Small Methods - 2022 - Wang - Iron Based Nanocatalysts For Electrochemical Nitrate Reduction

Review
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Iron-Based Nanocatalysts for Electrochemical Nitrate

Reduction
Chuqi Wang, Yingbing Zhang, Hongxia Luo, Hui Zhang,* Wei Li, Wei-xian Zhang,
and Jianping Yang*
pollutants such as nitrate (NO3–) in
Nitrate has a high level of stability and persistence in water, endangering water.[1–3] Because of its extreme solu-
human health and aquatic ecosystems. Due to its high reliability and effi- bility and stability, concentrated nitrate
ciency, the electrochemical nitrate reduction reaction (NO3RR) is regarded as the (NO3–) in the water body may cause a
best available option for mitigating excess nitrate in water and wastewater, slew of environmental and human health
issues.[4–7] According to the survey and
especially for the removal of trace levels of nitrate. One of the most critical
summary results by Zhang et al., in 2020,
factors in the electrochemical reduction are the catalysts, which directly affect more than 7.83 percent of rivers have
the reaction efficiency of nitrate removal. Iron-based nanocatalysts, which NO3–-N content that exceeds the standard,
have the advantages of nontoxicity, wide availability, and low cost, have and some areas are severely polluted,
emerged as a promising electrochemical NO3RR material in recent years. This particularly the Yangtze River estuary.[8]
These pollutions are primarily caused by
review covers major aspects of iron-based nanocatalysts for electrochem-
human activities that have a significant
ical NO3RR, including synthetic methods, structural design, performance impact on the natural nitrogen cycle, as
enhancement, electrocatalytic nitrate reduction test, and reduction mecha- evidenced by the use of fossil fuels, the
nism. The recent progress of iron-based nanocatalysts for electrochemical excessive use of nitrogen fertilizers, and
NO3RR and the mechanism of functional advantages for modified structures the emission of animal manure.[9–12] In
are reviewed from the perspectives of loading, doping, and assembly strate- response to this dire situation, various
approaches, such as biological reduction
gies, in order to realize the conversion from pollutant nitrate to harmless
methods, physical reduction methods,
nitrogen or ammonia and other sustainable products. Finally, challenges and chemical reduction methods, photocata-
future directions for the development of low-cost and highly-efficient iron- lytic reduction methods, and so on, have
based nanocatalysts are explored. been proposed.[13–16] As for physical reduc-
tion method cannot achieve complete
removal and necessitates secondary pro-
1. Introduction cessing. The additional reducing agent added in the chemical
reduction method will cause secondary pollution and easily
The surface water environment in China is facing serious form by-products. Biological reduction method is hampered
challenges. One of the primary causes of the harsh water by low generation efficiency and biological sludge. On the con-
environment is the high concentration of nitrogen-containing trary, due to the intriguing advantages, electrochemical nitrate
reduction reaction (NO3RR) has emerged as the most prom-
C. Q. Wang, Y. B. Zhang, H. X. Luo, H. Zhang, J. P. Yang ising NO3– removal technology: 1) using electrons as a green
State Key Laboratory for Modification of Chemical reducing agent, which has no additional additives and no sec-
Fibers and Polymer Materials
ondary pollution, can avoid the security risks associated with
College of Materials Science and Engineering
Donghua University using hydrogen as a reducing agent; 2) the working electrode
Shanghai 201620, China in the water body can be recycled, overcoming the difficulty of
E-mail: zhanghui@dhu.edu.cn; jianpingyang@dhu.edu.cn separation and recovery; 3) the electrocatalytic nitrate reduction
W. Li has a high efficiency that can be carried out under normal tem-
Department of Chemistry perature and pressure.[17–21]
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,
and State Key Laboratory of Molecular Engineering of Polymers The electrochemical NO3RR process is heavily reliant on elec-
Fudan University trode material selection, which can reduce overpotential, accel-
Shanghai 200433, China erate reaction rate, and improve the selectivity of deeply reduced
W.-x. Zhang products.[22,23] Non-metallic carbon-based materials, monome-
College of Environmental Science and Engineering tallic based materials (including precious metals such as Pd, Pt,
State Key Laboratory of Pollution Control and Resources Reuse
Rh, Ru, Ir and transition metals such as Cu, In, Sn, Fe, Ni, Ti,
Tongji University
Shanghai 200092, P. R. China Co), and bimetallic based materials have been widely studied
in the literature (precious and transition metals).[24–31] Among
The ORCID identification number(s) for the author(s) of this article these, bimetallic electrocatalysts (e.g., CuPd alloys) that com-
can be found under https://doi.org/10.1002/smtd.202200790.
bine the benefits of different metals exhibit high catalytic activity
DOI: 10.1002/smtd.202200790 and product selectivity. However, due to a scarcity of precious
Small Methods 2022, 6, 2200790 2200790 (1 of 21) © 2022 Wiley-VCH GmbH

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Figure 1. a) Elements that can be used for electrochemical NO3RR (the shade of color is related to the amount of the relevant publications).
b) Some representative iron-based nanocatalysts for electrochemical NO3RR in recent 5 years. Reproduced with permission.[44] Copyright 2019, American
Chemical Society. Reproduced with permission.[45] Copyright 2018, American Chemical Society. Reproduced with permission.[46] Copyright 2020, Elsevier.
Reproduced with permission.[47] Copyright 2021, Royal Society of Chemistry. Reproduced with permission.[48] Copyright 2022, PNAS. Reproduced with
permission.[49] Copyright 2022, American Chemical Society.
metal resources, the cost of producing such bimetallic catalysts be oxidized in the air, and a dense oxide film forms easily on the
has skyrocketed. Furthermore, platinum-based and other noble surface, preventing the catalytic reaction from progressing; 2) the
metal nanomaterials have high toxicity and a short cycle life, surface energy of the iron nanoparticles is high and easily agglom-
hindering the large-scale applications. To avoid the introduction erated, resulting in a reduction of active sites and thus decreasing
of new sources of contamination and to decrease reaction costs, the catalytic activity; 3) the reaction of iron nanoparticles is better
current research focuses on how to use precious and toxic heavy performed under acidic conditions to expose more active sites,
metals as little as possible.[32–36] Figure 1a shows the number of whereas the pH of actual wastewater is neutral.[42,43] Iron-based
publications in recent years about the nitrate reduction on the nanocatalysts designed with rational compositions and structures
database of web of sciences using “nitrate reduction” and dif- have performed well in a variety of catalytic processes. Some repre-
ferent metals as key words, with the specific number shown in sentative iron-based nanocatalysts, such as iron-carbon composites,
Figure S1 in Supporting Information. It can be seen that transi- space-confined iron-based materials, iron-based bimetallic mate-
tion metals such as Fe, Cu, Ni, Co and Ti have become more rials, heteroatom-doped iron-based materials, interface-assembled
and more attractive for nitrate reduction over the past ten years. iron-based materials, iron single-atom materials, etc., have been
Iron, a nonprecious metal discovered in 3500 BC, is abundant proposed and applied to electrochemical NO3RR in recent years
in the Earth’s crust. It has become a promising catalyst that can (Figure 1b).[44–49] These designs are advantageous for electro-
be used for electrochemical NO3RR due to its unique advantages catalytic nitrate reduction because they exhibit improved nitrate
(cheap and easy to obtain, non-toxic and harmless, and excellent adsorption, faster electron transport rate, more active sites, more
catalytic performance).[37–41] When using iron particles directly precise product selectivity, higher structural stability, and so on.
for electrochemical NO3RR, the following aspects should be con- Despite the fact that the fabrication of iron-based nanocata-
sidered: 1) under the room temperature, iron nanoparticles can lysts for electrochemical NO3RR has been thoroughly reviewed,

Figure 2. The schematic illustration of the general aspects over iron-based nanocatalysts for electrochemical NO3RR.
the relationship among their advanced synthetic strategies, electrocatalysts for improved electrocatalytic performance. This
and tunable compositional and structural features with electro- section provides an in-depth overview of our approach to the
chemical NO3RR performance has not been thoroughly evalu- structural characterization and electrochemical nitrate reduction
ated. Herein, the fundamentals of iron-based electrocatalysts performance of iron-based electrocatalysts (Figure 2).
