Carbon 148 (2019) 540e549

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Chemical activation of nitrogen and sulfur co-doped graphene as

defect-rich carbocatalyst for electrochemical water splitting
Xintong Li a, 1, Xiaoguang Duan b, 1, Chen Han c, Xiaobin Fan a, Yang Li a, Fengbao Zhang a,
Guoliang Zhang a, Wenchao Peng a, *, Shaobin Wang b
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China
b
School of Chemical Engineering, The University of Adelaide, Adelaide, SA, 5005, Australia
c
State Key Laboratory of Chemical Engineering, East China University of Science and Technology (ECUST), Shanghai, 200237, China

a r t i c l e i n f o a b s t r a c t

Article history: Heteroatom-doped carbonaceous materials are the most promising substitutes of noble metals as green
Received 21 January 2019 catalysts for electrochemical water splitting. In this study, nitrogen and sulfur co-doped graphene (N,S-G)
Received in revised form is synthesized via a one-pot calcination method. Subsequently, N,S-G is activated by ZnCl2 to enlarge the
17 March 2019
specific surface areas to construct a porous structure (a-N,S-G) The chemical activation can simulta-
Accepted 6 April 2019
Available online 9 April 2019
neously regulate the elemental composition and porous structure of SNG toward enhanced carbocatal-
ysis. As a result, in the OER process, the overpotential of a-N,S-G is only 330 mV vs. RHE at 10 mA cm
2 in
1 M KOH, which surpasses the most reported carbon catalysts. In the HER process,
10 mA cm
2 can be
achieved at an overpotential of 0.29 V vs. RHE in 1 M KOH and 0.31 V vs. RHE in 0.5 M H2SO4. By com-
bination with commercial carbon black (CB), the Tafel slopes of a-N,S-G@CB is lower than the metal-
based catalysts. A new turnover frequencies (TOF) calculation method is involved to analyze the reac-
tivity of specific active sites of carbocatalyst including both heteroatoms and structural defects. There-
fore, the study provides an effective strategy for simultaneous modifications of surface chemistry and
porous structure of graphene as high-performance and robust carbocatalysts toward electrochemical
water splitting.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction tolerance to extreme acidic/alkaline conditions [6e8].

Energy crisis is a critical challenge confronted with human be-
ings due to the increasing demand and fast consumption of fossil
fuels in modern society [1]. Hydrogen is considered as the most
promising and green fuels to solve the fossil fuel depletion thanks
to its high energy density and green-gas-free emission [2,3]. Elec-
trochemical water splitting is a vital process to produce hydrogen,
which contains hydrogen evolution reaction (HER) on the cathode
and oxygen evolution reaction (OER) on the anode [4]. Nobel metals
such as Pt and IrO2 are effective catalysts to drive the two reactions
accordingly, whereas their scarcity and poor durability limit the
large-scale applications [5]. Inversely, carbon materials have
attracted considerable interests for their natural abundance, great
electrical conductivity, environmental-friendly and excellent
* Corresponding author.
E-mail address: wenchao.peng@tju.edu.cn (W. Peng).
1
The authors contribute equally to this manuscript.
Graphene is a typical 2D carbon material with special advan-
tages, including large specific surface areas (SSA), high conductivity,
and facile modification in both structure and surface chemistry
[9,10]. Doping with non-metal heteroatoms (e.g. B, N, S, P) has been
proved to be able to improve the catalytic performance of graphene
for both HER and OER [11,12]. The metal-free dopants, such as N, S
and P, carry electron-donor property and can increase the electron
population of the homogeneous p system in carbon framework,
leading to a favorable Gibbs free energy toward Hþ and H2O
adsorption [13,14]. Nitrogen is the most widely used dopants
among the alien atoms owing to its remarkable electronegativity,
and N-doped graphene has demonstrated outstanding electro-
catalytic activities in water splitting [15e17]. Moreover, N-doped
graphene can be further manipulated by co-doping with a sec-
ondary heteroatom to improve the charge/spin distribution of
carbon lattice. In this regard, sulfur has been proved to be able to
enhance the catalytic activity of N-doped graphene [18,19].
It has been reported that the species, loading and doping

