Pi Is 2451929421000383
Pi Is 2451929421000383
Pi Is 2451929421000383
Review
Electrochemical ammonia synthesis: Mechanistic
understanding and catalyst design
Huidong Shen,1 Changhyeok Choi,2 Justus Masa,3 Xin Li,1 Jieshan Qiu,1 Yousung Jung,2,*
and Zhenyu Sun1,*
From these scenarios, three major clean routes for ammonia synthesis involving bio-
catalysis, photocatalysis, and electrocatalysis have sparked increasing research in-
terest in recent years, as illustrated in Figure 1. Biological nitrogen fixation in nature
is attained under mild conditions (<40 C, atmospheric pressure) by metalloenzyme
nitrogenases that are composed of FeMo, FeV, or FeFe cofactor as active sites with
FeMo being the most active and abundant enzyme for N2 reduction.4 A minimum of
16 moles of adenosine triphosphate (ATP) is necessary to reduce one mole of N2
(N2 + 8H+ + 8e + 16ATP / 2NH3 + H2 + 16ADP + 16PO43 where ADP is adenosine
diphosphate) with concomitant formation of one mole of H2 and a corresponding
1State Key Laboratory of Organic-Inorganic
transfer of 8(e /H+), not 6 (which could result in dissipative hydrolysis of 4 ATP).5 Composites, College of Chemical Engineering,
As a consequence, production of one NH3 consumes 8 ATP, requiring an energy Beijing University of Chemical Technology,
Beijing 100029, People’s Republic of China
input of 244 kJ mol 1. However, biological nitrogen fixation occurs only in a select
2Department of Chemical and Biomolecular
group of microorganisms, and the nitrogenases are susceptible to deactivation by
Engineering, Korea Advanced Institute of Science
oxygen.6 In addition, biological conversion of nitrogen into NH3 has a low space- and Technology (KAIST), Daejeon 34141,
time yield. Noteworthy, NH3 production via natural processes cannot meet the cur- Republic of Korea
3Max Planck Institute for Chemical Energy
rent and future NH3 needs. Photocatalytic NH3 synthesis only requires solar energy,
Conversion, Stiftstr. 34-36, 45470 Mülheim an der
water, and N2, encompassing two coupled redox half reactions, i.e., oxidization of Ruhr, Germany
water by photogenerated holes (3H2O [l] + 6h+ / 6H+ [aq.] + 3/2O2 [g]) in the *Correspondence: [email protected] (Y.J.),
valence band (VB) and reduction of N2 via photogenerated electrons (N2 [g] + 6H+ [email protected] (Z.S.)
[aq.] + 6 e / 2NH3 [g]) in the conduction band (CB). Nonetheless, the overall https://doi.org/10.1016/j.chempr.2021.01.009
Figure 2. Summary of state-of-the-art various metallic and nonmetallic materials for aqueous
electrocatalytic NRR under ambient conditions
(A) NH 3 yield rate at different applied potentials.
(B) FE of NH 3 at different applied potentials.
Full-filled circles and half-filled circles represent the process using purified N2 and unpurified N 2 ,
respectively. Acidic, basic, and neutral electrolytes are labeled by (a), (b), and (n) following the
electrocatalysts, respectively.
Because of the high interest and rapid advances pertaining to this reaction, this
article aims to provide a comprehensive and up-to-date review of nanostructured
heterogeneous catalysts for the electrochemical NRR, with emphasis on relation-
ships between structures and properties. A summary of the most important develop-
ments in catalyst design, and analytic tools and techniques for electrocatalytic N2
reduction, as well as possible reaction mechanisms and pathways are presented.
Next, we discuss the strategies available to tune the electronic structure of electro-
catalysts and other relevant parameters in order to further enhance the performance
and efficiency of electrochemical N2 reduction. We also introduce emerging in situ
and operando methods for investigations of the dynamic catalyst structure and other
reaction parameters during the NRR. Finally, future challenges and opportunities of
NH3 synthesis by NRR are outlined.
The overall cell voltage required for NRR involves potentials for both the anode and
cathode processes (Ecell = Eanode – Ecathode), where water oxidation (3 H2O # 6 H+ +
3/2 O2 + 6e–, E0[298 K] = +1.229 V [versus standard hydrogen electrode, SHE]) is
recognized as the default anode process. Coupling this to cathodic NRR generates
a minimum of several hundred millivolt overpotential for real-world electrocatalytic
NRR. The role of the anode in NRR should not be neglected because it consumes
almost half of the electrical input. Lowing oxygen evolution reaction overpotential
and improving the anode efficiency can reduce the total energy cost of electrochem-
ical NH3 synthesis, thus, promoting the prospects of its practical implementation.
Table 1. HER and electrochemical NRR processes with corresponding equilibrium potentials
Equation Reaction E0 (V)25,26
1 N2 (g) + 6H (aq.) + 6e # 2NH3 (g)
+
0.0577 (versus SHE)
2 N2 (g) + 8H+ (aq.) + 6e # 2NH4+ (aq.) +0.274 (versus SHE)
3 N2 (g) + 8HBase+ (MeCNa) + 6e # 2NH4+ +0.361 – 0.079 pKa (versus Fc+/0)
(MeCN) + 8Base
4 N2 (g) + 2H2O (l) + 6H+ (aq.) + 6e # +0.092 (versus SHE) or +0.23 (versus RHE)b
2NH3$H2O (aq.)
5 N2 (g) + 6HBase+ (MeCN) + 6e # 2NH3 +0.035 – 0.059 pKa (versus Fc+/0)
(MeCN) + 6Base
6 2H+ (aq.) + 2e # H2 (g) 0 (versus SHE)
7 N2 + 6H2O (l) + 6e # 2NH3 (g) + 6OH (aq.) 0.736 (versus RHE, pH 14)
8 2H2O (l) + 2e # H2 (g) + 2OH (aq.) 0.828 (versus normal hydrogen electrode,
NHE, pH 14)
9 N2 (g) + H+ (aq.) + e # N2H (g) 3.2 (versus RHE)
10 N2 (g) + 2H+ (aq.) + 2e # N2H2 (g) 1.10 (versus RHE)
11 N2 (g) + 2HBase+ (MeCN) + 2e # N2H2 1.22 – 0.059 pKa (versus Fc+/0)
(MeCN) + 2Base
12 N2 (g) + 4H+ (aq.) + 4e # N2H4 (g) 0.33 (versus RHE)
13 N2 (g) + 4HBase+ (MeCN) + 4e # N2H4 (g) + 0.398 – 0.059 pKa (versus Fc+/0)
4Base
14 N2 (g) + 4H2O (l) + 4e # N2H4 (g) + 4OH 1.16 (versus NHE, pH 14)
(aq.)
15 N2 (g) + 5H+ (aq.) + 4e # N2H5+(aq.) 0.23 (versus RHE)
16 N2 (g) + 5HBase+ (MeCN) + 4e # 0.153– 0.074 pKa (versus Fc+/0)
N2H5+(MeCN) + 5Base
17 N2 (g) + e # N2 (aq.) 4.16 (versus NHE) or 3.37 (versus RHE, pH
14)
a
Acetonitrile.
b
Thermodynamic equilibrium potential is calculated based on Nernst equation.
favorably than the latter one with lower energetic barriers, while the disruptive two-elec-
tron HER is also more severe at similar potentials in aqueous electrolytes (Equations 4
versus 6; Equations 7 versus 8). Multiple intermediates (such as N2H4 and N2H2) may be
involved during the concerted proton-electron transfer steps.25,26 The addition of the
first H atom to form N2H (Equation 9) demands a rather negative equilibrium potential
( 3.2 V versus reversible hydrogen electrode, RHE), while an even more negative po-
tential is needed for the first electron transfer to yield N2 (Equation 17). At a high
pH of 14, Equation 17 may compete with Equation 9 provided a weak affinity for
*N2H (* represents an active site on a catalyst) but a stabilizing interaction of the catalyst
with the N2 . The preferred pathway between concerted proton-electron transfer and
sequential proton-electron transfer was recently reported to be pH dependent. Howev-
er, the majority of theoretical calculations of NRR thus far did not consider the pH
impact. Hence, further exploration in this regard is necessary.
An advanced catalyst likely entails catalytic centers in favor of electron transport that
are in close proximity to sites providing protons. However, it is very unlikely for elec-
trochemical reduction of N2 to be kinetically limited by proton concentration in elec-
trolyte, which would occur if the mass transport of protons cannot match the NRR
rate that reaches the highest value for a specific system. In a typical electrochemical
process, the activity increases exponentially with overpotential. However, this is not
the case for the NRR, in which the performance first increases with overpotential in
the small overpotential regimes but declines at relatively larger overpotentials.
The drop of the NRR rate may be due to two possibilities: (1) the mass-diffusion lim-
itation and (2) fewer available *N2 molecules for further hydrogenation in light of the
fact that the electron and proton transfer steps of *N2 molecules are more rapid at
higher reducing voltages.27 This is likely to be associated with the competitive HER,
in which higher surface coverage of *H occurs at larger overpotentials, while the N2
adsorption rate does not lean on potential. The surface coverage of *N2 decreases
owing to occupation of active sites by *H, thus, resulting in the decline of NRR
activity.
The multi-step six-electron NRR involves several different transition states. N2 bound
to the surface may be directly broken into adsorbed N atoms or first partly reduced
by generating an N2–H bond followed by further hydrogenation and dissociation.
The adsorption energy of the intermediates and activation barrier for N2 dissociation
were encoded by the Brønsted-Evans-Polanyi (BEP) linear correlation typically on the
surfaces of metals.13 Transition metals were suggested to be limited by the scaling
relations between the binding energy of *N2H generation and *NH protonation.
Transition metal nitrides are also limited by the weak binding for *N2H formation
but strong binding for *N protonation. This renders it difficult to design an active
catalyst that can cleave the N–N bond to yield the *N2H intermediate but not
bind NHx intermediates too strongly for reasonable catalytic turnovers. Indeed, no
metals were found to display a combination of intermediate nitrogen binding and
low energy N2 scission transition state, as depicted at the bottom middle of the
plot in Figure 5.37 On the other hand, selectivity for NRR is restricted by the scaling
between the free energy changes of the HER step and *N (in the nitride case) or *NH
(in the metal case) protonation or *N2H formation. Consequently, to attain efficient
Figure 5. Linear scaling between nitrogen-binding energy and activation barrier for N2
dissociation (TOF: turnover frequency; Ea: activation energy)
Reprinted with permission from Medford et al. 37 Copyright 2015 Elsevier.
NRR, it is required to break the energetic linearity constrains between key interme-
diates (*H, *NHx, or N2Hx species where x = 0–2). To this end, new or coordinated
catalyst design schemes (through geometric and electronic effects as well as elec-
tronic dynamics) need to be developed. Exploration of promoters and solvents
beyond H2O may be another alternative route.38
compounds before carrying out NRR measurements. Isotopic labeling using mole-
cules such as 15N2 in combination with isotope-sensitive proton nuclear magnetic
resonance spectroscopy (1H NMR) should ideally be carried out to confirm the actual
reduction of N2 (especially for catalysts that either contain nitrogen in their structures
or are prepared from nitrates or ammonium precursors), namely detection of solely
15
NH4+ (featuring a symmetric doublet at 7.12 ppm with a spacing of ~73.2 Hz as
opposed to a triplet for 14NH4+ at 7.12 ppm with a spacing of ~52.2 Hz). If appre-
ciable 14NH4+ is generated, nitrogen is most likely present in other extraneous sour-
ces. Under the same conditions, the amount of NH3 produced by the 15N2 test
should be consistent with the corresponding 14N2 test. Also, repeats of measure-
ments (over 3 times) should be performed for each catalyst type/composition to vali-
date that NH3 production is repeatable and reliable.
species (NO, NO2, and N2O) are thermodynamically and kinetically more facile to be
reduced than N2.44 A 10 ppm of reducible N-impurities could potentially result in
about 4.0 mg per hour of NH3 or other nitrogen-containing compounds.39 This
dramatically affects precise quantification of NH3 from NRR in light of the fact that
typical NH3 yields are in the range of 10–1,000 nmol. It is worth noting that the level
of NH3 and NOx impurities in almost all 14N2 gas (with a purity %99.999%) reported
for NRR is uncertain or not specified. In addition, the isotopically labeled 15N2 feed-
stock (with a purity mostly %99.9%) can be contaminated with impurities (as high as
0.1%), mainly in the forms of 15N-ammonia, 15N-nitrite/nitrate, and 15N-nitrous ox-
ide.45 These point to the necessity of additional N2 purification. Removal of extra-
neous NH3 contamination can be readily addressed by passing the feed gas through
H2SO4 as adsorbent. The nitrite/nitrate and NO2 are soluble in water and therefore
can be effectively absorbed and eliminated from the stock gas by the aqueous solu-
tion. NO and other sparingly soluble NOx pollutants can be transformed into N2 and
H2O via selective catalytic reduction (SCR) of NOx with NH3 in a fixed-bed quartz
tube reactor over Cu-based catalysts or Ce0.1Ti0.9O246 at 300 C for 1 h, followed
by repeated absorption and removal of NH3 in H2SO4 solutions (confirmed by detec-
tion before NRR test). Alternatively, these N-species can be oxidized (to NO3 ) and
removed by use of a dual oxidant solution (H2O2/S2O82 ) at 50 C and pH of 11.47
During gas purification, special care should be taken to avoid new adventitious
contamination.
Quantification of ammonia
Six main types of techniques, including (1) spectrophotometry, (2) ion chromatog-
raphy, (3) ion-selective electrode (ISE), (4) fluorescence, (5) 1H NMR, and (6) ultra-
high-performance liquid chromatography mass spectrometry (UPLC-MS) have
been proposed to determine the amount of NH3 produced during NRR. Current
electrochemical NRR studies are heavily reliant on aqueous-based spectrophoto-
metric/colorimetric assays using indophenol blue48 and Nessler’s reagent,49 which
are well-established with advantages of good sensitivity (0–0.6 mgNH3-N L 1) and
low cost. The indophenol blue method, or the salicylate method, is based on the
modified Berthelot reaction, in which ammonia reacts with sodium salicylate and
Two types of ISEs have been demonstrated for measuring ammonia nitrogen.52 One is
ammonia-selective electrode via testing potential difference emanating from diffusion
of generated NH3 gas through a hydrophobic membrane (typically PTFE). The
ammonia/ammonium concentration in the solution can, thus, be determined according
to the Nernst equation. The other is ammonium-ion-sensing electrode with a polyvinyl-
chloride (PVC) membrane containing an ammonium carrier. All NH3 in samples is con-
verted to NH4+ by acidification for measurement. The ISE method offers advantageous
features of convenience, large detection range (0.03–1,400 mgNH3-N L 1) with high con-
centration of ammonia nitrogen, and suitability for continuous monitoring.52 However,
the inherent poor sensitivity of ISE especially for ammonia nitrogen at low concentra-
tions (< 0.5 mgNH3-N L 1) limits its widespread application.