are summarized in this review. Following a brief introduction, The testing of electrocatalytic nitrate reduction can be
iron-based electrocatalysts with various structures and their cat- divided into four main parts: characterization of each catalyst
alytic performances for NO3RR have been reviewed detailedly. material before the reaction; electrochemical testing during the
Finally, the challenges and opportunities for future research reaction; testing of the ion concentration in the solution after
and applications are discussed in the hope of shedding some the reaction; and characterization testing to reveal the reaction
light on the preparation of highly efficient iron-based nanocata- mechanism. 1) Characterization of the catalyst morphology by
lysts for electrochemical NO3RR. scanning electron microscopy (SEM) and transmission electron
microscopy (TEM); analysis of the catalyst internal structure
and composition by non-in situ X-ray diffraction (XRD), X-ray
2. Brief Overview of Iron-Based Nanocatalysts photoelectron spectroscopy (XPS), non-in situ Raman, thermo-
gravimetric analysis (TG) and BET; electrochemical impedance
for Electrochemical NO3RR
(EIS) and cyclic voltammetry (CV) tests were performed to ana-
2.1. Characterization Techniques lyze the electron and proton transport capacity of the catalysts.
2) For the electrochemical testing of the reaction process, elec-
Various advanced characterization techniques were used to une- trochemical nitrate reduction is tested in a three-electrode reac-
quivocally reveal the relationship between the structural features tion system. The reaction vessel is usually based on a single
of iron-based materials and the nitrate removal performance. electrolyzer or an H-type electrolyzer. The structure of the cata-
The in-depth understanding of characterization techniques is lyst directly determines the performance of the catalyst for
expected to aid in the advanced structural design of iron-based nitrate reduction. Firstly, we perform CV test on the electrode

material before the performance test, the main function of this calculation of nitrogen as the main product is obtained by the
step of the test is to activate the electrode material to bring the indirect calculation method, and we lack a direct means of
catalyst to a stable state in the performance test. The main pur- quantitative calculation. This is one of the urgent problems in
pose of this test is to determine whether the catalyst material electrochemical NO3RR, and perhaps we can overcome this
has good nitrate reduction activity and to determine the electro- problem by means of coupling with gas chromatography, by
chemical nitrate reduction reaction potential, most often two means of an extremely closed container in order to exclude the
electrochemical reduction peaks can be observed in the LSV influence of nitrogen in the air. Second, in order to analyze the
curve, the first reduction peak is the reduction of NO3– to NO2– ion species in the solution more accurately, ion chromatog-
and the second reduction peak is the conversion of NO2– inter- raphy was used to qualitatively and quantitatively analyze each
mediates to nitrogen-containing products such as NH4+, N2 or ion in the solution. Finally, in order to verify that the nitrate
N2O. Then, constant voltage tests were performed over a reduction reaction was from nitrate in the waste solution rather
selected voltage range and for a given time to determine the than foreign nitrogenous contaminants, isotopic labeling was
optimal nitrate reduction potential of the iron-based catalyst. used to label the nitrogen elements in nitrate, and then the
Finally, the nitrate electroreduction performance was tested at source of the nitrogenous products (e.g., NH4+) was determined
the optimum potential for different times, different initial by NMR. It can be seen from the figure that 15NH4+ can appear
nitrate concentrations, different electrolyte types, and different as a duplex state by 1H-NMR while 14NH4+ shows a triplet state
initial pH solutions to obtain all the optimum conditions before in the NMR spectrum, and also the concentration of ammo-
measuring the cyclic stability of the nitrate electroreduction of nium can be quantified by the area of the NMR peak. 4) For the
the catalyst material. In electrochemical tests for nitrate reduc- analysis of the reaction mechanism of iron-based nanocatalysts,
tion, an inert gas should be blown into the electrolyte in order the detection of reaction intermediates, the identification of
to exclude the effect of dissolved oxygen, etc. in the electrolyte. reactive sites and how the reactive sites contribute to the con-
In addition, if the test is performed in an alkaline medium, the version and performance of intermediates are the three key ele-
tail gas should be collected for ammonia confirmation. The ments. For the detection of reaction intermediates, we usually
purpose of these operations was to lay the foundation for the use electrochemical in situ differential electrochemical mass
electrochemical reduction technique to treat actual nitrate-con- spectrometry, electrochemical in situ Fourier transform
taining wastewater. 3) For the determination of the ion concen- infrared spectroscopy and electrochemical in situ electron spin
tration in the solution after the electrocatalytic reduction perfor- resonance. Electrochemical differential mass spectrometry
mance, we mainly used UV–visible spectroscopy, ion chroma- (DEMS) is mainly used to detect volatiles (such as NO, N2O, N2,
tography, and NMR to qualitatively and quantitatively analyze etc.) produced during electrocatalytic nitrate reduction; electro-
the types and concentrations of nitrogen-containing com- chemical in situ Fourier infrared spectroscopy (in situ FTIR) is
pounds in the solution. First, UV spectroscopy is a common mainly used to characterize the chemical bonds of intermedi-
method to measure ion concentration in aqueous solutions. ates adsorbed on the surface of materials; electrochemical in
According to Lambert-Beer law, if the ion absorbs in a specific situ electron spin resonance (in situ ESR) is mainly used to
UV wavelength range (200 to 800 nm) when combined with a detect whether hydrogen radicals are generated in the electro-
specific chromogenic agent, a calibration curve can be plotted chemical nitrate electroreduction process, and thus determine
to quantify the ion concentration in the solution. It is known whether the nitrate electroreduction reaction is a direct or indi-
empirically that three main ions, nitrate, nitrite, and ammo- rect reduction process. In addition to the above three important
nium, are present in the solution after the nitrate reduction tests, in situ electrochemical ion chromatography (IC) and in
reaction. For nitrate, a certain amount of reaction solution is situ electrochemical scanning tunneling microscopy (EC-STM)
reacted with a certain concentration of hydrochloric acid and are also essential for the detection of intermediates in electro-
sulfamic acid solution after standing for a period of time, which chemical nitrate reduction reactions. For the determination of
exists at a wavelength of 220 nm; for nitrite ion, a certain reactive sites, we usually use tests such as electrochemical in
amount of reaction solution is reacted with homemade nitrite situ X-ray absorption spectroscopy (in situ XAS) and electro-
color developer after standing for a period of time to obtain chemical in situ Raman measurement. Both tests are basically
a purple-red test solution of different depths, which exists at a performed to detect changes in the structural composition of
wavelength of 540 nm for adsorption; for ammonium ion, a the catalyst during the reaction to determine the active site of
certain reaction solution was reacted with homemade sodium nitrate electroreduction. The formation of reaction intermedi-
potassium tartrate solution and Nessler’s reagent for a certain ates is inseparable from the role of reaction active sites, and we
period of time, and its adsorption existed at the wavelength describe the interconnection between these two accurately by
420 nm out. Based on this, the standard curves for NO3–, NO2– means of theoretical calculations. Combining the above tests,
and NH4+ were plotted and based on these curves, we can eval- we can have a clearer understanding of the iron-based catalyst
uate the nitrate electroreduction performance of the iron-based materials in the direction of nitrate reduction from material
nanocatalysts, and the nitrate removal rate, nitrite selectivity, preparation to performance to mechanism
ammonium selectivity, and N2 selectivity can be calculated as
C0 (NO3− -N) − C t (NO3− -N)
shown in the following equations. During the testing process, C (NO3− ) % = × 100% (1)
the amounts of by-product gases such as NO, N2O and NH2OH C0 (NO3− -N)