https://doi.org/10.1016/j.carbon.2019.04.021
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
 X. Li et al. / Carbon 148 (2019) 540e549
methods of nitrogen and sulfur would affect the catalytic activities
of N, S co-doped graphene (N,S-G) [20,21]. The structural defects
are also catalytically reactive for HER and OER [14]. Therefore,
introducing structure defects into N,S-G by physical/chemical ac-
tivations may be also an effective approach to further enhance its
electrochemical performances [22]. In addition, the activation
treatment could also increase the specific surface area (SSA) of
doped graphene, thus providing more exposed active sites and a
better contact between glassy carbon electrode and the catalyst,
which is necessary for better electrocatalytic activity [15,16].
Traditional activation methods including KOH, ZnCl2, and CO2 ac-
tivations can afford pristine graphene with a porous structure and
large SSA [19,23]. Compared with KOH activation, ZnCl2 activation
process has a higher yield and weaker corrosion to the material
[24]. While in the comparison with CO2 activation, ZnCl2 activation
process involves more micro and meso porous structure and larger
SSA [25].
In this study, sulfur and nitrogen co-doped graphene was first
synthesized, zinc chloride (ZnCl2) was then used for the activation
of N,S-G to obtain a porous structure (a-N,S-G) [25]. The chemical
activation with ZnCl2 was able to introduce abundant structure
defects, meanwhile, most of the heteroatom dopants could be
reserved. Thus, the tailored SNG gave rise to enhanced electro-
activity for both HER and OER, attributed to the enlarged SSA and
synergies between the structural defects and dual-doping effect.
2. Experiment section
2.1. Chemicals and materials
The chemical reagents were purchased from Sigma-Aldrich,
including graphite flakes, sulfur acid (H2SO4, 95%e98%), potas-
sium permanganate (KMnO4, 99%), hydrogen peroxide (H2O2, 30%),
dopamine hydrochloride, 2-mercaptoethanol, zinc chloride (ZnCl2,
98%), hydrochloric acid (HCl, 35%e37%), potassium hydroxide
(KOH, 95%), phenol, potassium peroxymonosulfate (2KHSO5$3KH-
SO4$K2SO4, available as Oxone, PMS). All chemicals were used as
received without further purification.
2.2. Preparation of GO
GO was synthesized using a modified Hummers’ method [26].
Specifically, graphite (7.5 g) was mixed with NaNO3 (7.5 g) and
added into concentrated H2SO4 (360 mL) at 0  C. Then KMnO4
(45 g) was slowly added into the system and stirred for 3 h. Distilled
water (1200 mL) was slowly added into the system, and the tem-
perature was kept below 98  C and stirred for another 2 h. The
mixture was further treated with 30% H2O2 (20 mL), filtered and
washed with HCl (5%) and distilled water.
2.3. Preparation of N,S-G
34 mL (15 mg mL
1) GO dispersion was first mixed with 30 mL
dopamine hydrochloride solution (1.25 mg mL
1). The mixture was
dissolved in 161 mL distilled water and sonicated for 5 min before
adding 25 mL PBS buffer (0.4 M, pH ¼ 8.5). The mixture was stirred
at room temperature for 24 h, then 125 mg ME was added into the
system and stirred for another 12 h. The solution was centrifuged
with distilled water, and the obtained solid was dried in a vacuum
drying oven at 60  C for 24 h. The dried products were transferred
to a tube furnace under N2 atmosphere. The temperature was
increased to 400  C at a heating rate of 1  C min
1, then was kept for
2 h. Subsequently, the temperature was raised to 800  C at a heating
rate of 5  C min
1 and kept at this temperature for 3 h.
541
2.4. Prepared of a-N,S-G
The obtained N,S-G was then activated by ZnCl2. In detail, N,S-G
was mixed with ZnCl2 in different ratios, 10 mL of distilled water
was then charged in. After sonicated for 30 min, the dispersion was
stirred and heated to remove most of the water. The mixture of N,S-
G and ZnCl2 was dried and placed into a tube furnace. Increased the
temperature to 800  C at 5  C min
1 and kept for 2 h under N2 at-
mosphere. Cooling down naturally. The obtained powder was
etched by HCl (3%) for 24 h at 80  C. The activated materials were
labelled as a-N,S-G-x, where x represented the ratio of m (ZnCl2): m
(N,S-G).
2.5. Characterization
The samples were characterized by Fourier transform infrared
spectroscopy (FT-IR, Thermal-Nicolet 380). Raman spectra
(Renishaw inVia confocal microscopy)., X-ray powder diffraction
(XRD, Bruker Nonius D8 FOCUS), X-ray photoelectron spectroscopy
(XPS, PerkinElmer PHI 1600). Scan electron microscopy (SEM,
Hitachi S-4800), transmission electron microscopy (TEM, Philips
Tecnai G2F20), and N2 sorption isotherms (SSA-7000).
2.6. Electrochemical characterizations
Electrochemical measurements were performed using a three-
electrode system on a CHI660E workstation. Briefly, 10 mg of
catalyst and 40 mL of 5 wt% nafion solution were dispersed in 500 mL
of water/ethanol solution by sonication. Then 5 mL of the catalyst
ink (containing 100 mg catalyst) was loaded onto a glassy carbon
electrode as the working electrode. Ag/AgCl (3.5 M KCl solution)
and graphite rod were used as the reference electrode and counter
electrode, separately. The acidic and alkaline environment was
provided by 0.5 M H2SO4 or 1 M aqueous KOH as the electrolytes.
All the measured potentials were calibrated to RHE by using the
following equation: E (RHE) ¼ E (Ag/AgCl) þ 0.205 V þ 0.059  pH.
The HER and OER polarization curves were recorded by using linear
sweep voltammetry (LSV) at a scan rate of 5 mVs
1.
3. Results and discussion
3.1. Materials characterization
The synthesis procedures of N,S-G and a-N,S-G are shown in
Fig. 1. GO was mixed with DA and ME as nitrogen and sulfur pre-
cursors, respectively. Most of the oxygen containing groups would
disappear after the first-stage thermal treatment, meanwhile, S and
N were doped into the carbon matrix. The as-prepared N,S-G was
then mixed with ZnCl2 and calcined again under nitrogen atmo-
sphere to obtain the final porous carbon.
The SEM image of N,S-G in Fig. 2a shows few layered graphene
nanosheets with the rough and crumpled surface. Many holes can
be observed on the surface of a-N,S-G in Fig. 2b, indicating that a
porous structure was formed after the ZnCl2 activation. The TEM
image of a-N,S-G is shown in Fig. 2c, where some mesopores are
distributed on the surface of few-layered graphene with average
diameters of 4e5 nm, which may provide more active sites for
electro-catalytic process [27]. The TEM elemental mapping images
of a-N,S-G (Fig. 2 d-g) indicate that nitrogen and sulfur dopants are
uniformly distributed over the carbon lattice.
The nitrogen adsorption/desorption isotherms and pore size
distributions of N,S-G and a-N,S-Gs are displayed in Fig. 3. Their
corresponding SSA are shown in Fig. 4. It can be found that the SSA
of N,S-G is only 35.50 m2/g, which can be increased to 554.40 m2/g
when the ratio of m (ZnCl2): m (N,S-G) is 5 : 1. Meanwhile, the
542 X. Li et al. / Carbon 148 (2019) 540e549

Fig. 1. The synthesis process of the N,S-G and a-N,S-G. (A colour version of this figure can be viewed online.)

