Research Article

Cite This: ACS Catal. 2018, 8, 9312−9319 pubs.acs.org/acscatalysis

Ambient Electrochemical Ammonia Synthesis with High Selectivity

on Fe/Fe Oxide Catalyst
Lin Hu,† Asim Khaniya,‡ Jun Wang,‡,§ Gang Chen,∥ William E. Kaden,‡,§ and Xiaofeng Feng*,†,‡,§
†
Department of Materials Science and Engineering, University of Central Florida, Orlando, Florida 32816, United States
‡
Department of Physics, University of Central Florida, Orlando, Florida 32816, United States
§
Energy Conversion and Propulsion Cluster, University of Central Florida, Orlando, Florida 32816, United States
∥
Department of Chemistry, University of Central Florida, Orlando, Florida 32816, United States
*
S Supporting Information
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ABSTRACT: Electrochemical reduction of N2 to NH3 under ambient

conditions can provide an alternative to the Haber−Bosch process for
distributed NH3 production that can be powered by renewable
electricity. The major challenge for realizing such a process is to
develop efficient electrocatalysts for the N2 reduction reaction (N2RR),
as typical catalysts show a low activity and selectivity due to the barrier
for N2 activation and the competing hydrogen evolution reaction
(HER). Here we report an Fe/Fe3O4 catalyst for ambient electro-
chemical NH3 synthesis, which was prepared by oxidizing an Fe foil at
300 °C followed by in situ electrochemical reduction. The Fe/Fe3O4
catalyst exhibits a Faradaic efficiency of 8.29% for NH3 production at
−0.3 V vs the reversible hydrogen electrode in phosphate buffer
solution, which is around 120 times higher than that of the original Fe
foil. The high selectivity is enabled by an enhancement of the intrinsic (surface-area-normalized) N2RR activity by up to 9-fold
as well as an effective suppression of the HER activity. The N2RR selectivity of the Fe/Fe3O4 catalyst is also higher than that of
Fe, Fe3O4, and Fe2O3 nanoparticles, suggesting Fe/Fe oxide composite to be an efficient catalyst for ambient electrochemical
NH3 synthesis.
KEYWORDS: electrocatalysis, ammonia synthesis, nitrogen reduction, selectivity, iron, iron oxide

1. INTRODUCTION promising route, which may enable sustainable, distributed

Ammonia (NH3) is one of the most highly produced inorganic
chemicals in the world, as it is widely used for the production
of fertilizers, plastics, explosives, nitric acid, and intermediates
for pharmaceuticals. It has been primarily produced via the
Haber−Bosch process, which produces NH3 from N2 and H2
with an Fe-based catalyst under harsh conditions: high
temperature (400−500 °C) and high pressure (150−250
bar).1,2 However, this NH3 production process is energy
intensive and has severely relied on the consumption of fossil
fuels. For example, around 146 million tons of NH3 was
produced globally via the Haber−Bosch process in 2015,3
which consumes 3−5% of the world’s natural gas production,
amounting to 1−2% of the global annual energy supply.4,5 It
also accounts for >1% of the global CO2 emissions.4
Considering the global energy and climate challenge, there is
an urgent need to develop a sustainable ammonia synthesis
technology that can decrease our reliance on fossil fuels and
mitigate the CO2 emissions.
Numerous efforts have been made to facilitate NH3
synthesis under milder conditions or using renewable
energy.6−13 Among them, the electrochemical synthesis of
NH3 from N2 and H2O under ambient conditions is a
production of NH3 when it is powered by solar- or wind-
generated electricity.14−17 This electrically driven process is
compatible with an intermittent renewable energy supply and
can eliminate CO2 emissions in the NH3 production process.
In addition, electrochemical reduction of N2 to NH3 also
enables a process for renewable energy storage in NH3, which
is a potential carbon-neutral fuel due to its high energy density
(4.32 kWh/L), high hydrogen content (17.8 wt %), and easy
liquidation (boiling point −33.3 °C at 1 atm).18−20 Actually,
NH3 has been proven to work efficiently in internal
combustion engines21 and direct ammonia fuel cells,22,23
confirming it to be a promising liquid transportation fuel.
