2D Metal Free Electrocatalysts For The Nitrogen Reduction Reaction

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2D, Metal-Free Electrocatalysts for the Nitrogen

Reduction Reaction
Chuangwei Liu, Ang Tian, Qinye Li, Tianyi Wang, Gaowu Qin, Song Li,*
and Chenghua Sun*
Environmentally friendly ammonia production is important for addressing Figure 1 shows a diagram of the wide range
of chemicals produced from ammonia.[3]
the carbon emissions and substantial energy consumption that are currently
Ammonia is also an environmentally
associated with the chemical industry. In recent decades, many achievements friendly energy carrier and an alternative
are made in this area; however, low production yield, poor selectivity, and fuel because of its high energy density,
unsatisfactory Faradaic efficiency hinder large-scale applications. 2D, metal- without carbon dioxide (CO2) emissions.[4]
free electrocatalysts stand out from other candidates because of their physical, The current industrial production method
still relies on the Haber–Bosch (HB) pro-
electronic, and chemical properties. In this work, recent developments of
cess, which is one of the most impactful
2D-based electrochemical materials for converting dinitrogen into ammonia in inventions of the twentieth century.[5] In
ambient conditions are systematically reviewed. First, recent unique progress the HB method, a mixture of dihydrogen
and challenges on novel 2D electrocatalysts for the nitrogen reduction reac- (H2) and dinitrogen (N2) passes through
tion are summarized. Then, various synthetic strategies for electrochemical iron- and molybdenum-based catalysts,
materials and the influence of these methods have on the intrinsic material under pressures of 130–170 bar at tempera-
tures of ≈400–500 °C.[6]
performance are highlighted. Last, by comparing current engineering strate-
The reaction is exothermic. However,
gies, electrochemical tests, and computational calculations, the opportuni- much energy and high pressures are
ties, critical issues, and scientific challenges for 2D nanomaterials as stable, required for completion because nonpolar
efficient catalysts, are analyzed. On the basis of this comparison, technology N2 has a strong triple bond, high ioniza
solutions are provided and rational principles for future work are proposed. tion energy, and negative electron
affinity.[7] Overall, the HB method accounts
for 1% of the world’s yearly natural gas
consumption and for burning more than
1. Introduction 1.4% of fossil fuel energy.[8] HB production accounts for 1.6%
of global CO2 emissions because the main source of hydrogen
Ammonia (NH3) is the most indispensable fundamental chem- is natural gas.[9] Since the Haber–Bosch was invented, the
ical for urea feedstocks in agriculture and is a reagent precursor process has been improved and optimized substantially.
for producing many other chemicals.[1] Especially in the fertilizer Numerous researchers have developed catalysts that can facilitate
area, the need for ammonia production continues to increase ammonia synthesis in ambient conditions.[10] Co-containing
in the context of supporting a growing global population; abun- catalysts are a notable development for traditional fused iron cat-
dant, low-cost ammonia production is ultimately necessary alysts.[11] Cobalt-doped, iron-based catalysts enhance the effect of
to provide a sustainable, stable, and affordable food supply.[2] iron on nitrogen chemisorption, and ammonia can be released
C. Liu, G. Qin, S. Li A. Tian

Key Lab for Anisotropy and Texture of Materials Liaoning Provincial Key Laboratory of Metallurgical
School of Materials Science and Engineering Resources Circulation Science
Northeastern University Northeastern University
Shenyang 110819, P. R. China Shenyang 110819, P. R. China
E-mail: lis@atm.neu.edu.cn Q. Li, C. Sun
The ORCID identification number(s) for the author(s) of this article Department of Chemistry and Biotechnology and Centre for
can be found under https://doi.org/10.1002/adfm.202210759. Translational Atomaterials
Swinburne University of Technology
© 2022 The Authors. Advanced Functional Materials published by
Hawthorn, Victoria 3122, Australia
Wiley-VCH GmbH. This is an open access article under the terms of
E-mail: chenghuasun@swin.edu.au
the Creative Commons Attribution-NonCommercial-NoDerivs License,
which permits use and distribution in any medium, provided the original T. Wang, C. Sun
work is properly cited, the use is non-commercial and no modifications Science and Technology Innovation Institute
or adaptations are made. Faculty of Science
Dongguan University of Technology
DOI: 10.1002/adfm.202210759 Dongguan 523808, P. R. China
Adv. Funct. Mater. 2022, 2210759 2210759 (1 of 23) © 2022 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
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Table 1. Mechanisms of the electrocatalytic NRR with various intermedi-

ates. (* denotes an adsorption site on the catalyst surface).
Mechanism routes Elementary reaction steps

Dissociative N2 + 2* → 2*N
N + e− + H+ → *NH
*
*
NH + e− + H+ → *NH2
*
NH2 + e− + H+ → NH3 + *
Associative distal N2 + * → *N2
*
N2 + e− + H+ → *NNH
*
NNH + e− + H+ → *NNH2
*
NNH2 + e− + H+ → *N + NH3
*
N + e− + H+ → *NH
*
NH + e− + H+ → *NH2
*
NH2 + e− + H+ → NH3 + *
Associative Alternating, and enzymatic N2 + * →*N2
*
N2 + e− + H+ → *NNH
*NNH + e− + H+ → *NHNH
*NHNH + e- + H+ → *NHNH

2
*
NHNH2 + e− + H+ → *NH2NH2
*
NH2NH2 + e− + H+ → *NH2 + NH3
*
NH2 + e− + H+ → NH3 + *
Figure 1. Schematic overview of ammonia applications in modern society.

