulting in non-faradaic formation of NH3 termediates of nitrate reduction to ammonia. Therefore, in-
and FE exceeded 100%. To avoid this problem, the authors vestigations on nitrate reduction are of significant importance for
employed LiH to replace Li3N and declared that a truly catalytic the electrochemical reduction of nitrogenous pollutants. Wang
path to ammonia formation was possible in the LiCleKCleLiH et al. proposed that the reduction of nitrate could be used as a
molten salt. A peak NH3 yield rate of 2.4 108 mol cm2 s1 and a method to produce ammonia [22]. In this work, Co3O4 nanorod
maximum FE of 4.2% were obtained for the LiCleKCleLiH molten arrays supported on Ti mesh were used as the catalyst, which
salt system [153]. Nonetheless, it is subject to be further clarified achieved an NH3 selectivity of 33.6% and an NH3 yield rate of
whether LiH directly reacted with N2 in this work because LiH can 14.5 mg h1 cm2. After that, their group prepared TiO2 nanotubes
react with N2 to generate Li3N and NH3 at elevated temperatures. with rich oxygen vacancies for electrochemical synthesis of
ammonia from nitrate [156]. With a concentration of 50 ppm
3. Electrochemical recycling of nitrogenous pollutants into nitrate-N, a conversion rate of 95.2%, an NH3 selectivity of 87.1%, a
ammonia 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.
As shown in Table 1, the reduction of nitrate to ammonium ions SCE. Oxygen vacancies in TiO2 can not only be filled with the oxygen
is a reaction that involves eight electrons and ten protons. It is more in nitrate to weaken the NeO bond but also can modulate the
thermodynamically preferred compared with NRR and HER (Eqs. interaction between intermediates and catalysts to optimize the
(1)e(4)), and can usually achieve high NH3 yield rate and FE. Given reaction pathway and hinder the formation of byproducts. There-
the ease of nitrogenous pollutants reduction and the great difficulty fore, the nitrate reduction performance of TiO2 with oxygen va-
in electrochemical NRR, researchers have attempted to electro- cancies is much better than that without vacancies. They further
chemically recycle nitrogenous pollutants into value-added investigated the performance and activity origin of copper-based
ammonia. catalysts for electrochemical nitrate reduction to ammonia [157].
It is generally considered that the main challenge in the elec- The reduction process induced the structure evolution of initial CuO
trochemical reduction of nitrogenous pollutants to ammonia lies in nanowire arrays (NWAs) to Cu/Cu2O NWAs. An electron transfer
the diversity of products. The oxidation state of N varies from þ5 from Cu2O to Cu occurred at the interface of Cu/Cu2O, which led to
to 3 and stable nitrogenous species exist for all oxidation states in an increased electron density of Cu, thus facilitating the formation
this range. Taking nitrate as an example, a variety of intermediates 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%,
Table 1 81.2%, and 0.2449 mmol h1 cm2, respectively. Wang et al. elec-
Reactions related to the reduction of nitrogenous pollutants to ammonia and cor-
trochemically deposited dendritic CueNi alloys on different sub-
responding standard equilibrium potentials [21].
strates for electrochemical nitrate reduction to ammonia [158]. The
Reactions E0/V vs. NHE introduction of Ni positively shifted the d-band center of Cu to-
NO þ þ 8e / NH þ þ 3H O wards the Fermi level and modulated the intermediate adsorption.
3 þ 10H 4 2 0.875 (7)
NO
3 þ 2H þ þ 2e / NO þ H O
2 2 0.835 (8) With the increasing amount of Ni in CueNi alloys, a volcano-type
NO
3 þ 4H
þ þ 3e / NOðgÞ þ 2H O
2 0.958 (9) relationship was seen between the nitrate adsorption energy and
2NO3 þ 10H þ þ 8e / N OðgÞ þ 5H O
2 2 1.116 (10) the experimental nitrate reduction overpotential. Cu50Ni50 was
2NO3 þ 12H
þ þ 10e / N ðgÞ þ 6H O
2 2 1.246 (11)
located at the top of the volcano plots and had the optimal inter-
NO
3 þ 8H
þ þ 6e / NH OH þ þ 2H O
3 2 0.727 (12)
mediate adsorption. As a result, Cu50Ni50 exhibited the best elec-
NOðgÞ þ 6Hþ þ 5e / NH4þ þ H2 O 0.836 (13)
þ þ 6e / NH þ þ 2H O
trochemical nitrate reduction performance among CueNi alloys
NO
2 þ 8H 4 2 0.897 (14)
with different compositions, including a 0.12 V upshift of the half-
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T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
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 prepared MnO2 nanoarrays supported on Ti mesh (MnO2 NA/TM)
activity compared with pure Cu. Fu et al. adopted a strategy of for nitrite detection and reduction [23]. Wide detection range, low
crystal facet engineering and prepared copper nanosheets enclosed detection limit, and high response sensitivity were obtained when
with (111) facets. Compared with copper nanocubes covered by MnO2 NA/TM was used as a nitrite sensor and a transformation
(110) facets and irregular nanoparticles, the copper nanosheets efficiency of 6% was achieved when MnO2 NA/TM catalyzed nitrite
exhibited lower HER activity and higher activity towards nitrate reduction to ammonia. Long et al. investigated the electrochemical
reduction to ammonia [159]. Chen et al. incorporated copper into reduction of exhaust NO into ammonia [24]. DFT calculations
crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) to revealed that copper was the most active transition metal catalyst
form a copper-molecular solid catalyst for electrochemical reduc- for NO reduction. Experiments with commercial copper foam as the
tion of nitrate to ammonia [160]. The PTCDA substrate can facilitate catalyst were conducted to validate the theoretical prediction. A
the conduction of electrons and protons while the uniformly record-high NH3 yield rate of 517.1 mmol cm2 h1, a FE of 93.7%,
distributed copper has stronger adsorption for nitrate and lower and stable electrochemical performance of 100 h were achieved.
