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Ammonia Synthesis Very Important Paper
High Efficiency Electrochemical Nitrogen Fixation Achieved with
a Lower Pressure Reaction System by Changing the Chemical
Equilibrium
Hui Cheng+, Peixin Cui+, Fangrui Wang, Liang-Xin Ding* und Haihui Wang*
Abstract: We demonstrate a simple and effective chemical
equilibrium regulation strategy to improve the efficiency of
electrochemical ammonia synthesis by constructing electro-
chemical reaction system that works at significantly lower
pressure than the Haber–Bosch process. Transferring the ni-
trogen reduction reaction from ambient conditions to a lightly
pressurized environment not only accelerates the activation of
the N/N triple bond but also inhibits the competing reaction of
hydrogen evolution while promoting the dissolution and dif-
fusion of nitrogen. The verification experiment of using well-
designed Fe3Mo3C/C composite nanosheets as the nitrogen
reduction catalyst shows that the lower pressure reaction sy-
stem can improve the Faradaic current efficiency by one order
of magnitude. Moreover, the comparatively low-pressure
reaction system can greatly reduce the cell voltage of the am-
monia synthesis reaction (up to 33 %) even at the relatively low
pressure of 0.7 MPa, which is of significance for decreasing the
energy consumption of electrochemical ammonia synthesis
under mild conditions.
Introduction
Ammonia (NH3) is one of the most fundamental bulk
chemical materials in modern industrial and agricultural
production,[1] helping to solve the food supply problem for
billions of people in todayQs world and playing a crucial role in
promoting the development of human society.[2] In addition,
the NH3 molecule is also considered to be a good hydrogen
carrier because the mass percentage of hydrogen is as high as
17.6 % and it is easily liquefied, stored, and transported.[3]
Currently, the source of NH3 throughout the world mainly
depends on synthesis by the Haber–Bosch method.[4] Alt-
hough this synthesis technology has experienced nearly one
hundred years of development, it still needs to be conducted
[*] H. Cheng,[+] F. Wang, Prof. L.-X. Ding, Prof. H. Wang
School of Chemistry and Chemical Engineering, South China Uni-
versity of Technology
No. 381 Wushan Road, Guangzhou 510640 (China)
E-Mail: lxding@scut.edu.cn
hhwang@scut.edu.cn
Dr. P. Cui[+]
Key Laboratory of Soil Environment and Pollution Remediation, In-
stitute of Soil Science, the Chinese Academy of Sciences
Nanjing 210008 (China)
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201910658.
Angew. Chem. 2019, 131, 15687 – 15693 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemie
Deutsche Ausgabe: DOI: 10.1002/ange.201910658
Internationale Ausgabe: DOI: 10.1002/anie.201910658
at a high temperature and high pressure,[5] and the energy in
synthetic NH3 is close to 2 % of the total energy consumption
every year.[6] Moreover, because the hydrogen is converted
from fossil fuels, its acquisition process will inevitably in-
crease the emission of CO2.[7] Therefore, in view of the in-
creasing energy and environmental problems, it is necessary
to develop green synthetic NH3 technology under mild con-
ditions.
Compared with the Haber–Bosch process, the elec-
trocatalytic nitrogen reduction reaction (NRR) synthesis of
NH3 can be conducted at mild conditions,[8] and the source of
nitrogen and water is extensive,[9] so it is considered to be
a potential replacement technology for synthetic NH3.[10]
However, although a large number of studies have confirmed
that NH3 synthesis under mild conditions can be achieved via
electrochemical strategies, the efficiency of NH3 synthesis is
far from comparable to that of the Haber–Bosch method. In
general, the main factors restricting the development of the
electrochemical synthesis of NH3 technology are as follows:
1) The bond energy of the nitrogen molecule (N/N) is very
high (940.95 kJ mol@1), and it has difficulty being catalyzed
and activated under mild conditions and especially under
ambient conditions.[11] 2) Since the hydrogen evolution po-
tential and the nitrogen reduction potential are very close, the
hydrogen evolution reaction (HER) as a competitive reaction
can severely restrict the efficiency of the nitrogen reduction
synthesis of NH3.[12] 3) The solubility of nitrogen especially
under ambient conditions is fairly low, and the enrichment
and overflow of hydrogen will limit the nitrogen available for
the reaction and its diffusion adsorption.[13] Therefore, it is
difficult to achieve a high NH3 yield rate in terms of the
amount of reactive materials.
