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Electrochemical nitrogen reduction to ammonia
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at ambient conditions on nitrogen and
Cite this: Chem. Commun., 2019,
55, 687 phosphorus co-doped porous carbon†
Received 21st November 2018,
Accepted 11th December 2018 Pengfei Song, * Hao Wang, Li Kang, Baocheng Ran, Honghong Song and
Rongmin Wang
DOI: 10.1039/c8cc09256g
rsc.li/chemcomm
Reduction of nitrogen (N2) under ambient conditions and under-
standing the mechanism have been hugely challenging problems
for decades. Herein, we for the first time report that N,P co-doped
hierarchical porous carbon (NPC) can serve as an electrocatalyst for
the nitrogen reduction reaction (NRR) in an acid aqueous solution
under ambient conditions. The faradaic efficiency (FE) and yield of
production of NH3 on the NPC electrode reached as high as 4.2%
and 0.97 lg h 1 mg-1cat., respectively. Furthermore, the electro-
catalytic NRR mechanism on the NPC electrode was undoubtedly
confirmed by electrochemical in situ Fourier transform infrared
spectroscopy, and follows an associative pathway. These results
are predicted to offer a new platform in the rational design and
synthesis of highly efficient electrocatalysts for the NRR under
ambient conditions.
Ammonia (NH3) is one of the most common industrial chemicals
produced in today’s economy, which not only exhibits a strong
foothold in the agricultural, plastic, and textile industries, but
also represents a stable hydrogen carrier.1 The reduction of N2 to
NH3 is a kinetically complex and energetically challenging multi-
step reaction due to the chemical inertness of N2 and limited by
thermodynamics.2 Currently, the industrial production of NH3 is
dominated by the traditional Haber-Bosch process on a Fe-based
catalyst under extreme conditions (15–30 MPa, 350–550 1C),
wherein the input of H2 and energy are largely derived from
burning of fossil fuels and thus result in a large amount of CO2
emission.3 In contrast, in the natural world, plants and bacteria
have been producing NH3 from N2 and solvated protons under
ambient conditions, enabled by the FeMo cofactor of the
metalloenzyme nitrogenase (N2 + 6H+ + 6e - 2NH3).4 Inspired
Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of
Education, Key Laboratory of Polymer Materials of Gansu Province, Gansu
International Scientific and Technological Cooperation Base of Water-Retention
Chemical Functional Materials, College of Chemistry and Chemical Engineering,
Northwest Normal University, Lanzhou 730070, P. R. China.
E-mail: songpf@nwnu.edu.cn
† Electronic supplementary information (ESI) available: Experimental section
and supplementary figures. See DOI: 10.1039/c8cc09256g
This journal is © The Royal Society of Chemistry 2019
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by this biological nitrogen fixation process, intensive efforts
have been devoted to finding ways to mimic this process under
similarly mild conditions.
The electrocatalytic reduction approach is regarded as an
environmentally-benign process for NH3 production, since it
can be powered by a renewable electricity source and performed
at room temperature and atmospheric pressure.5 Since the
pioneering work of Pickett et al. reported the electrosynthesis
of NH3 by protonation of cis-[W(N2)2(PMe2Ph)4] under ambient
conditions,6 a variety of heterogenous electrocatalysts have
recently been experimentally investigated7 or it has been theoreti-
cally predicted that they are active to activate N2 under ambient
conditions.8 For example: a Bi4V2O11/CeO2 hybrid with an
amorphous phase,7a Au/CeOx–RGO,7b and a Li+/poly(N-ethyl-
benzene-1,2,4,5-tetracarboxylic diimide) system,7c just to name a
few, have been experimentally demonstrated to efficiently convert
N2 to NH3 in aqueous solution by an electrochemical process.
Meanwhile, a single Mo atom supported on defective boron nitride
monolayers,8a FeN3-embedded graphene,8b zincblende surfaces of
metal nitrides8c etc.8d,e,f have been theoretically predicted to be
electroactive for the NRR. Undoubtedly, producing NH3 by electro-
chemical conversion of N2 in aqueous solution under ambient
conditions is one of the most attractive processes in current
chemistry. However, one of the challenges associated with achiev-
ing the artificial scalable conversion of N2 to NH3 under mild
conditions is how to develop a highly chemically active and
selective yet low-cost electrocatalyst to activate N2 under ambient
conditions, because it is difficult to cleave the NRN triple bond
due to the extremely high bond energy (940.95 kJ mol 1) together
with its lack of a permanent dipole. Another huge challenge of the
NRR is how to unambiguously understand the NRR mechanism
because of the multistep and complex reaction in the N2
conversion process. These pose significant limitations on the
creation of a useful catalyst that can massively convert N2 to
NH3 under ambient conditions.