Despite these potential advantages, the development of the
electrochemical process has been hindered by the lack of
efficient electrocatalysts for the N2 reduction reaction (N2RR)
under ambient conditions.14−17 One major challenge for N2
reduction in aqueous electrolyte is the low selectivity due to
the competing hydrogen evolution reaction (HER):24,25
Received: July 3, 2018
Revised: August 22, 2018
Published: August 27, 2018

© XXXX American Chemical Society 9312 DOI: 10.1021/acscatal.8b02585

ACS Catal. 2018, 8, 9312−9319
ACS Catalysis
2H+ + 2e− F H 2 E° = 0 V (1)
Although the standard potential for N2RR is 0.058 V vs the
reversible hydrogen electrode (RHE)
N2(g) + 2H 2O + 6H+ + 6e− F 2NH4OH(aq)
E° = 0.058 V (2)
the breaking of the strong NN bond requires a reduction
potential where the HER readily occurs, leading to a low
selectivity for NH3 production. Specifically, most studies of the
N2RR in aqueous electrolyte under ambient conditions showed
a Faradaic efficiency <1%:26−33 that is, less than 1% of the
electrons are used for reducing N2 while the remaining
electrons go toward evolving H2. To overcome the selectivity
challenge, an optimal catalyst should be able to enhance the
N2RR activity and suppress the activity of the competing HER.
To date, electrochemical NH3 synthesis has been demon-
strated on precious metals including Ru, Pt, Pd, and
Au, 26−29,34−37 nonprecious metals such as Fe and
Ni,8,9,30−33,38 and carbon-based materials.39,40 Among them,
Fe-based catalysts have received considerable attention due to
their low cost and high activity for NH3 production. In
particular, Licht et al. reported a high NH3 production rate and
Faradaic efficiency (up to 35%) using Fe2O3 catalysts in a
molten hydroxide electrolyte cell at temperatures ≥200 °C.8,9
Nevertheless, high-temperature electrolysis has high require-
ments on the power supply and facilities, making it less
compatible with intermittent renewable sources such as solar
and wind.14 In contrast, a recent study of N2RR on carbon-
nanotube-supported Fe2O3 nanoparticles at room temperature
exhibited an NH3 yield rate of 0.22 μg cm−2 h−1, but only a low
Faradaic efficiency of 0.15%.32 To date, all of the studies of Fe-
based catalysts for N 2 RR have mainly focused on
Fe2O3,8,9,32,33,38 while Fe-based materials in other chemical
states (such as Fe and Fe3O4) remain to be investigated.
Furthermore, the standard potentials for Fe/Fe oxide redox
equilibria are as follows:41,42
3Fe2O3(s) + 2H+ + 2e− F 2Fe3O4 (s) + H 2O
E° = 0.66 V (3)
Fe3O4 (s) + 8H+ + 8e− F 3Fe(s) + 4H 2O
(4)
E° = 0.085 V
Thus, under a typical potential for N2RR (e.g., −0.3 V vs
RHE), Fe2O3 might be possibly reduced to different chemical
states such as Fe3O4 and Fe. Therefore, it is necessary to
understand the effect of different chemical states of Fe on the
N2RR activity and selectivity, which may facilitate the
development of efficient, cost-effective catalysts for electro-
chemical NH3 synthesis.
In this work, we investigate Fe-based materials for
electrocatalytic NH3 synthesis and reveal the effect of different
chemical states of Fe on the N2RR catalysis. We find that a
preoxidized Fe foil will be reduced to an Fe/Fe3O4 material in
0.1 M phosphate buffer solution (PBS) electrolyte when a
reduction potential is applied. The resulting Fe/Fe3O4 catalyst
shows enhanced activity and selectivity for N2RR in the PBS
electrolyte in comparison to the original Fe foil, achieving a
Faradaic efficiency of 8.29% for NH3 production at −0.3 V vs
RHE, which is around 120 times higher than that of the Fe foil.
The high selectivity is enabled by an enhancement of the
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intrinsic N2RR activity as well as an effective suppression of the
HER activity. Additional comparative experiments have been
performed to further understand the effect of chemical state
and composition of Fe-based catalysts on their N2RR
selectivity.