1
H NMR has been widely used for quantification of NH4+ in biocatalytic and homo-
geneous catalytic N2 reduction.54 In contrast to indirect spectrophotometry and ion
chromatography protocols, the 1H NMR method is direct and highly selective for
analysis of both 14NH4+ and 15NH4+ (concentration in the range 5–10 mM with a
600-MHz NMR spectrometer and 1 mM with a 900-MHz NMR spectrometer).55 How-
ever, it suffers from laborious ammonia isolation via distillation. In addition, subop-
timal NMR settings lead to lengthy data acquisition time and influence accurate
quantification.
UPLC-MS was recently reported to distinguish and quantify 14NH3 (MS peak at m/z =
251.0854 for 14N) and 15NH3 (MS peak at m/z = 252.0825 for 15N).56 This analytical
method was developed based on a dansyl chloride derivatization process by mixing
dansyl chloride and ammonia solutions at optimal pH (~9.5 G 0.5). An ammonia con-
centration in the range of 0.6–43.5 mM was claimed to be rapidly measured for both
14
NH3 and 15NH3.
Note that each of these methods has advantages and limits for assaying ammonia.
To evaluate the overall level of accuracy and accountability, it is strongly recommen-
ded to use a combination of different approaches. Moreover, it is imperative to
develop more selective, sensitive, accurate, and robust protocols for ammonia
quantification, as well as in situ and continuous processes for monitoring the NRR.
Quantification of by-products
From the Equations 10 and 12 (Table 1), N2H2 and N2H4 are also produced during
NRR as by-products, respectively. Such by-products may reduce the FE of ammonia;
however, these are important indicators for identifying reaction pathway of NRR. The
observation of N2H2 and N2H4 is an evidence for that the alternative pathway is
preferred to the distal pathway (Figure 8), and thus, the observation of by-products
has been employed for in situ mechanistic studies of NRR (discussed in detail in the
subsequent Mechanistic understanding of NRR section).57,58 Diazene is unstable
and can be easily decomposed into ammonia and nitrogen in the electrolyte.
Thus, diazene has not been quantified during the NRR while it has been detected
by in situ mechanistic studies on NRR.57,58 For example, in a spectroscopic method
to quantify the hydrazine in electrolytes, known as the method of Watt and Chrisp,59
a mixture of p-dimethylaminobenzaldehyde, ethanol, and concentrated HCl is used
as a color reagent. Calibration curve is obtained by using a mixture of color reagent
and N2H4 solution in dilute HCl (0.1 M) with different N2H4 concentrations. The
absorbance of the resulting solution is obtained at 458 nm. In this method, the op-
timum concentration range of hydrazine is 0.06 to 0.47 ppm, where the relative error
does not exceed 1%.
Electrolytes
Electrolytes serve as a hydrogen source and also provide a medium to trap N2 and
transfer protons and intermediates. Engineering of electrolytes can decrease the
ionic resistance in the electrochemical reactor, which is particularly critical for energy
efficiency at high currents. Akin to many other electrochemical reactions, the proton
activity, donor identity, the acid dissociation constant, and ion conductivity of elec-
trolytes affect activation barriers and reaction rates of NRR. However, further in-
depth experimental and theoretical investigations of electrolyte effects are
required. Electrolytes are generally classified into six types, including (1) liquid elec-
trolytes (aqueous solutions, organic solvents, and ionic liquids with operating tem-
perature %50 C),15,41,60 (2) molten salt electrolytes (molten 0.5 NaOH/0.5 KOH,
molten LiOH, eutectic of LiCl, KCl, and CsCl with Li3N operated between 200 C
and 500 C),60 (3) polymer membrane electrolytes (Nafion N117 and 102 mem-
branes, sulfonated polysulfone membrane operated from room temperature to
80 C),60 (4) composite membrane electrolytes (Na, K, and Li carbonates mixed
with LiAlO2 operated at 400 C),60 (5) O2 -conducting membrane electrolytes
(doped ZrO2, doped Bi2O3, doped CeO2, doped LaGaO3 at A and B sites, doped
BaSrO3 and SrCeO3, and Y2O3-ZrO2 operated at 650 C),60 and (6) ceramics/inor-
ganic proton conducting solid electrolytes (Yb doped Sr-cerate, SrCe0.95Yb0.05O3 d,
BaCe0.9Sm0.1O3 d + BaCe0.8Gd0.1Sm0.1O3 d complex perovskites, Gd-doped
barium cerate, Ce0.8M0.2O2 d [M = La, Y, Gd, Sm], Ba3(Ca1.18Nb1.82)O9 d,
Ba3CaZr0.5Nb1.5O9 d, Ba3Ca0.9Nd0.28Nb1.82O9 d, La1.9Ca0.1Zr2O6.95, Ca2+-doped
La2M2O7 [M = Ce, Zr], La1.95Ca0.05Zr2O7, La1.95Ca0.05Ce2O7, and SrZr0.95Y0.05O3 d
operated in the range 450 C–750 C).60 The majority of ambient electrocatalytic
NRR studies are conducted in liquid electrolytes. Recent progress in this regard
will be discussed in the following. For the other electrolytes, readers are referred
to earlier reviews.60
Specifically, adsorbed alkaline cations in the inner Helmholtz plane (IHP) alter the po-
tential of the outer Helmholtz plane (OHP) and can also block hydrogen adsorption,
thereby limiting the HER.17,62 Meanwhile, cations were proposed to be solvated by
water in the OHP, favoring N2 adsorption. Unlike CO2 reduction, cations with a
smaller radius were found to favor better NRR activity, following the trend Li+ >
Na+ > K+ > Cs+.63 In addition, the 2p orbitals of adsorbed nitrogen were calculated
to shift to lower energies in the presence of K+, which facilitated electron transfer to
*NNH for N–N activation.17
Hitherto, the effects of anionic species on NRR have been rarely explored. Anions
with different buffer capacities (e.g., HCO3 and H2PO4 ) are likely to affect the local
pH at the electrode and hence the NRR selectivity. Also, PO43 was calculated to
easily adsorb N2 via bonding thus increasing N2 solubility in water.64 Adsorbed
phosphate and halides (i.e., Br , Cl , or I ) may form a bond with metal electrodes,
thus, promoting electron transfer from these anions to the vacant orbital of N2 and
boost N2 reduction. Additionally, specifically adsorbed halides may hinder proton
adsorption and induce a larger HER overvoltage.
Organic electrolytes
Most organic electrolytes exhibit an N2 solubility that is 1 or 2 orders of magnitude
higher than that of water. Use of organic solutions affords substantially enhanced N2
dissolution (toluene: 5 mmol L 1, trifluorotoluene: 10 mmol L 1, cyclohexane:
7 mmol L 1, 1H,1H,2H-heptafluorocyclopentane: 12 mmol L 1, heptane:
9.1 mmol L 1, perfluoroheptane: 17.9 mmol L 1, perfluorotributylamine:
11.8 mmol L 1, ethanol: 20.0 mmol L 1, 2-propanol: 23.0 mmol L 1)65,66 and also
regulates the supply of H+ to favor N2 adsorption onto electrode surface, benefiting
NRR. In this context, a number of organic-based electrolyte mixtures, such as 0.2 M
LiClO4 in ethanol/tetrahydrofuran,67 0.1 M LiClO4 in methanol/0.03 mol L 1
H2SO4,68 0.01 M H2SO4 in 2-propanol/water (9: 1, v/v),69 0.1 M LiCl in ethylenedi-
amine,70 0.2 M LiCF3SO3 in ethanol/dry tetrahydrofuran,71 and 1 M LiBF4 in
ethanol/dry tetrahydrofuran72 have been applied to enhance NRR over the
competing HER. In lithium (Li)-mediated N2 reduction, Li+ ions from solution in a po-
lar, aprotic solvent are reduced to Li metal, which easily splits the nitrogen triple
bond to form lithium nitride (Li3N). The Li3N then reacts with a proton source/carrier
(such as ethanol) to yield NH3. The proton carrier was claimed to play important roles
in promoting both Li nitridation to form Li3N and its further protonation to evolve
NH3.72 However, the stability and mechanistic understanding of organic electrolytes
need to be further elucidated.
Ionic liquids
Ionic liquids (ILs) with wide electrochemical stability windows are promising elec-
trolytes for efficient NRR.15 A family of phosphonium-based ILs with highly fluori-
nated anions were reported to have remarkable N2 solubility (Figures 7A and
7B).73 The already high N2 solubility of these ILs could be further enhanced by
the addition of fluorinated solvents, trifluorotoluene, 1H,1H,2H-heptafluorocyclo-
pentane, and 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (FPEE)
that lack strong interactions (i.e., from hydrogen bonding, or functional groups).66
The ionic conductivity and fluidity were improved as well. Notably, the (1-butyl-1-
methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([C4mpyr][eFAP])-
FPEE binary electrolytes were observed to enable NRR with a high FE (32.0%)
and yield rate (2.35 3 10 11 mol cm 2 s 1) for NH3 formation over a-Fe nano-
rods.74 Despite this success, 15N2 isotopic labeling experiments need to be per-
formed to confirm the accuracy of the activity data. Manipulation of IL structures
by changing electric potential or nanopore confinement provide another way to
further improve the solubility of N2.75 Apart from high solubility for N2, the IL,
[C4mpyr][eFAP], was also found to stabilize the N2H intermediate via interaction
of the F–CF2 atom in [FAP] with the N2H group, thus, increasing both NRR activity
and selectivity (Figure 7C).76
The high price and viscosity (causing diffusional transport limitations) are downsides
of ILs for practical use in N2 electrolysis. Nevertheless, the high viscosity of ILs can be
circumvented by dilution with a controlled quantity of an aprotic solvent (or a mixture
of solvents), while retaining their functionality. Despite the high cost of ILs, some can
be recovered and reused, rendering electrolyzers that use ILs economic to a certain
extent. To date, only a limited number of ILs have been examined for NRR, further
Figure 9. Possible NRR mechanism on Ru surface including various N–N bond dissociation steps
and reaction free energy obtained by DFT calculations
(A) Activation energy of N–N bond dissociation in all reaction intermediates of NRR on Ru surface.
Gray, blue, and ivory atoms indicate Ru, N, and H atoms, respectively.
(B) A summary of various possible reaction mechanisms of NRR on Ru surface. PDS and U L indicate
PDS and limiting potential, respectively.
Reprinted with permission from Back et al.80 Copyright 2016 Royal Society of Chemistry.
A theoretical study on NRR over Ru surface showed that reaction pathways involving
various N–N bond dissociation steps yield the NRR activity that is comparable with
the associative mechanism with a similar limiting potential, suggesting the impor-
tance of considering all possible reaction pathways in addition to the conventional
associative mechanism (Figure 9).80 For example, *NNH2, *NHNH2, and *NH2NH2
can be dissociated into *N + *NH2, *NH + *NH2, and *NH2 + *NH2, respectively,
with low activation energy (0.20~0.52 eV), while these reaction steps are not
involved in the conventional associative mechanism. Also, in situ studies of NRR
on Ru thin film using surface-enhanced infrared absorption spectroscopy (SEIRAS)
found N2H2 (diazene) as an intermediate product where the N2H2 can be decom-
posed or further protonated to ammonia. It can be noted that the latter reaction
steps have not been considered in conventional associative mechanism. Thus, it is
important to consider various potential pathways in order to describe correctly the
mechanism and activity of NRR on heterogeneous catalysts.
Now, we turn to the strategies for designing efficient NRR catalysts informed by in-
depth understanding of the reaction mechanism of NRR. The overall reaction and
equilibrium potential for NRR involving one N2 molecule and six proton-electron
pairs can be expressed below:
The equilibrium potentials of several reaction intermediates (N2H, N2H2, and N2H4)
in the associative pathway are known, and are presented in Table 1.
Although the formation of NH3 (g) from N2 (g) and H2 (g) is slightly exothermic
(DGf0 = 16.4 kJ/mol), NRR is thermodynamically hindered by the negative equilib-
rium potentials of these reaction intermediates. Notably, the equilibrium potential
of N2H (g) formation, corresponding to the first protonation step in NRR, is highly
negative, indicating that NRR via the associative mechanism is limited by the first
protonation step.26 Theoretical volcano plots of NRR also have shown that the first
protonation step (*N2H formation) is the thermodynamic limiting step for most cat-
alysts, and hence, catalysts that can strongly bind N2H favor NRR (Figures 10A and
10B).26,29,38 In addition to stabilizing adsorbed N2H (*N2H), destabilization of *NH2
is also important to design catalysts with low overpotential for NRR. A previous theo-
retical study has shown that the limiting step for NRR is the first protonation step
(N2 + [H+ + e–] / *N2H) on weak N-binding metal surfaces, meanwhile, for strong
N-binding metal surfaces, the limiting step is the final protonation step (*NH2 +
(H+ + e–) / NH3) (Figure 8).38 Thus, the strategies for lowering NRR overpotential
include stabilizing *N2H and destabilizing *NH2 independently to reduce the free
energy change for N2 + (H+ + e–) / *N2H and *NH2 + (H+ + e–) / NH3, respectively.
Figure 10. Volcano plot for limiting potentials (UL) of NRR as a function of *N-binding energy descriptor for fcc metal surfaces and surface-
hydrogenation mechanism on noble-metal catalysts
(A) UL for NRR as a function of *N binding on fcc(111) surfaces.
(B) U L for NRR as a function of *N binding on fcc(211) surfaces. Reprinted with permission from Montoya et al. 38 Copyright 2015 Wiley-VCH.
(C) *NNH formation free energy via * + N2 (g) / *NNH on Au and Pd surfaces.