at mild temperatures (≈100 °C).[10c,23] The Faradaic efficiency
(FE) of production can be up to 78% when the experiment
from the catalyst surface at a relatively low temperature.[11a] uses a solid-state proton conductor.[22] Compared with the solid
Subsequently, noble metals with various supports (such as conductor, ionic liquids or molten salts can provide excellent
silica,[12] aluminum oxide,[13] zeolites,[14] and graphitized carbon) catalytic performance at room temperature; their activity sub-
are common in such research.[15] Whereas many improved stantially relies on the ionic structures.[24] Proton-conducting
catalysts and drastic reaction conditions are applied in the HB ceramic membranes exhibit an excellent ammonia conversion
method, the efficiency is still less than 15%. Although industrial rate because the product can be more readily separated from
processes use harsh conditions, plants and bacteria can convert the reactants.[25]
gaseous dinitrogen into ammonia even below room Generally, electrocatalytic reduction of dinitrogen and
temperature.[6,10b] This process can be achieved by metalloen- hydrogen to produce ammonia on heterogenous catalysts can
zymes.[16] In addition, the entire reaction is carbon-neutral be divided into two main mechanisms: dissociative and associa-
because hydrogen is generated from renewable sources, which tive. Table 1 shows the intermediates.[26] In Figure 2a, the triple
can reduce the environmental burden.[17] The entire enzymatic bond of dinitrogen is first broken before the hydrogenation in
reaction requires 16 equivalents of adenosine triphosphate the dissociative mechanism. The process not only is limited by
coupled with the formation of one equivalent of dihydrogen per Brønsted–Evans–Polanyi relation but also needs much energy
turnover of ammonia.[18] to break the inert covalent N2 bond. By contrast, in the asso-
Although extensive efforts have focused on synthesizing NH3 ciative pathway, the adsorbed N2 molecule is hydrogenated into
from coordinated N2, typically by protonolysis, molecular cata- *NNH.[26] Considering different sequences of adding H to the
lysts for NH3 synthesis are rarely reported in ambient condi N atoms, the hydrogenation in the associative mechanism can
tions.[19] Since a transition metal (TM)–nitrogen compound proceed via two pathways: distal and alternating. In the distal
was first synthesized in 1965,[20] three major classes of catalysts pathway (Figure 2b), the distal N atom (far away from the
have been discovered, including Mo–nitrogenase, Fe protein, end-on adsorption site) preferentially undergoes hydrogena-
and the MoFe protein cycle. The reduction of nitrogen gas with tion until release the first NH3; subsequently, the remaining N
proton sources and electron carriers occurs on the TM active atoms repeat the same hydrogenation to produce a second NH3
site in the aforementioned catalysts.[21] Among these candi- molecule.[27] By contrast, the alternating pathway proceeds with
dates, Mo–nitrogenase provides the best catalytic performance the two N atoms hydrogenated in addition to proton-coupled
for N2 binding and reduction. The other two alternative nitro- electron transfer, and two NH3 molecules are released sequen-
genases—V- and Fe-nitrogenase—were investigated, with the tially at the final step of the pathway (Figure 2c). In addition,
names reflecting the replacement of Mo with the two metals. the enzymatic pathway shares a similar hydrogenation process
Inspired by the electron and proton transfer in nitrogenases with an alternating pathway, but with both N atoms bonding to
and molecular catalysts, electrochemical methods and catalysts the catalysts surface subsequent to a side-on coordination mode
have been developed in recent decades. In 1998, ammonia was (Figure 2d). Moreover, nonpolluting and renewable energy
successfully produced in a solid electrolyte cell by an electro- drives the electrochemical reduction, and ammonia is produced
chemical processes in ambient conditions.[22] Then, a series of directly from N2 and water (proton sources) in ambient condi-
electrochemical technologies were used to synthesize ammonia tions, which can alleviate the greenhouse gas problem.[28]
Figure 2. Nitrogen reduction reaction: possible mechanisms on catalyst surface: dissociative, associative distal, associative alternating, and associa-
tive enzymatic.
Currently, most electrocatalysts are based on TMs because of states.[31] Such materials help a relatively simple type of
the ability to partially inject d-orbital electrons into the empty active site with nearly the same coordination number to be
π orbital of N2, decreasing the N–N bond order. In recent obtained, whereas the atomic thickness and ultrahigh spe-
decades, many excellent TM-based electrocatalysts have been cific surface area render the number of active sites compa-
synthesized and used to produce ammonia at room tempera- rable with the total number of atoms.[32] Moreover, because
ture.[29] However, the ammonia production and FE of these of the many exposed surface atoms, the defect structure,
TM-based materials are still far away from those required for crystal twinning, and corrugated sheet easily form on an
synthetic applications on an industrial scale. These disadvan- ultrathin 2D sheet. This can affect the intrinsic properties
tages can be ascribed to the following factors. The first and and enhance the activity of the catalytic sites. The useful
most important aspect is the selectivity in the electrolyte cell. properties of 2D electrocatalysts originate from their intrinsic
The catalytic site of TM materials might be poisoned by some features as well as the ability to use engineering to system-
species in aqueous solution, especially *OH or *H. In other atically improve the properties. For example, a high density
words, the competing hydrogen evolution reaction (HER) domi- of active sites can be produced on a 2D material surface by
nates the main reaction in TM-based catalysts, instead of the N2 considering the edges, defects, dopants, twist, and size.[33] In
activation reaction. Second, the strong connection between the addition to the aforementioned syntheses, some 2D mate-
TM to the intermediates, leading to a high barrier for ammonia rials can change from semiconductors to metallic catalysts
desorption. Last, most heterogeneous catalysts exhibit low by strain engineering.[34] Therefore, 2D materials provide a
corrosion resistance and are environmentally unfriendly in acid versatile platform for tuning properties toward desired func-
or alkali solution. tions, which is an active field of research and facilitates a
Since graphene was produced in 2004, the unique proper- wide range of applications.[35] In particular, 2D metal-free
ties of 2D materials have been used in numerous catalytic catalysts exhibit substantial potential for converting nitrogen
applications, such as photocatalysts, electrocatalysts, and into ammonia in ambient conditions. Compared with con-
heterogeneous catalysts.[30] Compared with conventional ventional TM-based catalysts, they offer good conductivity,
structural electrocatalysts, 2D materials have several intrinsic an environmentally friendly nature, and controllable porosity.
features, including a large specific surface area, tunability, In the past few years, the favorable nitrogen reduction reac-
uniformly exposed lattice planes, and unique electronic tion (NRR) selectivity of numerous metal-free catalysts has
been confirmed; their structures and catalytic activities can be 2. Categories of 2D Materials
experimentally tuned.
In this review, we focus on investigate the NRR performance In addition to graphene, many graphene-like, 2D, metal-free
of pristine metal-free 2D materials and p-block-doped, non- materials have been discovered and synthesized in the past
metal atom, 2D materials by comprehensively experimental 20 years.[34a,37] These 2D materials have been widely studied
and theoretical aspects.[36] Especially, we build up the struc- in the context of research on energy conversion and catalysis.
ture–activity correlations from the computational mind, and Catalysts play an important role in current industrial applica-
provide the new data-driven computational method, machine tions; the unique geometric and electronic properties of 2D
learning, to design new 2D materials for NRR. Then, we dis- materials enable useful performance toward numerous catalytic