N-doped carbon materials have recently sparked world-
wide interests owing to their low cost, high efficiency and long-
term stability.9 Both quantum mechanical calculations10 and
Chem. Commun., 2019, 55, 687--690 | 687
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experimental investigations11 have reported that the incorporation

of nitrogen, especially pyridinic or/and pyrrolic nitrogen in the
carbon frameworks plays an indispensable role in the electro-
catalytic activity. Co-doping N-doped carbon materials with a
secondary heteroatom, such as B, S or P, can modulate the
electronic properties and regulate surface polarities to further
increase the electrocatalytic activity.12 However, the performance
and mechanism of Co-doping N-doped carbon in the NRR remains
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unexplored.
Herein, we firstly report a N,P co-doped hierarchically structured
nanocarbon (NPC) foam that can electrochemically convert N2
into NH3 in acidic aqueous solution at room temperature and
atmospheric pressure. The faradaic efficiency and yield of NH3
produced on the NPC electrode in 0.1 M HCl solution are as
high as 4.2% and 0.97 mg h 1 mg 1 catalyst, respectively. It is
noted that the achievable faradaic efficiency of the NRR on NPC is
higher than that of N-doped carbon containing a trace amount of Fe
(1.45%).13 The unprecedented performance results from sufficient Fig. 1 (a) A digital photograph of NPC foam. (b) SEM image of NPC, and
(c) low-magnification TEM image of NPC. (d) High-resolution TEM image
catalytic active sites in the carbon network and strong adsorption
of NPC in a particular area. (e) TEM image and corresponding C, N and P
capacity toward N2, and the hierarchical pore architecture covering element mappings.
from mesopore to macropore structures of NPC. More importantly,
the mechanism of the NRR process on N,P co-doped carbon has
been unambiguously demonstrated to follow an associative pathway
by electrochemical in situ FTIR spectroscopy, which is a milestone to
design novel efficient NRR electrocatalysts in the future.
NPC was prepared by the pyrolysis of polyaniline (PANi)
aerogels in the presence of phytic acid (details was provided in
ESI†). The scanning electron microscope (SEM) image of PANi
aerogels shows the hierarchical porous structure composed of
interconnected fibers of PANi aerogels (Fig. S1, ESI†). NPC foam
(Fig. 1a) could be easily prepared by direct pyrolysis of the PANi
aerogels. The NPC foam exhibits an interconnected pore structure
(Fig. 1b and c). It should be noted that there are massive graphitic
carbons existing in the NPC foam (Fig. 1d), implying that the
NPC foam has a high conductivity, a mandatory property for an
excellent electrocatalyst. A transmission electron microscopy
(TEM) image and the corresponding elemental mappings (Fig. 1e) Fig. 2 (a) N2 adsorption–desorption isotherms and (b) corresponding
pore size distributions. High-resolution XPS spectra of (c) N1s and
show a uniform distribution of N and P in the NPC.
(d) P2p of NPC.
Specific surface area plays a crucial role in electrocatalytic
activity for heterogeneous catalysts. Fig. 2a shows the Brunauer–
Emmett–Teller (BET) specific surface area of NPC, which is oxidized pyridinic-N (405.7 eV) (Fig. 2c), and the populations
measured to be 422 m2 g 1 with a pore volume of 0.22 cm3 g 1. It of them are 20.5%, 33.0%, 44.8 and 1.7%, respectively. It is
is clear from the SEM and TEM imaging and pore size distribution relevant that the pyridinic and pyrrolic N content in NPC form
(Fig. 2b) studies that the pore architecture of the NPC is hierarchical in excess of 50% of the total N content. Previous reports have
in nature, comprising macropores with pores traversing the entire demonstrated that the pyridinic and pyrrolic N atoms are the
ultrafine meso- to macropore range. In addition the large mesopores catalytic active sites in N-doped carbon.10 Moreover, the high
and macropores form interconnected three-dimensional networks, electronegativity of N (3.04) in the carbon framework influences
which can serve as transport highways to accelerate mass diffusion the charge density of the adjacent carbon atoms and leads to an
and promote electron exchange efficiency, which in turn will NPC catalyst with strong adsorption capacity towards molecular N2.