Fig. 2. SEM images of N,S-G a) and a-N,S-G b). TEM images of a-N,S-G c). TEM image d) and the corresponding mapping images of a-N,S-G e-g). (A colour version of this figure can
be viewed online.)

corresponding pore volume can be increased from 0.266 to
3.92 m3/g accordingly. Fig. 3f shows that there is an obvious peak at
2e4 nm for all the activated samples, which indicates the forming
of a mesoporous structure after ZnCl2 activation. The total pore
volume between 2 and 4 nm of a-N,S-G-5 and a-N,S-G-7.5 is much
larger than the other materials. Some macrospores (>50 nm) can
also be observed in the insert of Fig. 3f for a-N,S-G-5 and a-N,S-G-
7.5, while the macrospores aren't presented on a-N,S-G-2.5 and a-
N,S-G-10. For a-N,S-G-2.5, small amount of ZnCl2 is not enough for
the generation of macrospores. Too much ZnCl2 will destroy the
skeleton of graphene sheets into smaller pieces and diminish the
mesoporous and macrospores for a-N,S-G-10, which will decrease
the SSA [28].
Fig. 5a shows the FT-IR spectra of GO, N,S-GO and a-N,S-G-7.5.
The intense peaks of GO at 1626, 1394 and 1060 cm
1 correspond to
C¼C, C-OH and C-O stretching vibrations, respectively. The peaks of
GO at 1626, 1394 and 1060 cm
1 correspond to the C¼C, C-OH and
C-O stretching vibrations, respectively. The peak intensities at 1394
and 1060 cm
1 decreased in N,S-G, indicating a successful reduc-
tion of GO by removing the oxygen containing groups during the
thermal treatment. Meanwhile, new peaks appeared at 1527 and
651 cm
1, corresponding to the stretching vibrations of N-C and C-S
bonds, suggesting the successfully doping of N and S into the
carbon matrix. The subsequent chemical activation process would
further remove the oxygen-containing groups, while the peaks of
N-C and C-S were still visible. This suggests that the ZnCl2 activa-
tion might not significantly affect the foreign dopants (S and N).
Fig. 5b shows the Raman spectra of the carbon materials. Typical
D and G bands of graphene can be observed at 1331 cm
1 and
1591 cm
1, respectively. Fig. 5c shows the corresponding ID/IG
values for all the samples. The ID/IG of N,S-G (1.414) is much higher
than GO (1.182). The ID/IG values can be further increased for a-N-S-
Gs of
2.5 (1.551),
5 (1.552),
7.5 (1.538), and
10 (1.501) after
activation. ID/IG can represent the defect degree of carbon materials
[29,30]. Therefore, more defects should be generated after the
doping process and ZnCl2 activation. The XRD patterns in Fig. 5d
show that the sharp peak (at ~10 ) corresponding to the (001) plane
of GO disappeared after the thermal treatment, indicating the
successful reduction of GO. Furthermore, the peak at ~21.3 rep-
resenting for the (002) plane of graphene red shifted to ~25.6 . This
could be attributed to the decreased inter-lamellar spacing of gra-
phene layers as a result of the decomposition of surface/boundary
oxygen functional groups.
The XPS spectra in Fig. 6 analyze the compositions and chemical
status of the elements in the as-prepared materials. The peaks of C,
O, N and S of the GO, N,S-G and a-N,S-G are clearly identified in the
 X. Li et al. / Carbon 148 (2019) 540e549 543

Fig. 3. Nitrogen adsorption/desorption isotherms of N,S-G a), a-N,S-G-2.5 b), a-N,S-G-5 c), a-N,S-G-7.5 d), a-N,S-G-10 e) at
196  C as well as the corresponding pore size distri-
butions f). (A colour version of this figure can be viewed online.)

Fig. 4. The BET SSA a) and pore volume b) of N,S-G and a-N,S-Gs. (A colour version of this figure can be viewed online.)

XPS full-range surveys in Fig. 6a. The peak of O diminished and the
peaks of nitrogen and sulfur occurred after the doping process. The
atomic ratio of nitrogen in N,S-G and a-N,S-G are 2.02% and 2.77%
respectively, while the corresponding sulfur loadings are 0.70% and
0.61%. According to the high-resolution C1s spectra of GO (Fig. 6b),
N,S-G (Fig. 6c) and a-N,S-G (Fig. 6d), the oxygen functionalities exist
predominantly in the forms of C¼O (286.2 eV) and O¼C-O
(288.5 eV) [31]. During nitrogen and sulfur doping processes, O¼C-
O and C¼O groups decreased slightly. The two groups decreased
substantially during the ZnCl2 activation, because O¼C-O and C¼O
groups are not stable during the activation and will be decomposed
into gases (CO, CO2 and H2O) at high temperature [28,32]. ZnCl2
catalyzed the dehydration process and filled into the defected sites
during the thermal treatment. Most of ZnCl2 was volatilized at
732e800  C and the rest was removed by hydrochloric acid treat-
ment and water washing. Therefore, numerous mesopores were
created and the SSA of N,S-G would be significantly improved after
the activation.
The chemical composition and valence state of N,S-G before and
after the activation process were further confirmed by XPS analysis
(Fig. 7). High-resolution N1s spectra of N,S-G and a-N,S-G are
shown in Fig. 7a and b. It can be found that the content of N-Ox
decreased from 25.78 to 18.53 at.% after the activation, and
graphitic N decreased from 32.30 to 18.83 at.%. While the per-
centage of pyrrolic N increased from 21.93 to 37.76 at.%, due to the
reconstruction of N-dopants during the activation process. In
addition, the binding energy of graphitic N shifted to a higher value,
while other N dopants nearly unchanged, suggesting the stronger
binding between C and N which might affect the adsorption and
catalytic ability [33,34]. High-resolution S 2p spectra in Fig. 7c and
d shows that the contents of S-O structure decreased from 17.08 to
10.39 at.%. The decrease of N-Ox and S-O further verified the
dehydration effect of ZnCl2 during the activation process. To
compare the variation of the signals, the spectra of N and S in N,S-G
and a-N,S-G are shown in Fig. 7e and f. The amount of N kept un-
changed while the content of S decreased slightly, indicating that
544 X. Li et al. / Carbon 148 (2019) 540e549

Fig. 5. FT-IR spectra of GO, N,S-G and a-N,S-G a), Raman spectra of GO, N,S-G, and a-N,S-Gs b), ID/IG changed with the ratio of m (ZnCl2): m(N,S-G) c), XRD spectra of GO, N,S-G and
a-N,S-Gs d). (A colour version of this figure can be viewed online.)