(D) Minimum-energy pathway of *N 2 H2 formation via the hydrogenation of N 2 (N 2 (g) + 2*H / *N 2 H 2 ) on Au(100) surface.
(E) Schematic of NRR on noble-metal-based catalysts via the surface-hydrogenation mechanism. Reprinted with permission from Ling et al. 81 Copyright
2019 American Chemical Society.
Figure 11. FTIR spectra and reaction mechanisms of NRR on Au, Ru, and Rh thin film electrodes
(A) FTIR spectra during NRR on an Au film electrode in N 2 -saturated 0.1 M KOH solutions.
(B) Proposed NRR mechanism on Au surface. Reprinted with permission from Yao et al. 83 Copyright
2018 American Chemical Society.
(C) Proposed NRR mechanism on Ru surface. Reprinted with permission from Yao et al. 57 Copyright
2019 American Chemical Society.
More recently, the SEIRAS technique revealed the NRR mechanism on a Ru surface. Dur-
ing NRR, the IR signal of N=N in *N2Hx (0 % x % 2) species was detected at potentials
below 0.2 V in 0.1 M HClO4 solutions.57 However, these bands were not observed in
alkaline solutions, indicating that N2 molecules are not easily adsorbed on Ru in alkaline
electrolytes. Unlike Au (Figure 11B), Ru involved N2H2 as reaction intermediate not
N2H4. The N2H2 on the Ru surface could then be decomposed or further reduced to
ammonia (Figure 11C). In contrast to Ru that is inactive in alkaline media, Rh was shown
to manifest apparent IR signals from the end-on *N2Hx between 0.2 and 0.4 V in KOH
solutions.58 The NRR on Rh was inferred to proceed via a two-electron transfer pathway
to form an N2H2 intermediate, which subsequently decomposed to produce NH3 in the
electrolyte. Based on in situ Fourier-transform infrared (FTIR) investigations, an associa-
tive alternating mechanism was also deduced for NiFe-MoS2 nanocubes,84 Fe-doped
ReS2,85 Al-doped Co3O4 nanospheres,86 and nonmetallic N, B dual doped carbons,87
while the NRR was speculated to proceed through an associative distal pathway over
phosphorus-doped carbon nanotubes.88
detectable in this work was as low as 50 mV (versus RHE) for PdH0.43. Laser sources
are required in Raman spectroscopy and thus may affect the formation and detection
of NRR intermediates. To minimize such impact and avoid other optical responses
(such as fluorescence) from catalysts, near-infrared laser is preferable.
In situ DEMS. The NRR process can be tracked with the aid of online differential
electrochemical mass spectroscopy (DEMS) to monitor the volatile intermediates
and products.90 Such analysis provides important complementary direct information
on electrocatalytic mechanisms. The co-existence of mass-to-charge ratio (m/z) sig-
nals at 27, 30, 31, and 33 indicates the formation of N2H4, while the signal at 15 can
be attributed to either NH3 or N2H4. Although the signals of NH3 and water overlap
(m/z = 17 and 16, respectively), the signal intensity of NH3 varies with applied poten-
tial, which is not the case for water. Recently, Shao and co-workers58 detected the
signal of N2H+ (m/z = 29) with the H2 signal (m/z = 2) at potentials below –0.3 V
on Rh, whereas the signals of N2H2+ (m/z = 30) and N2H3+ (m/z = 31) were undetect-
able during the NRR. This provides evidence that a two-step reaction pathway may
occur over Rh involving a two-electron transfer to form N2H2 followed by a subse-
quent decomposition in electrolyte (KOH) generating NH3.
In situ XPS. By virtue of in situ X-ray photoelectron spectroscopy (XPS), the evolu-
tion of valence states of catalysts and adsorbed intermediate species can be probed.
This helps to provide insight on possible active components and reaction pathways.
Valov et al. demonstrated that N2 can be electrochemically activated at the interface
between an iridium micro-electrode and a (111)-orientated 9.5 mol % doped yttria
stabilized zirconia (YSZ) singe crystal at 450 C and 10 5 Pa by means of in situ XPS
(Figure 13).92 A broad N 1s XPS peak between 397 and 398 eV was identified under
cathodic voltages more negative than 1.5 V, which were deconvoluted into three
components. The first peak with a binding energy (BE) at 397.2 eV was assigned
to an N3– ion and the other two components at BEs of 397.7 and 398.6 eV corre-
sponded to (di)nitrogen ions in more positive oxidation states. The N 1s peak was
reversible, indicating that the nitrogen species reduced at the electrode possibly
accumulated only in the first top monolayers and easily desorbed from the surface
when the voltage was switched off. Only at potentials more negative than 2.0 V,
did reduction of the solid electrolyte take place, which could be confirmed by the
appearance of new components of Zr 3d and Y 3d signals with a lower formal charge.
Figure 13. Scheme of the cell arrangement for electrochemical and XPS experiments
Reprinted with permission from Valov et al.92 Copyright 2011 Royal Society of Chemistry.
on the catalyst. However, the purity of both N2 and Ar used in this work was not
provided. Additionally, the origin and quantity of NH3 formed were not investi-
gated by using 15N2 isotope labeling. The NH3 yield rate was further improved
up to 228.85 G 12.96 mg h 1 mgRh 1 on high-index facets of Rh2Sb nanorods im-
mobilized on commercial carbon at 0.45 V (versus RHE) in 0.5 M Na2SO4.95 A
zeolitic imidazole framework (ZIF)-modified Pt/Au (Figure 14A) was recently shown
to drive NRR with an FE of >44.0% and an NH3 yield rate of >161.0 mg h 1 mgcat. 1
at 2.9 V (versus RHE) using dry tetrahydrofuran (THF) solution containing lithium
trifluoromethanesulfonate as an electrolyte (Figure 14B).96 Coating with ZIF was
supposed to lower the d-band position of the electrocatalyst leading to weakening
of H adsorption, and concurrently creating electron-deficient sites to enhance
catalyst-N2 interaction. The hydrophobic ZIF layer also effectively suppressed
HER. The metal-Nimidazole interaction was further posited to be crucial for kinetic
promotion of the NRR (Figure 14C). The good thing is that the authors subtracted
all FE and NH3 yield rate against control Ar experiments, which is important to
avoid the risk of misinterpretation due to background interferences. However,
the effect of contaminants in the supplied N2 was not clarified. Furthermore,
whether nitrogen in the catalytic system could have contributed to the formation
of NH3 was not confirmed by 15N-isotope labeling.
Metal oxides comprising Ti4+, Nbx+ (NbO2, Nb2O5), Fex+ (Fe2O3, Fe3O4), Cox+
(Co3O4), Mnx+ (MnO, MnO2, Mn3O4), Mo3+, W6+, Bi3+, Ta5+, Sn4+, Cr3+, and Cex+,
V4+, Zr4+, and La4+ have been evaluated for NRR (Table S1). Among these oxides,
oxygen-vacancy-rich TiO2 NPs in situ grown on conductive Ti3C2Tx nanosheets ex-
hibited an impressive NH3 yield of 32.17 mg h 1 mgcat. 1 at 0.55 V (versus RHE)
and an FE of 16.1% at 0.45 V (versus RHE) in 0.1 M HCl.98 Despite this promising
efficiency in NRR, the purity of N2 employed in this work was not reported. In addi-
tion, 15N-isotope labeling was not conducted to verify the actual reduction of N2 to
yield NH3. Nb4+ with one 4d electron was demonstrated to be more prone to back-
donation than Nb5+ without 4d electrons.99 Hence, superior NRR activity was at-
tained over NbO2 with an NH3 FE approaching 32.0% at 0.60 V (versus RHE) in
0.05 M H2SO4 solution. It is worth noting that reduction of metal oxides and removal
of surface oxygen vacancies during long-term NRR may be an issue that merits
attention.
Transition metal nitrides, such as VN, MoN, W2N3, LaN, ZrN, NbN, and CrN, have
been reported to catalyze electrochemical ammonia formation through the Mars-
van Krevelen mechanism (Table S1).100 Only those surface N sites in oxygen-modi-
fied VN catalyst involved in the NRR were claimed to be active at the steady state
(Figure 15A). The fraction of active sites could be quantified using an isotopic ex-
change method (Figures 15B and 15C).32 Activation of adsorbed N2 on the N va-
cancy of oxygen-modified VN (VNO) to adsorbed N2H was predicted to be the
rate-limiting step in the NRR. However, a recent work from Qiao et al. showed
that N-vacancy engineered 2D W2N3 nanosheets followed a distal mechanism,
and the last step of releasing the second NH3 was the PDS.101 The nitrogen va-
cancies lowered the thermodynamic limiting potential and boosted the NRR reac-
tion with an average NH3 formation rate of 11.66 G 0.98 mg h 1 mgcat. 1 (3.80 G
0.32 3 10 11 mol cm 2 s 1) and FE of 11.67% G 0.93% at 0.2 V (versus RHE) in
0.1 M KOH solution. Only 15NH4 was detected in NMR when using 15N2 as a supplied
gas, ruling out the possibility that the NH3 was generated from the decomposition of
W2N3 or other contaminants. However, quantitative isotope-labeling experiments
were not presented. Note that the chemical stability of nitrides during NRR remains
2D d2-d4 M3C2 MXenes without terminal groups were shown to exhibit good activity
toward the NRR.103 M2C was inferred to be more effective due to its least number of
atomic layers relative to M3C2 and M4C3 MXenes. In particular, 4d4-Mo2C was calcu-
lated to possess the lowest free energy barrier among the synthesized M2C
MXenes.104 Other metal carbides such as MoC6, MoC, Cr3C2, Fe3C, and V8C7
were also demonstrated to display reasonable activity for NRR at moderate overpo-
tentials (Table S1). It was predicted that introducing carbon vacancies to increase the
ratio of surface metal to carbon atoms could reduce the adsorption of hydrogen
atoms and improve the adsorption capacity of nitrogen molecules.105 Further inte-
gration of carbon vacancies and mesoporous structure brings about more coordina-
tively unsaturated sites to adsorb and activate N2 molecules over vanadium carbide
(V8C7), promoting the NRR to NH3 with an FE of 18.3% and an NH3 yield rate of
23.2 mg h 1 mgcat. 1 at 0.1 V (versus RHE) in 0.1 M HCl.106
Perhaps inspired by nature’s nitrogenase enzymes, MoS2 has sparked research inter-
est for NRR.84 The Mo-edge was suggested to have a relatively low barrier in the
PDS.107 Other sulfides, such as Fe3S4, FeS2, NbS2, ReS2, Sb2S3, VS2, and Re2MnS6,
have also been reported to catalyze electrochemical ammonia formation. Notably,
the Li+ interactions with S-edge sites of MoS2 were found to suppress HER by
reducing H* adsorption free energy while increasing N2 adsorption free energy,
thus, decreasing the activation energy barrier of the NRR controlling step.108 An
NH3 yield rate of 43.4 mg h 1 mgMoS2 1 and FE of 9.81% were observed in the pres-
ence of strong Li–S interactions, more than eight and eighteen times compared with
the same electrocatalyst in the absence of Li–S interactions, respectively. FeS2 can
prohibit HER. Further, due to possibility of FeS2 inhibiting the HER, doping of
FeS2 with Mo(IV) ions could favor adsorption and activation of N2, permitting selec-
tive NRR to NH3 at mild overpotentials.109 Additionally, selenides of ReSe2110 and
NbSe2111 have been explored for electrocatalytic NRR. In particular, selenium va-
cancy-rich ReSe2 nanofibers sandwiched by hydrophobic and porous carbonized
bacterial cellulose layers could effectively drive NRR with an FE of 42.5% and an
NH3 yield rate of 28.3 mg h 1 cm 2 at 0.25 V (versus RHE) in 0.1 M Na2SO4 electro-
lytes.110 However, 15N2 isotopic labeling to quantify the amount of NH3 was not
provided.
The negatively charged phosphorus can induce electron cloud density deviation of
metals and modulate the surface charge state of metal phosphides, thereby
improving their intrinsic catalytic properties. Indeed, phosphides, such as MoP,
PdP2, Ru2P, RhPx, FeP, FeP2, Ni2P, CoP, CoP3, and Cu3P, have been demonstrated
to be capable of catalyzing ambient electrochemical NH3 synthesis (Table S1).
Bismuth oxyhalides (BiOX, X = Cl, Br, I) possess a unique, layered structure, tunable
energy band gap, and strong light response to boost solar energy conversion,
showing potential in photocatalysis.112 The interlayer can induce a built-in field to
separate the charges and make the electrons be assembled in the Bi-O layer for acti-
vating N2 molecules. The edge of BiOX is constructed by O atoms and oxygen va-
cancies can easily form at the surface of BiOX under mild conditions. However, appli-
cation of BiOX in electrocatalytic NRR has been rarely reported. Only Bi4O5I2
modified with oxygen vacancies and hydroxyl groups on the surface was demon-
strated to electrocatalyze the conversion of N2 to NH3 with a prominent FE of
32.4%, outperforming most p-block-element-based catalysts.113
The size of a metal catalyst is a key factor in determining the catalytic performance
since the specific activity per metal atom increases with downsizing metal particle.
The ultimate specific activity can be achieved by using single-atom catalyst (SAC),
which contains atomically dispersed metal atoms in support materials. In addition
to ultimate specific activity, SAC shows distinct catalytic activity due to its size ef-
fects, such as low-coordination environment of metal center, quantum size effects,
and metal-support effects. Many SACs, such as N-doped carbon or metal-oxide-
supported single-metal atoms, have been reported in literature for various applica-
tions. In recent years, applications of SACs for NRR also have notably increased. In
2018, Choi et al. screened 120 N-doped or defective graphene-based SACs for
NRR by DFT calculations and suggested several promising SACs including Ti@N4
and [email protected] The key finding of this work was that SACs can suppress HER during
NRR compared with metal surfaces owing to the lack of atomic ensemble in the
active sites. These results indicate that SACs can be a promising platform for
increasing faradic efficiency of NRR. Several SACs have indeed been experimentally
proven to be very active for NRR in the literature (Table S1). For example, Sun and
coworkers prepared Ru single atoms embedded at ZrO2 and N-doped carbon
(Ru@ZrO2/NC), and the Ru@ZrO2/NC exhibited high NH3 yield rate (3.665 mg h 1
mgRu 1) and FE (21.0%) at 0.21 V (versus RHE) (Figure 16) in 0.1 M HCl solution.118
These data need to be further confirmed by quantitative NMR measurements. DFT
calculations revealed that Ru single atoms anchored at surface O-vacancies in ZrO2
and N-doped graphene showed low free energy for NRR and improved *N2/*H
adsorption selectivity. In addition to Ru SAC, SACs consisting of Mo, Fe, Y, and Pt
have also been experimentally demonstrated to be efficient for NRR (Table S1).