To overcome the above obstacles, extensive studies have
focused on the development of efficient nitrogen reduction
catalysts and sought suitable strategies to inhibit hydrogen
evolution.[14] However, while these efforts have to some ex-
tent increased the selectivity and the NH3 yield rate of ni-
trogen reduction NH3 synthesis, the performance of the
electrochemical synthesis of NH3 is still far below the level
that can be practically applied. Moreover, it is very difficult to
further improve the current efficiency and the NH3 yield rate
of electrochemical NH3 synthesis according to the widely used
current strategy because protons are easier to activate than
N/N and the inhibition of the hydrogen evolution will in-
evitably restrict the nitrogen activation ability of the catalyst,
with hydrogen remaining indispensable as the raw material
for the reaction.[15] As a consequence, the unavoidable com-
petitive reaction of hydrogen evolution makes it difficult to
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simultaneously obtain a high activity and high selectivity for
a nitrogen reduction catalyst. Therefore, how to further im-
prove the current efficiency and yield of synthetic NH3 syn-
chronously still remains a challenge.
Herein, we look beyond the conventional catalyst design
and the pursuit of an inhibition hydrogen evolution strategy,
and for the first time have proposed utilizing a comparatively
low-pressure electrochemical reaction system to improve the
efficiency of electrochemical NH3 synthesis under mild con-
ditions. The advantages of this strategy include: 1) The direct
reaction of nitrogen and water to the synthesis of NH3 is
a volume-reduced reaction because NH3 exists in the form of
NH4+. Therefore, according to Le ChatelierQs principle, the
increased pressure is favorable for the balance to move in the
direction of the synthetic NH3. 2) Because the process of
hydrogen production by water electrolysis is a reaction of an
increasing volume, the increased pressure is also beneficial for
inhibiting the hydrogen evolution and thus to improve the
selectivity of the nitrogen reduction. 3) The increased pres-
sure is beneficial for increasing the dissolution concentration
of nitrogen in an aqueous solution,[16] which not only ensures
the supply of the nitrogen source but also helps the diffusion
of nitrogen to the catalyst electrode to participate in the
reaction.[17] Attracted by these advantages, herein we selected
a well-designed Fe3Mo3C/C composite as a nitrogen reduction
catalyst candidate to verify the NH3 synthesis efficiency of the
proposed lower pressure electrochemical reaction system.
Specifically, the verification experiment shows that, compa-
red to the ambient conditions, the lower pressure reaction
system can improve the Faradaic current efficiency by one
order of magnitude. Furthermore, the employment of the
lower pressure reaction system can also greatly reduce the
reaction cell voltage.
Results and Discussion
The selection of bimetallic Fe-Mo carbide (Fe3Mo3C) as
the candidate for nitrogen reduction catalyst is mainly in-
spired by biological nitrogenase and the industrial NH3 syn-
thesis catalyst.[1c] Considering that many nitrogen reduction
catalysts may have false positive results,[18] we first evaluate
the possible nitrogen activation ability of Fe3Mo3C via
a theoretical prediction with a density of state (DOS) and
density functional theory (DFT). According to the DOS cal-
culation and analysis (Figure 1 a), when the Fe and Mo ele-
ments are combined to form bimetallic carbides, the top va-
lence band (@4.0 eV–0.0 eV) near the Fermi level is mainly
composed of Fe d and Mo d valence orbitals. The abundant
valence electron orbitals suggest that Fe3Mo3C may have
a strong N2 activation ability. To better understand the N2
adsorption and activation mode of Fe3Mo3C, the DOS cal-
culation was further performed to analyze the overall elec-
tronic structure of Fe3Mo3C after N2 adsorption (Figure 1 a–

Figure 1. a) The density of state (DOS) of Fe3Mo3C and the projected density of state (pDOS) of Fe3Mo3C (440) and Fe3Mo3C (440) after N2
adsorption. b) Top view of the crystal structure of Fe3Mo3C (440). c) The crystal structure of Fe3Mo3C (440) after N2 adsorption. d) Gibbs free-
energy diagrams of the electrochemical reduction of N2 to NH3 on Fe3Mo3C (440). The inset in (d) is the N2 adsorption energy of Fe3Mo3C.