Fig. 6. XPS survey spectrum of GO, N,S-G and a-N,S-G a), C1s high-resolution XPS spectra of GO b), N,S-G c), a-N,S-G d). (A colour version of this figure can be viewed online.)

the mass loss of N,S-G during the activation was primarily due to
the release of O and C (as CO or CO2). The XPS spectra of O and the
comparison of the spectra of O in N,S-G and a-N,S-G (Fig. 7ge7i),
indicating that the C-O structure is the dominated existence form of
O in N,S-G. However, C-O decreased from 82.9% to 38.1% after the
ZnCl2 activation. These conclusions can be inferred more obviously
by comparison of the O1s spectra of in N,S-G and a-N,S-G, which is
consisting with their C1s spectra, which further verifies the ZnCl2
catalytically eliminated the oxygen and hydrogen elements in the
form of H2O. Structure defects were then created as new active sites
in a-N,S-G.
3.2. Electrocatalytic performance
The electro-catalytic activity of the as-prepared materials to-
wards OER was tested in alkaline (1 M KOH) aqueous solution. The
 X. Li et al. / Carbon 148 (2019) 540e549 545

Fig. 7. High-resolution XPS spectra of N of N,S-G a), a-N,S-G b), high-resolution XPS spectra of S of N,S-G c), a-N,S-G d), high-resolution XPS spectra of O of N,S-G e), a-N,S-G f),
comparison of the spectra of N g) in N,S-G and a-N,S-G, comparison of the spectra of S h) in N,S-G and a-N,S-G, comparison of the spectra of O i) in N,S-G and a-N,S-G. (A colour
version of this figure can be viewed online.)

polarization curves were recorded by LSV measurements at a
sweep rate of 5 mV s
1. As shown in Fig. 8a, a-N,S-G-7.5 showed
enhanced OER activity than N,S-G by 148 mV at 10 mA cm
2. To find
the optimal activation condition, the a-N,S-Gs were tested and the
results are shown in Fig. S10. Although a-N,S-G-5 has larger SSA and
ID/IG value, the a-N,S-G-7.5 shows however the best OER activity
compared to other actived graphenes. Therefore, a stage 2 defect
status might present for these materials, and a-N,S-G-7.5 has more
active strucutre defects than the other samples [35e37]. The
earliest overpotential was obtained by a-N,S-G-7.5 as 0.323 V at
10 mA cm
2, which surpassed most metal-free materials and was
even comparable to some metal-based materials [38e41]. Addi-
tionally, the a-N,S-G-7.5 exhibited a Tafel slope of 114.4 mV deca-
de
1, which was smaller than that of N,S-G (168.6 mV decade
1,
Fig. 8b), a-N,S-G-2.5 (131.1 mV decade
1), and a-N,S-G-10
(209.8 mV decade
1), but larger than that of a-N,S-G-5
(88.9 mV decade
1, Fig. S11). This is consistent with the nitrogen
absorption results of the materials in Fig. 3. The results indicate that
a larger SSA could result in the exposure of more active sites and
lead to smaller Tafel slopes. The electrochemical impedance spec-
troscopy (EIS) spectra of the samples are shown in Fig. 8c. The Rct of
N,S-G slightly changed after ZnCl2 activation, and the smallest Rct