are usually neglected due to their extreme scarcity. This is the
accepted calculation method in most studies, but in practice it Ct (NO−2 -N)
S (NO−2 ) % = × 100% (2)
is not completely accurate when used for nitrogen testing. The ∆C (NO3− -N)

C t (NH+4 -N) hydrogenation, N* and other substances may also form NH4+ in
S (NH+4 ) % = × 100% (3) this process. Furthermore, the intermediate products NO* and
∆C (NO3− -N)
N2O* may fall off to form by-products NO and N2O, lowering
the selectivity of N2.[9,45,51,52] For different catalysts, the differ-
∆C (NO3− -N) − Ct (NO−2 -N) − C t (NH+4 -N) ence in power source can lead to a difference in the determining
S (N 2 ) % =
(4) × 100%
∆C (NO3− -N) step. For example, for Fe SACs, the determining step is different
from what we have just described. The N–O decomposition of
NO3* gradually produces NO2* and NO*. The first protonation
where C0(NO3–-N) (mg L–1) is the initial concentration. of NO* to NHO* requires overcoming a large energy barrier
Ct(NO3–-N), Ct(NO2–-N), and Ct(NH4+-N) are the concentration (1.33 eV), and thus NO* → NHO* is reported as the decisive
of NO3–-N, NO2–-N, and NH4+-N with varying electrocatalytic speed step of the reaction.[47] Improving this critical step is the
reduction time, respectively. ΔC(NO3–-N) is the concentration main challenge that needs to be addressed to make electro-
difference of NO3–-N at a given time. chemical NO3RR a competitive method. H* produced by H2O
reduction or H2 cracking produces a strong reducing environ-
ment, and the H* is critical to NO3RR. The efficiency of nitrate
2.2. The Electrochemical Reaction Mechanism electroreduction is limited by the hydrogen evolution reaction
caused by the combination of H*, which is a competition reac-
The electrochemical nitrate reaction is a cathodic reduction tion for NO3RR.[7,53,54] Two requirements must be met with for
reaction that converts nitrate into a series of nitrogen-contained iron-based nanocatalysts to maintain a sustainable rate in elec-
products such as nitrite, ammonia, and nitrogen by accepting trochemical NO3RR: 1) sufficient iron active sites are exposed;
electrons on the electrode surface by active substances in solu- 2) sufficient protons are provided for nitrate reduction. When
tion (Figure 3a). First, NO3– is adsorbed on the catalyst surface iron-based nanocatalysts were served as reduce nitrate alone,
and reduced to the intermediate product NO2* (* denotes the NO3– was strongly adsorbed on the iron surface first, and then
state of being adsorbed). NO2* is a stable intermediate for elec- the adsorbed NO3* and NO2* could acquire electrons or H* and
trochemical nitrate reduction to ammonia or nitrogen, and its be reduced (Figure 3b).[45,55] Compared with copper-based nano-
formation is the rate-limiting step in the entire reaction for catalysts and other highly active metal catalysts for nitrate reduc-
some catalysts due to the difficulty of breaking N–O.[50] Then, tion, iron-based nanocatalysts have some unique advantages
NO2* absorbs more charge and decomposes into NO* and in activity and selectivity. Because of its unstable 3D orbit, iron
N*. N* combines to form N2, and nitrides such as N2O* or is a relatively active transition metal compared to other highly
N2OH2* can also absorb charge to form N2. Through gradual active metal catalysts for nitrate reduction, such as copper-based
Figure 3. a) Pathway of the electrocatalytic NO3RR (the blue path generates NH4+, the yellow path generates N2). b) Schematic representation of
nitrate reduction by iron.

Figure 4. Comparison of three kinds of iron-based electrocatalysts for nitrate reduction (including schematic diagram of structure, preparation method,
advantages, and areas to be improved).
catalysts. It has some distinct advantages in terms of activity and while reducing reactivity and solves the problem of iron particle
selectivity. During the rate determination step, iron easily pairs aggregation through confinement. Organic materials (alginate,
with the extranuclear electrons of O in the nitrate NO bond to chelating resin, polystyrene resin, polymer glass powder, metal
form Fe(II) or Fe(III) intermediates, which can be regenerated organic framework), inorganic materials (zeolite, montmoril-
into Fe(0) on the cathode electrode surface by H*. Following the lonite, kaolinite, carbon ball), metals (Pd, Cu, Ni, Al) and their
formation of NO2* by an O deprivation, the NO bond is again oxides (aluminum oxide, titanium dioxide) have all been inves-
attacked, and O is paired with Fe to produce NO, N2O, NH4+, tigated.[62–74] For instance, Lubphoo et al. used Pd–Cu as a car-
and N2. Copper and other metals may exhibit strong NOH* rier material to load nZVI particles, while Khalil et al.[66] used
adsorption and weak NH3* adsorption compared to iron, and treated activated carbon as a carrier material.[75]
tend to produce ammonia due to differences in coordination Carbon carriers (primarily carbon balls, carbon nanotubes,
environment and electronic states of surface atoms.[56–59] carbon fibers, graphene, carbon nanofibers, etc.) have many
advantages over other organic and inorganic carriers, including
low cost, simple preparation, easy adjustment, diverse shapes,
3. Structural Designs and Electrochemical NO3RR high electrical conductivity, large specific surface area, and high
mechanical stress. Carbon substrates of various structures can
Performance
be used to control iron particle size, content, and spatial dis-
The catalytic performance of iron-based nanocatalysts for tribution. In addition, Iron in carbon-based composite mate-
electrochemical NO3RR is determined by the catalytic activity rials can be recycled and reused by burning them in the air to
of the iron active sites themselves as well as the number of remove carbon. Carbon carriers not only provide ample space
available active sites. In light of this, by designing the shape for Fe nanoparticles, but their selection is also closely related
and size of iron-based materials, manipulating the electron to the nitrate removal rate and selectivity, as catalytic activity is
transport mode, modifying the catalytic interface, and so on, dependent on the synergistic effect of carbon carriers and Fe
excellent electrocatalytic nitrate activity and durability can be nanoparticles. Some carrier structures may be better suited
obtained.[9,60,61] As previously stated, iron-based electrocatalysts for nitrate or key intermediate adsorption and product des-
can be broadly classified into three types based on differences orption.[59,76–81] Lan et al. used Prussian blue (PB) as the iron
in structural design: supported iron-based nanocatalysts, doped source to uniformly embed iron nanoparticles into 1D N-rich
iron-based nanocatalysts, and assembled iron-based electro- carbon nanofibers and the corresponding schematic diagram
catalysts. This section will highlight some recent iron-based of a typical iron-based material supporting structure is shown
nanocatalysts with controllable structures, with a focus on the in Figure 5a.[82] Carbon nanofibers have a large specific surface
relationship between their structural features and electrochem- area, high flexibility, low density, and unique anisotropic prop-
ical NO3RR performance, as illustrated in Figure 4. erties as support materials.[83,84] Prussian blue was pyrolyzed to
create a monodisperse, highly conductive carbonaceous skel-
eton that effectively inhibited nanoparticle aggregation and
3.1. Supported Iron-Based Nanocatalysts overgrowth. After thermal reduction, iron exists as iron/iron
carbide (Fe/Fe3C) composites uniformly supported in nitrogen-
One of the most common solutions is to fix the iron-based doped carbon nanofibers, as shown in Figure 5b–d. For elec-
material to the support material, which improves performance trocatalytic reaction, a carbon layer and nanoconfined space

Figure 5. a) The schematic structure mode, b) SEM image, c) TEM image, and d) HRTEM image of Fe/Fe3C-NCNF. Reproduced with permission.[82]
Copyright 2020, Royal Society of Chemistry. e) Synthetic scheme of Fe3Ni-N-C cathode materials and f) EDS-mapping of Fe3Ni-N-C. Reproduced with
permission.[104] Copyright 2021, Elsevier.
wrapped around Fe/Fe3C nanoparticles should be provided, bimetallic compounds (M stands for a metal atom other than
which can effectively alleviate Fe/Fe3C corrosion and inhibit iron) is therefore critical.[4,97–102] As a result, Lan et al. neatly
Fe/Fe3C escaping from the carbon matrix. The iron in the com- loaded Fe–Cu bimetal in the N-doped carbon nanofibers.[103]
posite provides the material with excellent properties (strong Cu has a high capacity for NO3– reduction and, in terms of
electrical conductivity, strong corrosion resistance), as well as kinetics, can achieve the fastest conversion of NO3– to NO2–.