15688 www.angewandte.de T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. 2019, 131, 15687 – 15693
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c). The results show that the N2 p valence orbitals are con- tively. Furthermore, X-ray photoelectron spectroscopy (XPS)
tained and overlap with the d valence orbitals of Fe and Mo, and X-ray absorption near-edge structure (XANES) spec-
indicating that, when Fe3Mo3C adsorbs N2, the d valence troscopy were also employed to analyze the valence state of
electron orbitals of Fe and Mo can be simultaneously hy- the metal elements in Fe3Mo3C. The high resolution XPS
bridized with the p valence electron orbitals of N, thus wea- spectra in Figure 2 a show that the valence states of Fe in
kening the N/N to better activate N2. Furthermore, the fea- Fe3Mo3C/C are + 2 and + 3,[20] while the main valence state of
sibility of the N2 reduction on the Fe3Mo3C surface was ana- the Mo elements is + 3 (Figure 2 b).[21] The Fe absorption edge
lyzed by using the free energy of the NRR reaction. The of Fe3Mo3C/C in Figure 2 c suggests that the Fe species in
analysis results show that the N2 adsorption and catalytic re- Fe3Mo3C/C is in a high state, which is similar to that of the
duction mode on Fe3Mo3C are unique, with a combined as- Fe2O3 reference. Therefore, we can confirm that the main
sociative path and dissociative path to develop a more energy valence state of Fe in Fe3Mo3C/C is + 3. In addition, according
favorable path: an associative-dissociative path.[19] In this to the K-edge XANES spectra in Figure 2 d, the Mo absorp-
process, Fe3Mo3C utilizes one Fe atom and two Mo atoms to tion edge of Fe3Mo3C/C is located between the Mo foil and
connect with the N atoms at both ends of N2 and activate them MoO2 reference and is close to MoO2, inferring that the va-
via the dissociative path; later, the N2 molecule is gradually lence state of the Mo element is approximately + 3. In other
hydrogenated with the associative path (Figure 1 c,d). Be- words, the main valence states of the Fe and Mo elements in
nefiting from this unique mode, Fe3Mo3C possesses a strong Fe3Mo3C/C are both + 3.
N2 adsorption capacity (Figure 1 d inset). Besides, the free The electrocatalytic nitrogen reduction performance of
energy analysis for the N2 reduction reaction on Fe3Mo3C Fe3Mo3C/C was first assessed under ambient conditions using
shows that the hydrogenation reaction path of N2 can be a gas-tight two-compartment cell with continuous injection of
followed via exothermic reaction 1 or reaction 2 (Figure 1 d), nitrogen. To accurately conduct a qualitative and quantitative
theoretically indicating that the NRR reaction can be per- analysis of NH3 after an NRR test, the indophenol blue me-
formed on Fe3Mo3C. Based on the calculation and analysis thod combined with nuclear magnetic method was adopted
results of the DOS and DFT, it can be predicted that Fe3Mo3C (Figure S5–S6). Before systematically evaluating the NRR
has potentially superior catalytic activity for nitrogen reduc- performance of Fe3Mo3C/C materials, some of the necessary
tion. control experiments were carried out and the corresponding
According to the results of the above theoretical predic- results are as follows: 1) Under the argon conditions, NH3 was
tions, and in order to expose as many active sites as possible, not detected in the electrolyte, showing that the NRR process
Fe3Mo3C embedded in the carbon nanosheets (denoted as has not been disturbed by nitrogen impurities (Figure S7);
Fe3Mo3C/C) were designed and synthesized via a facile mol- 2) After testing in argon, the supplied gas was immediately
ten salt synthesis method. The X-ray diffraction (XRD) pat- switched to N2, and NH3 was detected in the electrolyte after
tern in Figure S1 in the Supporting Information shows that a 2 h electrolytic reaction test. This preliminary confirms that
the diffraction peak of the synthesized sample matches with the as-prepared Fe3Mo3C/C catalyst has NRR catalytic ac-
the Fe3Mo3C standard PDF card (47-1191, Table S1 in the tivity (Figure S7–S8); 3) The NH3 content in the electrolyte
Supporting Information). According to ScherrerQs
formula, the grain size of Fe3Mo3C is preliminarily
calculated to be approximately 22.5 nm (Table S2).