2. EXPERIMENTAL SECTION
2.1. Materials Preparation. A piece of polycrystalline Fe
foil (Alfa Aesar, 99.99%, 0.1 mm thick) was first etched in
dilute HCl solution to remove surface layers. After rinsing with
DI water and drying under a stream of Ar, the Fe foil was
placed in a tube furnace (Thermo Scientific) under flowing O2
at a specified temperature (200−500 °C) for 20 min to
produce Fe oxide. After it was cooled to room temperature, the
Fe oxide sample was subsequently assembled into a gastight
two-compartment electrochemical cell (Figure S1) in 0.1 M
phosphate buffer solution (PBS) electrolyte (pH 7.2) purged
with Ar gas. A potential of −0.5 V vs RHE was then applied,
and the Fe oxide sample was reduced until the current
decreased to a stable value (Figure S2). The resulting sample
should be relatively stable under reduction potentials and is the
focus of this study. Fe, Fe3O4, and α-Fe2O3 nanoparticle
samples (US Research Nanomaterials, purity ∼99.5%, 20−45
nm size) were prepared by dispersing a mixture of Fe or Fe
oxide nanoparticles (30 wt %) and carbon black powder (70 wt
%) in diluted Nafion ethanol solution, which was then
sonicated to form a homogeneous suspension. Subsequently,
the suspension was drop-casted onto a piece of carbon paper
(1 × 1 cm2) until a total mass loading of 1 mg was reached.
After drying at room temperature under vacuum, the electrode
could be directly used for electrochemical measurements.
2.2. Materials Characterization. Scanning electron
microscopy (SEM) images were acquired using a ZEISS
Ultra-55 FEG scanning electron microscope. Transmission
electron microscopy (TEM) images were acquired using a FEI
Tecnai F30 transmission electron microscope at 300 kV. X-ray
photoelectron spectra (XPS) were obtained using a SPECS
electron spectrometer with a PHOIBOS 100 hemispherical
energy analyzer and XR 50 Al Kα X-ray source (1486.67 eV).
XPS binding energies were calibrated using both the Fermi
edge and the known peak positions of metallic Ag(111) and
Au(111). In an effort to mitigate presumed surface oxidation
during transfer in air, mild Ar ion sputtering (500 V, Ar
pressure 5 × 10−7 Torr, 2 min) was used to remove the surface
oxide layers formed due to air exposure before each XPS study.
Grazing incidence X-ray diffraction (XRD) patterns were
collected using a PANalytical Empyrean diffractometer with a
1.8 kW copper X-ray tube at an incidence angle of 5°.
2.3. Electrochemical Studies. All electrochemical meas-
urements were performed using a CH Instruments 760E
potentiostat and a gastight two-compartment electrochemical
cell (Figure S1) separated by a Nafion 115 membrane at room
temperature (∼293 K). Prior to the measurements, the Nafion
115 membrane was heat-treated in 5% H2O2, 0.5 M H2SO4,
and water for 1 h, respectively. After being rinsed in water
thoroughly, the Nafion membrane was immersed in DI water
for future use. A piece of Pt gauze and Ag/AgCl electrode
(filled with saturated KCl solution) were used as the counter
electrode and reference electrode, respectively. The N2RR
activities of the electrodes were evaluated by controlled-
potential electrolyses in N2-saturated 0.1 M PBS electrolyte.
The PBS electrolyte was selected, as our previous study
suggested that it can suppress the HER.37 Prior to an N2RR
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Figure 1. Characterization of the Fe foil, the 300 °C oxidized sample, and the sample after the prereduction at −0.5 V vs RHE. (a) SEM images of
the three samples. (b) High-resolution XPS spectra of Fe 2p peaks of the three samples. Deconvolution of the peaks is shown for chemical state
analysis. (c) Grazing-incidence XRD patterns of the three samples.