greater adsorption capacity and catalytic activity than a single At the same time, Fe improves the selectivity of N2 while bal-
Fe or Fe3C.[85–87] Although the design concept of space-limited ancing the overall performance of electrocatalytic NO3– reduc-
domains improves the stability of Fe nanoparticles, it also intro- tion. The elimination capability is 5686 mg N g–1 Fe–Cu, which
duces some complications, such as the limited loading of Fe, is significantly higher than that of single metal iron. It results
which makes it difficult to maintain catalytic activity. To solve from the following factors: 1) N-doped carbon nanofibers that
these problems, Hong et al. created mesoporous carbon micro- act as loading nanoparticles and enhance NO3– adsorption in
spheres (Fe@C) that were loaded with nZVI particles.[88] The the solution while maintaining the structural integrity; and 2) it
resulted iron-based electrocatalyst has a NO3– conversion rate has bimetallic active sites with complementary electrochemical
of 75.9% and a N2 selectivity of up to 98.5%. This performance activity. Finally, the material’s remarkable performance is due
is enhanced by the mesoporous carbon spheres with signifi- to the synergy of the carrier, metal Cu, and metal Fe. The cata-
cantly increased specific surface area, which provides a larger lytic performance in the research above still falls short of cur-
load space. Furthermore, because of the porous structure, more rent national drinking water regulations, and the catalytic rate
active sites will be exposed on the surface of the nZVI particles. is slow (need 24 h). This could be due to carrier limitations,
It is worth noting that the catalyst produced by this simple syn- where the solution is unable to fully contact the metal sites in
thesis method has an astonishing gram-level output, implying the nitrogen-doped carbon nanofibers. Sun et al. described a
that it has the potential to be used in industry. MOF-derived iron–nickel bimetallic electrocatalyst that could
In general, bimetallic catalysts supported on inert substrates convert NO3– to N2 almost fully in 30 minutes.[104] The Fe–Ni
outperform single-metallic catalysts. The bimetallic structure bimetal is embedded on the porous carbon by using a com-
can not only provide a range of active sites, but also integrate bined metal from synthesis and encapsulation approach, as
and utilize the catalytic advantages of several metal atoms, well as carbonization of the ZIF-8 metal organic framework
resulting in synergistic effects that boost catalytic activity material (Figure 5e,f). The Fe–Ni–N coordination core disperses
and product selectivity.[32,89–92] During the carbonization pro- the metal and increases the catalytic active site. The carbonized
cess, the bimetallic catalysts can also prevent each other from carrier skeleton is an excellent platform for bimetallic catalysts
agglomerating. Most prior investigations, such as Fe–Pd bime- due to its high porosity, high specific surface area, and stable
tallic nanoparticle supported on chelating resin prepared by Shi skeleton structure. Furthermore, this coordinated structure
et al., have used Fe as a promoting metal to compound with val- reduced metal leaching and increased material stability. After
uable metals such as Pd and Pt.[69] Although the performance 5 h, the NO3– removal rate could reach 97.9%, and the nitrate
is better than single metal iron, scarce precious metals are content of the treated water could meet national drinking water
used.[93–96] Exploration of high-efficiency and low-cost iron–M regulations.

The most frequent loading methods for binding iron with nanocatalysts are classified as metal-doped or heteroatom-
the support material include dipping, hydrothermal, spinning, doped based on the type of doped atoms. The introduction of
and so on, while thermal treatment and chemical reduction metal atoms or heteroatoms changes the electronic structure,
procedures are common postprocessing methods for obtaining chemical bonds, and other interface characteristics, signifi-
iron active sites and highly conductive supports. The catalytic cantly improving the electrochemical performance of doped
activity and service life of iron-based electrocatalysts can be con- iron-based composites.[105]
siderably improved by selecting an appropriate carrier material, Metal-doped iron-based nanocatalysts are a type of composite
owing to: 1) the specific surface area and pore structure of the formed by combining an iron-based material with another one
carrier affect the particle size and spatial distribution of iron- or more metals. Cu, Ni, Pd, and other metals are commonly
based materials; 2) the pore structure of the carrier influences used to create a bimetallic alloy nanocrystalline structure.[4]
the mass transfer of NO3– and its intermediate products to the The ratio of doped metal, in addition to the type of doped
iron surface in solution; 3) the surface functional groups and metal, influences the electrocatalytic performance of the com-
charge environment of the carrier impact the adsorption and posite material. Using the schematic diagram in Figure 6a as
desorption of some products; and 4) the carrier, in addition to an example, Chen et al. used dip coating and a carbothermal
being a support material for iron active subs, affects the adsorp- reduction strategy to form a self-supporting Fe–Ni alloy nano-
tion and desorption of some products. However, there is still particle catalyst (FeNi/g-mesoC/NF) in situ on foam nickel.[106]
the issue of easy leaching of active substances. During the thermal reduction process, the nickel in the nickel
foam oxidizes and combines with the iron ions dispersed in
the resin polymer to form Fe–Ni alloy nanoparticles with a size
3.2. Doped Iron-Based Nanocatalysts around 10 nm. They are uniformly distributed on the surface of
g-mesoC, and the outer graphitized carbon layer is the result of
In addition to the support design with the base material, one of pyrolysis at 900 °C (Figure 6b). The presence of Ni shares the
the effective methods for improving performance is the doping voltage that causes Fe to corrode and slows the rate at which Fe
of iron particles with another substance. Doped iron-based corrodes. The electrolyzed hydrogen is chemically adsorbed on
Figure 6. a) Schematic illustration of electrocatalytic reduction and b) TEM image of NO3−-N on FeNi/g-mesoC/NF electrode. Reproduced with per-
mission.[106] Copyright 2020, American Chemical Society. c) A schematic fabrication process, d) TEM images, and e) STEM elemental mapping images
of the B–Fe NCs. Reproduced with permission.[112] Copyright 2021, Elsevier. f) Synthetic route of nitride-carbon encapsulated N-doped iron (FeN-NC).
STEM-XEDS elemental mappings of g) Fe + N + C, N + C and Fe + C color overlays. Reproduced with permission.[46] Copyright 2020, Elsevier.

the surface of FeNi alloy nanoparticles, and H atom absorption as the active site for the nucleation and growth of iron nanopar-
is dominant, resulting in high NH4+ selectivity. Furthermore, ticles; and 4) Fe–N bonded in FeNx serves as the active site.[113,114]
the presence of oxygen vacancies on the alloy surface effectively N dopants interact with reactants and improve the catalytic
slows the oxidation of FeNi alloy nanoparticles and improves performance of metal nanoparticles. The addition of N may be
NO3–adsorption rate via the O atom trapping effect. This cata- important in adjusting the metal distribution.[115] Wang et al.
lyst converts 80% of the NO3– in the solution into NH4+ with recently developed N-doped iron nanoparticles (FeN) using
an ultra-low energy consumption of 0.7 kWh mol–1 and has a template assembly and pyrolysis.[46] As precursors, G-C3N4,
1 month long-cycle stability. This self-sufficient catalyst has the sucrose, and iron salts are used, and the FeN is coated with an
distinct advantage of not requiring the addition of binders or adjustable thickness layer of graphite N. The proper amount
conductive agents. The specifics are as follows: 1) it reduces of N optimizes the interface structure between iron and N,
the preparation cost and optimizes the operation process; resulting in the formation of high-density FeN active sites
2) it eliminates the problem of shedding caused by binder diges- (Figure 6f,g). The pyrrole N content in it can reach 17.4 at%. At
tion during the long-term cycle; and 3) this approach lowers the the same time, the NC thin layer coating promotes mass and
charge transfer resistance, thereby lowering the electron transfer electron transfer between interfaces. FeN doping and the NC
energy. It can also be applied to carbon cloth, carbon paper, shell layer work together to control FeN–NC electron transfer.