Xin and coworkers demonstrated that atomically dispersed Mo at N-doped porous
carbon (SA-Mo/NPC) could catalyze NRR with high efficiency.61 The SA-Mo/NPC
showed improved NH3 yield rate (34.0 mg h 1 mgcat. 1) and FE (14.6%) at room tem-
perature. Various types of Fe single atoms embedded at N-doped carbon have dis-
played improved catalytic activity toward NRR.119,120 Zheng and coworkers revealed
that Fe-N/C-carbon nanotube (Fe-N/C-CNT) containing Fe-N3 active sites achieved
34.83 mg h 1 mgcat. 1 of NH3 yield rate and 9.28% of FE in 0.1 M KOH solutions.120
Further DFT calculations established that Fe–N3 sites could strongly bind N2 and
reduce N2 to NH3 with 0.84 eV of free energy. FeN4 moiety embedded carbon cat-
alysts have also been reported for NRR in both neutral and alkaline media.121 A co-
ordination of Fe–(O–C2)4 as active sites supported on nitrogen-free lignocellulose-
derived carbon provided even higher NRR performance.122 The NH3 production
rate reached 307.7 mg h 1 mgcat. 1 with an FE of 51.0% at 0.1 V (versus RHE)
over Fe–(O–C2)4 immobilized on a glassy carbon electrode in 0.1 M KOH electro-
lytes. Li and coworkers demonstrated that Au single-atom-embedded C3N4 (Au1/
C3N4) exhibited outstanding NH3 formation (1,305 mg h 1 mgAu 1) and FE (11.1%)
at 0.1 V (versus RHE).123 Theoretical calculations suggested that Au1/C3N4
required lower free energy for NRR than Au(211) surface. However, whether the ni-
trogen in C3N4 had contributed to the evolution of NH3 remained unclear. The for-
mation of NH3 from NRR needs to be explored by 15N2-isotope labeling qualitatively
and quantitatively.
Metal-free carbon and its derivatives, boron and its compounds, polymeric carbon
nitride, black phosphorus, and red phosphorus
A number of carbon materials, such as heteroatom (N, S, F, Te, or Se)-doped carbon,
P-doped carbon nanotube, Cl-doped graphdiyne, defective graphene, (reduced)
graphene oxide, heteroatom (P, N, B, S, and F)-doped graphene, B-doped nano-
structured diamond, B- and N-codoped carbon, and N, P-codoped carbon, were
shown to exhibit comparable and even superior NRR activity than many metal-based
electrocatalysts (Table S1). A nanohybrid of S dots and graphene was also revealed
to be active for N2 fixation.124 Strikingly, an NH3 production rate of 19.1 mg h 1 cm 2
and FE as high as 21.2% were attained over boron-doped nanostructured diamond/
Ti electrodes in 0.05 M H2SO4 solution containing 0.2 M Li2SO4.125 Of interest is that
the electrode retained stability for over 8 days without obvious decay in activity.
Boron doping was supposed to induce NRR active sites in diamond lattices and
buildup of surface charges, leading to enhanced catalytic performance.
Zigzag and diff-zigzag edges of exfoliated black phosphorous (BP) nanosheets were
recently shown to be active centers for N2 adsorption and NhN triple bond activa-
tion, which enable NRR via an alternating hydrogenation pathway, delivering a high
NH3 production rate of 31.37 mg h–1 mgcat.–1 albeit with a moderate FE of 5.07% at
0.6 V (versus RHE) in 0.1 M HCl solution.129 The FE for NH3 formation was stated to
be improved by N and O doping of BP surfaces to impart hydrophobicity and hinder
the competitive HER.130 However, BP suffers from oxidative degradation especially
in the presence of water,131 thus, limiting its practical application in NRR. Nanorib-
bons of red phosphorus, a more stable allotrope of phosphorus, were shown to facil-
itate NRR, providing an FE of 9.4% and an NH3 yield of 15.4 mg h–1 mgcat.–1 at –0.5 V
(versus RHE) in 0.1 M Na2SO4.132 The NRR performance was credited to the
apparent anisotropy and the quasi-one dimensional morphology of nanoribbons,
endowing red phosphorus with efficient charge transfer and abundant exposed-
edge sites.
Figure 17. Volcano plot for NRR activity on transition metal sulfides
(A) Simplified schematic of the end-on bound transition metal-N 2 complexes (left) and borylene-N2
complex (right). Reprinted with permission from Légaré et al. 127 Copyright 2018 American
Association for the Advancement of Science.
(B) Different boron doping sites in various 2D materials and maximum free energy required for NRR.
Reprinted with permission from Liu et al. 134 Copyright 2019 American Chemical Society.
(C) Volcano plot for limiting potential of NRR on various transition metal sulfides via associative
mechanism (left) and dissociative mechanism (right). Reprinted with permission from Abghoui
et al. 136 Copyright 2019 Wiley-VCH.
Mo2B, Fe2B, and Co2B are suggested for NRR with ( 0.75 ~ 0.84 V versus RHE) be-
ing the optimal limiting potential.135
transition metal and sulfur atoms, offer some similarity to the structure of active sites
of the enzyme.136 NRR on various low-index surfaces of transition metal sulfides such
as rocksalt(100), NiAs-type(111), pyrite(100), and pyrite(111) via associative and
dissociative mechanisms were investigated. They obtained a volcano plot for NRR
activity on transition metal sulfides (Figure 17C). RuS2 was predicted to have low
overpotential (0.3 V), and the other promising candidates (CrS, NbS, VS, and TiS)
showed 0.7~1.1 V of overpotential.
Kim et al.138 screened various transition metal alloys for NRR by developing a slab
graph convolutional neural network (SGCNN), which is an extended model of the ex-
isting crystal graph CNN (CGCNN).142 The CGCNN has proven its accuracy in pre-
dicting bulk properties but not yet tested for surface-related properties at that time.
To incorporate surface effects, surface graph (S1 or S2) and bulk graph (B) are con-
structed (Figure 18A). Total 3,040 binding energies, which consist of 465 catalysts
with different crystal spaces (fcc, bcc, hcp, L10, B2, and core-shell), and 5 adsorbate
types (H, N2, N2H, NH, and NH2) and sites were used for the SGCNN training. For
input features, a combination of 5 low-level input features (group number [GR], Paul-
ing-scale electronegativity [EN], atomic volume [AV], electron affinity [EA], and
atomic weight [AW]) was used since it shows minimum mean absolute error (MAE)
of 0.23 eV (Figure 18B). The SGCNN model trained by 465 catalysts was used for
screening 870 candidates consisting of (111) facet of A3B structure (Figure 18C).
Among 870 candidates, 10 catalysts (e.g., V3Ir, Tc3Hf, V3Ni, and Tc3Ta) were
included in the screening criteria (Figure 18D).
ML accelerates not only the catalysts screening process but also optimization of the
material morphology. Liu and coworkers explored how the electrode’s morphology
contributes to NRR activity and provided the means to quickly optimize wire-array
morphology.140 About 200,000 finite element methods (FEM)143 simulations were
conducted to yield values of total current density (itotal) and FE of NRR as a function
of feature variable vector x, which is described in Figure 18F. The variable vector x
consists of physical features of morphologies such as diameter (d), length (l), and
array periodicity in a square lattice (p) and kinetics information such as exchange cur-
rent density of the Volmer step of HER (i1,0,HER), the Heyrovsky step of HER (i2,0,HER),
Figure 18. Studies of ML on screening promising NRR catalysts and optimizing morphologies of
catalysts
(A) Schematic of the main architecture of the SGCNN model. B and S 1 (or S 2 ) represent the bulk
graph and surface graph with the top layer (or top two layers), respectively.
(B) MAE values as a function of various feature combinations.
(C) Bulk and (111) surface of the L1 2 ordered phase of A 3 B (left) and screening process to search for
stable and efficient NRR catalysts, which potentially outperform Mo(110) (right).
(D) UL and F values predicted by the SGCNN model for 10 screened promising catalysts. Reprinted
with permission from Kim et al. 138 Copyright 2020 American Chemical Society.
(E) Structure of B-doped graphene with single-metal atoms considered for screening. Reprinted
with permission from Zafari et al. 139 Copyright 2020 Royal Society of Chemistry.
(F) ANN (10 neurons in each hidden layer) architecture and criteria for eligible NRR catalysts.
(G) Selection of hypothetical promising catalysts for NRR among over 4,000,000 scenarios
generated by trained MLPNNs. Reprinted with permission from Hoar et al. 140 Copyright 2020
American Chemical Society.
the first electron transfer step of NRR (i1,0,NRR) and the first proton transfer step of
NRR (i2,0,NRR), and overpotential (h). The two feed-forward144 multilayer perceptron
neural networks (MLPNNs) were used for training the FEM datasets. The MLPNN
prediction shows an accuracy of 2.810%2 and 6.76 3 10 4 mA2/cm4 of mean squared
error (MSE) for FE of NRR and total current density, respectively. In total, 4,000,000
scenarios were generated by trained MLPNNs and over 200 scenarios, which meet |
itotal| > 2.0 mA/cm2 and FE > 90.0% were shown in Figure 18G. Top 4 scenarios which
are denoted in Figure 18G, converge to a similar range of parameter values, h z
0.7 V versus RHE, d z 8 mm, l z 40 mm, p z 10 mm, i1,0,NRR z 10 3, i2,0,NRR z
10 3, i1,0,HER z 10 8, and i2,0,HER z 10 8 mA/cm2, corresponding to the reasonable
kinetic reactivity and geometry for optimal NRR catalyst.
All of these ML approaches efficiently predict NRR activity. For example, 870 cata-
lysts were screened by the SGCNN model trained by data of 465 catalysts (53% of
screening data)138 and 4,000,000 scenarios were investigated by using the MLPNNs
trained by 200,000 FEM data (5%).144 In other words, noticeable amounts of poten-
tially unnecessary simulations (from 47% to 95%) were eliminated.
One of the most significant problems in current DFT calculations is that the reported
theoretical limiting potentials disagree with the experimental electrode potential at
maximum NRR activity in most cases. The theoretical limiting potentials (UL), where
the overall electrochemical reaction becomes thermodynamically exothermic, on
various fcc transition metal surfaces are at least –1 V (versus RHE) theoretically (Fig-
ure 10). However, maximum NRR activities are often observed at –0.05 ~ –0.60 V
(versus RHE), highly more positive than theoretical UL (Table S1). For example,
maximum NH3 yield rates were obtained at –0.1 V (versus RHE) on Ru nanopar-
ticles145 and –0.2 V (versus RHE) on Au nanorods,146 while their theoretical UL are
around at –1.0 V (versus RHE) and –3.0 V (versus RHE), respectively. The origin for
such large discrepancy has not been clearly clarified; however, a possible reason
has been suggested, namely dominant H coverages at negative electrode poten-
tials. The H adsorption via * + (H+ + e ) / *H (due to its electrochemical nature
of the reaction) increases faster than the N2 adsorption (* + N2 / *N2, non-electro-
chemical reaction) with more negative electrode potential.27 Thus, dominant H cov-
erages at negative electrode potentials block the N2 adsorption after which NRR ac-
tivity decreases although the electrochemical reduction rates of NRR themselves
might increase with more negative potential. However, this possibility has not
been quantitatively established or validated since the in situ measurements of N2
and H coverage during NRR is still highly challenging. Thus, the in situ investigation,
either experimentally or theoretically, of N2 versus H coverage changes and NRR ac-
tivity with electrode potential would provide invaluable insights to fully understand
the origin of the decreasing NRR activity with electrode potential.
Most of theoretical studies on NRR neglected the kinetics and focused on the ther-
modynamic reaction energies.147 Only a few studies considered activation energy
during the proton-electron transfer reactions in NRR.148,149 To fully understand
the NRR, theoretical studies should consider the potential-dependent competition
between NRR and HER including the N2 versus H binding and kinetics.
Electrolytes as well as the active sites are important in enhancing the NRR activity. By
tuning the electrolytes (e.g., ILs and non-aqueous electrolytes), enhancement in N2
solubility and FE of NRR can be achieved.15,74 Several theoretical studies on the ef-
fect of electrolyte have been reported. For example, Zhang et al. demonstrated that
HER can be suppressed during NRR by utilizing a non-aqueous bulky proton
donor150 and Ortuño et al. showed stabilization of reaction intermediates of NRR
by ILs.76 We expect that further theoretical studies on electrolytes at atomic level
will be helpful for designing electrolytes.
So far, ML techniques have been rarely used in the NRR field, while they have been
widely utilized for various chemical reactions. We believe that ML approaches devel-
oped in other catalytic reactions would be also helpful in investigating the NRR. For
example, Ulissi and coworkers identified the most likely reaction pathways of syngas
on Rh(111) among more than 2,000 potential pathways by using the Gaussian pro-
cess with group additivity descriptors.151 Similar ML approaches will be applied
for investigating the reaction mechanism and reaction kinetics of NRR. While various
catalysts have been theoretically suggested, synthesizability as well as NRR activity is
also quite important. Recently, Jang et al. proposed data-driven metric of the crys-
tal-likeness score, which estimates the synthesizability of crystalline material.152 This
ML approach will be employed to estimate the synthesizability of proposed catalysts
before its experimental validation.