cuss the corresponding physicochemical properties and elec- processes.[38] Since FeN3-embedded graphene was reported as
trocatalytic performance for the NRR in ambient conditions. In the catalyst for the NRR in 2016,[33b] many 2D metal-free mate-
the second part, we discuss the state-of-the-art in design strate- rials have been evaluated for converting nitrogen into ammonia
gies and syntheses for preparing electrocatalysts, by using experi- by using experimental and/or numerical methods in ambient
ments and density functional theory (DFT) calculation results. conditions. These materials include graphene, graphdiyne
We subsequently conduct a comprehensive review of the devel- (Figure 3a,b),[33b,39] graphitic carbon nitride (Figure 3c–e),[40]
opment of 2D electrocatalysts with a focus on the reduction hexagonal boron nitride (h-BN; Figure 3f),[41] boron sheets
mechanisms, catalytic activity milestones, and rational design. (Figure 3g),[42] black phosphorus (BP; Figure 3h),[42] and boron
In addition, we discuss the relationship between 2D electro phosphide (Figure 3i).[42]
catalysts and their corresponding electrocatalytic performances by
bridging fundamental theoretical calculations with experiments
and infer a universal principle for rational design of new 2D 2.1. 2D Carbon-Based Materials Used in NRR Catalysis
electrocatalysts. By comparing current engineering strategies,
electrochemical tests, and computational calculations, we ana- N-doped carbon nanotubes were confirmed to exhibit
lyze the opportunities and critical issues for 2D nanomaterials as Pt-compatible catalytic performance for the oxygen reduction
stable, efficient catalysts. Last, we discuss the remaining scientific reaction in alkaline fuel cells in 2009.[43] Then, a series of
reduction challenges and target yields of ammonia. We also pro- carbon-based electrocatalysts (including carbon nanotubes,
vide outlooks and principles for designing new 2D electrocatalysts. graphene, graphdiyne, and carbon dots) were reported to be
Figure 3. Schematic molecular configurations of a) graphene, b) graphdiyne, c) nitrogenated hole-containing graphene C2N, d) s-triazine-constructed
g-C3N4, e) tri-s-triazine-constructed g-C3N4, f) black phosphorus, g) hexagonal boron nitride, h) boron sheet, i) boron phosphide, and j) the timeline
of the major development on 2D metal-free materials in electrochemical nitrogen reduction. Black, blue, purple, and pink spheres represent C, N, P,
and B atoms, respectively.
Table 2. Experimental activity of 2D carbon-based electrocatalysts for the NRR.
Catalyst Yield FE Potential [V] Detection method Electrolyte

N/carbon[47] −1 −1 NA −0.90 Nessler’s 0.05 m H2SO4
23.8 µg h mg
O/graphene[48] 20.2 µg h−1 mg−1 4.9% −0.60 Indophenol 0.1 m HCl
15Graphdiyne[49]
44.1 µg h−1 mg−1 25.9% −1.20 Nessler’s 0.1 m Na2SO4
15
B4C[50] 28.6 µg h−1 mg−1 16.7% −0.45 Indophenol 0.1 m HCl
B/graphene [51] −1 −2 10.8% −0.50 Nessler’s 0.05 m H2SO4
9.8 µg h cm
Graphene oxide[52] 22.3 µg h−1 mg−1 11.0% −0.30 Indophenol 0.1 m Na2SO4
15
B@N/carbon[53] −1 −1 13.8% −0.30 Indophenol 0.1 m KCl
7.8 µg h mg
Cl/carbon[54] 4.3 µg h−1 cm−2 6.2% −0.55 Nessler’s 0.05 m H2SO4
15
O/graphene[55] 21.3 µg h−1 mg−1 12.6% −0.55 Indophenol 0.1 m HCl
N/graphene [56] −1 −1 8.5% −0.40 Nessler’s 0.01 m H2SO4
4.3 µg h mg
F/carbon[57] 6.9 µg h−1 cm−2 12.1% −0.55 Nessler’s 0.05 m H2SO4
N/Carbon[58] 5.8 µg h−1 cm−2 10.2% -0.30 Indophenol 0.1 m HCl
Graphene oxide [59]
17.0 µg h−1 mg−1 4.8% −0.75 Indophenol 0.5 m LiClO4
15
Graphdiyne[60] 219.7 µg h−1 mg−1 58.6% −0.20 Nessler’s 0.1 m Na2SO4
B@N/carbon[61] 41.0 µg h−1 mg−1 14.0% −0.40 Indophenol 0.05 m H2SO4
S@N/graphene[62] 7.7 µg h−1 mg−1 5.8% −0.60 Indophenol 0.1 m HCl
N@P/carbon[63] 1.1 µg h−1 mg−1 0.9% −0.10 Indophenol 0.1 m HCl
Graphene oxide[64] 9.9 µg h−1 mg−1 38.1% −0.04 Indophenol 0.1 m Na2SO4
Carbon[65] 15.9 µg h−1 cm−2 6.9% −0.30 Indophenol 0.1 m Na2SO4
O/carbon[66] 18.0 µg h−1 mg−1 10.3% −0.45 Indophenol 0.1 m HCL
P/graphene [67]
32.3 µg h−1 mg−1 20.8% −0.65 Indophenol 0.5 m LiClO4
N/carbon[68] 16.4 µg h−1 mg−1 10.6% −0.20 Indophenol 0.1 m HCl
15Graphene oxide[69] 7.3 µg h−1 mg−1 22.0% −0.12 Indophenol 0.1 m HCl
15S/graphene[70]
28.6 µg h−1 mg−1 7.1% −0.85 Indophenol 0.1 m HCl
Note: “15” in from the catalyst means 15N2 as the feeding gas was used in the experiment. All data are listed with consistent effective numbers, which may be slightly
different from the references.
efficient catalysts for water-splitting, the carbon dioxide reduc- specific surface area and good electrical conductivity. At pre-
tion reaction, the NRR, and other reactions.[44] Thermodynami- sent, defect engineering and heteroatom doping can reduce the
cally, the catalytic properties of 2D carbon-based materials have reaction barrier, Bader charge, and spin density of materials;
been improved by doping with various heteroatoms, defects, thus, there is competition between the NRR and HER, through
edges, and heterojunctions.[44a,45] Kinetically, the catalytic activi- synergistic electron transfer interactions between the dopants
ties of 2D carbon-based materials have been further enhanced and surrounding carbon atoms.[73]
by constructing 2D architectures; the mesoporous framework Owing to the straightforward synthesis as well as good
can provide a large specific surface area and thus exhibit thermal stability and electrocatalytic activity, N-doped graphene
many catalytically active sites, a multidimensional conductive is the most popular carbon-based electrocatalysts in experi-
network for efficient electron transport, a large space to accom- mental work. In addition, N is immediately to the right of
modate electrolyte/reactant diffusion, Table 2 and mechanical carbon in the periodic table. They have similar atomic radii and
stability.[46] nitrogen is more electronegative. The electronic configuration
Among these carbon-based catalysts, graphene is an allotrope of graphene can be tuned by doping with nitrogen yet retaining
of carbon and exhibits a 2D structure of single-atom thickness. the 2D planar configuration. Moreover, N-doped graphene
Graphene forms a hexagonal close-packed carbon network, and (metal-free) exhibits unique properties compared with metal-
each atom is connected to three neighboring atoms by covalent based electrocatalysts, yet it is also environmentally friendly.[74]
σ bonds (Figure 3a).[71] Although pristine graphene has been For example, researchers synthesized the first reported N-atom-
used in many applications, some challenges and opportunities doped carbon-based electrocatalysts by carbonization, which
exist for converting dinitrogen into ammonia in ambient exhibit substantial performance in terms of NRR activity.[47]
conditions.[37b,72] The main limitation is that the delocalized π N-doped carbon electrocatalysts are cheap, stable materials for
bonding network of graphene exhibits a low catalytic activity, ammonia synthesis at room temperature (Figure 4), in which
resulting in a high barrier for dinitrogen adsorption. However, the N2 content regulates the N2 chemical adsorption during the
graphene is a useful substrate for the NRR because of its large synthesis. On the basis of electrochemical testing, the catalysts
Figure 4. a) Schematic of N-doped porous carbon (NPC). SEM images of b) NPC-750 °C, c) NPC-850 °C, and d) NPC-950 °C. Ammonia yield:
e) NPC-750 at −0.5 to −1.1 V and f) NPC-750, NPC-850, and NPC-950 at −0.7 and −0.9 V. g) Current efficiency of NPC-750. h) Ammonia production
rates and current efficiency of NPC-750 over ten consecutive cycles at −0.9 V (all data obtained under N2). Reproduced with permission.[47] Copyright
2019, American Chemical Society.
exhibit good performance for the NRR, affording a high Table 3. Calculated activity of 2D carbon-based electrocatalysts to the
ammonia yield of 23.8 µg h−1 mg−1 in 0.05 m H2SO4 Table 3. NRR. (* denotes an adsorption site on the catalyst surface).
N-doped graphene can also exhibit good stability in alkaline
conditions because of its stable chemical structure. The NRR Catalyst Functional Barrier [eV] RDS
performance was improved by tuning the electronic character
N/carbon[47] PBE 0.7 *NHNH2
of the neighboring carbon atoms and by introducing defect
sites to enhance molecular nitrogen adsorption. From both B/graphene[51] PBE 0.43 *NH
2
experimental and numerical results, the NRR activity of the B/graphene[75] RPBE 0.31 *NH
catalyst was strongly dependent on the carbonization at