foamed copper, foamed titanium, and other materials, making it Nitrate and nitrite are easily adsorbed on nitrogen-containing
a good starting point for the design of self-supporting catalysts. spherical shells, where they gain electrons via FeN and generate
The doping design of boron (B), nitrogen (N), sulfur (S), N2. Overall, with the reaction extended, the catalyst demon-
phosphorus (P), and other atoms is the most common in the strated 6004 mg N g-1 Fe removal activity and 91% N2 selectivity.
design of heteroatom doping.[107–110] Combining heteroatoms In general, dopant atoms can be added in the precursor
with a carbon matrix is one direction of doping. The above- or during post-processing. Doping can improve the catalytic
mentioned supported iron-based nanocatalysts frequently intro- activity and product selectivity of iron-based electrocatalysts for
duce N elements into the matrix material, such as nitrogen- nitrate reduction, and the selectivity of some doped iron-based
containing carbon nanofibers, nitrogen-containing carbon electrocatalysts after catalysis is even close to 100%, owing to
spheres, and so on. It is more about fusing heteroatoms and the controlled charge distribution in the reaction. Unfortu-
iron atoms. Then, the charge arrangement on the iron surface nately, there are not enough studies to thoroughly investigate
is changed and iron-contained complexes are formed. the active sites of iron-based composites after atomic doping,
It is well known that heteroatom B can cause metal atom and determining the doping reaction mechanism is difficult. In
electron rearrangement.[111] Based on this, Ni et al. created addition, research into suitable doping atom species for iron-
controllable cross-linked chain-like boron–iron nanochains based electrocatalysts is still incomplete. The synergistic effect
(B–Fe NCs).[112] The advantages of the simple wet chemical of polyatomic codoping in combination with metal atoms or N,
method and thermal reduction strategy are low cost and scal- B, P, S should also be investigated. There have been successful
ability (Figure 6c). This method produces a good B–Fe cross- applications in this regard; for example, Li et al. developed a
linked chain structure with a channel for electron transmission single-atom catalyst with Fe active centers on the S, N co-doped
and a uniform distribution of iron, boron, and oxygen in the carbon basal plane. It can achieve ultra-high performance when
iron oxide shell confinement frame (Figure 6d,e). The elec- used to produce N2 or NH4+ and nitrate removal is excellent
tronic configuration of B alters the electronic structure of the (7822 mg N g–1 Fe).[116]
catalyst, causing the 2p orbital and iron 3d orbital to hybridize.
Electrons are thus transferred from boron atoms to metallic
iron. As a result, the metal bond in iron is weakened, and the 3.3. Assembled Iron-Based Nanocatalysts
electron density near the active center is rearranged, reducing
steric hindrance to electron transfer. B-based optimized cata- It is well known that traditional “spatial confinement” strate-
lyst has a high NO3- conversion rate (80%), high N2 selectivity gies can avoid agglomeration by confining iron in core–shell
(99%), and long-term cycle stability (20 days). structures or porous frameworks, but the random packing
Combining with N is another effective way to obtain highly morphology of particles reduces efficient electron trans-
active catalysts, which has been extensively and intensively port.[49,117,118] Precise surface modification of nanoparticles to
researched in recent decades. At the moment, the research impart specific role information can cause nanoparticles to
focus of catalytic active sites is primarily on the various chem- assemble into desired target nanostructures such as spher-
ical bond states of doped nitrogen. According to reports, pyrrole ical, rod-like, disc-like, and dumbbell-like morphologies. As
N, pyridine N, and graphite N are effective catalytically active a result, assembled iron-based nanocatalysts with direction-
sites among the five bonding forms of nitrogen doping.[109] ally distributed iron nanoparticles as assembled units have
Duan et al., for example, created nitrogen-doped graphene- been developed, which can improve electron transport speed
coated iron by adjusting the electron distribution of iron via a while also exhibiting excellent electrochemical performance
nitrogen-containing carbon layer.[59] As a result, the rate of NO3– when used as electrode materials for electrocatalysis and
removal was increased to 83.0 percent. Four conclusions can be supercapacitors.
drawn about the active sites of nitrogen-doped iron catalysts: Fe3O4 nanoparticles were among the first to be studied as
1) it lowers the cost of preparation and optimizes the operation self-assembled nanoparticles.[119] Such assembled iron-based
process;2) N acts as active sites, and iron acts as a promoter to pro- materials can acquire a variety of specific functions due to
mote N active sites; 3) iron serves as the active site, and N serves the specific arrangement or orientation of the active species.

Figure 7. a) Schematic illustration in situ confined thermal reduction strategy for preparation of corchorifolius-like structure carbon-coated Fe micro-
spheres (CL-Fe@C microspheres), b) SEM image, c,d) TEM images, and e) dark-field TEM image of a single microsphere and the corresponding
elemental mapping. Reproduced with permission.[44] Copyright 2019, American Chemical Society. f) Schematic of the preparation of CC/Fe@C, g) SEM
images and corresponding mapping scan image of CC/Fe@C, and h) schematic of the interface assembly structure for electrocatalytic NO3RR.
Reproduced with permission.[125] Copyright 2021, Royal Society of Chemistry.
Yang et al., for example, reported carbon-coated Fe3O4 super- ditions, the catalyst can achieve 1816 mg N g-1 Fe removal
lattice microspheres (Fe3O4@C) for lithium battery perfor- activity and up to 98% N2 selectivity. This improved perfor-
mance evaluation.[120] Ma et al. proposed a one-step synthesis mance is due to the following factors: 1) Iron exists in the
of Fe3O4 nanoparticles in graphene nanosheet self-assem- spherical superlattice structure formed by the self-assembly
bled composites that effectively increased the dielectric and of multiple small nanoparticles of about 20 nm, which greatly
magnetic losses.[121] Wang et al. used the versatility of Fe3O4 increases the iron content (74%); 2) The self-assembled iron
nanoparticles to in situ synthesize heteroatom-doped highly particles greatly enhance the electron transport rate due
ordered mesoporous carbon framework materials with highly to their directional arrangement; 3) The surface-modified
ordered, interconnected, and doped structural features.[122] carbon coating effectively prevents abnormal growth and oxi-
This was used to evaluate the performance of oxygen reduc- dation; 4) The synergistic effect of the interface between iron
tion, and could effectively promote the carbon skeleton’s elec- and carbon can regulate electron transfer and promote elec-
tron transport ability. Similarly, this assembled structure of tron transfer from NO3– to other intermediate products.[123,124]
iron nanoparticles can fully exploit its structural advantages Following that, Su also expanded the research to include
in the electrochemical nitrate reduction reaction. Su et al. flexible self-supporting materials and continued to use this
used a self-assembly strategy to create oleic acid-coated Fe3O4 precursor to perform interface assembly with carbon cloth
as a precursor. The precursors were controlled to form an (CC). A short-range orderly layer assembly structure (at least
ordered structure with cyclohexane evaporation at a suitable 4 layers) is formed on a single carbon fiber (CC/Fe3O4@C)
thermal reduction temperature, and the ligands were car- (Figure 7f,g).[125] Each isolated iron nanoparticle serves as
bonized into a uniform carbon coating. Finally, a rough sur- an active site (Figure 7h), resulting in exceptional catalytic
face was formed of raspberry-like carbon-coated iron micro- performance (NO3– conversion rate of 92%, N2 selectivity of
spheres (CL-Fe@C) (Figure 7a–e).[44] This unique structure 82%). Specially, the use of a binder-free strategy allows it to
not only inhibits abnormal nanoparticle growth and prevents have a long cycle stability of 120 h.
agglomeration, but also fully exploits the complementary or Above all, the self-assembled iron-based catalyst is a novel
synergistic effect between the core and the shell, improves structural design that fully utilizes the synergistic catalysis
electron transfer ability at the interface, and exhibits stronger between the Fe–C interface and improves electron directional
adsorption capacity than uncoated iron particles, resulting conduction. This encapsulation-like structure, although pre-
in more excellent catalytic performance. The experimental vents direct contact of the solution with the catalyst, remains a
results show that after adjusting the optimal reaction con- significant disadvantage that must be overcome.