Surface engineering
Surface modification
Surface functionalization with chemical moieties offers an effective way to tune elec-
trocatalysis through modulating the electronic properties of catalyst surfaces and
the resultant adsorption energies of reaction intermediates.12 Surface selenation
was recently demonstrated to greatly boost NRR performance (Figure 20).153 An up-
shift of the d-band center was observed for surface selenated Rh nanocrystals (NCs),
which was hypothesized to strengthen N2 adsorption. The Se sites may also play a
role in promoting electron transfer between N-species and nearby Rh-sites. Alterna-
tively, introducing –O or –OH species was shown to facilitate improved NRR. Oxygen
functional groups in oxidized carbon nanotubes or graphene oxide alter the electron
distribution in the surrounding carbon atoms, resulting in optimized binding
strengths of N2 and NRR reaction intermediates on carbon to enhance NRR.154 Sur-
face hydroxyl modification of Ti3C2 MXene either by alkalization intercalation and
agitation155 or via ethylene glycol solvothermal treatment156 was manifested to in-
crease the electronic density of states at the Fermi level and lower resistance, as
compared with oxygen termination and original Ti3C2. This favors electron transfer
to the 2p orbitals of N2 and promotes its chemisorption and activation. By contrast,
Figure 19. Summary of strategies for improving the performance of electrocatalysts for NRR
Ti3C2 with –F groups was predicted to exhibit poor N2 adsorption capacity with
higher energy barrier, unfavorable for NRR. Li+ modification was shown to enable
suppression of the undesired HER.62 It may also afford positively charged active sites
that favor N2 capture and reduction.108 Enlightened by the metal-sulfur (M–S) link-
ages in the nitrogenase enzyme, surface tethering of Ru with aliphatic thiols was
applied to modify its electronic structure, thus, promoting adsorption and polariza-
tion of N2.157 Concomitantly, the organic and hydrophobic nature of the thiols
impeded proton transfer while allowing flow of N2 to the surface of the catalyst.
This synergistically boosted the rate of NH3 generation.
Figure 20. Schematic illustration of selenization process and comparison of Rh, Pt, Pd, and Ru for
NRR before and after surface selenization
(A) Schematic illustrating selenization of Rh NCs.
(B) Schematic showing the proposed mechanism for NRR on the catalytic surface of the Rh NCs/C
and Rh-Se NCs/C.
(C) NH3 yield at 0.10 V (versus RHE) of various catalysts.
(D) FE for NH3 formation at 0.10 V (versus RHE) on various catalysts.
Reprinted with permission from Yang et al.153 Copyright 2020 Wiley-VCH.
pyridinic nitrogen and one neighboring atomic vacancy site, was predicted to pro-
mote N2 chemisorption and reduction with relatively lower free energy require-
ments. The content of pyridinic-N in carbons can be further improved by addition
of a secondary dopant (B or F), resulting in higher NRR activity.87 In contrast to pris-
tine and O-doped carbon atoms that barely adsorb N2, S-, Se-, and Te-substituted C
exhibited substantially increased N2 adsorption, benefiting NRR.159 Apart from the
above-mentioned effects, doping of elements (such as B, F, and low-valence transi-
tion metal dopants)160 into metal oxides or oxide-hydroxides may enrich surface ox-
ygen vacancies by replacing the O atom rather than the metal atom.161 Alternatively,
doping of TiO2 with stable Zr4+ induced tensile and compressive strains, hence,
generating oxygen vacancies associated with adjoining bi-Ti3+ sites.161 The oxygen
vacancies promoted the back-donation of electrons to N2 and accelerated the con-
version of *NH2NH2 to *NH2 and *NH3. The dopant and oxygen vacancies jointly
contribute to efficient conversion of N2. Incorporation of Fe into reducible CeO2
also facilitated formation of active Ce3+–Ce3+ pairs to improve the selectivity of
NRR with respect to HER.162 Additionally, morphology evolution from CeO2 nano-
particles to nanosheets with a larger surface area was induced upon Fe doping.
These coupling impacts led to enhanced NH3 yield. A recent work from Chen
et al.85 showed that M4+-positioned Re in ReS2 nanosheets could be replaced by
metal species (e.g., Fe, Co, Ni, Cu, and Zn), leading to intensified charge density
around the dopant cations. The low-valent metal domain was revealed to offer more
active sites for N2 chemisorption and weaken the NhN bonds for easier dissociation
through proton coupling.
To further boost NRR activities, there are continuous efforts to modify the bulk and
surface electronic properties and physical characteristics of electrocatalysts by
tailoring the types and location of dopant atoms. Elucidation of active sites and opti-
mization of activity are critically required as well. This is likely to be addressed by
combining knowledge-guided controllable synthesis complimented by improved
in situ and operando characterization techniques. Noteworthy, electrocatalysis of
the NRR on N-doped materials should be studied with scrutiny to confirm the origin
of evolved NH3.
Crystal facets play a pivotal role in determining activity and selectivity of reactions.
Surface facets differ in Lewis acidity and polarizing power and can therefore affect
the adsorption and activation of N2. Exposed facets may also influence adsorption
of electrolytes on the catalyst surface, thus, affecting the catalytic performance. Fac-
ets that can selectively stabilize *N2H or destabilize *NH2 are favorable to reduce N2
to NH3. Guided by these findings, Mo(110) nanofilms,164 Au(730) nanorods,146 and
RhSb nanorods with high-index facets95 were designed for effective N2 electrore-
duction. For most metals except Re, the (211) step was modeled to be more reactive
with lower theoretical overpotential than the (111) terrace.38
Strain (by changing the lattice spacing) can increase surface reactivity and selectivity
of electrocatalysts by breaking the linear scaling relationship. In the d-band model,
lattice expansion mitigates orbital overlap in transition metal atoms, thus, narrowing
d-band along with shift to a higher energy level. This leads to a stronger interaction
with adsorbates. In the eigenstress model, eigenstress takes place where adsorbates
evoke strain at the catalyst surface. The binding energies of different intermediates
can vary independently according to sizes and binding interactions with the strained
surface. It is worth pointing out that the explicit use of strain to enhance the NRR is
rarely reported.
Design of catalysts with high active surface areas can enrich the accessibility of cat-
alytic sites for reactions.165 This allows large physicochemical contact between the
catalyst surface and N2, which is essential for ambient N2 conversion. The interac-
tions between electrode and electrolyte are also strengthened, promoting interfa-
cial adsorption-desorption dynamics and mass transport. Likewise, creation of a hi-
erarchical architecture with high porosity and interconnected micro-, meso-, and
macroporous texture offers a way to enhance the adsorption and capture of N2,
potentially enhancing N2 conversion rate and efficiency.165 Macropores (>50 nm)
accelerate transport and diffusion of reactants and products over electrodes,
whereas mesopores (2–50 nm) and micropores (<2 nm) facilitate a high exposure
of active sites. Further tailoring the diameter, volume, structure, and hydrophobicity
of pores or channels allows for effective regulation of activity and selectivity.
Edges have coordination unsaturation and dangling bonds, providing useful cata-
lytic sites. Increase of edge defects was demonstrated to promote NRR electrocatal-
ysis. N2 molecules were observed to preferably interact with the middle Ti atoms at
the edge plane of Ti3C2 MXenes with low activation barriers.166 As opposed to the
basal plane that is inert for NRR, the edges of MoS2 are capable of polarizing and
converting N2 to NH3.167 The positively charged Mo-edge was revealed to aid the
formation of Mo N bonds and reduce energy barriers for the PDS of *N2 proton-
ation to form *NNH.
Construction of heterostructures
Heterostructure formation can enhance charge transfer and induce combined elec-
tronic and geometric effects to facilitate N2 conversion. Relevant parameters such as
interfacial compositions and facets, active surface areas, interfacial defects, and elec-
tronic coupling can be tuned to reach an optimum for NRR. For example, optimizing
the interaction between entities at the interface permits creation of remarkably stable
active sites for N2 activation.116 Hydrogen evolution is also impeded. In particular,
the synergy arising from the interaction of different components can be attuned to
maximize the orbital overlap with N2 for optimal adsorption and reduction. Alterna-
tively, a synergistic interplay between one phase as N2 binding and activation sites
and nearby phases as centers for hydrogenation could facilitate NH3 formation. Such
concept has been underscored by introducing a CoOx layer to modulate the local elec-
tronic structure of Au NPs with positive valence sites.174 The Au1+ active sites on Au NPs
facilitate break of the NhN bond and formation of N=N– intermediates via NRR, while
Au0 likely binds N–N– intermediates for subsequent hydrogenation reaction.
SUPPLEMENTAL INFORMATION
Supplemental Information can be found online at https://doi.org/10.1016/j.chempr.
2021.01.009.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of China
(21972010); Beijing Natural Science Foundation (2192039); the State Key Laboratory
of Organic-Inorganic Composites (oic-201901001); Beijing University of Chemical
Technology (XK180301, XK1804-2); and National Research Foundation of Korea
(NRF-2019M3D1A1079303 and NRF-2019M3D3A1A01069099).
AUTHOR CONTRIBUTIONS
Conceptualization, Z.S.; writing – original draft, Z.S., H.S., X.L., C.C., and Y.J.;
writing – review & editing, Z.S., J.M., and J.Q.; funding acquisition, Z.S. and Y.J.; su-
pervision, Z.S.
DECLARATION OF INTERESTS
The authors declare no competing interests.
REFERENCES
c, V., Yang, S., Schwalbe,
1. Andersen, S.Z., Coli 15. Zhou, F., Azofra, L.M., Ali, M., Kar, M., 26. van der Ham, C.J.M., Koper, M.T.M., and
J.A., Nielander, A.C., McEnaney, J.M., Simonov, A.N., McDonnell-Worth, C., Sun, C., Hetterscheid, D.G.H. (2014). Challenges in
Enemark-Rasmussen, K., Baker, J.G., Singh, Zhang, X., and MacFarlane, D.R. (2017). reduction of dinitrogen by proton and
A.R., Rohr, B.A., et al. (2019). A rigorous Electro-synthesis of ammonia from nitrogen electron transfer. Chem. Soc. Rev. 43, 5183–
electrochemical ammonia synthesis protocol at ambient temperature and pressure in ionic 5191.
with quantitative isotope measurements. liquids. Energy Environ. Sci. 10, 2516–2520.
Nature 570, 504–508. 27. Hu, L., Xing, Z., and Feng, X. (2020).
16. Chalkley, M.J., Del Castillo, T.J., Matson, B.D., Understanding the electrocatalytic interface
2. Ye, T.N., Park, S.W., Lu, Y., Li, J., Sasase, M., and Peters, J.C. (2018). Fe-mediated nitrogen for ambient ammonia synthesis. ACS Energy
Kitano, M., Tada, T., and Hosono, H. (2020). fixation with a metallocene mediator: Lett. 5, 430–436.
Vacancy-enabled N2 activation for ammonia exploring pKa effects and demonstrating
synthesis on an Ni-loaded catalyst. Nature electrocatalysis. J. Am. Chem. Soc. 140, 6122– 28. Sippel, D., Rohde, M., Netzer, J., Trncik, C.,
583, 391–395. 6129. Gies, J., Grunau, K., Djurdjevic, I., Decamps,
L., Andrade, S.L.A., and Einsle, O. (2018). A
3. Soloveichik, G. (2019). Electrochemical 17. Hao, Y.C., Guo, Y., Chen, L.W., Shu, M., Wang, bound reaction intermediate sheds light on
synthesis of ammonia as a potential X.Y., Bu, T.A., Gao, W.Y., Zhang, N., Su, X., the mechanism of nitrogenase. Science 359,
alternative to the Haber–Bosch process. Nat. Feng, X., et al. (2019). Promoting nitrogen 1484–1489.
Catal. 2, 377–380. electroreduction to ammonia with bismuth
nanocrystals and potassium cations in water. 29. Skúlason, E., Bligaard, T., Gudmundsdóttir,
4. Liu, T., Gau, M.R., and Tomson, N.C. (2020). Nat. Catal. 2, 448–456. S., Studt, F., Rossmeisl, J., Abild-Pedersen, F.,
Mimicking the constrained geometry of a Vegge, T., Jónsson, H., and Nørskov, J.K.
nitrogen-fixation intermediate. J. Am. Chem. 18. Ma, J.L., Bao, D., Shi, M.M., Yan, J.M., and (2012). A theoretical evaluation of possible
Soc. 142, 8142–8146. Zhang, X.B. (2017). Reversible nitrogen transition metal electro-catalysts for N2
fixation based on a rechargeable lithium- reduction. Phys. Chem. Chem. Phys. 14, 1235–
5. Foster, S.L., Bakovic, S.I.P., Duda, R.D., nitrogen battery for energy storage. Chem 2, 1245.
Maheshwari, S., Milton, R.D., Minteer, S.D., 525–532.
Janik, M.J., Renner, J.N., and Greenlee, L.F. 30. Pool, J.A., Lobkovsky, E., and Chirik, P.J.
(2018). Catalysts for nitrogen reduction to 19. Koh, C.S.L., Lee, H.K., Fan Sim, H.Y., Han, X., (2004). Hydrogenation and cleavage of
ammonia. Nat. Catal. 1, 490–500. Phan-Quang, G.C., and Ling, X.Y. (2020). dinitrogen to ammonia with a zirconium
Turning water from a hindrance to the complex. Nature 427, 527–530.
6. Lancaster, K.M., Roemelt, M., Ettenhuber, P., promotor of preferential electrochemical
Hu, Y., Ribbe, M.W., Neese, F., Bergmann, U., 31. Iwamoto, M., Akiyama, M., Aihara, K., and
nitrogen reduction. Chem. Mater. 32, 1674–
and DeBeer, S. (2011). X-ray emission Deguchi, T. (2017). Ammonia synthesis on
1683.
spectroscopy evidences a central carbon in wool-like Au, Pt, Pd, Ag, or Cu electrode
the nitrogenase iron-molybdenum cofactor. 20. Wang, J., Yu, L., Hu, L., Chen, G., Xin, H., and catalysts in nonthermal atmospheric-pressure
Science 334, 974–977. Feng, X. (2018). Ambient ammonia synthesis plasma of N2 and H2. ACS Catal. 7, 6924–
via palladium-catalyzed 6929.
7. Davy, H. (1807). I. The Bakerian Lecture, on electrohydrogenation of dinitrogen at low
some chemical agencies of electricity. Phil. 32. Yang, X., Kattel, S., Nash, J., Chang, X., Lee,
overpotential. Nat. Commun. 9, 1795. J.H., Yan, Y., Chen, J.G., and Xu, B. (2019).
Trans. R. Soc. 97, 1–56.