Fig. 8. OER polarization curves a), the corresponding Tafel plots b) and the EIS spectra c) of GO, N,S-G, and a-N,S-G in 1 M KOH. (A colour version of this figure can be viewed online.)
546
was achieved by a-N,S-G-7.5 in Fig. S12.
The HER performances of these samples were also investigated
in both alkaline and acidic conditions. As shown in Fig. 9a, the
overpotential of a-N,S-G decreased to 0.292 V vs. RHE at
10
mA cm
2 compared to 0.407 V of N,S-G in 1 M KOH solution. This
value is even better than many previous studies with non-metal
doped graphene catalysts in alkaline solution [14,42]. The Tafel
slope is however increased from 145.5 (N,S-G) to 182.4 mV (a-N,S-
G) decade
1 after activation (Fig. 9b). Based on the OER and HER
results, a-N,S-G could be used as a bifunctional catalyst for overall
water splitting in 1 M KOH solution [4,41]. In this system, a cell
voltage of 1.94 V (Fig. 9c) was obtained. Similar trends could be
found for the HER polarization curves in 0.5 M H2SO4 in Fig. 9d. The
operating potentials at
10.0 mA cm
2 were
0.397 V
and
0.309 V vs. RHE for N,S-G and a-N,S-G, respectively, which is
delayed than the values in alkaline condition. However, the corre-
sponding Tafel slope of N,S-G and a-N,S-G were 127.3 mV decade
1
and 146.1 mV decade
1 accordingly, which are smaller than those
in alkaline condition (Fig. 9b).
Based on the above results, it can be concluded that a-N,S-Gs
demonstrate better HER performances both in alkaline and acidic
conditions. More specifically, N,S-G performs better in acidic elec-
trolyte, whereas a-N,S-G shows an earlier overpotential in alkaline
electrolyte. This should be attributed to the distinct reaction
mechanisms under different conditions. Hydrone is absorbed on
the catalyst surface as the electron acceptor in alkaline conditions
for HER, while proton is the electron acceptor in acidic electrolyte.
Generally, the presence of oxygen functional groups makes it easier
to absorb a proton than a hydrone [43,44], leading to the better HER
performance of N,S-G under acidic condition. The ZnCl2 activation
process will remove most of the oxygen-containing groups (Fig. 7).
Herein, the absorption of hydrone becomes easier in alkaline
electrolyte, resulting in a better activity of a-N,S-G in alkaline
condition.
HER is a multi-step process taking place on the surface of an
electrode. During the Volmer step, an electron transfers to the
electrode and combines with a proton. Two absorbed hydrogen
atoms then combine on the electrode surface to generate H2, which
Fig. 9. HER polarization curves a), the corresponding Tafel plots b) of GO, N,S-G and a-N,S-G in 1 M KOH, water splitting polarazation of a-N.S-G c), HER polarization curves d), the
corresponding Tafel plots e) and the EIS spectra f) of GO, N,S-G and a-N,S-G in 0.5 M H2SO4. (A colour version of this figure can be viewed online.)
X. Li et al. / Carbon 148 (2019) 540e549
is called Tafel step. Both the two steps determine the water splitting
performance, while the Tafel slope is only dominated by the Tafel
step [45]. Specifically, the number of exposed active sites and the
electrical conductivity together determine the water splitting per-
formance. While the Tafel slope of a material is mainly related with
its conductivity. Therefore, the good performance of a-N,S-G for
Tafel (Fig. 9b and e) and EIS (Figs. 8c and 9f) only indicates its better
electric conductivity. However, more active sites are involved to the
material after activation. The Volmer step is obviously promoted so
that the a-N,S-Gs carries better HER performance. Therefore, the
activation process will not only increase the number of active sites,
but also break the periodic units of graphene to form structural
defects (edges and vacancies), leading to the deteriorated electrical
conductivity and increased Tafel slopes.
The durability tests were conducted in both acidic and alkaline
solutions for 1000 CV cycles at a scan rate of 50 mV s-1. It is shown
in Fig. 10a, b and c that no obvious deactivation was observed for a-
N,S-G in both OER and HER after 1000 cycles. Moreover, the insets
of Fig. 10a, b and c show the stability test of a-N,S-G, and the current
kept steady at 10 mA cm
2 after 10 h operation. The results prove
that a-N,S-G manifested excellent durability both in acidic and
alkaline environments.
Since the high Tafel slope of a-N,S-G might originate from the
destruction of graphene matrix, carbon black with excellent con-
ductivity is coupled with a-N,S-G to improve the Tafel slope. 5%
graphitized carbon black (CB) is used to modify the activated
samples by a simple sonication-assisted mixing process. As shown
in Fig. 11, although the overpotential at 10 mA cm-2 of a-N,S-G@CB
after modification did not change, the Tafel slope was improved
obviously. Specifically, the Tafel slope decreased to 90.4 mA dec-1
for OER and 110.5 mA dec-1 for HER in alkaline environment. The
slope in acidic condition dramatically decreased to 95.5 mA dec-1,
which is comparable to the reactive metal-free catalysts of defected
N-coped graphene and N,S-codoped graphene in the previous
report [19]. The EIS spectra before and after the addition of carbon
black were also investigated in Fig. 11g and h. Apparently,
decreased Rct could be observed both in alkaline and acidic con-
ditions. As expected, the addition of carbon black can decrease the
 X. Li et al. / Carbon 148 (2019) 540e549 547

Fig. 10. Durability test of a-N, S-G for OER process a), HER process in 0.5 MH2SO4 b), and 1 M KOH c). (A colour version of this figure can be viewed online.)

Fig. 11. OER polarization curves a), the corresponding Tafel plots b) of a-N,S-G with carbon black added in 1 M KOH, HER polarization curves c), the corresponding Tafel plots d) of a-
N,S-G with carbon black added in 1 M KOH, HER polarization curves e), the corresponding Tafel plots f) of a-N,S-G with carbon black added in 0.5 M H2SO4, and the EIS spectra of a-
N,S-G with carbon black added in 1 M KOH g) in 0.5 M H2SO4 h), (A colour version of this figure can be viewed online.)