Figure 8. Effects of design methods on a) nitrate removal and b)selectivity for N2 or NH4+. c) Effects of initial NO3–-N concentration, reducing time,
and different electrolyte solutions on nitrate removal and selectivity for N2 or NH4+. A represents sodium sulfate solution, B represents sodium chloride
solution. The red column represents the supported type, the blue column represents the doped type, and the green column represents the assembled
type.[44,47,59,103,104,106,112,125]
3.4. Influence of Structural Designs on Electrochemical NO3RR addition of metal atoms or heteroatoms will alter the central
Performance structure of iron metal and change the coordination environ-
ment, thereby affecting catalytic performance. This regula-
A clear structure–property relationship aids in the design of tion greatly improves nitrogen selectivity, while doping with
effective iron-based nanocatalysts as well as the understanding different atoms makes the reaction mechanism more com-
of their reaction mechanisms. It is important to note that the plex and unpredictable. Thirdly, ordered particle assembly
definitions and divisions of these three types are not absolute, benefits fast directional electron transport, which is a prom-
and the examples above are merely examples. Figure 8a,b visu- ising modification method. However, particle stacking causes
ally summarizes the nitrate removal efficiency and product insufficient exposure of the active area, and the coating of the
selectivity of these improved iron-based electrocatalysts with outer layer causes insufficient contact with the solution. It is
different structures and compositions to compare the effects impossible to assess the relative merits and drawbacks of these
of different design methods on catalytic performance. When three methods, and the iron-based nanocatalyst prepared by
compared to pure iron catalysts, their performances have combining their advantages is the ultimate ideal goal.[126–130]
improved to varying degrees. First of all, the influence of sup- Figure 8c summarizes some data on the effect of test condi-
ported catalyst on performance is related to matrix selection. tions on catalytic performance, including initial NO3–-N con-
A suitable carrier can distribute iron nanoparticles evenly, pre- centration, reducing time, and different electrolyte solutions
vent oxidation inactivation, and improve overall stability. The on the catalytic process. And Table S1 in Supporting Informa-
synergistic interaction between the carrier and iron nanopar- tion has been supplemented for a more visual description of
ticles determines catalytic activity and selectivity, but exposing reported Fe-based nanocatalysts with under different test con-
more active sites increases the risk of iron particle shedding. ditions.[44,46,47,59,82,88,103,104,106,112,125,131] Most catalysts require
Secondly, in the case of doped iron-based nanocatalysts, the an initial NO3–-N concentration of 50 or 100 mg L-1, since the
combining capacity of catalyst and nitrate is weakened at lower that are common in conventional electrochemical nitrate reduc-
concentrations, resulting in less effective active molecular colli- tion. As a result, improving the structure of the iron-based
sions. Accordingly, the way to achieve high-efficiency catalysis catalyst is expected to increase the proportion of our desired
in ultra-low nitrate solutions is a major issue to consider. Most product without adding chloride ions.
catalytic reactions are currently limited by the rate-limiting Although a variety of iron-based nanocatalysts have achieved
step, and the required catalytic time is relatively long, which is relatively high nitrogen selectivity for nitrate conversion, the
also one of the problems that must be addressed urgently in nitrogen selectivity in some catalytic systems, such as Fe(0)-
the future. The types and concentrations of electrolyte solutions dispersed ordered mesoporous carbon, is close to 100 percent
suitable for catalysis differ due to differences in target products (Figure 9a–c), the utilization value of N2 is not high in terms of
and material structures. A solution containing chloride ions active nitrogen utilization rate.[57] When compared to N2 reduc-
promotes nitrogen generation, whereas a solution containing tion, electrochemical NO3RR produces more ammonia (NH3)
sulfate ions promotes the conversion of nitrate to ammonium and has a higher Faradaic efficiency, which is an important
and promotes the improvement of the conversion rate. This is component in agriculture and a promising clean energy source
because hypochlorite oxidized from the chloride ion can reduce as a hydrogen carrier. Under realistic conditions of massive
the ammonium to N2, promoting the selectivity of the nitrogen, global energy consumption, nitrate, as a rich nitrogen source, is
but when the concentration is too high, excess chloride ions expected to turn waste into treasure through product directional
occupy catalytically active sites, decreasing the catalytic reaction regulation. The implementation of electrochemical NO3RR
efficiency. Furthermore, hypochlorite can reoxidize nitrite to ammonia production via a simple post-treatment process is
nitrate, resulting in a reverse reaction. expected to solve the problems of massive energy consump-
tion and serious environmental pollution caused by traditional
ammonia production methods, as well as to produce NH3 effi-
4. Challenges and Perspectives of Iron-Based ciently under environmental conditions.[140–147] For example,
Fang et al. through in situ electrochemical reduction prepared
Nanocatalysts for Electrochemical NO3RR
a 2D ferricyanyl coordination polymer nanosheet.[53] This iron-
Although iron-based nanocatalysts have shown great promise based catalyst can exhibit high electrocatalytic NO3RR activity
for electrochemical nitrate removal, there are still many major towards NH3 with a yield of 42.1 mg h−1 mgcat−1 due to the strong
issues that need to be addressed. To advance the field, the fol- adsorption of nitrate on the active sites of zero-valent iron gener-
lowing challenges should be considered in the future. ated by topological transformation and in situ electroreduction
(Figure 9d–f). The cobalt doping modulates the d-band center of
Fe in the MOF-derived cobalt-doped Fe@Fe2O3 catalyst proposed
4.1. Products beyond N2 by Zhang et al., allowing the adsorption of intermediates to be
tuned and suppressing the hydrogen evolution reaction. Finally,
NO3– is removed from the electrochemical NO3RR by gaining the highest ammonium selectivity (≈99 percent) is achieved.[48]
electrons and reducing it to NH4+ or N2.[52,72,132] For nitrate Combining the NO3RR reaction with appealing technologies
reduction reaction, the selectivity of reduction products is such as CO2 reduction to obtain highly selective C–N products
the key. According to thermodynamic theory, the most stable via electrochemically coupled reactions may change the way
compound for nitrate reduction is N2, since it has the highest carbon fuels are used today.[148–152] Wu et al. accomplished the
equilibrium potential of all possible N products. Based on preparation of methylamines using a molecular cobalt catalyst
environmental concerns, most studies in the published lit- supported on carbon nanotubes.[153] According to the catalytic
erature prefer to obtain N2 as the final product, which is 1 h and 5 h test results, Tao et al. found that electrochemical
nontoxic and harmless and can be directly emitted into the CO2 reduction and NO3– reduction first proceed independently
atmosphere.[57,133–138] According to the “breakpoint chlorina- under the catalysis of oxide-derived Cu nanoparticles, resulting
tion” theory combined with the mechanism diagram analysis, in cascade catalysis and the formation of ethylamine after the
ClO– can react with NH4+ to generate N2, but it is important formation of key reaction intermediates (Figure 9g–i).[154]
to note that the chlorinated by-products generated when more Due to intense competition for hydrogen evolution reac-
Cl– is added to the electrolyte, which bring new sources of pol- tions, achieving high current density and high ammonia yield
lution to water bodies. In addition, Cl2 and HClO/ClO– can at low nitrate concentrations remains difficult to date. At the
cause pitting, and electrochlorination can reduce the stability of same time, the pH value has a significant impact on the form
Fe-based catalyst electrodes. Xu et al. published an article on of ammonia present, and an efficient method for collecting
an electron-rich Co-containing open-frame cathode for indirect ammonia to avoid its reconversion to NH4+ due to its dissolu-
electrochemical nitrate reduction mediated by atomic hydrogen tion in aqueous solution is still lacking. Notably, because of this
(H*) with remarkable N2-selective supply, which gave us a new high solubility, ammonia detection may be influenced by the
research idea.[139] The accumulation of electrons on Co sites environment, and either atmospheric or human respiration
increases the energy required to overcome the potential barrier may cause uncertainty in the experimental results. For iron-
to generate H2, which is beneficial for H* generation and stabi- based nanocatalysts, the sustainable synthesis of these high
lization. The H* generation rate can also be precisely matched value-added organic nitrogen compounds is also expected, but
by tuning the electronic structure of the Co site. This electro- it may take some time. Nitrogen, as a non-harmful transforma-
chemical system can achieve remarkable N2 selectivity without tion product that requires no subsequent treatment, is an excel-
using Cl–, avoiding the formation of chlorinated by-products lent choice for our current study.