enhance the catalytic activity.14 Equally important, P–C (131.9 eV, 11.1%) and P–O (133.9 eV,
The X-ray photoelectron spectrum (XPS) for NPC (Fig. S2, 88.9%) bonds are present in the NPC (Fig. 2d), indicative
ESI†), shows typical C, N, P and O peaks. The elemental of the successful doping of P atoms into the carbon network
compositions provided in Table S1 (ESI†) show that the N and P (Fig. S2, ESI†).15 It was reported that P doping can create an
content of NPC is 3.6 at% and 3.3 at%, respectively. The XPS N1s asymmetry in the spin density and improve the activity of
spectra of the NPC sample can be separated into pyridinic-N carbon materials.16 In what follows, we will discuss the highly
(399.0 eV), pyrrolic-N (400.7 eV), graphitic-N (401.7 eV), and efficient NRR performance of NPC.

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All the electrochemical experiments were conducted at room
temperature using NPC as the working electrode in 0.1 M HCl
aqueous solution (pH = 1) electrolyte. Firstly, cyclic voltam-
metry (CV) measurements on the NPC cathode were carried out.
The CV exhibited a cathodic shoulder under a N2 atmosphere
(Fig. S3, ESI†), which suggests pronounced electrocatalytic
activity of NPC for the NRR. During the electrocatalytic process,
N2 gas with a flow rate of 10 mL min 1 is supplied through a
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feed gas stream to the electrolytic cell, and protons (H+ ions)
from the electrolyte react with N2 on the surface of NPC to form
NH3 with potentiostatic reduction at the cathode,7b the integrated
system was tested for 3 h. The highest faradaic efficiency (FE) and
ammonia yield are achieved at 0.2 V vs. RHE, wherein the best
values can reach 4.2% and 0.97 mg h 1 mg 1 catalyst, respectively
(Fig. 3a and b). The reaction product NH3 was measured by the
indophenol blue method (Fig. S4–S6, ESI†). It is noted that there
was no hydrazine (N2H4
H2O) detected (Fig. S7 and S8, ESI†),
indicating the excellent selectivity of the NPC for the production
of NH3. In Fig. 3a, the yields of NH3 decrease significantly beyond
0.2 V vs. RHE, which is attributed to a competitive reduction of
N2 and hydrogen species on the electrode surface (Fig. S9–S11,
ESI†).17 It is clear that the faradaic efficiency of ammonia
formation is related to the side reaction of hydrogen evolution,
thus the formation of a mixture of NH3 and H2 in the N2 stream
leaves the electrolytic cell. As shown in Fig. 3c, the current density
exerts good stability at different potentials. Moreover, Fig. 3d
shows that both the ammonia yield and faradaic efficiency
undergo no obvious changes during 12 h, and then decreased
about 0.26 mg h 1 mg 1 catalyst and 0.65% after 24 h (Fig. S12
and S13, ESI†), which is probably attributed to the loss of P
species from NPC in the NRR process (Table S1 and Fig. S2, ESI†).
To confirm N2 gas as the source of ammonia in the present
system, the NRR with isotope-labeled 15N2 gas was performed
and the product was collected by freeze-drying of the electrolyte.18
The indophenol assays of electrocatalytically reacted 15N2 sam-
ples showed a strong 15N-labeled indophenol anion at 199 m/z
Fig. 3 (a) The yields of NH3 and (b) faradaic efficiencies on the NPC
electrode at the corresponding potential. (c) Chronoamperometric curves
of the NPC electrode at the corresponding potentials. (d) The yields of NH3
and faradaic efficiencies of NPC by bubbling electrolyte with pure N2
during 24 h stability test under 0.2 V vs. RHE.