B/graphdiyne[76] B3PW91 0.44 *NH
different temperatures. The main reason is that there are
different extents of N-doping at different temperatures. Nitrogen- B/graphene [77]
PBE 0.55 *NH
2
doped graphene includes three species: pyridinic-N, pyrrolic-N, SiC[78] RPBE 0.55 *N H
2
and graphitic-N. Pyridinic-N is presented to nitrogen atoms at
the edge of the carbon nanosheet (NS) planes, where each atom B@N/graphene[79] RPBE 0.72 *N
2H2
connects to two carbon atoms and transfers one p-electron to SiC[80] PBE 0.44 *N H
2
the aromatic π system. Pyrrolic-N refers to a nitrogen atom that [81] *NH
O/graphdiyne PBE 0.57
links to two carbon atoms and donates two p-electrons to the
π system. Graphitic-N refers to nitrogen atoms that are incorpo- or other boron compounds (Figure 5a,b).[51] Interestingly, the
rated into the graphene framework and bonded to three carbon NRR activity of graphene was substantially improved by boron-
atoms. As indicated by Zhao and co-workers,[47] the electro doping. The main reason for the improvement was that the
catalyst of the highest nitrogen content obtained at 750 °C matrix charge of the graphene was modulated by the dopants,
carbonization exhibited the best performance: pyridinic (6.2 at%), which were lower in electronegativity than those of carbon
pyrrolic (5.3 at%), and graphitic (2.1 at%). Increasing the atoms. Compared with carbon, boron is electron-deficient and
pyridinic N content of the catalyst can facilitate ammonia acquire electron from substrate. The BC3 site was the dominant
production. DFT calculations confirmed the aforementioned structure. The structure, in which one boron atom was con-
results, indicating that the pyridinic N site exhibits a relatively nected to three carbon atoms in an sp2 conformation, was the
low energy barrier for ammonia synthesis. The improved NRR predominant configuration (>50% abundance when the
activity of this material can be ascribed to a charge-transfer sample was prepared in an H2/Ar mixture), which decreased to
effect associated with the nitrogen dopants. The DFT results ≈35% upon annealing in an Ar atmosphere. The B4C site was
indicate that the doping-induced spin or charge redistribu- produced in the defect of the lattice, whereas the BC2O and
tions of the active site are critical to the improved NRR activity. BCO2 structures were evident at the edge sites of graphene.
However, the identity of the catalytic site remains contentious, Figure 5c shows the ratios of these four types of B-doped struc-
mainly because of 1) the complexity of the nitrogen function- tures (BG-1, BOG, BG-2, and G).
ality in the N atoms and 2) the difficulty of directly ensuring The NRR performances of the aforementioned four species
the source of the N atoms in the NRR catalyst that contains the were studied under N2-saturation in an H-shaped electrochem-
nitrogen species. Researchers have used the Perdew–Burke– ical cell with 0.05 m H2SO4. To study the type of N2 adsorp-
Ernzerhof (PBE) or revised Perdew–Burke–Ernzerhof (RPBE) tion, temperature-programmed desorption was carried out in
functional to evaluate the NRR performance of most catalysts. the first step (Figure 5d). All the main adsorption peaks were
Recently, other p-block-doped 2D carbon materials were located at 100 °C, which corresponds to physisorption, whereas
synthesized for the NRR by electrochemical methods under the chemisorption peaks were almost negligible (260 °C). The
ambient conditions, including B-doped graphene and O-doped peak was enlarged in the BG-1 and BG-2 samples, suggesting
carbon nanosheets (NSs).[48,51,75,82] Analogously to the nitrogen that boron dopants improved the chemical adsorption for dini-
atom, the electronic properties of pristine carbon materials trogen. The NH3 yield and FE of the aforementioned electro-
can be modulated by the doped neighbor atoms, which had catalysts were tested at various applied potentials (Figure 5e,f).
different sizes and electronegativities than the carbon atom. A The BG-1 species exhibited the best NRR performance: an NH3
B-doped graphene electrocatalyst was prepared by annealing yield rate of 9.8 µg h−1 cm−2 and an FE of up to 10.8% at −0.5 V,
oxide graphene at high temperatures (900 °C) with boron oxide which is ten times than the performance of pristine graphene.
Figure 5. a) TEM image of BG-1. b) EDS mappings of BG-1 for B (green), C (red), and O (purple). c) Percentages of different B types in the three BG
samples. d) N2 TPD curves of BG-1, BOG, BG-2, and G. e) NH3 production rates of BG-1, BOG, BG-2, and G at various potentials. f) Ammonia FE values
of BG-1, BOG, BG-2, and G at various applied potentials. Reproduced with permission.[51] Copyright 2018, Cell Press.
Thus, of the four species the BC3 structure is the best site terminal groups, which play key roles in catalytic activation. In
for the NRR in ambient conditions. Double p-block-doped addition to the bandgap, the nitrogen-rich carbon framework
graphene (O/N[48] and B/N[53]) also exhibited substantially of g-C3N4 is another important feature for electrocatalysis.
enhanced NRR activity compared with their single-doped Nitrogen- or sulfur-doping can enhance the electron-donor
counterparts. DFT calculations indicate that the origin of this properties of graphene and other carbon networks, resulting in
enhancement is the synergy between two or more dopants. improved interactions between the carbon and intermediates
Although direct experimental observation of this synergy within during the electrocatalytic processes.[89,93] Researchers typically
the graphene matrix is difficult, theoretical analysis indicates use two basic design principles for synthesizing g-C3N4-based
that dual dopants can tailor the electron–donor properties of electrocatalysts: 1) optimization of the material conductivity
nearby carbon atoms in a manner that enhances intermediate and 2) appropriate tuning of the active sites. To optimize the
adsorption. The most widely studied dual pair for carbon mate- conductivity, g-C3N4 has been composited with conductive
rials is B–N. In 2019, Wang and co-workers synthesized B@N carbon materials. For example, g-C3N4 was incorporated into
doped graphene by three steps.[53] The B–N codoping cases a mesoporous carbon framework to improve the NRR activity
exhibited poor activity toward the HER, which facilitated the of pristine g-C3N4.[98] Active sites can be tuned by various
NRR. Notably, the potential HER active site of the catalytic site means, but the intention is to favorably modify the adsorption
was the inner C atom near the NB pair; the H2 formation step energy of the target intermediates. In one example, a g-C3N4
was energetically unfavorable on the edge C site. Because of the and N–graphene composite achieved NRR performance that
high activation toward the NRR and high overpotential to the is comparable to that of metallic catalysts.[89] Atomic imaging,
HER, the FE of the B–N pair was 9.77% at −0.2 V, exceeding spectroscopic analysis, and DFT calculations revealed that the
most electrocatalysts in ambient conditions. The ammonia interfacial structure of the composite optimized the electronic
concentration was quantified by the indophenol blue method state and ΔGN*, which facilitated electron/charge transfer and
and the ammonia-selective electrode method to ensure the accu- enhanced catalytic activity.[75]
racy of the measured ammonia yield. In addition to B–N-pair Nitrogen vacancies (NVs) of g-C3N4 are usually investigated
graphene, Sun and co-workers synthesized O–N carbon NSs in for the NRR by the electrochemical process (Table 4).[89,94–96]
2019 by using tannin as the precursor.[48] Metal-free polymeric carbon nitride was first chosen in 2018
to convert dinitrogen in the presence of NV defects.[94] Yu et
el. reported that the underlying role of NVs in modulating the
2.2. 2D Carbon Nitride-Based Materials Used in NRR Catalysis π-electron delocalization in the conjugated system of p-doped
g-C3N4 might overcome the high barrier of N2 activation.
Carbon nitride materials are a novel 2D structure with a van However, an ammonia yield of 2.9 µg h−1 mg−1 was achieved
der Waals layered crystal.[83] Similarly to graphene, the struc- on pristine carbon nitride. Chang et al. synthesized S dopants
ture of carbon nitride is a hexagonal carbon framework with in g-C3N4 by annealing at 650 °C in Ar for 4 h, and the S site
nitrogen-atom-substituted carbons through the sp2 hybridiza- exhibited a higher activity for the NRR than did the NVs by
tion of carbon and nitrogen atoms (Figure 2c,e).[84] Currently, both experiments and theoretical work. By DFT calculations,
three structural isomers of carbon nitride are produced by the NRR scaling relation was broken, the reaction barrier was
different experimental processes. Its general formula is g-C3N4 reduced, and the competing HER was suppressed by the S
and it has two major substructures based on heptazine and dopants in the structure. A boron atom has been introduced
poly(triazine imide) units, which exhibit various degrees of into the carbon nitride; boron-doped CN exhibited outstanding
condensation, properties, and reactivities depending on the NRR performance.[92] The boron Lewis acid sites were easily
reaction conditions. g-C3N4 can be synthesized by polymeriza regulated by adjusting the ratios of B and N in boron-doped
tion of urea, thiourea, cyanamide, dicyandiamide, or mela- CN electrode materials, which were closely related to the NRR
mine.[85] The C2N-h2D crystal was successfully prepared via a performance.
straightforward wet chemical reaction (Figure 3c).[86] The third In 2020, Liu and co-workers prepared CN coated on carbon
structure was constructed by condensed triazine (1,3,5-triazine, fiber paper at 600 °C (CN/C600),[95] Figure 6a shows the
C3N3) units with a periodic array of single carbon atom vacan-
cies.[87] Analogously to graphene, 2D g-C3N4 can be obtained by Table 4. Experimental activity of 2D graphitic carbon nitride electro
exfoliation of bulk g-C3N4 materials. Corresponding techniques catalysts to the NRR.
include ultrasonication-assisted liquid exfoliation, liquid-
ammonia-assisted lithiation, post-thermal oxidation etching, Catalysts Yield Detection method Aqueous
and thermal delamination combined with sonication.[88] 15NVs/C N [89]
3 4 21.1 µg h−1 mg−1 Indophenol 0.1 m Na2SO4
In recent decades, pristine and doped g-C3N4 have been used BP/C3N4[90] 347.5 µmol L−1 h−1 Nessler 0.5 m Na2SO4
in various electrocatalytic applications, including the oxygen
Cyano/C3N4[91] 13.4 mg L−1 h−1 Nessler 0.5 m Na2SO4
reduction reaction, HER, and NRR.[88,89] Because of its bandgap
(≈2.7 eV), the semiconducting properties of g-C3N4 render it
15
B/CN[92] 41.9 µg h−1 mg−1 Indophenol 0.5 m Na2SO4
suitable for visible light.[97] However, the degree of condensation S/C3N4[93] 32.7 µg h−1 mg−1 Indophenol 0.5 m LiClO4
of g-C3N4 directly affects its electronic structure and bandgap, NVs/C3N4 [94]
8.1 µg h−1 mg−1 Indophenol 0.1 m HCl
which in turn affect its activity.[90,91] In this regard, bulk g-C3N4 15NVs/C N [95]
2.9 µg h−1 mg−1 Indophenol 0.1 m HCl
3 4
exhibits low activity. By contrast, 2D g-C3N4 exhibits desirable
NVs/C3N4[96] 5.0 µg h−1 mg−1 Indophenol 0.1 m KaSO4
activity because of the abundant structural defects and surface
Figure 6. a) Schematic of CN/C600 synthesis and the carbon nitride structure containing N vacancies. The gray and blue spheres represent carbon and
nitrogen atoms, respectively. b) Cross-sectional SEM image of an individual CN-coated fiber. Inset: enlarged SEM image. c) TEM image of a CN sheet
peeled off from the CN/C600 fiber. Inset: corresponding SAED pattern. d) NH3 yield rate of CN/C500 and CN/C600 at various potentials. e) Faradaic
efficiency of CN/C500 and CN/C600 at various potentials. f) NH3 yield and Faradaic efficiency of CN/C600 over ten successive measurements. g) 1H NMR
spectra of 0.1 m HCl electrolyte background and the electrolytes at various reaction durations when feeding with 15N2 at −0.3 V versus RHE. Reproduced
with permission.[95] Copyright 2020, American Chemical Society.
synthesis. As indicated by the SEM image (Figure 6b), the CN indicate a lattice spacing of 3.23 Å. The NRR performance on
layer was synthesized on carbon fiber; the thickness of the 2D CN/C500 and CN/C600 was evaluated by the indophenol blue
layer was ≈42 nm. The transmission electron microscopy image method. The concentration of NH4+ in the electrolyte was
of the CN thin layer in Figure 6c indicates continuous layered measured by a standard plot, which indicates a highly linear
structures. The diffraction peak of (002) was evident in the relationship between the absorbance and concentration. The
selected area electron diffraction pattern, indicating its closely blank, 0.1 m aqueous HCl, contained ammonium impurities as
packed structure (inset, Figure 6e). Consistent with the selected indicated in the attached chemical impurity list, which explains
area electron diffraction pattern, the (002) diffraction peak at the non-negligible NH3 background in blank 0.1 m HCl. To
27.6° was also evident in the X-ray diffraction patterns, which achieve more-accurate results regarding the NH3 yield rate, the
slope of a yield–time plot was used to eliminate the contami- to their advantageous combination of empty sp2 orbitals
nation from the background. The ammonia catalytic activities (Figure 7a). Because of the presence of the lone-pair electrons
of the two aforementioned catalysts were presented at different of N2, the boron (B) center must have empty p orbitals to accept