Besides, transmission electron microscopy (TEM)
and scanning transmission electron microscopy-en-
ergy dispersion spectrum (STEM-EDS) mapping
were used to analyze the morphological features and
element distribution of Fe3Mo3C/C. The TEM ana-
lysis result in Figure S2 shows that the structure of the
material is composed of Fe3Mo3C nanoparticles em-
bedded in the carbon nanosheet layer. The size of the
nanoparticles is approximately 20 nm, which is con-
sistent with the results calculated by ScherrerQs for-
mula. In addition, the EDS mapping reveals the
uniform distribution of the Fe, Mo and C elements in
the nanoparticles (Figure S3). The high-resolution
electron microscopy (HRTEM) analysis results show
that the Fe3Mo3C nanoparticles have clearly visible
lattice fringes (Figure S4), indicating the high cry-
stallinity of Fe3Mo3C nanoparticles. The analysis of
the fast-Fourier transform (FFT) technique identifies
that the interplanar spacing of the lattice fringes in
Figure 2. a) High-resolution Fe 2p XPS spectra of Fe3Mo3C/C. b) High resolu-
the nanoparticles are 0.227 nm and 0.256 nm (Fig- tion Mo 3d XPS spectra of Fe3Mo3C/C. c) Fe K-edge XANES spectra of Fe3Mo3C/
ure S4 insets), which correspond to the (422) and C, Fe foil reference, FeO reference and Fe2O3 reference. d) Mo K-edge XANES
(331) crystal plane of the Fe3Mo3C crystal, respec- spectra of Fe3Mo3C/C, Mo foil reference, MoO2 reference and MoO3 reference.

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Forschungsartikel
with different reaction times was analyzed (Figures S7–S8).
The increase of NH3 content is proportional to the extension
of the reaction time, further proving the effectiveness of the
Fe3Mo3C/C material in the NRR performance; 4) Finally, the
15
N2 isotope tracer experiment was used to show that the NH3
product in the electrolyte was completely derived from the
supplied N2, because there is no triple peak signal of 14NH4+
when only 15N2 was supplied (Figure 3 a).[15, 18, 22]
After confirming the true nitrogen reduction activity of
the catalyst and the reliability of the NH3 detection methods,
the NRR properties of Fe3Mo3C/C at different potentials
were evaluated. The experimental results are shown in Fig-
ure 3 b and Figure S9–S10. As seen, the NH3 yield rate of
Fe3Mo3C/C gradually increases with the negative shift of
working potential and reaches the highest NH3 yield rate of
13.10 mg h@1 cm@2 at @0.5 V, which is comparable to that of the
recently reported NRR catalytic materials (Table S3) and
shows an expected nitrogen catalytic reduction performance.
The excellent NRR performance of Fe3Mo3C/C verifies the
forecast of the DFT theoretical calculation: that is, the reac-
tion energy required for the nitrogen reduction reaction is low
Figure 3. Catalytic performances of Fe3Mo3C/C in 1 m KOH aqueous solution:
a) 1H NMR spectra of the electrolyte fed by 14N2 and 15N2 after the electrolytic
reaction. b) The NH3 yield rate of Fe3Mo3C/C at different potentials under am-
bient conditions. c) NH3 yield rate of Fe3Mo3C/C under different pressurized
conditions. d) Faradaic efficiency of Fe3Mo3C/C under different pressurized con-
ditions. e) LSV curves of Fe3Mo3C/C recorded at approximately @0.4 V–0.4 V un-
der ambient and 0.7 MPa pressurized conditions. f) The chromatograms for
product H2 after 2 h electrolysis at @0.025 V under ambient and 0.7 MPa pres-
surized conditions.