The doped N and S atoms are generally considered as the active

Fig. 12. The illustration of active sites in a-N,S-G for overall water splitting processes.
(A colour version of this figure can be viewed online.)
resistance of the defective carbon materials, leading to an improved
Tafel slope. Therefore, coupling the defective nanocarbons with a
conductive substrate can provide a satisfactory metal-free catalyst
for electrochemical water splitting (see Fig. 12).
sites in carbon based materials. More specifically, the graphitic N
and pyridinic N are carry better electro-catalytic activity than pyr-
rolic N [20,21], the catalytic activity of doped S atoms significantly
enhances while it works synergistically with doped N atoms.
Moreover, the structure defects involved to the carbon materials
caused by activation process have also been proved to be the active
sites of the water splitting process. The activation process can in-
crease the specific surface areas and provide more intrinsic active
sites by creating abundant structure defects. The CV curves at
different scan rates are recorded in alkaline environment (Fig. S1-
S2), which can be used to estimate the electrochemical active sur-
face area (ECSA) [46]. The calculation results are shown in Fig. S3,
which implicated that a-N,S-G possessed a larger ECSA and more
active sites than N,S-G. The density function theory (DFT) calcula-
tions in previous works have demonstrated that the Gibbs free
energy for H* adsorption (DG*H) on graphitic N is 0.80 eV, and DG*H
of pyridinic and pyrrolic N are 0.95 eV and 1.02 eV, respectively [13].
The DG*H of S is approximately 1.00 eV, which will sharply decrease
to 0.23 eV if the S atom is doped near an N atom. The defects (edges
and vacancies) created by thermal removal have a DG*H of
0.18e0.66 eV [14], which is smaller than N, S co-doping. Therefore,
both the heteroatom dopants and defects are the intrinsic active
sites for water splitting.
The turnover frequencies (TOF) values reflect the intrinsic
electro-catalytic activity of each active site in a catalyst [47]. For the
548 X. Li et al. / Carbon 148 (2019) 540e549
metal compounds based systems, metal containing nanoparticles
are often considered as the active sites for TOF calculation in the
water splitting reaction [47,48]. While for the doped carbon ma-
terials, only the doped heteroatoms are usually considered as the
active sites for TOF calculation. According to the DG*H analysis
above, it is considered that the structure defects caused by the
removal of doped atoms are also active sites [14]. Moreover, it is
found that the removing of C¼O and O-C¼O will also produce new
active sites (Fig. S14). Therefore, all of the three kinds of active sites
above are involved for the first time, and the TOFs of HER and OER
process are calculated and shown in Figs. S4-S6 [48,49]. If the active
sites only include the heteroatom dopants and defects left by the
heteroatom removal, the TOF values of a-N,S-G-7.5 can be ten times
larger than that of N,S-G in the OER process under alkaline envi-
ronment (Fig. S4a). Similar results can be obtained in HER process
(Fig S4b and c). However, the TOF value of one specific active site
should be identical in the same catalytic process. The decreased
graphitic N and ratio of N and S by chemical activation should result
in a declined average activity of each active site. Therefore, it can be
concluded that new active sites should appear during the carbon
activation according to the XPS results (Fig. 6). ZnCl2 activation
simultaneously removed most of oxygen and part of sulfur atoms.
Then, the carbon defects caused by the removal of oxygen func-
tionalities are considered as the new active sites in a-N,S-G. Based
on this hypothesis, the TOF results are re-calculated in Figs S7-S9,
illustrating that a larger population of active sites were created by
ZnCl2 activation. To verify the calculation, the ZnCl2 activated gra-
phene (a-G) was obtained and the electrocatalytic activities of the
pristine graphene (G) and a-G were tested in Figs S13-S15 a-G
performed a much better catalytic activity than G in both OER and
HER processes, suggesting that the structural defects brought in a
considerable enhancement in electro-catalytic activities.
4. Conclusion
In this work, N and S co-doped graphene is synthesized by
thermal pyrolysis with DA and ME as the nitrogen and sulfur pre-
cursors. The derived N,S-G was further activated by ZnCl2 to enlarge
the SSA, form a porous structure, and create rich defects. Compared
with the pristine N,S-G without chemical activation, a-N,S-G
demonstrated considerably enhancement in catalytic perfor-
mances toward both HER and OER, which can be used as an effi-
cient bi-functional carbocatalyst for overall water splitting. The
reactivity can be further promoted by coupling of a-N,S-G with
carbon black to enhance the conductivity. The study contributes to
providing a facile strategy to fabricate high-performance metal-free
electrode materials with rationally tailored structure and surface
chemistry for clean fuel production.
Acknowledgements
This research was supported by the project NO. 21506158 from
the National Natural Science Foundation of China (NSFC).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.carbon.2019.04.021.
References
[1] M.A.R. Anjum, H.Y. Jeong, M.H. Lee, H.S. Shin, J.S. Lee, Efficient hydrogen
evolution reaction catalysis in alkaline media by all-in-one MoS2 with