potentials by the proposed method. the lone-pair electrons. However, to enhance the BN bonds,
The ammonia production increased with increasing applied the B atoms should have extra electrons that can be donated
potential; the maximum yield was 2.87 µg h−1 mg−1 at −0.3 V. into the antibonding orbital and weaken the nitrogen triple
However, the production decreased at higher applied poten- bond. Substantial charge transfer between the anchored B
tials, which indicates that a more negative potential did not atom and N2 is evident for both adsorption patterns. Gener-
enhance the performance. The FE at −0.3 V versus revers- ally, the charge transfer is one-way from one species to another,
ible hydrogen electrode was 16.8%, whereas that at −0.1 and depending on their relative electron-accepting and -donating
−0.2 V was 62.1% and 33.9%, respectively (Figure 3d). The abilities. Interestingly, charge transfer here is two-way, where
FE at −0.1 V renders CN/C600 among the most selective NRR charge accumulation and depletion are evident for both the
catalysts to date (Table 4). The NH3 yields at −0.3 V were 5.2 and N2 molecule and B atom. This phenomenon is in accordance
3.9 µg h−1 mg−1 as determined by averaging the ammonia with the acceptance–donation process: the B atom accepts
concentration at 3 and 5 h, respectively. These values are lone-pair electrons and simultaneously donates electrons into
obviously exaggerated compared with using the slope of the the antibonding orbital of N2. Therefore, these calculation
mNH3–time plot as the NH3 yield, which indicates the greater results, including high binding strength and two-way charge
reliability of the proposed method. In addition, the NRR per- transfer between N2 and B/g-C3N4, support the design concept.
formance of the CN/C600 layer at −0.3 V was >21-fold higher Subsequently, two similar works were published in 2019:
than that of CN600 powder. The enhanced NRR results empha- the NRR performance on B-doped C2N by using DFT calcula-
size the pertinence of the electrical conductivity of CN to the tions.[102,103] The charge transfer between the B dopants and
NRR performance as confirmed by electrochemical imped- adsorbed N2 molecules on B/C2N follow the variation of B/C3N4.
ance spectroscopy, which indicates several-fold larger charge It inferred that adsorbed and substituted B species exhibit good
transport resistance of CN600 powder than that of the CN/ activity for the NRR because of the coexistence of unoccupied
CN600 layer. In addition, the NRR performance of CN elec- and occupied orbitals, and appropriate adsorption strengths
trodes exhibited a higher mass activity of 3.92 µg h−1 mg−1: for key intermediates. More importantly, the sp2-hybridized
an FE of 5.13% at −0.3 V for the thinner CN layer (11 nm). orbitals can suppress the HER.[102] In addition to the three
By contrast, the NRR performance was reduced to 1.16 µg aforementioned popular carbon nitride structures, Wang and
h−1 mg−1 for a thicker CN layer (59 nm). The decreased co-workers evaluated a theoretical structure: C9N4.[106] Based
FE for the thinner CN electrode was likely caused by the on DFT calculations, they indicated that the formation energy
incompletely CN-covered surface, whereas the better NH3 of C9N4 was lower than that of the experimentally synthesized
yield was a result of low CN mass-loading. The long-term C2N crystal. The bonding of boron on C9N4 was 6.29 eV, larger
stability of a material is a key evaluation standard in industrial than that of any other doped structures. This might be attribut-
applications. In Figure 6f, there was no obvious change in the able to the low coordination number of the N atoms around
NH3 yield and FE after ten successive NRR tests. The origin the holes. Then, the B atom can acquire more electrons from
of ammonia during the reaction was further checked by using N and offer strong adsorption energy to N2 in the initial step.
isotope-labeled 15N2 (Figure 6g). The trace 14NH4+ impurity in The rate-determining step (RDS) is the last step, indicating that
HCl was confirmed by 1H nuclear magnetic resonance meas- the desorption step is energetically costly process if B atom
urements, in accordance with the ultraviolet–visible spectra. receive more extra electrons from the substrate (Table 5).
There was an obvious peak at 6.99 ppm after 15N2 gas bubbling
for 1 h at 0.3 V, attributable to the 15NH4+ signal.
Compared with experimental works, researchers routinely 2.3. 2D BP Used in NRR Catalysis
use boron-decorated carbon nitride to improve the NRR
performance of pure materials in theoretical research.[99–107] BP has a 100-year-long history; its bulk form was first
As previously mentioned, g-C3N4 is a promising, active, stable, synthesized in 1914.[108] BP is a layered semiconductor with
and metal-free photocatalyst; and has been applied to various an orthorhombic crystal structure; one phosphorus atom is
reactions. It consists of threefold-coordinated and twofold- covalently bonded with another three atoms to form a puck-
coordinated N atoms, and threefold-coordinated C atoms that ered honeycomb structure in a single layer (Figure 3f).[109] The
are bonded to three N atoms (Figure 7d).[101] The twofold-coor- three bonds take up all three valence electrons of phosphorus,
dinated N atoms impart g-C3N4 with a capacity for incorpo- resulting in a bandgap of 2 eV that can be tuned by controlling
rating an extra atom. Wang generated two NB bonds and in the thickness of the layer. To date, BP has been widely studied
so doing stabilized the B atom on g-C3N4 yet left one occupied in electronic and optical devices. However, only a few studies
sp3 orbital and one empty sp3 orbital. Therefore, the anchored have reported on its applications in electrocatalysis, which may
B atoms exhibited strong interactions with the gas-phase N2 be because of its low stability in electrocatalytic conditions and
molecules. Moreover, large periodic vacancies of g-C3N4 impart poor electrical conductivity. Recently, researchers found that
sufficient space for adsorption and subsequent reduction of various forms of bulk BP (such as thin films and particles)
N2. Generally, the chemisorption of gas-phase N2 onto the exhibit electrocatalytic activity for the NRR that is comparable
surface of the catalysts is a prerequisite for an efficient NRR. to commercial TM-based catalysts. However, bulk BP has a low
For such catalysts, the strong bonding with N2 can be ascribed density of active sites, which likely limits its electrocatalytic
Figure 7. a) Simplified schematic of N2 bonding to transition metals. b) Electronic configuration of a pure B atom and a B atom with sp3 hybridization.
sp3 hybridization of B will result in four sp3 hybrid orbitals, in which three of them are half-filled and the remaining is empty. c) N2 binding motifs to
the B atom that is stabilized on the substrate. d) Design concept as a photocatalyst for N2 fixation. Gray, blue, and pink spheres represent C, N, and B
atoms, respectively. e) Optical absorption spectra of pure g-C3N4 and B/g-C3N4. (f) Free-energy files of the NRR by enzymatic mechanisms at various
applied potentials. Reproduced with permission.[101] Copyright 2018, American Chemical Society.
performance. Compared with its bulk, 2D BP NSs synthesized Atomic force microscopy confirmed that the flat and uniform
by liquid exfoliation has an increased number of exposed active BP NSs were <5 nm thick. The ammonia production perfor-
sites and increased surface area.[110] Therefore, the intrinsic mance of BP NSs was studied in an H-type electrochemical cell
benefits of this ultrathin lamellar structure can facilitate devel- with N2-saturated 0.1 m HCl.
opment of BP for efficient electrocatalysis. Yu and co-workers The researchers measured the quantity of ammonia
designed a highly efficient ammonia catalyst by depositing BP produced by the indophenol blue chromogenic response with
NSs onto an indium tin oxide substrate in ambient conditions or without optical illumination at various applied potentials.
by using solar and electric energy (Figure 8a).[111] In the experi- The ammonia production rate and FE under optical illumina-
mental work, ultrathin BP NSs were fabricated by an improved tion at −0.4 V were 102.4 µg h−1 mg−1 and 23.3%, respectively,
electrochemical method in which tetra-n-butylphosphonium which are respectively 3.25× and 4.24× that under no light at
was integrated into the substrate by the applied potential. −0.4 V. The synergy of the solar and electric energy facilitates
Figure 8c–f shows the results of BP NS characterization. the excellent ammonia yield and efficiency, decreases the reac-
tion kinetics barrier, and enhances the production selectivity.
Table 5. Calculated activity of 2D graphitic carbon nitride electro As predicted by Wang and co-workers, few-layered BP exhibited
catalysts to the NRR.
an improved NRR performance: an FE and NH3 production
rate for the NRR in acidic aqueous 0.01 m HCl as high as 5.07%
Catalyst Functional Barrier [eV] RDS
and 31.37 µg h−1 mg cat−1, respectively.[112] It confirmed that the
[99] *N
B/CN PBE 0.48 2H electron distribution in the molecular orbital of BP NSs is the
B/C2N[100] PBE 0.51 *NH
3 key factor for nitrogen fixation. DFT calculations identified the
B/C3N4[101] PBE 0.20 *NH
3
zigzag and diff-zigzag edges of the catalyst as active centers.
The performance of BP has been optimized by strategies such
B/C2 N[102] PBE 0.15 *NHNH
as defect and doping.[113] Zou and co-workers deposited BP NSs
B/C2N[103] PBE 0.35 *NH NH
2 3
on CdS, which improved the catalytic activities of the NSs for
B/C3N4[75] RPBE 0.89 NH3 ammonia synthesis.[113b] The researchers studied the effect of
B/g-C2N[104] PBE 0.31 *N H
2 the quantity of BP on the ammonia production performance
B/g-C2N[105] PBE 0.18 *NHNH of the BP/CdS. The catalytic activities of the catalysts initially
B/C9N4 [106]
PBE 0.52 *N H increased and then decreased with increasing quantity of BP.
2
The maximum amount of ammonia production increased
B/C2N[107] PBE 0 NA
to 4.08 µg h−1 mg−1 when the BP NSs content up to 1.5 wt%.
Figure 8. a) Schematic of the synthesis of BP NSs and BP electrodes. b) Optical image of bulk BP crystals. Reproduced with permission. [119] Copyright
2020, John Wiley & Sons, Inc. c) Structure of BP. d) SEM, c) TEM, and f) HRTEM images of BP. g) AFM image of a single sample. Reproduced with
permission.[111,112] Copyright 2019, John Wiley & Sons, Inc.
Ma and co-workers found that converting N2 into ammonia substrates for graphene- and MoS2-based electronic and optical
on defects phosphorene followed the dissociate mechanism devices. It is prohibitively inert for electrocatalysis. Pristine
and exhibited a high kinetic dissociation barrier (1.28 eV, h-BN also has other problems, such as poor conductivity and
Table 6).[113a] low selectivity. Researchers have enhanced the electrocatalytic
Researchers have studied the N2 fixation performance of activity of BN NSs by using physical and chemical methods
B-modified BP by DFT calculations (Table 7). Dinitrogen in various experimental works (Table 8). Sun and co-workers
adsorbed onto the B atom by end-on adsorption when B demonstrated that the edge sites of BN have the ability to con-
adsorbed onto a pristine BP surface.[115] Dinitrogen does not vert ordinarily inert N2 into NH3 by electrochemical methods
easily adsorb onto the surface of pristine BP; the large energy in ambient conditions.[120] There was a good NRR activity in
gap between the highest occupied molecular orbital and the acidic solution, and the unsaturated boron at the edge sites was
lowest unoccupied orbital can impart difficulties to driving the the catalytic site for N2 activation. Zhao and Chen[41] tuned the
charge transferred between the proton and the electron, which electronic properties of h-BN by coupling it with metal nano-
is one of the obstacles for N2 fixation. B modification reduced particles. The resultant composite exhibited increased the NRR
the reaction barrier by 150% compared with the energy of pris- activity, which originated from the activation of adsorbed N2
tine BP. In substituted catalysts, the dopant B atoms serve as and improved selectivity for the six-electron reduction pathway
Lewis’s acid and catalytic centers by side-on adsorption. Wang from nitrogen to ammonia.[41]
and co-workers indicated that B dopant exhibited a high N2 Similarly to other 2D NSs, heteroatom decoration is also a
fixation activity; the largest reaction barrier for the material was useful tool for improving the catalytic performance of h-BN.
0.19 eV in the distal pathway.[116] By using DFT calculations, Du and co-workers tested the
possibility of using boron-doped boron nitride edges as NRR
electrocatalysts: they evaluated the N2 adsorption activity and
2.4. 2D Boron-Based Materials Used in NRR Catalysis subsequent hydrogenation pathways.[126] The B atoms doped
onto the BN edges were one of two types: B adsorbed by two
h-BN is another family of graphite, known as white graphene.[118] nitrogen atoms on the zigzag edge (B@ZZBN) and bridge
Bulk h-BN has a layered structure with lattice constants of sites of BN armchair edges (B@ACBN) (Figure 9). The zigzag
2.50 Å and interlayer distances of 3.33 Å (Figure 3g).[119] Because edge of BN was the most stable site for boron-doping. For the
h-BN NSs are insulators, they are usually applied as dielectric armchair edge, B preferentially bonded at the vacant site and
Table 6. Experimental activity of 2D black phosphorus electrocatalysts to the NRR.
Catalyst Yield FE Potential [V] Detection method Electrolyte