15690 www.angewandte.de T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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when Fe3Mo3C is acting as the catalyst, and hence the ni-
trogen reduction reaction could be conducted rapidly. Ho-
wever, although Fe3Mo3C/C exhibits an excellent NH3 yield
rate perform, it should be noted that this high NH3 yield rate
of Fe3Mo3C/C is achieved at the expense of large working
current because the Faradaic efficiency of Fe3Mo3C/C at dif-
ferent potentials is very low (Figures S9–S10). The low Fara-
daic efficiency should be due to the dominant competitive
reaction of hydrogen evolution, which has been proved in our
previous research work.[15] In addition, in view of the fact that
stability is also an important indicator for evaluating the
performance of catalysts, here the catalytic stability of
Fe3Mo3C/C during the electrolysis process was evaluated by
the cyclic electrolysis reaction, which was performed at the
potential corresponding to the highest NH3 rate of Fe3Mo3C/
C (@0.5 V). The experimental results in Figure S11 shows that
the NH3 yield rate of Fe3Mo3C/C still remained at 93.13 %
after 10 cycles, which proves that Fe3Mo3C/C possesses a high
catalytic stability. The high catalytic stability of Fe3Mo3C/C
should be attributed to its stable composition and structure. A
typical evidence is that the valence states of the Fe and Mo
elements in Fe3Mo3C/C do not change significantly
after electrolysis (Figure S12).
With a desire for the possible positive effect of
pressure on the chemical equilibrium movement of
NH3 synthesis, we constructed a electrochemical
reaction system to work under pressures that are
considerably lower than those of the Haber–Bosch
process and further evaluated the performance of
NH3 synthesis using Fe3Mo3C/C as a catalyst candi-
date for nitrogen reduction under the pressured
reaction system. Specifically, the pressurized reaction
system is achieved by moving the reaction device at
ambient conditions (i.e. 25 8C, 0.1 MPa) directly into
the pressured kettle in the form of an open system.
The typical pressurized reaction device is shown in
Figure S13. Note that, before starting the pressurized
reaction, the N2 pressure in the system was pressuri-
zed to the target pressures in this study (0.3, 0.5, and
0.7 MPa), and the system was kept static for 1 h to
make the N2 fully dissolve in the solution. That is to
say, the electrolytic process under pressurization
conditions is a closed and static reaction, and nitrogen
is no longer continuously injected into the electrolytic
cell during the electrolytic process. Moreover, to en-
sure that all components in the electrocatalytic device
can operate normally at the pressurized environment,
a series of control experiments were conducted be-
fore evaluating the NRR performance of Fe3Mo3C/C.
Typically, to probe the possible effect of pressure on
the reference electrode, the position of the Fe3+/Fe2+
redox peaks of the K3[Fe(CN)6]/K4[Fe(CN)6] (the
concentration of K3[Fe(CN)6] and K4[Fe(CN)6] are
both 0.1m, and the working electrode is replaced with
a blank carbon cloth without coating any catalysts) at
normal ambient and 0.7 MPa pressurized conditions
was compared via a cyclic voltammetric (CV) test.
The almost same peak position in Figure S14 shows
that the given pressurized conditions have negligible
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effect on the conventional electrochemical tests, suggesting
that the catalytic performance of nitrogen reduction can be
accurately evaluated in a pressurized (low pressure) reaction
system.
To systematically investigate the effect of the pressurized
conditions on the NRR catalytic performance of Fe3Mo3C/C,
the chronoamperometry curves of electrolysis for 2 h at ap-
plied potentials from @0.1 V to 0.1 V under different pres-
sured conditions (0.3, 0.5, and 0.7 MPa) were recorded (Fig-
ure S15) and the corresponding NRR performances were
quantitatively analyzed, and the results are shown in Fig-
ure 3 c,d. It can be clearly seen that there is a positive corre-
lation between the ammonia production performance and
pressure, and the highest NH3 yield rate and Faradaic ef-
ficiency can be obtained at 0.7 MPa pressurized conditions.