activity toward HER compared with other screened metals. The At present, studies on electrochemical synthesis of ammonia
catalyst with moderate amount of copper doping (OeCuePTCDA) from nitrogenous pollutants are much fewer compared with elec-
exhibited the best performance with an NH3 yield rate of trochemical NRR. The standard equilibrium potentials of nitroge-
436 ± 85 mg h1 cm2 and a FE of 85.9% at the potential of 0.4 V vs. nous pollutants reduction to ammonia are more positive than that
RHE. Li et al. designed Ru/oxygen-doped-Ru core/shell nanoclusters of electrochemical NRR but its optimum working potentials are not
with a diameter of ~2 nm to catalyze the reduction of nitrate necessarily higher than that of electrochemical NRR. The partial
(Fig. 12aec) [161]. The tensile strain effect, induced by the core- current density for nitrogenous reduction to ammonia can reach
shell structure, effectively prohibited the dimerization of hundreds of milliampere which is several orders of magnitude
hydrogen adatoms to form hydrogen, leading to their desorption higher than that of the electrochemical NRR. Thus, the performance
from the catalyst and formation of hydrogen radicals ($H). The of electrochemical nitrogenous reduction to ammonia has an
presence of $H significantly ameliorated the hydrogenation process overwhelming advantage over that of electrochemical NRR (Fig. 13).
of nitrate reduction, which is rate-limiting in nitrate reduction. However, it converts reactive N species into ammonia instead of
Benefiting from this, high FEs in a wide potential range and an fixing inert nitrogen from the atmosphere. Therefore, the electro-
ultrahigh NH3 yield rate of 1.17 ± 0.04 mmol h1 cm2 were ob- chemical nitrogenous reduction to ammonia is supposed as a
tained for 12% strained Ru/oxygen-doped-Ru core/shell nano- supplement to the nitrogen fixation technologies to prevent the
clusters (Ru-ST-12), which outcompeted most of the reported loss of the laboriously fixed nitrogen. Moreover, there are many
catalysts (electrolyte: 1 M KOH þ 1 M KNO3, Fig. 12e, f, and h). issues to be addressed for this technology. Firstly, the deep reason
Moreover, the Ru-ST-12 catalyst exhibited excellent stability why the ammonia production predominates over other products
without decay during 100 periods of 1 h running at 0.2 V vs. RHE such as N2 on the reported catalysts is important to defining the
(Fig. 12g). research directions to advanced catalysts but remains unclear.
Compared with nitrate, nitrite and NO can be reduced more Secondly, it has been reported that the catalysts for electrochemical
easily and have also been used to synthesize ammonia. Wang et al. nitrogenous pollutants reduction such as copper are susceptible to
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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 systematicity, and activities of many of the developed catalysts are
reported works have ignored this problem. Thirdly, synthetic at a not entirely convincing level. Accordingly, continuous efforts
electrolytes with high concentrations were utilized in most of the should be made with proposals given as follows. First of all, only
reported works while the low concentration and complex compo- reliable results can aid the screening of catalysts and promote the
sition of nitrogenous pollutants in real world may compromise the progress of electrochemical NRR, so the control experiments should
performance of nitrogenous pollutants reduction. be as rigorous as possible to rule out false-positive results caused by
the ubiquitous contaminants. The authors should reexamine their
4. Summary and outlook results and respond to the doubts on their works in time and
objectively, which can help eliminate errors and maintain
In this review, we summarized the recent progress in the elec- authenticity to ensure the healthy and rapid development of this
trochemical synthesis of ammonia through NRR or nitrogenous field. Secondly, the catalysts should be designed more accurately
pollutants reduction. On the whole, a lot of attempts and significant and systematically to make breakthroughs in both the activity and
progress have been made, but the electrochemical synthesis of selectivity. It has been proposed theoretically that the circumvent
ammonia is still in the infancy stage with great challenges of scaling relationships can lead to a leap of the electrochemical
remained to be addressed. NRR performance but specific methods to achieve this aim remain
As for the electrochemical NRR to ammonia, the NH3 yield rate to be implemented. In situ advanced characterizations should be
and FE fall far below the commercially viable targets released by the further developed and employed to provide insights into the cat-
U. S. Department of Energy (a current density of 300 mA cm2 with alytic process and set up correlation between structure and per-
a FE of 90% and energy efficiency of 60%) [162]. Basically, the in- formance. Moreover, theoretical calculations such as the high-
vestigations on electrochemical NRR suffer from the lack of throughput machine learning can significantly accelerate the
18
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
Acknowledgements
19
T. Wu, W. Fan, Y. Zhang et al. Materials Today Physics 16 (2021) 100310
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