BP[112] 31.4 µg h−1 mg−1 5.1% −0.7 Indophenol 0.01 m HCl
BP[114] 40.3 µg h−1 mg−1 N. A. N. A. Nessler’s 0.1 m HCl
BP[113b] 4.1 µg h−1 mg−1 N. A. N. A. Nessler’s 0.5 m Na2SO4
N/BP[113a] 18.8 µg h−1 mg−1 21.5% 0 Indophenol 0.1 m KOH
BP[111] 102.4 µg h−1 mg−1 23.3% −0.4 Indophenol 0.1 m HCl
Table 7. Calculated activity of 2D black phosphorus electrocatalysts to composition and phase of BN changed by incorporating the
the NRR. carbon dopant, indicate synthesis of C-BN. The excellent NRR
performance of C-BN NSs can be ascribed to the carbon dopant
Catalyst Functional Barrier [eV] RDS and the large quantity of introduced structural defects.
B/BP[115] PBE 0.34 *
NH3 Ismail-Beigi and Tang first predicted a 2D boron sheet in
B/BP[116] PBE 0.19 *N H
2
2007.[130] In the periodic table, boron is the neighbor of carbon
BP[113b] PBE 1.50 *N with three valence electrons in the 2s and 2p orbitals; thus, it
2H
[75] *
can undergo sp2 hybridization similarly to carbon.[131] A trian-
B/BP RPBE 0.89 N2H
gular and hexagonal motif structure is energetically more stable
BP[117] PBE 0.28 *
NH3 than those of only triangular lattices or hexagonal lattices. More
importantly, the special structure will provide rich chemistry
in so doing generated a five-membered ring. For the NRR on applications (Figure 3h).[34a,130,132] Currently, theoretical tools
the catalyst, apart from the chemisorption of N2 molecules onto predict new 2D boron sheets, including the snub-sheet,[133]
the catalyst surface, desorption of NH3 is another determining α-sheet,[130] β12-sheet,[134] g2/15-sheet,[135] and struc1/4-sheets.[136]
factor that might influence the catalytic performance. Among these structures, the α-sheet is the most stable struc-
Higher adsorption energy corresponds to higher surface ture,[137] which is directly pertinent to boron nanotubes.
activity for N2. However, this enhanced energy and activity Researchers synthesized the β12 sheet on Ag and Cu surface
might induce a higher bonding strength between NH3 and by direct evaporation of a pure boron source.[37e] These boron
the active sites. Although the catalysts exhibit sufficient cata- sheets are widely used in superconductors,[138] hydrogen
lytic performance for the NRR, the NH3 desorption step is not storages,[139] and the oxygen evolution reaction.[140] Remarkably,
straightforward because of the high free-energy change, which the 2D sheets exhibited a typically porous characteristic struc-
might result in catalyst poisoning. For example, the adsorp- ture because of the hexagonal hole, which provided sufficient
tion of N2 molecules to B@ACBN was as low as −1.97 eV; thus, space to accept foreign atoms.
desorption of NH3 from B@ACBN was as high as 0.85 eV. Distinct from other well-known 2D materials, the sp3 hybrid-
However, at the zigzag edge, desorption of NH3 was only ized orbital of the boron atom can form B-to-N π-back-bonding,
0.35 eV. On the basis of such calculations, boron-doped h-BN which can facilitate N2 activation; however, its use for NRR
exhibits promise as an ideal NRR catalyst; it can facilitate the electrolysis remains unstudied.[141] Researchers first studied the
NRR because of the lower energy barrier compared with that NRR performance on a 2D boron sheet by using DFT calcu-
of TM-based catalysts in acidic media. Similar experimental lations in 2018.[42] The geometrical configurations of pristine
work confirmed the aforementioned DFT results (Table 9).[120] boron sheets are ideal 2D materials; Figure 10a,b shows the
Sun and co-workers demonstrated that defect engineering optimized configurations, corresponding to the α-sheet and
can modify the activity of h-BN for the NRR; they improved β12-sheet top views, respectively.[42] Therefore, two different boron
its activity by the presence of edge boron atoms that were atoms exhibit different electronic properties: the hole atom,
energetically favorable for nitrogen adsorption. Therefore, labeled 1 in Figure 10a,b, is connected by two 3c–2e bonds and
these materials also have potential in NRR applications one 4c–2e bond; whereas the triangular atom, labeled as site
when appropriate engineering strategies are used. Tang and 2, is connected by delocalized π-bonds, in which site 3 is con-
co-workers doped carbon atoms into BN: although pristine nect by 3c–2e bonds. Starting from N2 adsorption, the barriers
BN exhibited moderate NRR performance,[127] the researchers of each elementary reaction with distal and alternating mecha-
substantially improved the catalytic activity for the NRR by nisms were estimated by DFT calculations.[33b,142] Hydrogen
doping carbon into BNs, where the barrier of the RDS was atoms were added one by one to the adsorbed species, and DFT
reduced to 0.55 eV. The C dopant can modulate the adsorption calculations were used to find the minimum energy configura-
energy of the intermediates, without influencing the activation tion (Figure 10c,d). Site 2 of the alpha sheet provided the best
ability of pristine BNs. Experimental work in 2020 confirmed NRR activity: ΔGmax = 0.77 eV.
such calculations.[121] Researchers also prepared C-BN powder To further check the potential of the aforementioned boron
by a template-based process at 900 °C for 6 h in an N2 atmos- sheet as an electrocatalyst for converting N2 into NH3 in
phere and characterized the structures of the samples by X-ray ambient conditions, researchers have studied the catalytic
diffraction and X-ray photoelectron spectroscopy. The chemical activity of a boron sheet deposited onto Ag(111) and Cu(111)
Table 8. Experimental activity of 2D boron-based electrocatalysts to the NRR.
Catalyst Yield FE [%] Potential [V] Detection method Electrolyte