Quantification of active sites and elucidation
21. Han, Z., Choi, C., Hong, S., Wu, T.S., Soo, Y.L.,
8. Fichter, F., and Suter, R. (1922). Zur Frage der of the reaction mechanism of the
Jung, Y., Qiu, J., and Sun, Z. (2019). Activated
kathodischen Reduktion Des elementaren electrochemical nitrogen reduction reaction
TiO2 with tuned vacancy for efficient
Stickstoffs. Helv. Chim. Acta 5, 246–255. on vanadium nitride. Angew. Chem. Int. Ed.
electrochemical nitrogen reduction. Appl.
Engl. 58, 13768–13772.
9. MacLaughlin, C. (2019). Role for Catal. B 257, 117896.
standardization in electrocatalytic ammonia 33. Abghoui, Y., Garden, A.L., Hlynsson, V.F.,
22. Jaecheol, C., Hoang-Long, D., Manjunath, C.,
synthesis: a conversation with leo liu, Lauren Björgvinsdóttir, S., Ólafsdóttir, H., and
Bryan, H.R., Alexandr, S., and Douglas, M.
Greenlee, and Douglas macfarlane. ACS Skúlason, E. (2015). Enabling electrochemical
(2020). Promoting nitrogen electroreduction
Energy Lett. 4, 1432–1436. reduction of nitrogen to ammonia at ambient
to ammonia with bismuth nanocrystals and
conditions through rational catalyst design.
potassium cations in water. https://chemrxiv.
10. Marnellos, G., and Stoukides, M. (1998). Phys. Chem. Chem. Phys. 17, 4909–4918.
Ammonia synthesis at atmospheric pressure. org/articles/preprint/Promoting_Nitrogen_
Science 282, 98–100. Electroreduction_to_Ammonia_with_ 34. Comer, B.M., Liu, Y.H., Dixit, M.B., Hatzell,
Bismuth_Nanocrystals_and_Potassium_ K.B., Ye, Y., Crumlin, E.J., Hatzell, M.C., and
11. Rod, T.H., Logadottir, A., and Nørskov, J.K. Cations_in_Water/11768814/1. Medford, A.J. (2018). The role of adventitious
(2000). Ammonia synthesis at low carbon in photo-catalytic nitrogen fixation by
temperatures. J. Chem. Phys. 112, 5343–5347. 23. Lazouski, N., Chung, M., Williams, K., Gala, titania. J. Am. Chem. Soc. 140, 15157–15160.
M.L., and Manthiram, K. (2020). Non-aqueous
12. Sun, Z., Ma, T., Tao, H., Fan, Q., and Han, B. gas diffusion electrodes for rapid ammonia 35. Sun, Z., Huo, R., Choi, C., Hong, S., Wu, T.S.,
(2017). Fundamentals and challenges of synthesis from nitrogen and water-splitting- Qiu, J., Yan, C., Han, Z., Liu, Y., Soo, Y.-L., and
electrochemical CO2 reduction using two- derived hydrogen. Nat. Catal. 3, 463–469. Joong, Y. (2019). Oxygen vacancy enables
dimensional materials. Chem 3, 560–587. electrochemical N2 fixation over WO3 with
24. Kitano, M., Inoue, Y., Yamazaki, Y., Hayashi, F., tailored structure. Nano Energy 62, 869–875.
13. Singh, A.R., Rohr, B.A., Statt, M.J., Schwalbe, Kanbara, S., Matsuishi, S., Yokoyama, T., Kim,
J.A., Cargnello, M., and Nørskov, J.K. (2019). S.W., Hara, M., and Hosono, H. (2012). 36. Yu, X., Han, P., Wei, Z., Huang, L., Gu, Z.,
Strategies toward selective electrochemical Ammonia synthesis using a stable electride as Peng, S., Ma, J., and Zheng, G. (2018). Boron-
ammonia synthesis. ACS Catal. 9, 8316–8324. an electron donor and reversible hydrogen doped graphene for electrocatalytic N2
store. Nat. Chem. 4, 934–940. reduction. Joule 2, 1610–1622.
14. Singh, A.R., Rohr, B.A., Schwalbe, J.A.,
Cargnello, M., Chan, K., Jaramillo, T.F., 25. Cui, X., Tang, C., and Zhang, Q. (2018). A 37. Medford, A.J., Vojvodic, A., Hummelshøj, J.S.,
Chorkendorff, I., and Nørskov, J.K. (2017). review of electrocatalytic reduction of Voss, J., Abild-Pedersen, F., Studt, F.,
Electrochemical ammonia synthesis—the dinitrogen to ammonia under ambient Bligaard, T., Nilsson, A., and Nørskov, J.K.
selectivity challenge. ACS Catal. 7, 706–709. conditions. Adv. Energy Mater. 8, 1800369. (2015). From the Sabatier principle to a
predictive theory of transition-metal nitrite and ammonia ions) in environmental 65. Battino, R., Rettich, T.R., and Tominaga, T.
heterogeneous catalysis. J. Catal. 328, 36–42. samples by ion chromatography. Pol. J. (1984). The solubility of nitrogen and air in
Environ. Stud. 15, 5–18. liquids. J. Phys. Chem. Ref. Data 13, 563–600.
38. Montoya, J.H., Tsai, C., Vojvodic, A., and
Nørskov, J.K. (2015). The challenge of 52. LeDuy, A., and Samson, R. (1982). Testing of 66. Kang, C.S.M., Zhang, X., and MacFarlane,
electrochemical ammonia synthesis: a new an ammonia ion selective electrode for D.R. (2019). High nitrogen gas solubility and
perspective on the role of nitrogen scaling ammonia nitrogen measurement in the physicochemical properties of [C4mpyr]
relations. ChemSusChem 8, 2180–2186. methanogenic sludge. Biotechnol. Lett. 4, [eFAP]–fluorinated solvent mixtures. J. Phys.
303–306. Chem. C 123, 21376–21385.
39. Suryanto, B.H.R., Du, H.L., Wang, D., Chen, J.,
Simonov, A.N., and MacFarlane, D.R. (2019). 67. Tsuneto, A., Kudo, A., and Sakata, T. (1994).
53. Cohn, V.H., and Lyle, J. (1966). A fluorometric
Challenges and prospects in the catalysis of Lithium-mediated electrochemical reduction
assay for glutathione. Anal. Biochem. 14,
electroreduction of nitrogen to ammonia. of high pressure N2 to NH3. J. Electroanal.
434–440.
Nat. Catal. 2, 290–296. Chem. 367, 183–188.
40. Halmann, M. (1984). Electrochemical 54. Liu, C., Sakimoto, K.K., Colón, B.C., Silver, 68. Köleli, F., and Röpke, T. (2006).
reduction of molecular nitrogen to ammonia P.A., and Nocera, D.G. (2017). Ambient Electrochemical hydrogenation of dinitrogen
in aqueous alakli: a re-examination. nitrogen reduction cycle using a hybrid to ammonia on a polyaniline electrode. Appl.
J. Electroanal. Chem. Interfacial Electrochem. inorganic-biological system. Proc. Natl. Acad. Catal. B 62, 306–310.
181, 307–308. Sci. USA 114, 6450–6455.
69. Kim, K., Lee, N., Yoo, C.-Y., Kim, J.-N., Yoon,
41. Tang, C., and Qiao, S.Z. (2019). How to 55. Hodgetts, R.Y., Kiryutin, A.S., Nichols, P., Du, H.C., and Han, J.-I. (2016). Communication
explore ambient electrocatalytic nitrogen H.L., Bakker, J.M., Macfarlane, D.R., and —electrochemical reduction of nitrogen to
reduction reliably and insightfully. Chem. Soc. Simonov, A.N. (2020). Refining universal ammonia in 2-propanol under ambient
Rev. 48, 3166–3180. procedures for ammonium quantification via temperature and pressure. J. Electrochem.
rapid 1H NMR analysis for dinitrogen Soc. 163, F610–F612.
42. Chen, Y., Liu, H., Ha, N., Licht, S., Gu, S., and reduction studies. ACS Energy Lett. 5,
Li, W. (2020). Revealing nitrogen-containing 736–741. 70. Kim, K., Yoo, C.Y., Kim, J.N., Yoon, H.C., and
species in commercial catalysts used for Han, J.I. (2016). Electrochemical synthesis of
ammonia electrosynthesis. Nat. Catal. 3, 56. Yu, W., Lewis, N.S., Gray, H.B., and Dalleska, ammonia from water and nitrogen in
1055–1061. N.F. (2020). Isotopically selective ethylenediamine under ambient temperature
quantification by UPLC-MS of aqueous and pressure. J. Electrochem. Soc. 163,
43. Chen, G.F., Ren, S., Zhang, L., Cheng, H., Luo, ammonia at submicromolar concentrations F1523–F1526.
Y., Zhu, K., Ding, L.X., and Wang, H. (2019). using dansyl chloride derivatization. ACS
Advances in electrocatalytic N2 reduction— Energy Lett. 5, 1532–1536. 71. Lee, H.K., Koh, C.S.L., Lee, Y.H., Liu, C.,
strategies to tackle the selectivity challenge. Phang, I.Y., Han, X., Tsung, C.K., and Ling,
Small Methods 3, 1800337. 57. Yao, Y., Wang, H., Yuan, X.Z., Li, H., and Shao, X.Y. (2018). Favoring the unfavored: selective
M. (2019). Electrochemical nitrogen reduction electrochemical nitrogen fixation using a
44. Choi, J., Du, H.L., Nguyen, C.K., Suryanto,
reaction on ruthenium. ACS Energy Lett. 4, reticular chemistry approach. Sci. Adv. 4,
B.H.R., Simonov, A.N., and MacFarlane, D.R. eaar3208.
1336–1341.
(2020). Electroreduction of nitrates, nitrites,
and gaseous nitrogen oxides: a potential 72. Lazouski, N., Schiffer, Z.J., Williams, K., and
58. Yao, Y., Zhu, S., Wang, H., Li, H., and Shao, M. Manthiram, K. (2019). Understanding
source of ammonia in dinitrogen reduction
(2020). A spectroscopic study of
studies. ACS Energy Lett. 5, 2095–2097. continuous lithium-mediated electrochemical
electrochemical nitrogen and nitrate nitrogen reduction. Joule 3, 1127–1139.
45. Dabundo, R., Lehmann, M.F., Treibergs, L., reduction on rhodium surfaces. Angew.
Tobias, C.R., Altabet, M.A., Moisander, P.H., Chem. Int. Ed. Engl. 59, 10479–10483. 73. Kang, C.S.M., Zhang, X., and MacFarlane,
and Granger, J. (2014). The contamination of D.R. (2018). Synthesis and physicochemical
commercial 15N2 gas stocks with 15N-labeled 59. Watt, G.W., and Chrisp, J.D. (1952). properties of fluorinated ionic liquids with
nitrate and ammonium and consequences for Spectrophotometric method for high nitrogen gas solubility. J. Phys. Chem. C
nitrogen fixation measurements. PLoS One 9, determination of hydrazine. Anal. Chem. 24, 122, 24550–24558.
e110335. 2006–2008.
74. Suryanto, B.H.R., Kang, C.S.M., Wang, D.,
46. Shan, W., Liu, F., He, H., Shi, X., and Zhang, C. 60. Giddey, S., Badwal, S.P.S., and Kulkarni, A. Xiao, C., Zhou, F., Azofra, L.M., Cavallo, L.,
(2011). The remarkable improvement of a Ce– (2013). Review of electrochemical ammonia Zhang, X., and MacFarlane, D.R. (2018).
Ti based catalyst for NO x abatement, production technologies and materials. Int. J. Rational electrode–electrolyte design for
prepared by a homogeneous precipitation Hydrogen Energy 38, 14576–14594. efficient ammonia electrosynthesis under
method. ChemCatChem 3, 1286–1289. ambient conditions. ACS Energy Lett. 3,
61. Han, L., Liu, X., Chen, J., Lin, R., Liu, H., Lü, F., 1219–1224.
47. Wang, Z., Wang, Z., Ye, Y., Chen, N., and Li, H. Bak, S., Liang, Z., Zhao, S., Stavitski, E., et al.
(2016). Study on the removal of nitric oxide (2019). Atomically dispersed molybdenum 75. Yan, R., Antonietti, M., and Oschatz, M. (2018).
(NO) by dual oxidant (H2O2/S2O82 ) system. catalysts for efficient ambient nitrogen Toward the experimental understanding of
Chem. Eng. Sci. 145, 133–140. fixation. Angew. Chem. Int. Ed. Engl. 58, the energy storage mechanism and ion
2321–2325. dynamics in ionic liquid based
48. Ivancic, I., and Degobbis, D. (1984). An supercapacitors. Adv. Energy Mater. 8,
optimal manual procedure for ammonia 62. Chen, G.F., Cao, X., Wu, S., Zeng, X., Ding, 1800026.
analysis in natural waters by the indophenol L.X., Zhu, M., and Wang, H. (2017). Ammonia
blue method. Water Res. 18, 1143–1147. 76. Ortuño, M.A., Hollóczki, O., Kirchner, B., and
electrosynthesis with high selectivity under
López, N. (2019). Selective electrochemical
49. Yuen, S.H., and Pollard, A.G. (1954). ambient conditions via a Li+ incorporation
nitrogen reduction driven by hydrogen bond
Determination of nitrogen in agricultural strategy. J. Am. Chem. Soc. 139, 9771–9774.
interactions at metal–ionic liquid interfaces.
materials by the nessler reagent. II.—micro- J. Phys. Chem. Lett. 10, 513–517.
determinations in plant tissue and in soil 63. Köleli, F., and Kayan, D.B. (2010). Low
extracts. J. Sci. Food Agric. 5, 364–369. overpotential reduction of dinitrogen to 77. Li, X.F., Li, Q.K., Cheng, J., Liu, L., Yan, Q., Wu,
ammonia in aqueous media. J. Electroanal. Y., Zhang, X.H., Wang, Z.Y., Qiu, Q., and Luo,
50. Bower, C.E., and Holm-Hansen, T. (1980). A Chem. 638, 119–122. Y. (2016). Conversion of dinitrogen to
salicylate–hypochlorite method for ammonia by FeN3-embedded graphene.
determining ammonia in seawater. Can. J. 64. Zhang, Q., Liu, B., Yu, L., Bei, Y., and Tang, B. J. Am. Chem. Soc. 138, 8706–8709.