Especially when the highest NH3 yield rate is obtained, the
corresponding Faradaic efficiency is also improved, which
indicates that the increase of Faradaic efficiency under pres-
surization is not at the expense of the nitrogen activation
ability of the catalyst. Specifically, the highest NH3 yield rate
reaches 13.55 mg h@1 cm@2 at @0.025 V and the highest Faradaic
efficiency of 14.74 % is achieved at 0.1 V under 0.7 MPa
pressurized conditions, which is significantly higher than that
under ambient conditions. The significant increase of Faradaic
efficiency should be attributed to the inhibition of competi-
tion reaction of hydrogen evolution via pressurization, which
can be confirmed by the linear sweep voltammetry scanning
(LSV, Figure 3 e) and the detection results of hydrogen evo-
lution quantity (Figure 3 f). As shown in Figure 3 e, compared
with ambient conditions, the reaction current recorded by the
LSV curve decreases sharply in the range of @0.1 V–0.1 V
when the system pressure rises to 0.7 MPa, suggesting that the
hydrogen evolution reaction is significantly suppressed. In
contrast, the current under pressurized conditions tends to
increase under further negative scanning (< @0.1 V), which
should be due to the optimization of the gas mass transfer
process under pressure. Moreover, the total H2 output (Fig-
ure 3 f, S16, detailed calculation can be seen in the Supporting
Information) detected by the gas chromatograph further
verify the suppression of hydrogen evolution at pressurization
conditions, in which the H2 output at pressurization condi-
tions (0.71 mL at 0.7 MPa pressurized conditions) is three ti-
mes lower than that at ambient conditions (2.42 mL at
0.1 MPa). Moreover, it should be pointed out that, except for
the NH3 yield rate under 0.7 MPa pressurized conditions, the
NH3 yield rate under other pressurized conditions seems to be
lower than that under ambient conditions, which is mainly due
to the fact that, unlike the continuous injection of nitrogen
into the reaction cell under ambient conditions, it is a closed
and static reaction under pressurized conditions, and there is
no continuous injection of nitrogen during the electrolysis
process. This is well confirmed by the significant decrease of
NH3 yield rate without continuous nitrogen injection during
the electrolysis process under ambient conditions (Fig-
ure S17).
In addition, we also note that, with an increase in the
pressure, the working potentials corresponding to the highest
NH3 yield rate and Faradaic efficiency have a significantly
positive shift. The potential of the highest NH3 yield rate
Angew. Chem. 2019, 131, 15687 – 15693 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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shifts from @0.5 V (ambient conditions, Figure 3 b) to
@0.025 V (0.7 MPa pressurized conditions, Figure 3 c), which
is significantly better than other reported data (Figure S18)
and means that pressurization is beneficial for reducing the
overpotential of the nitrogen reduction reaction. This expe-
rimental phenomenon shows that pressurization can not only
inhibit hydrogen evolution but also affect the thermodynamic
process of NRR to a certain extent. In theory, according to Le
ChatelierQs principle, pressurization and the resulting increase
in nitrogen solubility should be beneficial for the movement
of the chemical equilibrium to ammonia formation. From this
point of view, here the significantly reduced overpotential of
the nitrogen reduction reaction should be attributed to the
increase in the dissolved nitrogen concentration in the pres-
surized environment, which strengthened the diffusion ad-
sorption of nitrogen on the catalyst and thus weakened the
restriction of the nitrogen mass transfer process on the ni-
trogen reduction reaction (Figure 4 a). Meanwhile, it is pre-
cisely because of the positive shift of the nitrogen reduction
potential and the suppression of the hydrogen evolution
competition reaction by pressurization that the nitrogen re-
duction reaction can obtain a high Faradaic efficiency at
a more positive potential.