electrolysis, the cathodic compartment was purged with N2 for
at least 30 min. During an electrolysis, N2 was delivered into
the cathodic compartment by N2 gas bubbling at a flow rate of
5 sccm, and the electrolyte was agitated with a stirring bar at a
rate of 400 rpm. All potentials were iR-compensated and
converted to the RHE scale via calibration (Figure S3).43 The
reported current densities were normalized to geometric
surface areas. Two possible products in the solution phase,
NH3 and N2H4, were determined using spectrophotometric
methods at the end of each electrolysis (Figure S4).44,45 NH3
was quantified at the end of each electrolysis using the
calibration curve established by the indophenol blue method,44
and no N2H4 was detected within the detection limit of the
spectrophotometric method developed by Watt and Chrisp.45
In particular, the absorbance peak of the background solution
(no NH3) was subtracted from the measured peaks of N2RR
experiments to calculate the NH3 yield rates (RNH3) and
Faradaic efficiencies. Argon control experiments were
performed for each type of sample to verify the N source of
the detected NH 3. 15N-labeling experiments were not
performed in this work. Additional experimental methods are
provided in the Supporting Information.
3. RESULTS AND DISCUSSION
To understand the chemical state of Fe-based materials for
N2RR, both metallic and oxidized Fe samples were prepared. A
polycrystalline Fe foil was first cleaned by etching in HCl
solution and then heated in flowing O2 at 300 °C for 20 min to
produce Fe oxide. A previous study indicated that oxidation of
etched Fe surfaces at 300 °C in O2 forms α-Fe2O3 first with
subsequent nucleation of Fe3O4 at the α-Fe2O3−Fe interface;46
thus, α-Fe2O3 and Fe3O4 are expected to form on the surface.
After it was cooled, the oxidized Fe foil was assembled into the
cathodic compartment of an electrochemical cell filled with 0.1
M PBS electrolyte and purged with Ar gas. A potential of −0.5
V vs RHE was then applied and a large reduction current was
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observed for a couple of hours until a lower, stable current was
reached, as shown in Figure S2, indicating some change to the
chemical state of the sample. Different potentials were also
tested for the prereduction of oxidized Fe foil in Ar-saturated
PBS electrolyte, and it turned out that the prereduction at −0.5
V resulted in a very efficient catalyst for the N2RR (Figure S5);
therefore, −0.5 V was selected for the prereduction of oxidized
Fe samples in the remainder of this work. Such an Fe oxide
derived sample should have a relatively stable chemical state
for N2RR under a similar potential. Representative SEM
images of the Fe foil, the oxidized sample, and the further
electrochemically reduced sample are shown in Figure 1a. The
surface of the Fe foil is flat, and rough nanostructures are
grown on the surface after oxidation, which becomes relatively
flat again but slightly porous after the prereduction at −0.5 V,
consisting of nanocrystallites of around 50−100 nm in size.
XPS was used to reveal the composition and chemical state
of the surface layer in the samples. XPS survey spectra of the
three samples are shown in Figure S6, and high-resolution XPS
spectra of Fe 2p peaks are exhibited in Figure 1b.
Deconvolution of the Fe 2p peaks has been performed to
reveal the chemical state of Fe (i.e., metallic vs oxidic) in the
samples. We have deliberately chosen to fit all oxidic
components with a single doublet to avoid reporting
potentially misleading Fe2+:Fe3+ peak fitting comparisons,
which would be difficult to quantitatively justify due to the
strong overlap of these components within the region of our
broad oxidic features centered near 711 eV. The 2p3/2 and
2p1/2 doublets for each fitting are constrained to have 2:1 peak
area ratios47 and a peak separation of 13.1 eV. On the basis of
this analysis, our fitting results indicate that the Fe foil is
mainly composed of an Fe0 state with a small amount of Fe
oxide, probably due to the oxidation by air during sample
transfer. In contrast, no Fe0 is detected within the oxidized Fe
sample, which only shows oxidic Fe 2p features and indicates
complete oxidation of the surface layer. On the basis of the
clear presence of a Fe3+ satellite at ∼719 eV, we can definitively
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Figure 2. Comparison of the N2RR catalytic performance on the Fe foil and the derived Fe/Fe3O4 catalyst. (a) Chronoamperometric curves of the
two electrodes measured at −0.3 V vs RHE in N2-saturated 0.1 M PBS electrolyte, with the Faradaic efficiency (FE) for NH3 production indicated.