Figure 9. Different products for electrochemical NO3RR. a) Fe#OMC formation from lignin, non-ionic surfactant F127 and Fe3+ by evaporation induced
self-assembly (EISA) method using ethanol solvent, b) electrocatalytic reduction of NO3–-N with time by Fe#OMC material in electrolyte showing
products formed, and c) recycling of electrocatalytic reduction of NO3–-N by Fe#OMC. Reproduced with permission.[57] Copyright 2022, Elsevier. d) SEM,
e) selectivity from −0.2 to −0.6 V in 0.1 m KNO3 aqueous electrolyte, and f) electrocatalytic NO3RR activity of Fe-cyano-R NSs. Reproduced with per-
mission.[53] Copyright 2021, American Chemical Society. g) Oxide-derived Cu catalyst under reductive potential and h) product distribution (FE) for CO2
reduction, NO3− reduction, and CO2 and NO3− co-reduction. 1 h electrolysis were performed. i) Product distribution and total current density for a 5 h
co-reduction electrolysis; the average liquid product FEs were measured after the electrolysis. Reproduced with permission.[154] Copyright 2022, Elsevier.
4.2. Emerging Iron-Based Nanocatalysts for Electrochemical iron-based materials in single-atom form are thought to have
NO3RR more available active sites and better catalytic performance.
Wu et al. developed a catalyst containing Fe SACs for the
4.2.1. Iron Single-Atom Catalysts conversion of NO3– to NH4+. The employed silicon dioxide
powder as a hard template and obtained an interconnected
Since the birth of “single-atom catalysts (SACs)” in 2011, porous carbon frame with a good pore structure after auxiliary
research on single-atom catalysts has remained intense in carbonization and etching (Figure 10a).[131] The TEM image of
recent years.[155–158] The intrinsic activity of the active mate- Fe SACs revealed an interconnected vesicle-like structure with
rial, the design of the electrode structure, and the utilization of clear pores derived from the SiO2 hard template (Figure 10b).
active sites can all improve catalyst performance. Reducing the Figure 10c clearly identified the isolated iron single atoms dis-
particle size of iron in iron-based nanocatalysts can increase the persed on the porous carbon matrix as bright spots, while com-
solution contact area and expose more active sites, which is why bining X-ray absorption fine structure (XAFS) spectroscopy and
Figure 10. a) Schematic illustration of the synthesis of Fe SACs, b) TEM image, and c) AC MAADF-STEM, and EDS mapping images of Fe SACs. Reproduced
with permission.[131] Copyright 2021, Springer Nature. d) Schematic of the synthesis process of FeSA/MoS2, e) SEM, and f) high-magnification AC
HAADF-STEM images and intensity profile analysis of FeSA/MoS2. Reproduced with permission.[171] Copyright 2022, John Wiley and Sons.
theoretical calculations, the structure of Fe SACs was elucidated To summarize, single-atom catalysts have high active site
and regarded as active center. The resulting supported Fe SACs utilization, the total loading capacity of Fe SACs total loading
outperform iron nanoparticles in terms of Faraday efficiency capacity is very limited, and even if all active sites are used, the
(75%) and ammonia yield with a lower loading ratio (1.51%). It total amount is still insufficient. Some studies on the relation-
still fluctuates steadily after 20 cycles in the H-type electrolyzer ship between the size (single atoms, clusters of atoms, and
without drastically decreasing. Similarly, Li prepared a polypyr- sub-nanoclusters) of Ag, Ru, and other elements and intrinsic
role (PPy) hydrogel loaded with Fe SACs using a polymer- activity have shown that when the active center exists in the
hydrogel strategy.[47] The ammonia selectivity is nearly 100%, form of atomic clusters, the catalytic performance and intera-
and the active site turnover rate is 12 times higher than that of tomic stability are improved.[159] Overall, the effect of iron
iron nanoparticles. A large number of studies have shown that particle size on electrocatalytic nitrate reduction performance
when the iron content reaches a certain level, the iron nanopar- remains inconclusive, but it is undeniably promising in the
ticles agglomerate and reduce the active sites. SACs can also future, which needs to be investigated further.
be used to convert nitric acid to innocuous nitrogen products,
and the product selectivity is determined by the reaction direc-
tion of the NO3– reducing intermediate N* on Fe monoatom. 4.2.2. Iron-Based Nanocatalysts Mimicking the Structure
For example, Li et al. used the stable curing effect of defective of Biological Enzymes
carbon to develop a highly dispersed iron monatomic catalyst
material supported by sulfur and nitrogen co-doped carbon Enzymes are the most powerful catalysts in the nature with
materials for electrochemical removal of nitrate from ground- numerous advantages such as high activity, high specificity,
water. Among these, the highly dispersed active site contributes and controllable activity. The high reactivity of natural enzymes
to increased metal Fe utilization and nitrate removal efficiency frequently benefits from synergy between adjacent reaction
via electrochemical reduction. In the presence of chloride ions, sites. When biological enzymes adsorb reactants, the binding
nitrate can be completely converted into harmless nitrogen.[131] site undergoes structural changes, which are transmitted to
Figure 11. a) 1H NMR spectra for the electrolytes after three independent nitrate reduction tests at −0.66 V and b) 1H NMR spectra for electrolytes after
15NO - reduction tests at different time. Reproduced with permission.[131] Copyright 2021, Springer Nature. c,d) DEMS measurements of Fe Ni-N-C in
3 3
electrocatalytic NO3RR. In situ IR spectra of Fe3Ni-N-C as a function of e) reaction time and f) the applied potential. Reproduced with permission.[104]
Copyright 2021, Elsevier.
adjacent sites and improve the site. Adsorption of subsequent form a structure with iron ions preferentially anchored on the
reactants can achieve the synergistic adsorption effect.[160–162] surface, as shown in the SEM of Figure 10e. According to the
Lu et al. designed and synthesized reductive sulfite synthetic STEM image of Figure 10f, the MoS2 nanosheets have a 2H
metalloenzymes by introducing iron-sulfur cluster groups into triangular prismatic symmetry structure, and the final isolated
cytochrome c peroxidase and modifying amino acids in the iron atom sits on top of the molybdenum atom and coordi-
secondary coordination region of the metal-substrate binding nates with three adjacent sulfur atoms. When this catalyst is
site.[163] For many years, it has been a technical bottleneck in used to selectively oxidize benzyl alcohol to benzaldehyde, the
the field of biocatalysis, providing a new idea for the design formed structures, which are similar to natural iron-containing
of more enzymes. Many synthetic catalysts inspired by nature, enzymes, can achieve 99% selectivity at nearly 100% conver-
such as peroxidase-like, iron porphyrin, and other similar metal sion.[171] Interestingly, in nature, nitrate reductases that catalyze
macrocyclic complexes, have been designed and successfully the reduction of nitrate ions to nitrite ions and nitrite reduc-
used for carbon dioxide adsorption and dissociation, oxygen tases that degrade nitrite to NO or NH3 exist. Electron donors
electrolysis catalysis, electrochemical ammonia production, and transporters are required to participate in the catalytic reac-
photodegradation, and so on.[164–169] Xu et al., for example, used tion process. They are abundant in microorganisms and plants
a template molecule to introduce bridging nonsulfur ligands and play an important role in the nitrogen cycle in nature. The
into the core structure of a Fe–S cluster, thereby resolving the internal structure of nitrate reductase contains three functional
coordination competition between sulfur ligands and 2p non- regions: molybdenum coenzyme MoCo, heme-Fe, and FAD,
sulfur ligands. The 2p non-sulfur ligand was embedded in which are the nitrate binding and degradation areas. Nitrite
the core structure of the Fe–S cluster for the first time, and a reductases are classified into four groups based on the cofac-
highly approximate analog of the Mo-containing substructure tors and reaction products they use, including ferric redoxin-
of the Fe–Mo coenzyme molecule was synthesized and used dependent nitrite reductases. Nitrite is further reduced to
for efficient biological nitrogen fixation.[170] Similarly, Liu et al. ammonium by nitrite reductase, which uses 6-ferredoxin to
used spontaneous reduction to create an atomically dispersed do so.[172–175] By simulating nitrate reductase and nitrite reduc-
iron atom supported on defect-containing MoS2 nanosheets. tase in living organisms and specifically designing and synthe-
According to the typical synthesis diagram in Figure 10d, the sizing catalysts for multi-electron transfer reactions based on
defect-containing MoS2 nanosheets obtained through solvo- simple protein skeletons, it may be a promising strategy for
thermal and etching treatments have typical redox proper- developing high-efficiency iron-based nanocatalysts for electro-
ties that make them suitable for combining with iron ions to chemical NO3RR.