15C/BN[121]
36.7 µg h−1 mg−1 6.5 −0.55 Indophenol 0.1 m HCl
15BN[120]
22.4 µg h−1 mg−1 4.7 −0.75 Indophenol 0.1 m HCl
15B C[122]
4 26.6 µg h−1 mg−1 15.9 −0.75 Indophenol 0.1 m HCl
Boron[123] 3.1 µg h−1 mg−1 4.8 −0.14 Indophenol 0.1 m HCl
Boron [124]
13.2 µg h−1 mg−1 4.0 −0.80 Indophenol 0.1 m Na2SO4
15
Boron[125] 23.1 µg h−1 mg−1 25.2 −0.40 Indophenol 0.05 m Na2SO4
Figure 9. a–d) Optimized configurations of N2 bonding to B@ZZBN and B@ACBN edge. e–h) Charge density difference patterns of N2 end-on
B@ZZBN, side-on B@ZZBN, end-on B@ACBN, and side-on B@ACBN; the positive and negative charges are shown in yellow and cyan, respec-
tively. Blue, pink, and white spheres represent the N, B, and H atoms, respectively. Reproduced with permission.[126] Copyright 2019, Royal Society of
Chemistry.
surfaces, corresponding to experimental work.[33b,142] Ammonia methods is still low and far away from the requirements of
was experimentally synthesized on a 2D boron sheet in 2019.[124] industry. There are two main reasons that limit the efficiency
Sun and co-workers exfoliated the material by the ultrasonic of this type of reaction. First, the strong nonpolar bond of the
method for 4 h and characterized the NSs (Figure 10e). In the N2 molecule has a considerably high activation barrier. This
context of analyzing the possibility of N2 adsorption onto the property is inherent to the N2 molecule, which is not readily
electrocatalyst, Figure 10f shows the electron density difference activated. The other limitation is the restriction of the catalytic
of N2 adsorbed onto various catalytic sites f. From a Bader anal- capability, which can be substantially increased after modifica-
ysis, 0.45 and 0.38 electrons were injected into the N2 molecule. tion. With the high demand for NRR catalysts, some research
The boron sheet achieved an NH3 yield of 13.22 µg h−1 mg−1 groups have focused on developing strategies for designing
and an FE of 4.04% in neutral media at −0.8 eV. The B atoms catalysts. This section summarized strategies—based on recent
of both oxidized and H-deactivated boron NSs exhibited better work—for efficiently designing nanostructured N2 fixation cata-
NRR activity than pristine BN NSs (by DFT calculations). Theo- lysts, such as enlarging the active surface area, doping single
retical work studied the conversion of dinitrogen into ammonia atom, stabilizing vacancies, and developing biomimetic devices.
on boron phosphide and boron arsenide.[129] The (111) surfaces Although some strategies are not unique to the N2 fixation
of boron phosphide and boron arsenide exhibited superior reaction, these commonly reported strategies are widely recog-
catalytic performance for the NRR. nized as potential candidates to break through the limitation
of low-efficiency ammonia synthesis. The intrinsic NRR cata-
lytic reactivity and selectivity of electrocatalysts are improved
3. Catalyst Design and Development Protocols by rational strategies, including defect engineering and
heteroatom doping. In terms of the defect engineering method,
Although researchers have applied many nanostructured vacancy could obviously modulate the electronic structure of 2D
electrocatalysts to various dinitrogen conversion methods, to materials, improve the charge distribution of whole substrate,
date the efficiency of ammonia synthesis by electrochemical tune the surface-adsorption property for reaction intermediates
and further enhance the catalytic performance. And the
Table 9. Calculated activity of 2D boron-based electrocatalysts to the surface electronic structure and adsorption ability of inter
NRR. mediates are all modulated by introducing the foreign atom
in the original 2D metal-free materials. Especially, the incor-
Catalyst Functional Barrier [eV] RDS poration of non-metal atoms can not only tune the bandgap
BN[126] PBE 0.29 *NH of catalysts resulting in enriched charge density and higher
2
intrinsic conductivity but also lower the binding energies of
C/BP[127] PBE 0.55 *N H
2
reactants, leading to a low-onset overpotential required to drive
Si/BN[128] RPBE 1.22 *N H
2 the electrocatalytic process.
*NH
Boron PBE 1.21 3
phosphide[129]
Boron[123] PBE 0.39 *N H
2 3.1. Defect Engineering
[124] *NH
Boron PBE 1.80 3
Advanced catalyst syntheses are accompanied by introducing
Boron[42] RPBE 0.77 *N H
2
intrinsic defects and impurity phases.[143] Defect engineering
BN[75] RPBE 0.43 *NH
2
is an effective strategy for tuning and controlling the nature of
Figure 10. Optimized structure of boron monolayers: a) α-sheet and b) β12-sheet. Calculated reaction free energy ΔG: c) site 2 of α-sheet, d) site 1 of
β12-sheet. e,f) SEM and TEM images of boron nanosheets. g) Time-dependent current density curves of BNS/CP at various potentials in 0.1 m Na2SO4.
h) NH3 yields and FEs for BNS/CP at the corresponding potentials. i) Mass of NH3 production at the electrodes at −0.8 V with a boron sheet, bulk
boron, and carbon. Reproduced with permission.[124] Copyright 2019, American Chemical Society.
materials, such as electronic and chemical properties. Generally, In addition to the desired effects on the catalytic activity of
engineered defects are classified into three main categories the materials, intrinsic defects have negative effects. Dong et al.
based on the dimensions of the defects: point, line planar, and are one of the first research groups to have introduced NVs as
volume. Depending on the catalytic purposes, researchers have defects in graphitic carbon nitride photocatalysts for ammonia
used various types of defects. This section discusses the posi- production.[89] Researchers have also developed sulfur vacan-
tive and negative impacts of defects. Defect materials usually cies as efficient catalysts for the NRR.[144] The excited electrons
exhibit remarkable activities compared with those of defect-free can be relaxed at the defect states that form in the bandgap
materials. Many studies reveal that induced intrinsic defects energy. Therefore, only electrons that can absorb high photon
in 2D electrocatalysts help to reduce these limitations and energies and overcome the defect level are useful in terms of
enhance electroactivity. Such improvements might be attribut- the NRR. To control the formation of desired defects, various
able to the following aspects. First, engineered defects, such syntheses are useful in terms of controlling the surface and
as anion vacancies and dopant-induced impurity phases, can bulk defects. Several recent approaches can be used to con-
act as trapping centers that capture electrons or holes, which trol the defect formation; such as high-temperature treatment
inhibit charge recombination and promote their separation. in a reducing or an inert atmosphere, chemical reduction,
Additionally, point defects play an important role as active sites vacuum activation, ultraviolet irradiation, phase transforma-
that facilitate adsorption and activation of reactant molecules. tion via fast heating, ball milling, plasma etching, and lithium-
Third, creating defects can reduce bandgap energy, resulting induced conversion.[145] Accordingly, NVs can be effective for
in an increase in the light absorption ability. Exhibiting many NRRs. Because the NVs sites can exhibit an enhanced ability to
generated electron–hole pairs benefit for N2 activation if the activate N2. NVs can also affect the electronic and band struc-
semiconductor can absorb light in a long-wavelength region. ture of the nanomaterials. Researchers have studied many
types of TM nitrides by computational studies.[27,146] Many the catalytic reaction.[47,90,93] Heteroatom doping can induce
experiment-based achievements have been reported. Recently, charge redistribution, which can change the chemisorption
Yu and co-workers reported a defect engineering strategy for mode of the reaction gas, and thus enhance the NRR activity.
introducing NVs into metal-free carbon nitrides and in so doing Heteroatom dopants can change the electronic properties of
attained active electrocatalytic NRR performance.[94] In the neighboring carbon atoms because of atomic sizes and electro
context of further studying the effect of the NVs on N2 activa- negativities that differ from those of carbon atoms. Inspired
tion, theoretical calculations confirmed that the N-defect site is by this understanding and the effect of doping, researchers
the N2 activation position and feasibility of N2 activation. The hypothesize that ideal doped carbon materials can also exhibit
calculations indicate that dinitrogen can adsorb to a slight extent high NRR activities. Doped carbon materials facilitate chemical
onto the pristine material; N2 can adsorb in the form of binu- adsorption of N2 and further speed up dissociation of N2 at the
clear, end-on coordinated mode in the presence of NVs in the defect sites.[127] However, different groups may report different
materials. Some studies have investigated the effect of NVs in NRRs, even though they designed nearly the same catalysts,
carbon nitrides on the electrochemical NRR. Such studies can because there was no recognized experimental standard and
help researchers design various catalysts that exhibit enhanced means of detection until recently. Researchers recently prepared
performance by inducing NVs, and in so doing generate more an N-doped carbon electrocatalyst as a cheap, stable material
active sites for activating N2. The positive effect of NVs can for ammonia synthesis at room temperature, in which the N
also be expanded into photocatalysis. Graphitic carbon nitride content during the synthesis regulated the N2 chemical adsorp-
(g-C3N4) is a common photocatalyst for various reactions; many tion. Regarding electrochemical testing, the catalyst exhib-
strategies have been developed to engineer its properties and ited good performance for the NRR: a high ammonia yield of
thus enhance performance. For example, Wang and co-workers 23.8 µg h−1 mg−1 in 0.05 m H2SO4. In addition, the material
designed various types of g-C3N4 that exhibit excellent perfor- exhibited good stability in alkaline conditions. Thus, tuning
mance in the photocatalytic HER or some organic reactions.[147] the electronic character of the neighboring carbon atoms
Introducing NVs into g-C3N4 generates N2 activation sites and by introducing defect sites in a manner that enhanced mole-
enhances its photocatalytic NRR activity. cular nitrogen adsorption improved the NRR performance of
Recently, Wang and co-workers synthesized g-C3N4 with nitrogen-doped carbon materials. As evaluated by both experi-
NVs by annealing it in nitrogen gas.[89] After inducing the NVs, mental and calculation results, the NRR activity of the catalyst
the NV sites selectively adsorbed and activated N2. The NVs was strongly dependent on the carbonization at and tempera-
can enhance the separation efficiency of the photogenerated ture. The main reason for this dependence is that there were
electron, and the carriers transfer from the g-C3N4 to the different extents of N-doping at different temperatures.[47]
adsorbed N2. Therefore, g-C3N4 with NVs converts N2 into NH3 Boron is an important doping element that imparts electron
in ambient conditions. Thus, vacancy sites in the catalysts can deficiency to a substrate, leading to an improved electrocatalytic
induce extra sites for N2 activation and adsorption in a manner activity. In particular, boron has three valence electrons in the
that enhances the electrocatalytic and photocatalytic NRR per- 2s22p1 and an empty orbital that is similar to the d orbital of
formance. Many other nitrides exhibit substantial potential in TMs (Figure 10b).[132] The empty orbital of B sites can also
catalysis; researchers should search for ideal nitrides for the prevent binding of Lewis acid H+ at those sites (under acidic
NRR in accordance with DFT results. Then, NVs in the nitrides conditions), which can promote the NRR FE and decrease the
can be further induced in a manner that enhances the corre- HER. To investigate the NRR effect of various boron structures,
sponding NRR performance by various defects engineering our group built 21 models by incorporating one boron atom
strategies, such as plasma etching and electrochemical corro- into eight 2D materials: graphene, BN, boron sulfide (BS),
sion. Researchers should study the NV effect on the NRR by BP, s-triazine-based g-C3N4 (S), tri-s-triazine-based g-C3N4 (T),
experimental and computational strategies to gain clear insight h-MoS2 (h), and T-MoS2 (t) (Figure 11a).[42] To evaluate the NRR
into the effect. activity on the boron active sites (Figure 11b), we summarized
the elementary reactions that are pertinent to distal and alter-
nating pathways. We evaluated the NRR performance that was
3.2. Heteroatom Doping examined by the maximum energy, ΔGmax, which is an indi-
cator of all the required reaction energy input; thus, researchers
As previously mentioned, most pristine 2D NSs are inert usually apply ΔGmax to determine the RDS for the NRR.
toward electrocatalysis. Therefore, preparing high-performance Figure 11c shows the calculated ΔGmax versus E(N*) − E(N*)Ru,
2D catalysts that exhibit favorable compositions, thicknesses, where E(N*) is the binding energy of a single N and is an indi-
defects, and surface properties is important for practical appli- cator for NRR catalysts.[148]
cations. Many dopant atoms improve the catalytic activity of We used N-adsorption on Ru as a reference. In the volcano
2D monolayers. Chemical doping with heteroatoms can tune curve, the closer to peak, the better NRR catalytic performance
electronic properties, manipulate surface chemistry, and of single-boron-based materials. The δ exhibits an intrinsic
modify the elemental composition of 2D nanomaterials in a relationship with the N2 adsorption and catalytic activities.