(b) Total current densities of the two electrodes measured in N2-saturated 0.1 M PBS electrolyte at selected potentials and corresponding (c)
geometric NH3 yield rates (RNH3) and (d) Faradaic efficiencies for NH3 production at the potentials. (e) Surface-area-normalized NH3 yield rates
and (f) H2 evolution activities of the two samples. The error bars correspond to the standard deviations of measurements over three separately
prepared samples under the same conditions.

conclude that some (if not all) of the Fe present in the surface
of this sample is in the form of Fe2O3. The electrochemically
reduced sample shows both Fe0 and oxidic Fe components,
which indicates a partial reduction of the surface oxide layer to
metallic Fe0,48 consistent with the prereduction process
revealed by the chronoamperometric curve in Figure S2. In
addition, the Na and other trace amounts of species observed
in the survey XPS spectrum (Figure S6c) were from the PBS
electrolyte, and no N species were observed in the sample
within the XPS detection limit.
Grazing-incidence XRD was then used to further determine
the structure and composition of the near-surface layer in the
three samples. As shown in Figure 1c, the XRD pattern of the
Fe foil shows two characteristic peaks with 2θ values of 44.7
and 65.0°, corresponding to the (110) and (200) peaks of α-
Fe. The oxidized sample shows mainly α-Fe2O3 components,
as well as a small fraction of Fe and Fe3O4. The observation is
highly consistent with a previous study that oxidation of etched
Fe surfaces at 300 °C in O2 forms α-Fe2O3 first with
subsequent nucleation of Fe3O4 at the α-Fe2O3−Fe interface,46
and the Fe and Fe3O4 are most likely from a deeper layer in the
sample due to a greater depth sensitivity of XRD in
comparison with XPS. The prereduction at −0.5 V vs RHE
has largely changed the sample composition, and the XRD
pattern indicates that the resulting sample consists of α-Fe and
Fe3O4 crystallites in the near-surface layer, which agrees with
the XPS data. The observed reduction of Fe2O3 to Fe and
Fe3O4 in PBS electrolyte is also consistent with previous in situ
X-ray absorption spectroscopy (XAS) studies,48 suggesting that
this sample may represent a state of Fe oxide derived catalyst
equilibrated under the reduction potential, which is the major
focus of this work and hereafter referred to Fe/Fe3O4 catalyst
in the following.
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The Fe foil and the derived Fe/Fe3O4 sample were then
evaluated for electrocatalytic synthesis of NH3 . The
electrolyses were performed using a two-compartment electro-
chemical cell with N2-saturated 0.1 M PBS electrolyte (Figure
S1). Figure 2a shows representative chronoamperometric
curves of the two samples at −0.3 V vs RHE. The Fe foil
exhibited a total current density of ∼0.15 mA cm−2 and a low
Faradaic efficiency of 0.07% for NH3 production. In
comparison, the Fe/Fe3O4 catalyst showed a lower current
density (∼0.024 mA cm−2) but a much higher Faradaic
efficiency of 8.29% for NH3 production, which is around 120
times higher than that of the Fe foil. Apparently, the Fe/Fe3O4
sample, which was derived by electrochemical reduction of an
oxidized Fe foil, has a distinct composition and structure that
make it a more efficient catalyst for electrochemical NH3
synthesis. Such a Faradaic efficiency is comparable to
previously reported state of the art catalysts for N2RR under
ambient conditions.26−40
A systematic comparison of the N2RR catalytic performance
of the Fe foil and the Fe/Fe3O4 catalyst was performed. The
total current densities of the two electrodes from −0.25 to
−0.45 V vs RHE are shown in Figure 2b, and the current
density of the Fe/Fe3O4 catalyst is lower than that of the Fe
foil by 5−10 times. Figure 2c shows NH3 yield rates per
geometric surface area (geometric RNH3) of the two samples at
the selected potentials, and the geometric RNH3 value of the
Fe/Fe3O4 catalyst is much higher than that of the Fe foil,
particularly at low overpotential. Specifically, the Fe/Fe3O4
catalyst achieved the highest yield rate of ∼0.19 μg cm−2 h−1 at
−0.3 V vs RHE, which is around 25 times higher than that of
the Fe foil. Accordingly, the Faradaic efficiencies for NH3
production on the Fe/Fe3O4 catalyst are also significantly
higher than that of the Fe foil in the potential range, achieving
a 120-fold improvement at −0.3 V, as shown in Figure 2d.