multifunctional active sites, Adv. Mater. 30 (20) (2018).
[2] M. Zang, N. Xu, G. Cao, Z. Chen, J. Cui, L. Gan, H. Dai, X. Yang, P. Wang, Cobalt
molybdenum oxide derived high-performance electrocatalyst for the
hydrogen evolution reaction, ACS Catal. 8 (6) (2018) 5062e5069.
[3] Y. Ito, W. Cong, T. Fujita, Z. Tang, M. Chen, High catalytic activity of nitrogen
and sulfur Co-doped nanoporous graphene in the hydrogen evolution reac-
tion, Angew. Chem. Int. Ed. 54 (7) (2015) 2131e2136.
[4] X. Wang, W. Li, D. Xiong, D.Y. Petrovykh, L. Liu, Bifunctional nickel phosphide
nanocatalysts supported on carbon fiber paper for highly effi cient and stable
overall water splitting, Adv. Funct. Mater. 26 (23) (2016) 4067e4077.
[5] S. Anantharaj, P.E. Karthik, B. Subramanian, S. Kundu, Pt nanoparticle
anchored molecular self-assemblies of DNA: an extremely stable and efficient
HER electrocatalyst with ultralow Pt content, ACS Catal. 6 (7) (2016)
4660e4672.
[6] J. Zhang, L. Dai, Nitrogen, phosphorus, and fluorine tri-doped graphene as a
multifunctional catalyst for self-powered electrochemical water splitting,
Angew. Chem. Int. Ed. 55 (42) (2016) 13296e13300.
[7] Y.-N. Zhu, C.-Y. Cao, W.-J. Jiang, S.-L. Yang, J.-S. Hu, W.-G. Song, L.J. Wan, Ni-
trogen, phosphorus and sulfur co-doped ultrathin carbon nanosheets as a
metal-free catalyst for selective oxidation of aromatic alkanes and the oxygen
reduction reaction, J. Mater. Chem. 4 (47) (2016) 18470e18477.
[8] X. Yu, M. Zhang, J. Chen, Y. Li, G. Shi, Nitrogen and sulfur codoped graphite
foam as a self-supported metal-free electrocatalytic electrode for water
oxidation, Adv. Energy Mater. 6 (2) (2016).
[9] J. Zhu, M. Xu, M. Gao, Z. Zhang, Y. Xu, T. Xia, S. Liu, Graphene oxide induced
perturbation to plasma membrane and cytoskeletal meshwork sensitize
cancer cells to chemotherapeutic agents, ACS Nano 11 (3) (2017) 2637e2651.
[10] M.-R. Gao, X. Cao, Q. Gao, Y.-F. Xu, Y.-R. Zheng, J. Jiang, S.-H. Yu, Nitrogen-
doped graphene supported CoSe2 nanobelt composite catalyst for efficient
water oxidation, ACS Nano 8 (4) (2014) 3970e3978.
[11] J. Zheng, X. Chen, X. Zhong, S. Li, T. Liu, G. Zhuang, X. Li, S. Deng, D. Mei, J.-
G. Wang, Hierarchical porous NC@CuCo nitride nanosheet networks: highly
efficient bifunctional electrocatalyst for overall water splitting and selective
electrooxidation of benzyl alcohol, Adv. Funct. Mater. 27 (46) (2017).
[12] A. Song, L. Cao, W. Yang, W. Yang, L. Wang, Z. Ma, G. Shao, In situ construction
of nitrogen-doped graphene with surface-grown carbon nanotubes as a
multifactorial synergistic catalyst for oxygen reduction, Carbon 142 (2019)
40e50.
[13] Y. Jiao, Y. Zheng, K. Davey, S.-Z. Qiao, Activity origin and catalyst design
principles for electrocatalytic hydrogen evolution on heteroatom-doped gra-
phene, Nat. Energy 1 (2016).
[14] Y. Jia, L. Zhang, A. Du, G. Gao, J. Chen, X. Yan, C.L. Brown, X. Yao, Defect gra-
phene as a trifunctional catalyst for electrochemical reactions, Adv. Mater. 28
(43) (2016) 9532eþ.
[15] S. Liu, H. Yang, X. Huang, L. Liu, W. Cai, J. Gao, X. Li, T. Zhang, Y. Huang, B. Liu,
Identifying active sites of nitrogen-doped carbon materials for the CO2
reduction reaction, Adv. Funct. Mater. 28 (21) (2018).
[16] L. Zhao, X.-L. Sui, J.-Z. Li, J.-J. Zhang, L.-M. Zhang, G.-S. Huang, Z.-B. Wang,
Supramolecular assembly promoted synthesis of three-dimensional nitrogen
doped graphene frameworks as efficient electrocatalyst for oxygen reduction
reaction and methanol electrooxidation, Appl. Catal. B Environ. 231 (2018)
224e233.
[17] H. Wang, T. Maiyalagan, X. Wang, Review on recent progress in nitrogen-
doped graphene: synthesis, characterization, and its potential applications,
ACS Catal. 2 (5) (2012) 781e794.
[18] X. Duan, K. O'Donnell, H. Sun, Y. Wang, S. Wang, Sulfur and nitrogen Co-doped
graphene for metal-free catalytic oxidation reactions, Small 11 (25) (2015)
3036e3044.
[19] K. Qu, Y. Zheng, X. Zhang, K. Davey, S. Dai, S.Z. Qiao, Promotion of electro-
catalytic hydrogen evolution reaction on nitrogen-doped carbon nanosheets
with secondary heteroatoms, ACS Nano 11 (7) (2017) 7293e7300.
[20] B. Zhang, H.-H. Wang, H. Su, L.-B. Lv, T.-J. Zhao, J.-M. Ge, X. Wei, K.-X. Wang,
X.-H. Li, J.-S. Chen, Nitrogen-doped graphene microtubes with opened inner
voids: highly efficient metal-free electrocatalysts for alkaline hydrogen evo-
lution reaction, Nano Res. 9 (9) (2016) 2606e2615.
[21] J. Ma, M. Wang, G. Lei, G. Zhang, F. Zhang, W. Peng, X. Fan, Y. Li, Polyaniline
derived N-doped carbon-coated cobalt phosphide nanoparticles deposited on
N-doped graphene as an efficient electrocatalyst for hydrogen evolution re-
action, Small 14 (2) (2018).
[22] S. Deng, Y. Zhong, Y. Zeng, Y. Wang, Z. Yao, F. Yang, S. Lin, X. Wang, X. Lu,
X. Xia, J. Tu, Directional construction of vertical nitrogen-doped 1T-2H MoSe2/
graphene shell/core nanoflake arrays for efficient hydrogen evolution reac-
tion, Adv. Mater. 29 (21) (2017).
[23] Z. Yan, W. Yao, L. Hu, D. Liu, C. Wang, C.-S. Lee, Progress in the preparation and
application of three-dimensional graphene-based porous nanocomposites,
Nanoscale 7 (13) (2015) 5563e5577.
[24] L.L. Jiang, Z.J. Fan, Design of advanced porous graphene materials: from gra-
phene nanomesh to 3D architectures, Nanoscale 6 (4) (2014) 1922e1945.
[25] S. Liu, W. Peng, H. Sun, S. Wang, Physical and chemical activation of reduced
graphene oxide for enhanced adsorption and catalytic oxidation, Nanoscale 6
(2) (2014) 766e771.