4.3. Unveiling the Mechanism of NO3RR Understanding the complicated reaction mechanism is critical
for producing excellent electrocatalysts from intrinsic struc-
The actual reaction process is more complicated due to the tures. Using in situ DEMS results, the reaction pathway of
carrier’s synergistic effect, heteroatom regulation, interface nitrate electroreduction was elucidated using the mechanism
assembly effect, and other factors. Due to the complexity and analysis of Fe3Ni-N-C catalyst (Figure 11c,d). The N2 signal was
variability of intermediates, as well as the difficulty in deter- detected at 1.0 V ratio SCE, which was lower than the other
mining the true active site, there are still many controversies in three products, confirming that N2 generation requires more
determining the reaction mechanism in this reaction process. energy. In situ FT-IR measurements of Fe3Ni-NCs revealed that
Some advanced characterization methods and theoretical cal- the strength of NO3– was significantly reduced in a pronounced
culation of the mechanism are gradually applied to clarify the tensile mode at −1.3 V versus SCE (Figure 11e). These results
changes of intermediates during the reaction process. show the reaction path from NO3– to NO2–, NO and N2O. Fur-
Monitoring the transient products at various time intervals thermore, the effect of different potentials on MRI was investi-
during the reaction process is an effective method of deter- gated using in situ infrared imaging (Figure 11f). It is possible
mining the reaction mechanism. As previously stated, the use to speculate on the entire reaction process. The reaction bar-
of isotope labeling experiments in conjunction with NMR can rier for NO3– conversion is lowered by Fe sites, and the adsorp-
frequently trace the source of nitrogen and is also useful in tion and activation of reaction intermediates (NO2*, NO*, and
analyzing the transfer of N-containing species during the reac- N2O*) is facilitated by Ni centers. To begin with, iron promotes
tion. Figure 11a,b shows NMR measurements of one Fe SAC the conversion of NO3* to NO2*, and the generated NO2* can
catalyst after electrolysis at -0.66 V for 0.5 h, with three peaks only be transferred to the Ni surface after a very short distance
corresponding to 14NH4+ clearly visible in the electrolyte. The to achieve the purpose of relay catalysis and, ultimately, satis-
peak intensity of 15NH4+ increases with electrolysis time, indi- factory performance.[104]
cating that NH3 is formed via electrochemical nitrate reduc- Theoretical simulation is also useful for determining the
tion.[131] Furthermore, because the majority of these interme- interactions between reaction intermediates and catalytically
diates are unstable and transient, they are difficult to detect active species. Density functional theory (DFT) calculations
using traditional testing methods. As a result, we can study the aid in determining the root cause of nitrate reduction by iron-
mechanism using in situ characterization techniques. These based nanocatalysts.[47,104,131] As an example, consider the DFT
advanced in situ characterization methods enable the identifi- calculation of a Fe SACs electrode.[131] The lowest energy reac-
cation and evolution of active centers under operating condi- tion mechanism for NO3– reduction to NH3 on single-atom Fe
tions, as well as an examination of the entire reaction process. sites is depicted in Figure 12a. As shown in Figure 12b, only the
Figure 12. a) The minimum energy pathway that results in NH3 as the main product and b) free energy diagram showing the minimum energy
pathway at U = 0.0 V versus RHE (green) and at the calculated limiting potential of −0.30 V versus RHE (black). Reproduced with permission.[131]
Copyright 2021, Springer Nature.
limiting potential of U = −0.30 V can cause all reaction steps to NO3RR. We hope that this review will spark new ideas for the
proceed thermodynamically spontaneously when compared to design of iron-based nanocatalysts, paving the way for the early
U = 0.0 V. The calculated limiting potential (≈ −0.30 V) matches realization of large-scale industrial applications of low-cost and
the experimentally observed onset potential (≈ −0.40 V). Because highly-efficient iron-based nanocatalysts.
of the lack of adjacent metal sites, the N–N coupling step cannot
be realized on Fe single-atom catalysts, effectively preventing
the formation of N2 and improving ammonia product selec-
tivity. Finally, Fe SACs have highly efficient intrinsic active sites, Supporting Information
namely Fe–N4 centers, which contribute to their high NH3 yield Supporting Information is available from the Wiley Online Library or
and activity. The thermodynamic reaction barrier is much lower from the author.
in comparison to Fe NPs, Co–N4, and Ni–N4.
Acknowledgements
5. Summary
This work was supported by the National Key R&D Program of China
Excess nitrate in water bodies is a critical and pressing issue (2018YFE0201701), National Natural Science Foundation of China
that has piqued the interest of the public, governments, (No. 52172291 and No. 52122312), Shanghai Science and Technology
researchers, and funding agencies due to the potential threat to Committee (19DZ2270100), State Key Laboratory for Modification of
water bodies and human health. Because of their excellent per- Chemical Fibers and Polymer Materials, Donghua University.
formance and energy-economical and environmentally friendly,
electrochemical reduction methods for treating nitrate contami-
nation in water have received a lot of attention. Since electrode
Conflict of Interest
materials are essential for nitrate reduction, iron-based nano-
catalysts with high cost-effectiveness and electrochemical per- The authors declare no conflict of interest.
formance have emerged as a promising class of materials. The
research progress of iron-based nanocatalysts for electrochem-
ical NO3RR is summed up in this review. To begin, a thorough
understanding of fundamental concepts such as composition,
Keywords
structure, performance, and mechanism is required in order to ammonia synthesis, electrocatalysts, iron, nitrate reduction, structure
facilitate the controllable structural design of iron-based nano- engineering
catalysts. The synthesis, characterization, and nitrate reduction
Received: June 20, 2022
performance of iron-based nanocatalysts with various structures
Revised: July 28, 2022
prepared using various strategies are then highlighted, and the Published online: September 14, 2022
relationship between structure and performance is thoroughly
examined. The number of active sites, active area, and electron
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Chuqi Wang received her bachelor’s degree from the College of Materials Science and Engineering
at Donghua University in 2020. She is currently pursuing her MS degree under the supervision of
Prof. Hui Zhang at Donghua University. Her research interests focus on iron-based materials for
electrochemical nitrate reduction.
Hui Zhang is an associate professor and deputy director in the center for civil aviation compos-
ites at Donghua University (China). His bachelor degree (2007) and master (2010) were received
from Donghua University. He received his Ph.D. degree (2014) at University of Freiburg. He then
worked as a postdoctoral at University of Freiburg and Donghua University. His research inter-
ests include high-performance fibers and composites, carbon-based structural and functional
composites.
Jianping Yang is appointed as a professor and associate dean in the College of Materials Science
and Engineering at Donghua University (China). He received his bachelor degree (2007) at
Huazhong University of Science and Technology. His master (2010) and Ph.D. degree (2013)
were received from Fudan University supervised by Professor Dongyuan Zhao. He then worked
as a postdoctoral and visiting research fellow at Tongji University, University of Wollongong and
Monash University. His research interests focus on interfacial design of functional materials for
environmental remediation, electrocatalytic denitrification, energy conversion, and storage.

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