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Figure 3. Comparison of Fe-based catalysts that were prepared by oxidizing an Fe foil in O2 gas flow at different temperatures followed by
electrochemical reduction at −0.5 V vs RHE until a stable state was reached. (a) Chronoamperometric curves of the five electrodes measured at
−0.3 V vs RHE in N2-saturated 0.1 M PBS electrolyte and corresponding (b) geometric NH3 yield rates and (c) Faradaic efficiencies of the five
samples. (d) Surface-area-normalized NH3 yield rates of the five samples measured at −0.3 V vs RHE. The error bars correspond to the standard
deviations of measurements over three separately prepared samples under the same conditions.

To understand the origin of the enhanced N2RR activity,
surface areas were measured for the samples using electro-
chemical double-layer capacitance,49 so that intrinsic activity
(surface area normalized) can be obtained to exclude the
influence of surface roughness. As shown in Figure S7, the Fe/
Fe3O4 catalyst has a roughness factor of 2.77, assuming a
roughness factor of 1 for the Fe foil. Thus, surface-area-
normalized NH3 yield rates (normalized RNH3) of the two
samples can be determined, as shown in Figure 2e. The
normalized RNH3 of the Fe/Fe3O4 catalyst is still higher than
that of the Fe foil, with a 9-fold increase at −0.3 V, indicating
an enhancement of the intrinsic activity for N2RR on the Fe/
Fe3O4 catalyst. In addition, the Fe/Fe3O4 catalyst reached a
maximum activity and selectivity at −0.3 V, and the Fe foil
reached a maximum efficiency at −0.35 V; thus, the Fe/Fe3O4
catalyst requires a lower overpotential to achieve its best
performance. The improved catalytic performance of the Fe/
Fe3O4 catalyst may be attributed to the interface sites between
Fe and Fe3O4 nanocrystallites. As suggested by computational
studies,24,50 due to the scaling relations of the binding energies
of *NxHy intermediates on metal and metal oxide surfaces,
some catalysts that bind *N2H strongly to activate N2 may be
poisoned by a later *NH2 intermediate, while other catalysts
that avoid poisoning by *NH2 species may have difficulty in
activating N2. In our catalyst, Fe and Fe3O4 surface sites may
have different binding affinities with *NxHy intermediate
species (possibly one binds *N2H strongly and the other binds
*NH2 relatively weakly), so that the interface sites between Fe
and Fe3O4 nanocrystallites may allow both the reductive
adsorption of N2 to form *N2H and the reductive desorption
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of *NH2 to form NH3, thus mitigating the limitations by the
scaling relations and enhancing the intrinsic N2RR activity.
In addition to the enhanced N2RR activity, the high
selectivity of the Fe/Fe3O4 catalyst is also attributed to a
lower total current density due to a suppression of the HER
activity. To understand the HER suppression effect, the
produced H2 was quantified by gas chromatography and used
to determine the surface-area-normalized HER activity
(normalized jH2). As shown in Figure 2f, the normalized jH2
value of the Fe/Fe3O4 catalyst is lower than that of the Fe foil
by more than 1 order of magnitude, which is similar to a
previous study of Pb oxide induced suppression of H+
reduction on Pb electrodes.51 We propose that the addition
of Fe3O4 nanocrystallites to the Fe surface may cause slower
kinetics for charge transfer at the electrode−electrolyte
interface,52 as Fe3O4 is intrinsically less conductive than
metallic Fe. Indeed, the electrochemical impedance spectra of
the Fe foil and the Fe/Fe3O4 catalyst in Ar-saturated 0.1 M
PBS electrolyte reveal a larger barrier and thus slower kinetics
for HER on the Fe/Fe3O4 catalyst, as shown in Figure S8. In
addition, it is necessary to point out that the PBS electrolyte
plays an important role in suppressing the HER.37 A
comparison of the two samples for N2RR in 0.1 M NaOH
electrolyte was made (Figure S9): the surface-area-normalized
HER activities of the two samples are similar in NaOH, but
much higher than those in PBS, revealing the importance of
the PBS electrolyte in boosting the N2RR selectivity.