Fish. Aquat. Sci. 37, 794–798. (2020). Synergistic promotion of the
electrochemical reduction of nitrogen to 78. Einsle, O., Tezcan, F.A., Andrade, S.L.A.,
51. Michalski, R., and Kurzyca, I. (2006). ammonia by phosphorus and potassium. Schmid, B., Yoshida, M., Howard, J.B., and
Determination of nitrogen species (nitrate, ChemCatChem 12, 334–341. Rees, D.C. (2002). Nitrogenase MoFe-protein
at 1.16 Å resolution: a central ligand in the under ambient conditions. Angew. Chem. Int. 104. Wang, S., Li, B., Li, L., Tian, Z., Zhang, Q.,
FeMo-cofactor. Science 297, 1696–1700. Ed. Engl. 59, 3511–3516. Chen, L., and Zeng, X.C. (2020). Highly
efficient N2 fixation catalysts: transition-metal
79. Yandulov, D.V., and Schrock, R.R. (2003). 92. Valov, I., Luerssen, B., Mutoro, E., Gregoratti, carbides M2C (MXenes). Nanoscale 12,
Catalytic reduction of dinitrogen to ammonia L., De Souza, R.A., Bredow, T., Günther, S., 538–547.
at a single molybdenum center. Science 301, Barinov, A., Dudin, P., Martin, M., and Janek,
76–78. J. (2011). Electrochemical activation of 105. Matanovic, I., and Garzon, F.H. (2018).
molecular nitrogen at the Ir/YSZ interface. Nitrogen electroreduction and hydrogen
80. Back, S., and Jung, Y. (2016). On the Phys. Chem. Chem. Phys. 13, 3394–3410. evolution on cubic molybdenum carbide: a
mechanism of electrochemical ammonia density functional study. Phys. Chem. Chem.
synthesis on the Ru catalyst. Phys. Chem. 93. Xue, Z.H., Zhang, S.N., Lin, Y.X., Su, H., Zhai, Phys. 20, 14679–14687.
Chem. Phys. 18, 9161–9166. G.Y., Han, J.T., Yu, Q.Y., Li, X.H., Antonietti,
M., and Chen, J.S. (2019). Electrochemical 106. Zhang, C., Wang, D., Wan, Y., Lv, R., Li, S., Li,
81. Ling, C., Zhang, Y., Li, Q., Bai, X., Shi, L., and reduction of N2 into NH3 by donor-acceptor B., Zou, X., and Yang, S. (2020). Vanadium
Wang, J. (2019). New mechanism for N2 couples of Ni and Au nanoparticles with a carbide with periodic anionic vacancies for
reduction: the essential role of surface 67.8% faradaic efficiency. J. Am. Chem. Soc. effective electrocatalytic nitrogen reduction.
hydrogenation. J. Am. Chem. Soc. 141, 141, 14976–14980. Mater. Today 40, 18–25.
18264–18270.
94. Liu, Y., Huang, L., Zhu, X., Fang, Y., and Dong, 107. Li, X., Li, T., Ma, Y., Wei, Q., Qiu, W., Guo, H.,
82. Yang, X., Nash, J., Anibal, J., Dunwell, M., S. (2020). Coupling Cu with Au for enhanced Shi, X., Zhang, P., Asiri, A.M., Chen, L., et al.
Kattel, S., Stavitski, E., Attenkofer, K., Chen, electrocatalytic activity of nitrogen reduction (2018). Boosted electrocatalytic N2 reduction
J.G., Yan, Y., and Xu, B. (2018). Mechanistic reaction. Nanoscale 12, 1811–1816. to NH3 by defect-rich MoS2 nanoflower. Adv.
insights into electrochemical nitrogen Energy Mater. 8, 1801357.
reduction reaction on vanadium nitride 95. Zhang, N., Li, L., Wang, J., Hu, Z., Shao, Q.,
nanoparticles. J. Am. Chem. Soc. 140, 13387– Xiao, X., and Huang, X. (2020). Surface- 108. Liu, Y., Han, M., Xiong, Q., Zhang, S., Zhao, C.,
13391. regulated rhodium–antimony nanorods for Gong, W., Wang, G., Zhang, H., and Zhao, H.
nitrogen fixation. Angew. Chem. Int. Ed. Engl. (2019). Dramatically enhanced ambient
83. Yao, Y., Zhu, S., Wang, H., Li, H., and Shao, M. 59, 8066–8071. ammonia electrosynthesis performance by in-
(2018). A spectroscopic study on the nitrogen operando created Li–S interactions on MoS2
96. Sim, H.Y.F., Chen, J.R.T., Koh, C.S.L., Lee, electrocatalyst. Adv. Energy Mater. 9,
electrochemical reduction reaction on gold
H.K., Han, X., Phan-Quang, G.C., Pang, J.Y., 1803935.
and platinum surfaces. J. Am. Chem. Soc. 140,
Lay, C.L., Pedireddy, S., Phang, I.Y., et al.
1496–1501.
(2020). ZIF-induced d-band modification in a 109. Wang, H.-B., Wang, J.Q., Zhang, R., Cheng,
84. Zeng, L., Li, X., Chen, S., Wen, J., Huang, W., bimetallic nanocatalyst: achieving over 44 % C.-Q., Qiu, K.-W., Yang, Y.-J., Mao, J., Liu, H.,
and Chen, A. (2020). Unique hollow Ni– efficiency in the ambient nitrogen reduction Du, M., Dong, C.-K., et al. (2020). Bionic
Fe@MoS2 nanocubes with boosted reaction. Angew. Chem. Int. Ed. Engl. 59, design of a Mo(IV)-doped FeS2 catalyst for
electrocatalytic activity for N2 reduction to 16997–17003. electroreduction of dinitrogen to ammonia.
NH3. J. Mater. Chem. A 8, 7339–7349. ACS Catal. 10, 4914–4921.
97. Wang, Y., Shi, M.-M., Bao, D., Meng, F.-L.,
85. Lai, F., Chen, N., Ye, X., He, G., Zong, W., Holt, Zhang, Q., Zhou, Y.T., Liu, K.-H., Zhang, Y., 110. Lai, F., Zong, W., He, G., Xu, Y., Huang, H.,
K.B., Pan, B., Parkin, I.P., Liu, T., and Chen, R. Wang, J.-Z., Chen, Z.-W., et al. (2019). Weng, B., Rao, D., Martens, J.A., Hofkens, J.,
(2020). Refining energy levels in ReS2 Generating defect-rich bismuth for enhancing Parkin, I.P., and Liu, T. (2020). N2
nanosheets by low-valent transition-metal the rate of nitrogen electroreduction to electroreduction to NH3 by selenium vacancy-
doping for dual-boosted electrochemical ammonia. Angew. Chem. Int. Ed. Engl. 58, rich ReSe2 catalysis at an abrupt interface.
ammonia/hydrogen production. Adv. Funct. 9464–9469. Angew. Chem. Int. Ed. Engl. 59, 13320–13327.
Mater. 30, 1907376. 98. Fang, Y., Liu, Z., Han, J., Jin, Z., Han, Y., Wang, 111. Wang, Y., Chen, A., Lai, S., Peng, X., Zhao, S.,
F., Niu, Y., Wu, Y., and Xu, Y. (2019). High- Hu, G., Qiu, Y., Ren, J., Liu, X., and Luo, J.
86. Lv, X.W., Liu, Y., Hao, R., Tian, W., and Yuan,
performance electrocatalytic conversion of N2 (2020). Self-supported NbSe2 nanosheet
Z.Y. (2020). Urchin-like Al-doped Co3O4
to NH3 using oxygen-vacancy-rich TiO2 in situ arrays for highly efficient ammonia
nanospheres rich in surface oxygen vacancies
grown on Ti3C2Tx MXene. Adv. Energy Mater. electrosynthesis under ambient conditions.
enable efficient ammonia electrosynthesis.
9, 1803406. J. Catal. 381, 78–83.
ACS Appl. Mater. Interfaces 12, 17502–17508.
99. Huang, L., Wu, J., Han, P., Al-Enizi, A.M., 112. Sun, Z., Talreja, N., Tao, H., Texter, J., Muhler,
87. Ren, J.T., Wan, C.Y., Pei, T.Y., Lv, X.W., and Almutairi, T.M., Zhang, L., and Zheng, G. M., Strunk, J., and Chen, J. (2018). Catalysis of
Yuan, Z.Y. (2020). Promotion of (2019). NbO2 electrocatalyst toward 32% carbon dioxide photoreduction on
electrocatalytic nitrogen reduction reaction faradaic efficiency for N2 fixation. Small nanosheets: fundamentals and challenges.
on N-doped porous carbon with secondary Methods 3, 1800386. Angew. Chem. Int. Ed. Engl. 57, 7610–7627.
heteroatoms. Appl. Catal. B 266, 118633.
100. Abghoui, Y., and Skúlason, E. (2017). 113. Lv, C., Zhong, L., Yao, Y., Liu, D., Kong, Y., Jin,
88. Yuan, L.P., Wu, Z.Y., Jiang, W.J., Tang, T., Niu, Electrochemical synthesis of ammonia via X., Fang, Z., Xu, W., Yan, C., Dinh, K.N., et al.
S., and Hu, J.S. (2020). Phosphorus-doping Mars-van Krevelen mechanism on the (111) (2020). Boosting electrocatalytic ammonia
activates carbon nanotubes for efficient facets of group III–VII transition metal production through mimicking ‘‘p back-
electroreduction of nitrogen to ammonia. mononitrides. Catal. Today 286, 78–84. donation’’. Chem 6, 2690–2702.
Nano Res. 13, 1376–1382.
101. Jin, H., Li, L., Liu, X., Tang, C., Xu, W., Chen, S., 114. Lv, C., Yan, C., Chen, G., Ding, Y., Sun, J.,
89. Fu, Y., Li, T., Zhou, G., Guo, J., Ao, Y., Hu, Y., Song, L., Zheng, Y., and Qiao, S.Z. (2019). Zhou, Y., and Yu, G. (2018). An amorphous
Shen, J., Liu, L., and Wu, X. (2020). Dual-metal- Nitrogen vacancies on 2D layered W2N3: a noble-metal-free electrocatalyst that enables
driven selective pathway of nitrogen stable and efficient active site for nitrogen nitrogen fixation under ambient conditions.
reduction in orderly atomic-hybridized reduction reaction. Adv. Mater. 31, 1902709. Angew. Chem. Int. Ed. Engl. 57, 6073–6076.
Re2MnS6 ultrathin nanosheets. Nano Lett. 20,
4960–4967. 102. Hu, B., Hu, M., Seefeldt, L., and Liu, T.L. (2019). 115. Liu, X., Jang, H., Li, P., Wang, J., Qin, Q., Kim,
Electrochemical dinitrogen reduction to M.G., Li, G., and Cho, J. (2019). Antimony-
90. Yao, D., Tang, C., Li, L., Xia, B., Vasileff, A., Jin, ammonia by Mo2N: catalysis or based composites loaded on phosphorus-
H., Zhang, Y., and Qiao, S.Z. (2020). In situ decomposition? ACS Energy Lett. 4, 1053– doped carbon for boosting faradaic efficiency
fragmented bismuth nanoparticles for 1054. of the electrochemical nitrogen reduction
electrocatalytic nitrogen reduction. Adv. reaction. Angew. Chem. Int. Ed. Engl. 58,
Energy Mater. 10, 2001289. 103. Peng, J., Chen, X., Ong, W.J., Zhao, X., and Li, 13329–13334.
N. (2019). Surface and heterointerface
91. Xu, W., Fan, G., Chen, J., Li, J., Zhang, L., Zhu, engineering of 2D MXenes and their 116. Fang, Y., Xue, Y., Li, Y., Yu, H., Hui, L., Liu, Y.,
S., et al. (2020). Nanoporous palladium nanocomposites: insights into electro- and Xing, C., Zhang, C., Zhang, D., Wang, Z., et al.
hydride for electrocatalytic N2 reduction photocatalysis. Chem 5, 18–50. (2020). Graphdiyne interface engineering:
highly active and selective ammonia 129. Zhang, L., Ding, L.X., Chen, G.F., Yang, X., and material properties. Phys. Rev. Lett. 120,
synthesis. Angew. Chem. Int. Ed. Engl. 59, Wang, H. (2019). Ammonia synthesis under 145301.
13021–13027. ambient conditions: selective
electroreduction of dinitrogen to ammonia on 143. Logan, D.L. (2011). A First Course in the Finite
117. Choi, C., Back, S., Kim, N.Y., Lim, J., Kim, Y.H., black phosphorus nanosheets. Angew. Chem. Element Method (Cengage Learning).
and Jung, Y. (2018). Suppression of hydrogen Int. Ed. Engl. 58, 2612–2616.
evolution reaction in electrochemical N2 144. Goodfellow, I., Bengio, Y., and Courville, A.
reduction using single-atom catalysts: a 130. Xu, G., Li, H., Bati, A.S.R., Bat-Erdene, M., (2016). Deep Learning (MIT Press).
computational guideline. ACS Catal. 8, 7517– Nine, M.J., Losic, D., Chen, Y., Shapter, J.G.,
7525. Batmunkh, M., and Ma, T. (2020). Nitrogen- 145. Wang, D., Azofra, L.M., Harb, M., Cavallo, L.,
doped phosphorene for electrocatalytic Zhang, X., Suryanto, B.H.R., and MacFarlane,
118. Tao, H., Choi, C., Ding, L.X., Jiang, Z., Han, Z., ammonia synthesis. J. Mater. Chem. A 8, D.R. (2018). Energy-efficient nitrogen
Jia, M., Fan, Q., Gao, Y., Wang, H., Robertson, 15875–15883. reduction to ammonia at low overpotential in
A.W., et al. (2019). Nitrogen fixation by Ru aqueous electrolyte under ambient
single-atom electrocatalytic reduction. Chem 131. Zhang, Y., Dong, N., Tao, H., Yan, C., Huang, conditions. ChemSusChem 11, 3416–3422.