[26] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev,
L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS
Nano 4 (8) (2010) 4806e4814.
[27] Y. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W. Cai, P.J. Ferreira, A. Pirkle,
R.M. Wallace, K.A. Cychosz, M. Thommes, D. Su, E.A. Stach, R.S. Ruoff, Carbon-
based supercapacitors produced by activation of graphene, Science 332 (6037)
(2011) 1537e1541.
 X. Li et al. / Carbon 148 (2019) 540e549
[28] T.E. Rufford, D. Hulicova-Jurcakova, K. Khosla, Z. Zhu, G.Q. Lu, Microstructure
and electrochemical double-layer capacitance of carbon electrodes prepared
by zinc chloride activation of sugar cane bagasse, J. Power Sources 195 (3)
(2010) 912e918.
[29] Y. Li, H. Wen, J. Yang, Y. Zhou, X. Cheng, Boosting oxygen reduction catalysis
with N, F, and S tri-doped porous graphene: Tertiary N-precursors regulates
the constitution of catalytic active sites, Carbon 142 (2019) 1e12.
[30] M.J. Yoo, H.B. Park, Effect of hydrogen peroxide on properties of graphene
oxide in Hummers method, Carbon 141 (2019) 515e522.
[31] Y. Liu, Y. Zhu, X. Fan, S. Wang, Y. Li, F. Zhang, G. Zhang, W. Peng, (0D/3D) MoS2
on porous graphene as catalysts for enhanced electrochemical hydrogen
evolution, Carbon 121 (2017) 163e169.
[32] X.-L. Dong, A.-H. Lu, B. He, W.-C. Li, Highly microporous carbons derived from
a complex of glutamic acid and zinc chloride for use in supercapacitors,
J. Power Sources 327 (2016) 535e542.
[33] J. Sun, S.E. Lowe, L. Zhang, Y. Wang, K. Pang, Y. Wang, Y. Zhong, P. Liu, K. Zhao,
Z. Tang, H. Zhao, Ultrathin nitrogen-doped holey Carbon@Graphene bifunc-
tional electrocatalyst for oxygen reduction and evolution reactions in alkaline
and acidic media, Angew. Chem. 57 (50) (2018) 16511e16515.
[34] J. Han, G. Huang, Z. Wang, Z. Lu, J. Du, H. Kashani, M. Chen, Low-temperature
carbide-mediated growth of bicontinuous nitrogen-doped mesoporous gra-
phene as an efficient oxygen reduction electrocatalyst, Adv. Mater. 30 (38)
(2018).
[35] J.-B. Wu, M.-L. Lin, X. Cong, H.-N. Liu, P.-H. Tan, Raman spectroscopy of
graphene-based materials and its applications in related devices, Chem. Soc.
Rev. 47 (5) (2018) 1822e1873.
[36] E.H. Martins Ferreira, M.V.O. Moutinho, F. Stavale, M.M. Lucchese, R.B. Capaz,
C.A. Achete, A. Jorio, Evolution of the Raman spectra from single-, few-, and
many-layer graphene with increasing disorder, Phys. Rev. B 82 (12) (2010).
[37] A. Eckmann, A. Felten, A. Mishchenko, L. Britnell, R. Krupke, K.S. Novoselov,
C. Casiraghi, Probing the nature of defects in graphene by Raman spectros-
copy, Nano Lett. 12 (8) (2012) 3925e3930.
[38] J. Huang, Y. Sun, X. Du, Y. Zhang, C. Wu, C. Yan, Y. Yan, G. Zou, W. Wu, R. Lu,
Y. Li, J. Xiong, Cytomembrane-structure-inspired active Ni-N-O interface for
enhanced oxygen evolution reaction, Adv. Mater. 30 (39) (2018).
[39] X.-L. Wang, L.-Z. Dong, M. Qiao, Y.-J. Tang, J. Liu, Y. Li, S.-L. Li, J.-X. Su, Y.-Q. Lan,
Exploring the performance improvement of the oxygen evolution reaction in
a stable bimetal-organic framework system, Angew. Chem. Int. Ed. 57 (31)
549
(2018) 9660e9664.
[40] R. Prasannachandran, T.V. Vineesh, A. Anil, B.M. Krishna, M.M. Shaijumon,
Functionalized phosphorene quantum dots as efficient electrocatalyst for
oxygen evolution reaction, ACS Nano 12 (11) (2018) 11511e11519.
[41] M.A.R. Anjum, M.H. Lee, J.S. Lee, Boron- and nitrogen-codoped molybdenum
carbide nanoparticles imbedded in a BCN network as a bifunctional electro-
catalyst for hydrogen and oxygen evolution reactions, ACS Catal. 8 (9) (2018)
8296e8305.
[42] B. Deng, D. Wang, Z. Jiang, J. Zhang, S. Shi, Z.-J. Jiang, M. Liu, Amine group
induced high activity of highly torn amine functionalized nitrogen-doped
graphene as the metal-free catalyst for hydrogen evolution reaction, Carbon
138 (2018) 169e178.
[43] L. Hui, Y. Xue, B. Huang, H. Yu, C. Zhang, D. Zhang, D. Jia, Y. Zhao, Y. Li, H. Liu,
Y. Li, Overall water splitting by graphdiyne-exfoliated and -sandwiched
layered double-hydroxide nanosheet arrays, Nat. Commun. 9 (2018).
[44] P.W. Menezes, C. Panda, S. Garai, C. Walter, A. Guiet, M. Driess, Structurally
ordered intermetallic cobalt stannide nanocrystals for high-performance
electrocatalytic overall water-splitting, Angew. Chem. Int. Ed. 57 (46) (2018)
15237e15242.
[45] C.G. Morales-Guio, L.-A. Stern, X. Hu, Nanostructured hydrotreating catalysts
for electrochemical hydrogen evolution, Chem. Soc. Rev. 43 (18) (2014)
6555e6569.
[46] Y.-Y. Chen, Y. Zhang, W.-J. Jiang, X. Zhang, Z. Dai, L.-J. Wan, J.-S. Hu, Pome-
granate-like N,P-doped Mo2C@C nanospheres as highly active electrocatalysts
for alkaline hydrogen evolution, ACS Nano 10 (9) (2016) 8851e8860.
[47] W. Chen, J. Ji, X. Feng, X. Duan, G. Qian, P. Li, X. Zhou, D. Chen, W. Yuan,
Mechanistic insight into size-dependent activity and durability in Pt/CNT
catalyzed hydrolytic dehydrogenation of ammonia borane, J. Am. Chem. Soc.
136 (48) (2014) 16736e16739.
[48] S. Deng, F. Yang, Q. Zhang, Y. Zhong, Y. Zeng, S. Lin, X. Wang, X. Lu, C.-Z. Wang,
L. Gu, X. Xia, J. Tu, Phase modulation of (1T-2H)-MoSe2/TiC-C shell/core arrays
via nitrogen doping for highly efficient hydrogen evolution reaction, Adv.
Mater. 30 (34) (2018).
[49] X. Li, X. Huang, S. Xi, S. Miao, J. Ding, W. Cai, S. Liu, X. Yang, H. Yang, J. Gao,
J. Wang, Y. Huang, T. Zhang, B. Liu, Single cobalt atoms anchored on porous N-
doped graphene with dual reaction sites for efficient fenton-like catalysis,
J. Am. Chem. Soc. 140 (39) (2018) 12469e12475.