Furthermore, control experiments have been performed to
verify the N source of the detected NH3. Figure S10 presents
the UV−vis absorption spectra of the indophenol blue
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Figure 4. Comparison of the N2RR selectivity of the Fe/Fe3O4 catalyst with those of Fe, Fe3O4, and Fe2O3 nanoparticles. (a) NH3 yield rates of the
nanoparticles measured at −0.3 V vs RHE in N2-saturated 0.1 M PBS electrolyte. The inset shows corresponding chronoamperometric curves. (b)
Faradaic efficiencies of the Fe-based catalysts for NH3 production at −0.3 V vs RHE. The error bars correspond to the standard deviations of
measurements over three separately prepared samples under the same conditions.
measurements for the electrolytes obtained after electrolysis
under different situations. First, after the prereduction
treatment, Ar gas was purged (instead of N2) for electrolysis
under the same conditions (Fe/Fe3O4 + Ar), and no apparent
NH3 was detected within the detection limit of the indophenol
blue method. Second, when the Fe/Fe3O4 catalyst was
replaced by carbon paper in the electrolysis (carbon paper +
N2), no apparent NH3 was detected as well. These control
experiments indicate that the NH3 was produced by the
electroreduction of N2. In addition, to exclude the possible
influence of Fe ions on the indophenol blue method,53
electrolytes with additional Fe2+ or Fe3+ were examined, which
showed no interference with the NH3 quantification. Similar
control experiments have also been performed with alternately
flowing N2 and Ar into the electrochemical cell, which was
repeated three times consecutively to further verify the
production of NH3 (Figure S11).
To further understand the Fe/Fe oxide catalysts for the
N2RR, different samples were prepared by oxidizing an Fe foil
in O2 gas at various temperatures (200, 400, and 500 °C) for
20 min followed by prereduction in Ar-saturated PBS
electrolyte at −0.5 V vs RHE until a lower, stable current
was reached. A higher temperature will result in a thicker oxide
layer in the oxidized sample, and thus a higher ratio of Fe oxide
may remain in the prereduced sample. Figure S12 shows the
SEM images and XPS spectra of the samples derived at 200,
400, and 500 °C. Indeed, as revealed by XPS, the higher the
oxidation temperature, the more oxidic Fe components in the
derived samples. These samples were evaluated for the N2RR
by controlled-potential electrolysis. Figure 3a shows the
chronoamperometric curves of the samples at −0.3 V vs
RHE in N2-saturated 0.1 M PBS electrolyte. Interestingly, all
the oxidation−reduction-derived samples exhibit similar
current densities of around 0.024−0.03 mA cm−2, which are
lower than that of the Fe foil (∼0.15 mA cm−2) by 5−6 times,
indicating a similar HER suppression effect for these samples.
The NH3 yield rates of the samples derived at 200, 400, and
500 °C are around 0.13, 0.15, and 0.12 μg cm−2 h−1,
respectively, lower than that of the sample derived at 300 °C
(∼0.19 μg cm−2 h−1), as shown in Figure 3b. A similar trend is
observed for the N2RR selectivity, with a maximum Faradaic
efficiency obtained for the 300 °C sample (Figure 3c). Since
the samples have different surface morphologies, as indicated
by the SEM images in Figure S12, their electrochemical surface
areas were also measured (Figure S7) and used to calculate the
surface-area-normalized N2RR activity. As shown in Figure 3d,
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the normalized RNH3 values for the samples derived at 200 and
300 °C are similar to but higher than those of other samples.
The different N2RR activities of the samples derived at
different temperatures can be attributed to their different Fe/
Fe oxide ratios. It seems that the Fe/Fe oxide ratios in the
samples derived at 200 and 300 °C are similarly optimized to
enhance the N2RR activity, while the sample derived at 300 °C
is more effective in suppressing the HER activity (due to more
oxidic Fe components), leading to an even higher N2RR
selectivity for the sample derived at 300 °C.