5, 204–214. J., Liu, T., Robertson, A.W., Texter, J., Wang,
J., and Sun, Z. (2017). Exfoliation of stable 2D 146. Bao, D., Zhang, Q., Meng, F.L., Zhong, H.X.,
119. Lü, F., Zhao, S., Guo, R., He, J., Peng, X., Bao, black phosphorus for device fabrication. Shi, M.M., Zhang, Y., Yan, J.M., Jiang, Q., and
H., Fu, J., Han, L., Qi, G., Luo, J., et al. (2019). Chem. Mater. 29, 6445–6456. Zhang, X.B. (2017). Electrochemical reduction
Nitrogen-coordinated single Fe sites for of N2 under ambient conditions for artificial
efficient electrocatalytic N2 fixation in neutral 132. Liu, Q., Zhang, X., Wang, J., Zhang, Y., Bian, N2 fixation and renewable energy storage
media. Nano Energy 61, 420–427. S., Cheng, Z., Kang, N., Huang, H., Gu, S., using N2/NH3 cycle. Adv. Mater. 29, 1604799.
Wang, Y., et al. (2020). Crystalline red
120. Wang, Y., Cui, X., Zhao, J., Jia, G., Gu, L., 147. Choi, J., Suryanto, B.H.R., Wang, D., Du, H.L.,
phosphorus nanoribbons: large-scale
Zhang, Q., Meng, L., Shi, Z., Zheng, L., Wang, Hodgetts, R.Y., Ferrero Vallana, F.M.,
synthesis and electrochemical nitrogen
C., et al. (2019). Rational design of Fe–N/C MacFarlane, D.R., and Simonov, A.N. (2020).
fixation. Angew. Chem. Int. Ed. Engl. 59,
hybrid for enhanced nitrogen reduction Identification and elimination of false
14383–14387.
electrocatalysis under ambient conditions in positives in electrochemical nitrogen
aqueous solution. ACS Catal. 9, 336–344. 133. Qiu, W., Xie, X.Y., Qiu, J., Fang, W.H., Liang, reduction studies. Nat. Commun. 11, 5546.
121. Wang, M., Liu, S., Qian, T., Liu, J., Zhou, J., Ji, R., Ren, X., Ji, X., Cui, G., Asiri, A.M., Cui, G.,
et al. (2018). High-performance artificial 148. Tayyebi, E., Abghoui, Y., and Skúlason, E.
H., Xiong, J., Zhong, J., and Yan, C. (2019). (2019). Elucidating the mechanism of
Over 56.55% faradaic efficiency of ambient nitrogen fixation at ambient conditions using
a metal-free electrocatalyst. Nat. Commun. 9, electrochemical N2 reduction at the Ru(0001)
ammonia synthesis enabled by positively electrode. ACS Catal. 9, 11137–11145.
shifting the reaction potential. Nat. Commun. 3485.
10, 341. 149. Chen, L.Y., Kuo, T.C., Hong, Z.S., Cheng, M.J.,
134. Liu, C., Li, Q., Wu, C., Zhang, J., Jin, Y.,
MacFarlane, D.R., and Sun, C. (2019). Single- and Goddard, W.A. (2019). Mechanism and
122. Zhang, S., Jin, M., Shi, T., Han, M., Sun, Q., Lin, kinetics for both thermal and electrochemical
Y., Ding, Z., Zheng, L.R., Wang, G., Zhang, Y., boron catalysts for nitrogen reduction
reaction. J. Am. Chem. Soc. 141, 2884–2888. reduction of N2 catalysed by Ru(0001) based
et al. (2020). Electrocatalytically active Fe-(O- on quantum mechanics. Phys. Chem. Chem.
C2)4 single-atom sites for efficient reduction of Phys. 21, 17605–17612.
nitrogen to ammonia. Angew. Chem. Int. Ed. 135. Liu, X., Jiao, Y., Zheng, Y., and Qiao, S.Z.
Engl. 59, 13423–13429. (2020). Isolated boron sites for
electroreduction of dinitrogen to ammonia. 150. Zhang, L., Mallikarjun Sharada, S., Singh, A.R.,
ACS Catal. 10, 1847–1854. Rohr, B.A., Su, Y., Qiao, L., and Nørskov, J.K.
123. Wang, X., Wang, W., Qiao, M., Wu, G., Chen,
(2018). A theoretical study of the effect of a
W., Yuan, T., Xu, Q., Chen, M., Zhang, Y.,
136. Abghoui, Y., Sigtryggsson, S.B., and Skúlason, non-aqueous proton donor on
Wang, X., et al. (2018). Atomically dispersed
E. (2019). Biomimetic nitrogen fixation electrochemical ammonia synthesis. Phys.
Au1 catalyst towards efficient electrochemical
catalyzed by transition metal sulfide surfaces Chem. Chem. Phys. 20, 4982–4989.
synthesis of ammonia. Sci. Bull. 63, 1246–
1253. in an electrolytic cell. ChemSusChem 12,
4265–4273. 151. Ulissi, Z.W., Medford, A.J., Bligaard, T., and
124. Chen, H., Zhu, X., Huang, H., Wang, H., Wang, Nørskov, J.K. (2017). To address surface
T., Zhao, R., Zheng, H., Asiri, A.M., Luo, Y., and 137. Gu, G.H., Noh, J., Kim, I., and Jung, Y. (2019). reaction network complexity using scaling
Sun, X. (2019). Sulfur dots–graphene Machine learning for renewable energy relations machine learning and DFT
nanohybrid: a metal-free electrocatalyst for materials. J. Mater. Chem. A 7, 17096–17117. calculations. Nat. Commun. 8, 14621.
efficient N2-to-NH3 fixation under ambient
138. Kim, M., Yeo, B.C., Park, Y., Lee, H.M., Han, 152. Jang, J., Gu, G.H., Noh, J., Kim, J., and Jung,
conditions. Chem. Commun. 55, 3152–3155.
S.S., and Kim, D. (2020). Artificial intelligence Y. (2020). Structure-based synthesizability
125. Liu, B., Zheng, Y., Peng, H.Q., Ji, B., Yang, Y., to accelerate the discovery of N2 prediction of crystals using partially
Tang, Y., Lee, C.S., and Zhang, W. (2020). electroreduction catalysts. Chem. Mater. 32, supervised learning. J. Am. Chem. Soc. 142,
Nanostructured and boron-doped diamond 709–720. 18836–18843.
as an electrocatalyst for nitrogen fixation. ACS
Energy Lett. 5, 2590–2596. 139. Zafari, M., Kumar, D., Umer, M., and Kim, K.S. 153. Yang, C., Huang, B., Bai, S., Feng, Y., Shao, Q.,
(2020). Machine learning-based high and Huang, X. (2020). A generalized surface
126. Fan, Q., Choi, C., Yan, C., Liu, Y., Qiu, J., throughput screening for nitrogen fixation on chalcogenation strategy for boosting the
Hong, S., Jung, Y., and Sun, Z. (2019). High- boron-doped single atom catalysts. J. Mater. electrochemical N2 fixation of metal
yield production of few-layer boron Chem. A 8, 5209–5216. nanocrystals. Adv. Mater. 32, e2001267.
nanosheets for efficient electrocatalytic N2
reduction. Chem. Commun. 55, 4246–4249. 140. Hoar, B.B., Lu, S., and Liu, C. (2020). Machine- 154. Zhang, M., Choi, C., Huo, R., Gu, G.H., Hong,
learning-enabled exploration of morphology S., Yan, C., Xu, S., Robertson, A.W., Qiu, J.,
127. Légaré, M.A., Bélanger-Chabot, G., influence on wire-array electrodes for Jung, Y., and Sun, Z. (2020). Reduced
Dewhurst, R.D., Welz, E., Krummenacher, I., electrochemical nitrogen fixation. J. Phys. graphene oxides with engineered defects
Engels, B., and Braunschweig, H. (2018). Chem. Lett. 11, 4625–4630. enable efficient electrochemical reduction of
Nitrogen fixation and reduction at boron. dinitrogen to ammonia in wide pH range.
Science 359, 896–900. 141. Noh, J., Gu, G.H., Kim, S., and Jung, Y. (2020). Nano Energy 68, 104323.
Machine-enabled inverse design of inorganic
128. Lv, C., Qian, Y., Yan, C., Ding, Y., Liu, Y., Chen, solid materials: promises and challenges. 155. Jin, Z., Liu, C., Liu, Z., Han, J., Fang, Y., Han, Y.,
G., and Yu, G. (2018). Defect engineering Chem. Sci. 11, 4871–4881. Niu, Y., Wu, Y., Sun, C., and Xu, Y. (2020).
metal-free polymeric carbon nitride Rational design of hydroxyl-rich Ti3C2Tx
electrocatalyst for effective nitrogen fixation 142. Xie, T., and Grossman, J.C. (2018). Crystal MXene quantum dots for high-performance
under ambient conditions. Angew. Chem. Int. graph convolutional neural networks for an electrochemical N2 reduction. Adv. Energy
Ed. Engl. 57, 10246–10250. accurate and interpretable prediction of Mater. 10, 2000797.
156. Xia, J., Yang, S.Z., Wang, B., Wu, P., Popovs, I., electrocatalytic nitrogen fixation. J. Mater. on carbon fabric for electrochemical N2
Li, H., Irle, S., Dai, S., and Zhu, H. (2020). Chem. A 8, 5865–5873. fixation. ACS Sustain. Chem. Eng. 7, 8853–
Boosting electrosynthesis of ammonia on 8859.
surface-engineered MXene Ti3C2. Nano 163. Shi, M.M., Bao, D., Li, S.J., Wulan, B.R., Yan,
Energy 72, 104681. J.M., and Jiang, Q. (2018). Anchoring PdCu 170. Yang, X., Ling, F., Su, J., Zi, X., Zhang, H.,
amorphous nanocluster on graphene for Zhang, H., Li, J., Zhou, M., and Wang, Y.
157. Ahmed, M.I., Liu, C., Zhao, Y., Ren, W., Chen, electrochemical reduction of N2 to NH3 under (2020). Insights into the role of cation vacancy
X., Chen, S., and Zhao, C. (2020). Metal–sulfur ambient conditions in aqueous solution. Adv. for significantly enhanced electrochemical
linkages achieved by organic tethering of Energy Mater. 8, 1800124. nitrogen reduction. Appl. Catal. B 264,
ruthenium nanocrystals for enhanced 118477.
electrochemical nitrogen reduction. Angew. 164. Yang, D., Chen, T., and Wang, Z. (2017).
Chem. Int. Ed. Engl. 59, 21465–21469. Electrochemical reduction of aqueous
nitrogen (N2) at a low overpotential on (110)- 171. Chu, K., Li, Q.Q., Liu, Y.P., Wang, J., and
158. Zou, H., Rong, W., Long, B., Ji, Y., and Duan, L. oriented Mo nanofilm. J. Mater. Chem. A 5, Cheng, Y.H. (2020). Filling the nitrogen
(2019). Corrosion-induced Cl-doped ultrathin 18967–18971. vacancies with sulphur dopants in graphitic
graphdiyne toward electrocatalytic nitrogen C3N4 for efficient and robust electrocatalytic
reduction at ambient conditions. ACS Catal. 165. Nazemi, M., Panikkanvalappil, S.R., and El- nitrogen reduction. Appl. Catal. B 267,
9, 10649–10655. Sayed, M.A. (2018). Enhancing the rate of 118693.
electrochemical nitrogen reduction reaction
159. Yang, Y., Zhang, L., Hu, Z., Zheng, Y., Tang, C., for ammonia synthesis under ambient 172. Tong, W., Huang, B., Wang, P., Li, L., Shao, Q.,
Chen, P., Wang, R., Qiu, K., Mao, J., Ling, T., conditions using hollow gold nanocages. and Huang, X. (2020). Crystal-phase-
and Qiao, S.-Z. (2020). The crucial role of Nano Energy 49, 316–323. engineered PdCu electrocatalyst for
charge accumulation and spin polarization in enhanced ammonia synthesis. Angew. Chem.
activating carbon-based catalysts for 166. Huang, L., Gu, X., and Zheng, G. (2019). Int. Ed. Engl. 59, 2649–2653.
electrocatalytic nitrogen reduction. Angew. Tuning active sites of MXene for efficient
Chem. Int. Ed. Engl. 59, 4525–4531. electrocatalytic N2 fixation. Chem 5, 15–17. 173. Li, J., Chen, S., Quan, F., Zhan, G., Jia,
F., Ai, Z., and Zhang, L. (2020).
160. Yang, M., Huo, R., Shen, H., Xia, Q., Qiu, J., 167. Zhang, L., Ji, X., Ren, X., Ma, Y., Shi, X., Tian, Z., Accelerated dinitrogen electroreduction
Robertson, A.W., Li, X., and Sun, Z. (2020). Asiri, A.M., Chen, L., Tang, B., and Sun, X. to ammonia via interfacial polarization
Metal-tuned W18O49 for efficient (2018). Electrochemical ammonia synthesis via triggered by single-atom protrusions.
electrocatalytic N2 reduction. ACS nitrogen reduction reaction on a MoS2 Chem 6, 885–901.
Sustainable Chem. Eng. 8, 2957–2963. catalyst: theoretical and experimental studies.
Adv. Mater. 30, e1800191.
161. Wu, T., Zhu, X., Xing, Z., Mou, S., Li, C., Qiao, 174. Zheng, J., Lyu, Y., Qiao, M., Veder, J.P.,
Y., Liu, Q., Luo, Y., Shi, X., Zhang, Y., and Sun, 168. Guo, X., and Huang, S. (2018). Tuning Marco, R.D., Bradley, J., Wang, R., Li, Y.,
X. (2019). Greatly improving electrochemical nitrogen reduction reaction activity via Huang, A., Jiang, S.P., and Wang, S. (2019).
N2 reduction over TiO2 nanoparticles by iron controllable Fe magnetic moment: A Tuning the electron localization of gold
doping. Angew. Chem. Int. Ed. Engl. 58, computational study of single Fe atom enables the control of nitrogen-to-ammonia
18449–18453. supported on defective graphene. fixation. Angew. Chem. Int. Ed. Engl. 58,
Electrochim. Acta 284, 392–399. 18604–18609.
162. Chu, K., Cheng, Y.H., Li, Q.Q., Liu, Y.P., and
Tian, Y. (2020). Fe-doping induced 169. Li, Y., Kong, Y., Hou, Y., Yang, B., Li, Z., Lei, L., 175. McPherson, I., and Zhang, J. (2020). Can
morphological changes, oxygen vacancies and Wen, Z. (2019). In situ growth of nitrogen- electrification of ammonia synthesis decrease
and Ce3+–Ce3+ pairs in CeO2 for promoting doped carbon-coated g-Fe2O3 nanoparticles its carbon footprint? Joule 4, 12–14.