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with relative intensity higher than the natural abundance ratio of
14
N : 15N nuclei (Fig. S14, ESI†). Additionally, it was found that
there is no product of NH3 0.2 V vs. RHE under Ar gas bubbling
(Fig. S15 and S16, ESI†). These results indicate that the source of
nitrogen in the ammonia product is atmospheric N2.
The activity of activated carbon without heteroatom-doping
in the NRR has also been tested. As shown in Fig. S17 (ESI†),
there is no NH4Cl produced in acid solution at 0.2 V vs. RHE,
which confirmed that NH3 was produced exclusively from the
NRR by the NPC electrode. It is well known that pyridinic and
pyrrolic N atoms are defects, which could act as catalytic sites
for various catalytic reactions. The N,P co-doping can induce
charge redistribution, regardless of whether the dopants have a
higher (as N) or lower (as P) electronegativity than that of
carbon, which could create charged sites that are favorable
for N2 adsorption.19 In this context, it is considered that the
massive pyridinic and pyrrolic N atoms and the N,P co-doping
effect of NPC facilitate the NRR process.
Electrochemical in situ Fourier transform infrared spectros-
copy (in situ-FTIR) is a powerful tool to monitor the reaction
process and reveal the complex reaction mechanism. Fig. 4a
shows an in situ FTIR spectrum that was observed on the NPC
cathode surface at 0.2 V vs. RHE for 4000 s under bubbling
N2 in electrolyte solution. It is clear that the absorption at
1106 cm 1 is assigned to the N–N stretching, the intensity of
which increased with increasing reaction time. This clearly
demonstrated that the NRN bond is cleaved into a single
bond on the NPC cathode surface.20 In addition, two weak
absorptions at 1270 and 1461 cm 1 were clearly observed,
which are attributed to –NH2 wagging and H–N–H bending,
respectively.21 Simultaneously, the intensity of N–H stretching
of H–N–H bending at 3235 cm 1 in an in situ-FTIR spectrum
Fig. 4 (a) Electrochemical in situ-FTIR spectra of the NRR on the NPC
electrode. (b) Associative mechanism of the NRR process on NPC.
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increases with increasing reaction time.22 These results clearly
shows that N2Hy (1 % y % 4) species were formed on the surface
of NPC in the NRR process.
Accordingly, it is preferably suggested that the mechanism
of NPC in the NRR can be either associative or dissociative.23
The dissociative mechanism considers that the NRN bond is
cleaved into two nitrogen atoms on the catalyst surface before
the addition of hydrogen atoms. In contrast, the associative
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mechanism suggests the addition of protons prior to the
cleavage of the NRN bond. Based on the in situ FTIR results,
the N2Hy species clearly formed on the surface of NPC in the
electrocatalytic process, thus we confirmed that the NRR
mechanism on the surface of the NPC follows an associative
mechanism (Fig. 4b). The molecular N2 is firstly adsorbed on the
surface of the heterogenous catalyst, and then protons get attached
to N2 to form a –NRN–H bond, which could weaken the stable
NRN bond. In the second step, another proton further hydro-
genates the weakened –NRN–H bond and forms a –H–NQN–H
bond; thereafter, the continuous electron transfer and hydroge-
nation of –H–NQN–H intermediates occurs to form –H–N–NH2,
and eventually NH3 is formed on the surface of NPC and the NRR
is achieved under ambient conditions in 0.1 M HCl solution.
In summary, we demonstrated that N,P co-doped hierarchical
carbon can serve as an efficient electrocatalyst for the NRR under
ambient conditions in aqueous solution. Furthermore, electro-
chemical in situ-FTIR experiments undoubtedly revealed that the
NRR process on the N,P co-doped carbon follows an associative
pathway. Unambiguous understanding of the complex NRR
mechanism is very important for rationally designing useful
electrocatalysts for the NRR under ambient conditions. This study
offers potential to readily develop a highly efficient yet low-cost
electrocatalyst for N2 fixation in aqueous solution under ambient
conditions.
This work was supported by the National Natural Science
Foundation of China (no. 21564013), the Science and Technology
Program of Gansu Province (no. 1604GKCA010), the Foundation of
Lanzhou Science & Technology Bureau (no. 2014-2-4), and the
Foundation of northwest normal university (no. NWNU-LKQN-17-2).
Conflicts of interest
There are no conflicts to declare.
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