To date, all of the reported studies of Fe-based catalysts for
N2RR have mainly focused on Fe2O3 nanoparticles.8,9,32,33,38
To have a fair comparison between the Fe/Fe3O4 sample and
nanoparticle catalysts, commercial Fe, Fe3O4, and α-Fe2O3
nanoparticles were also evaluated for the N2RR under the same
conditions. Figure S13 shows representative TEM images of
the nanoparticles, which indicate particle sizes of around 20−
50 nm with high crystallinity. The Fe nanoparticles are coated
by passivating oxide layers on the surface, which contain both
Fe3O4 and Fe2O3. Accordingly, the XPS spectrum of Fe
nanoparticles also shows a major oxidic peak and a relatively
small metallic Fe peak. Electrodes were prepared by drop-
casting a suspension of the nanoparticles in a diluted Nafion
ethanol solution onto a piece of carbon paper with a total mass
loading of 1 mg cm−2 (of which 30 wt % is Fe or Fe oxide).
Figure 4a shows the chronoamperometric curves and NH3
yield rates of the three nanoparticle samples at −0.3 V vs RHE.
Despite similar current densities (∼0.2 mA cm−2), they show
different NH3 yield rates per mass catalyst, with the highest
yield rate of ∼2.5 μg mgcat.−1 h−1 for Fe nanoparticles, which is
around 2 times those of the Fe3O4 and Fe2O3 nanoparticles.
However, it is challenging to compare the surface-area-
normalized NH3 yield rates between the nanoparticles and
the Fe/Fe3O4 catalyst, as the surface area of the nanoparticles
cannot be measured using double-layer capacitance due to a
major contribution to the capacitance from the carbon
support.54 The Faradaic efficiencies for NH3 production on
the Fe, Fe3O4, and Fe2O3 nanoparticles are determined to be
1.9%, 0.9%, and 0.7%, respectively, which are comparable to
those in recent studies32,33,38 but much lower than that of the
Fe/Fe3O4 catalyst (∼8.29%) evaluated under the same
conditions. The comparative studies suggest that the Fe/Fe
oxide composite can be a more efficient catalyst for ambient
electrochemical NH3 synthesis.
DOI: 10.1021/acscatal.8b02585
ACS Catal. 2018, 8, 9312−9319
ACS Catalysis
4. CONCLUSIONS
We have developed an Fe/Fe3O4 catalyst for ambient
electrochemical NH3 synthesis, which was prepared by
oxidizing an Fe foil in flowing O2 at 300 °C followed by in
situ electrochemical reduction at −0.5 V vs RHE until a stable
state was reached. The Fe/Fe3O4 catalyst exhibits a high
Faradaic efficiency of 8.29% for NH3 production at −0.3 V vs
RHE in PBS electrolyte, which is around 120 times higher than
that of the Fe foil. The enhanced selectivity is enabled by a 9-
fold improvement of the intrinsic N2RR activity in comparison
to the Fe foil as well as an effective suppression of the HER
activity. Comparative studies of the Fe/Fe oxide samples
prepared at different oxidation temperatures suggest that the
N2RR catalytic performance may be correlated with the Fe/Fe
oxide ratio. The N2RR selectivity of the Fe/Fe3O4 catalyst is
also superior to those of Fe, Fe3O4, and Fe2O3 nanoparticles,
suggesting the Fe/Fe oxide composite to be an efficient
electrocatalyst for N2RR under ambient conditions. Our work
may provide new insights into the development of efficient,
cost-effective catalysts for ambient NH3 electrosynthesis.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b02585.
Additional experimental methods, materials character-
ization, and electrochemical measurements (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail for X.F.: Xiaofeng.Feng@ucf.edu.
ORCID
Xiaofeng Feng: 0000-0002-9473-2848
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Startup Fund and the VPR
Advancement of Early Career Researchers Award from the
University of Central Florida (UCF). L.H. acknowledges a
Doctoral Research Support Award from UCF. J.W. acknowl-
edges a Preeminent Postdoctoral Program (P3) Award from
UCF.
■
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9319 DOI: 10.1021/acscatal.8b02585

ACS Catal. 2018, 8, 9312−9319