manner that enhances the NRR performance, as reported in Compared with state-of-the-art descriptors such as molecular
recent decades.[76,113a,128] To date, heteroatom doping can impart orbital theory and the work function, δ of the p orbital is more
catalytic activity to various 2D nanomaterials. In addition to directly relevant to material properties and can be conveni-
metal-atom-doped catalysts, heteroatom (e.g., N, P, S, and B) ently used to activate N2. To further understand the relation-
doping can induce defects that serve as the active sites for ship between the catalytic performance and electron transfer,
Figure 11. a) Schematic of a single boron atom supported on eight 2D materials in various substitution environments. A indicates the most stable site
for boron adsorption on an ideal 2D substrate surface. S indicates one boron atom substitution in the 2D materials. D indicates direct dinitrogen fixa-
tion on different boron atoms of BN and BS. b) Model of NRR on a boron site. c) Volcano diagrams of ΔGmaxNRR versus E(N*)−E(N)Ru. d) Computational
screening of 14 catalyst combinations ΔGmaxHER and ΔGmaxNRR versus Bader charge transfer (eV) from the boron atom to the substrate. e) Kinetic barrier
path for N2 conversion into NH3 catalyzed by B–graphene.
Figure 11d shows ΔGmax for the NRR and ΔGmax for the HER the high-throughput screening with DFT calculation further
versus the Bader charge. Figure 11d indicates that the less enhance the rate of exploration process, However, the expen-
boron atom charge transfer to the substrate of the catalyst, the sive and time-consuming hinder it the industrial application.
smaller the energy barrier for the NRR, except for h-S1. Because Machine learning (ML) is a suite of data-driven computational
more electrons were remaining in the boron atom active site, methods that are ideally suited for modeling and interpreting
there was more electron injection into the antibonding state, vast amounts of complex multidimensional data.
and the sp3 hybrid orbitals were much more easily accepted N2. Compared with the traditional DFT calculation, ML
Furthermore, the proximal N atom was favorable for hydrogen- technique with trained models study the underlying rules
ation because it was always positively charged in the N2* inter- and patterns in a data set to produce a descriptor capable of
mediate species. Figure 11e shows the kinetic barrier of the best indicating predictions about new materials. And the process
electrocatalyst (B–graphene). includes data collection, featurization, algorithm selection and
model training, and model validation. Data collection is the
process of gathering and measuring material informatics from
3.3. Machine Learning reliable website and papers. At present most materials data
come from the following three sources: structure databases,
Currently, the discovery of higher efficiency, green electro experimental measurements or computation results, and the
catalysts synthesized still depends on the trial-and-error literature base. There are many database websites contain the
method in experimental works. With the development of structure or space group of most materials, containing Materials
computer, first-principles computational chemistry is being Project, Harvard Clean Energy Project, Inorganic Crystal Struc-
increasing applied to accelerate catalysts discovery. Especially ture, etc. And the near exponential rises in numbers of papers
published provides huge resource materials that scientists can can correspond to appropriate variation and adjustment of the
access to build data sets. The structures and properties of the bonding strengths of reaction intermediates on the catalyst
materials contained in these papers, synthesis and processing surface, affording improved catalytic properties. Constructing
conditions, and other provenance data are extremely valuable heterogeneous single atom catalysts (SACs) is another prom-
for elucidating materials structure–property relationships. ising approach for facilitating NRR performance because of
The collected data should be washed and transformed into a the high activities of single metal atoms. For example, single B
specifically mathematical for training ML models. The process atoms used for the NRR can exhibit improved ammonia yield
is called feature engineering, which divides into descriptor and selectivity. SACs can be conveniently synthesized from 2D
generation, and selection. The descriptor is applied to sum- nanosubstrates.
mary the relationship of between the materials property and Second, it is important to understand the obscure funda-
feature, describing structure, composition, and physicochem- mental mechanisms of heterogeneous NRRs. The NRR is a
ical. In the past decades, d-band center, electron occupancy, considerably complicated multistep reaction; many details
EXANES, Bader charge, and bandgap of materials were pro- remain unclear. DFT is a powerful tool that can be used to
vided by many research groups. However, no single descriptor predict possible active sites, the RDS, and the intermediates of
can be applied to describe all materials. Therefore, it is crucial the reaction. Combining theoretical analysis and experimental
to select the most suitable descriptors for training model in ML results is advantageous toward revealing the reaction mecha-
process. In other words, the simpler principle, the less time for nisms of the NRR on a molecular scale. More attention should
modeling. focus on building reasonable models that are close to the actual
reaction systems. Furthermore, theoretical computations based
on the material genome method and other approaches might
4. Current Achievements and Challenges provide a feasible means of designing novel catalysts. How-
ever, most research, even in theoretical research, ignores some
On the basis of thermodynamics, ammonia can be synthesized critical theoretical challenges. To achieve excellent NRR results
by an electrochemical NRR. Electrocatalytic artificial nitrogen for a catalyst, most papers ignore the desorption energy of
fixation is an active field of research interest because of the ammonia in the last step, even if the value is larger than 1 or
following advantages. 1) NH3 synthesis can be achieved by using 2 eV. Researchers have used the PBE functional to evaluate the
abundant N2 and H2O as raw materials in mild conditions, NRR performance of most catalysts, but they have calculated
leading to lower cost compared with current production. 2) The many NRR whole-reaction energies because the PBE cannot
NRR without carbon dioxide emissions can alleviate environ- exactly describe the energy of N2. Therefore, many values
mental damage. 3) The fixation can provide a potential route to have been reported, from −0.96 to −4.81 eV; one paper even
store nonpolluting and renewable solar energy and electricity, reported two different values. In accordance with the experi-
in the form of a hydrogen carrier and carbon-free fuel. To date, mental results of all the fundamental substances in the reaction
research indicates that such a method has two major problems: (N2, H2, and NH3), the reaction energy of an elementary reac-
low rate and selectivity. In addition, ammonia production is nor- tion is constant and equal to −0.39 eV. Nørskov and co-workers
mally accompanied by simultaneous generation of hydrogen and reported that the RPBE is a more reasonable functional for cal-
hydrazine, resulting in low selectivity toward NH3. More impor- culating the NRR because the value (−0.42 eV) of the revised
tantly, current understanding of the fundamental mechanisms PBE is close to the experiment value[6,149]
of N2 photoreduction and electroreduction remains limited
because of the considerably complicated reaction. To facilitate ∆ r H = HNH3 − 1 / 2HN2 − 3/2HH2 = ∆ f Hgas = − 45.90 kJmol −1 (1)
the development of heterogeneous nitrogen fixation in ambient
conditions, we propose suggestions for further improving the
∆ r S = SNH3 − 1 / 2SN 2 − 3 / 2SH 2 = 192.77 − 191.61 × 0.5 − 130.68 × 1.5
performance of electrocatalytic NRR systems.
First, the design of more-efficient, cost-effective, environ- = − 99.05 J mol−1K −1
mentally friendly, and robust catalysts is desirable. It is essen-
(2)
tial to develop novel technologies for nanomaterial synthesis
because the various compositions and morphologies of nano-
structured materials play important roles in enhancing the cata- ∆ r G = ∆ r H − ∆ r ST = − 45.90 + 0.099055 × 273.15
lytic nitrogen fixation performance. Interfacial control, surface (3)
= − 18.85 kJ mol−1 = − 0.195 eV
engineering, chemical modification, and other considerations
are promising means of optimizing the catalyst performance.
In particular, defect catalyst surface substantially impacts ∆Gtotal = 2 ∗ ∆ rG = − 0.39eV (4)
the catalytic performance. Compared with flat bulk surfaces,
roughened surfaces that exhibit many defects and doped heter- As we know, advanced characterization techniques act an
oatoms exhibit a larger catalytic active surface area and consid- important role in the design high efficiency catalysts, monitor
erably more low-coordination sites (such as vacancies, corners, the reaction intermediates, build up the structure–activity
edges, and steps), which substantially enhance the intrinsic correlations, those further improve the NRR performance.
catalytic activity. Introducing NVs could impart g-C3N4 with Although the significant efforts have been devoted to the devel-
excellent photocatalytic NRR activity.[89] In addition, the elec- opment of advanced electrocatalysts toward NRR, it is still
tronic and geometric effects induced by chemical modification challenging to better understand the structure–performance
Table 10. The calculated ammonia production rates based on different Conflict of Interest
detection methods.
The authors declare no conflict of interest.
Catalysts Nessler’s reagent Ion chromatography
(SmOCL)[150] 291 µmol h−1 g−1 259 µmol h−1 g−1
(TiO2)[151] 60.8 µmol h−1 g−1 L−1 52.4 µmol h−1 g−1 L−1 Keywords
TiO2–SiO2[152] 32 µmol L−1 30 µmol L−1 2D electrocatalysts, ammonia synthesis, electrochemistry, metal free
catalysts
Co/WO3 [153]
193 µmol h−1 g−1 170 µmol h−1 g−1
Received: September 15, 2022
relationship in some cases under environmental conditions. Revised: October 25, 2022
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Chuangwei Liu received his Ph.D. in 2019 in the School of Chemistry, Monash University,
Australia. After a stay as a postdoctoral fellow in the Technical University of Denmark, Denmark,
he joined Northeastern University as an associate professor in the School of Materials Science
and Engineering. His research interest is molecular modeling and the design of innovative mate-
rials for clean energy, catalysts, and environment through computation methods.
Qinye Li received her Ph.D. degree from Monash University with expertise in computational
chemistry. She is currently a postdoctoral fellow in Surface Engineering Advanced Materials, at the
ARC training center. Her current interest is the design of high-performance catalysts for ammonia
synthesis at room temperature, which is critical for the green production of fertilizer, her other
research topic is the understanding of materials interfaces, such as coatings, functional films, and
nanomaterials involved in the advanced manufacturing industry.
Tianyi Wang received her Ph.D. in 2022 in the School of Science, Computing and Engineering
Technologies, Swinburne University of Technology. She is currently a postdoctoral fellow at
Northeast University. Her interests focus on computer-aid design electrochemical catalysts for
nitrogen reduction reaction.
Song Li is a professor of Materials Science and Engineering at the Northeastern University, China.
He received his Ph.D. in materials physics from University of Lorraine in Metz and Northeastern
University in Shenyang (2009). He was a visiting scholar at Boston College, from 2015 to 2016.
Li’s recent research focuses on energy conversion and industrial decarbonization by developing
novel functional materials.
Chenghua Sun received his Ph.D. degree from the Chinese Academy of Sciences in 2007 and
then joined the University of Queensland as a postdoc fellow. In 2013, he joined the School of
Chemistry, at Monash University as a lecturer and established his group on Computer-Aided
Catalyst Design. He was awarded ARC Future Fellow and joined the Swinburne University of
Technology in 2017 as an associate professor. His research focuses on catalyst design for clean
energy and environment applications, particularly for ammonia synthesis at room temperature,
efficient methane combustion, and biomass conversion.

2D Metal Free Electrocatalysts For The Nitrogen Reduction Reaction

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16163028, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202210759 by University of Canterbury Library Access and Collections, Wiley Online Library on [09/02/2023].

2D, Metal-Free Electrocatalysts for the Nitrogen

C. Liu, G. Qin, S. Li A. Tian

Table 1. Mechanisms of the electrocatalytic NRR with various intermedi-

Mechanism routes Elementary reaction steps

NHNH + e- + H+ → NHNH

Figure 1. Schematic overview of ammonia applications in modern society.

Table 2. Experimental activity of 2D carbon-based electrocatalysts for the NRR.

Catalyst Yield FE Potential [V] Detection method Electrolyte

catalyst was strongly dependent on the carbonization at

Table 6. Experimental activity of 2D black phosphorus electrocatalysts to the NRR.

Catalyst Yield FE Potential [V] Detection method Electrolyte

Table 8. Experimental activity of 2D boron-based electrocatalysts to the NRR.

Catalyst Yield FE [%] Potential [V] Detection method Electrolyte

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