Based on the aforementioned results, we further assessed
the cell voltage of the synthetic ammonia in the pressure
reaction system. In general, employing a two-electrode sy-
stem to evaluate the cell voltage of the reaction system is the
most appropriate method, but considering that the water
electrolysis reaction will dominate, as a compromise, here the
cell voltage of the nitrogen reduction reaction system was
expressed as the sum of the absolute values of the cathode
NRR potential with the highest NH3 yield rate and the anode
oxygen evolution potential corresponding to the working
current at the highest NH3 yield rate (Figure 4 b, the potential
at a current of 37.5 mA under ambient conditions and
0.38 mA under 0.7 MPa pressurized conditions, respectively).
According to the above interim definition and from the res-
ults recorded by the anodic LSV curves (Figure S19 and
Figure 4 c), it can be seen that, corresponding to the cathodic
nitrogen reduction reaction, the anodic oxygen evolution
potential is 2.175 V and 1.767 V under ambient and 0.7 MPa
pressurized conditions, respectively. As mentioned earlier,
the cathode NRR potential with the highest NH3 yield rate
under 0.7 MPa pressurized conditions is @0.025 V, which is
significantly higher than that of under ambient conditions
(@0.5 V). According to the above data, the cell voltage under
ambient and 0.7 MPa pressurized conditions can be calcula-
ted to be 2.675 V and 1.792 V (Figure 4 d), respectively.
Clearly, compared with the cell voltage under ambient con-
ditions, the cell voltage at 0.7 MPa is reduced by about 33 %.
As a proof of concept, here the comparison results clearly
shows that the cell voltage of electrochemical ammonia syn-
thesis can be significantly reduced by pressurization when the
same or similar NH3 yield rate is obtained, further demon-
strating the superior advantages of the pressurized system.
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Figure 4. a) Schematic illustration of diffusion adsorption of N2 and H2O on a catalyst surface under ambient conditions (Top) and 0.7 MPa
pressurized conditions (Bottom). b) Chronoamperometry curves of Fe3Mo3C/C at the corresponding potential when the highest NH3 yield rate
was obtained under ambient and 0.7 MPa pressurized conditions. c) The corresponding LSV curves at anode side under ambient and 0.7 MPa
pressurized conditions (extract from Figure S19). d) Cell voltage of electrochemical ammonia synthesis under ambient and 0.7 MPa pressurized
conditions.

Conclusion BL14W1 at Shanghai Synchrotron Radiation Facility for

In summary, we have designed a lower pressure electro-
chemical NH3 synthesis system and demonstrated that ap-
plying a certain pressure is a simple and effective strategy to
improve the current efficiency without compromising the
NH3 yield rate. The verification experiment of using
Fe3Mo3C/C as a nitrogen reduction catalyst suggested that the
improvement in the current efficiency should be mainly due
to the inhibition of the hydrogen evolution competition
reaction and the optimization of the gas mass transfer process
by applying a relatively low-pressure reaction system. This
verification experiment also confirmed that applying pressure
can greatly reduce the cell voltage of the electrochemical
reaction system, which undoubtedly provides a new pathway
for the development of efficient and energy-saving electro-
chemical NH3 synthesis technology. In addition, although the
pressure reaction is expected to improve the yield and ef-
ficiency of NH3 synthesis, there is no doubt that the effective
implementation of the pressure reaction also requires an ef-
ficient nitrogen reduction catalyst. Therefore, the develop-
ment of high efficiency nitrogen reduction catalysts matching
the lower pressure reaction system will be attractive work.
Acknowledgements
This work was supported by National Natural Science Foun-
dation of China (21776099, 41701359), Guangdong Special
Support Program (2017TQ04N086), and National Key R&D
Program of China (2016YFA0202601). We thank Xusheng
Zheng and Peixin Cui for helpful XANES testing and ana-
lysis. We also acknowledge the beamline BL10B at National
Synchrotron Radiation Laboratory, and the Beamline
characterizations.
Conflict of interest
The authors declare no conflict of interest.
Stichwçrter: Ammoniaksynthese · Carbide · Elektrokatalyse ·
Stickstoff-Fixierung · Stickstoffreduktion
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Angew. Chem. 2019, 131, 15687 – 15693
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Manuskript erhalten: 20. August 2019
Akzeptierte Fassung online: 10. September 2019
Endggltige Fassung online: 24. September 2019
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