Progress in Natural Science: Materials International 30 (2020) 846–854

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Progress in Natural Science: Materials International

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Janus few layered graphene with asymmetric wettability as anti-flooding T

cathode supports in proton exchange membrane fuel cells
Jing Liua, Xiaoke Lia, Xiaojin Lib, Luhua Jianga,∗
a
College of Materials Science and Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao, Shandong, 266042, China
b
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong, 266101, China

ARTICLE INFO ABSTRACT

Keywords: Water balance in cathode catalyst layer (CCL) is crucial for proton exchange membrane fuel cells
Proton exchange membrane fuel cell (PEMFCs). Herein, we report a novel strategy to develop a Janus few layered graphene particles (FLGP) with
Anti-flooding asymmetric wettability by varying the carbon precursors in the chemical vapor deposition (CVD) process.
Few layered graphene Using the Janus FLGP supported Pt with asymmetric wettability as the cathode of a PEMFC, a peak power
Support
density of 632 mW cm−2 was achieved, which was about two-folds of the hydrophobic FLGP and three-folds of
Cathode
hydrophilic FLGP based cathode, respectively. The enhanced performance could be ascribed to the well-con­
structed three-phase boundary in an anti-flooding cathode, leading to enlarged electrochemical active surface
area and facilitated mass transfer. This work may provide new clues for improving water management in
PEMFCs.

1. Introduction occurs on catalyst surface. So a well-constructed triple phase (solid/

Proton exchange membrane fuel cells (PEMFCs) hold great promises
as a new generation of clean energy due to its merits of high energy
density, low noise and environmental-benign [1]. The performance of
PEMFC is significantly affected by the water balance in the cathode.
From one side, the ionic conductivity of the Nafion membrane and the
Nafion ionomer in catalyst layers is highly dependent on the hydration.
Inadequate humidity could result to high ohmic resistance of mem­
branes, and even local hotspots leading to membrane failure. From the
other side, the cathode would be in high risk being flooded in case of
the excessive water, generated by the cathodic oxygen reduction reac­
tion and that electro-osmatic dragged from the anode, being left in
electrodes [2–4]. Therefore, it is essential to keep the water balance in
cathodes to meet the criteria of membrane hydration and avoid a
flooded cathode.
In the past decades, the importance of cathode catalyst layer (CCL)
to prevent cathode flooding has attracted much attention and been
extensively studied [5–10]. Jiao and Zhou numerically simulated and
showed that the hydrophobicity of the electrode must be carefully
controlled, and the catalyst layer is expected to be more or similarly
hydrophobic comparing to the gas diffusion layer (GDL), so that liquid
water could be expelled monotonously from catalyst layer to GDL [11].
As known, in cathodes, it involves gaseous oxygen reacting with hy­
drated protons, together with electrons, to generate liquid water, which
liquid/gas) boundary (TPB) is expected to facilitate the reaction. With
the aim to tune the hydrophobicity of the CCL, a general strategy is to
introduce hydrophobic additives, such as polytetrafluoroethylene
(PTFE), silicone oil and polydimethylsiloxane etc., to modify the CCL
[12–16]. However, the introduction of nonconductive polymers un­
avoidably covers some active sites and thus decreases the electro­
chemical surface area (ECSA) of the Pt catalyst. It is a dilemma to
mediate the hydrophilic surface for proton conductivity and the hy­
drophobic surface for oxygen gas transport without any loss in active
sites. It was reported that employing oxygenophilic and hydrophobic
ionic liquids to modify the surface of nanocarbon by forming a water-
equilibrated secondary medium between solid catalyst and liquid
electrolyte. Qiao et al. generated more favorable triple-phase contact
points around the active sites [17]. Despite great efforts have been
devoted in addressing the above dilemma between proton transfer and
oxygen transport, it is still a great challenge to achieve water balance
without introduction of foreign additives.
Janus materials with different wetting properties on opposite sides
have attracted global interests for their potential applications in
membrane distillation, oil–water separation, water collection and sen­
sors [18,19]. Inspired by this a Janus few layered graphene with bi­
philicity as the catalyst support is designed. Specifically, the outer wall
of graphene is hydrophobic, which facilities expelling water generated
and provides the pathway for oxygen diffusion, while the inner wall of

∗
Corresponding author.
E-mail address: luhuajiang@qust.edu.cn (L. Jiang).

https://doi.org/10.1016/j.pnsc.2020.08.018
Received 12 August 2020; Accepted 27 August 2020
Available online 05 October 2020
1002-0071/ © 2020 Chinese Materials Research Society. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
J. Liu, et al.
Fig. 1. Illustration of the preparation route of Pt/FLGP samples.
the graphene is hydrophilic which could provide the pathway for
proton.
2. Experimental
2.1. Catalyst preparation
Firstly, Mg2(OH)2CO3 was prepared, which is used as the precursor
for template and catalyst for few layered graphene particles (FLGP).
6.44 g of Mg(OCH3CO)2 4H2O dissolved in 75 mL of water and 1.2 g of
urea in 25 mL of water were mixed and magnetically stirred for 30 min.
Afterwards, the above solution was transferred to a Teflon-lined auto­
clave, then kept at 180 °C for 2 h. Finally, white precipitate was col­
lected by filtration and dried in an air oven at 100 °C.
FLGP with tuned wettability were synthesized via the chemical vapor
deposition (CVD) process. The obtained Mg2(OH)2CO3 in a quartz boat was
placed in the center of the tube furnace with a gas flow of Ar
(1000 ml min−1) and heated to 450 °C and maintained for 2 h. During this
process, Mg2(OH)2CO3 could decompose into MgO that is known the cat­
alyst and the template for the formation of graphene [20–23]. After that the
furnace was heated to 900 °C, and another Ar steam flowing through a flask
of acetonitrile at room temperature was introduced to the reactor for
10 min. Subsequently, the Ar steam was switched to flow through benzene
for 5 min. Then, the tube furnace was cooled down to room temperature
naturally. The as-formed samples in the quartz boat were collected and
treated with 1 M hydrochloric acid for 8 h in the ambient to remove the
template. The mixture was filtrated and washed by copious of deionized
water, which was then dried in an oven at 100 °C overnight. The obtained
black powder was denoted as FLGP-A-B. For comparison, the sample ob­
tained by changing the sequence of the flowing gas, i.e., first through
benzene and then acetonitrile, was denoted as FLGP-B-A. The sample pre­
pared only by Ar flowing through acetonitrile or benzene were denoted as
FLGP-A and FLGP-B, respectively.
The FLGP samples were used as the support for depositing Pt na­
noparticles. The Pt colloid was synthesized by the polyol method [24].
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In brief, a required amount of hexahydrated chloroplatinic acid
(H2PtCl6·6H2O) was added to ethylene glycol (EG) under stirring to
obtain bright yellow solution with a concentration of 0.05 mg Pt4+/mL
EG. The pH value of the solution was then adjusted to 13 by adding
sodium hydroxide. The mixture was kept at 130 °C for 3 h to yield dark
brown Pt colloids. After the Pt colloids cooling down to room tem­
perature, a required amount of FLGP support was added. The obtained
precipitate was filtered, washed and dried in a vacuum oven at 75 °C for
8 h. The obtained sample was denoted as Pt/FLGP-A-B, Pt/FLGP-B-A,
Pt/FLGP-A and Pt/FLGP-B. The mass loading of Pt in the catalyst is
determined to be around 30 wt% by thermogravimetric analysis (TGA)
in Fig. S1.
2.2. Physicochemical characterization
Powder X-ray diffraction (XRD) was performed on a Rigaku Miniflex
II diffractometer with Cu Kα radiation at 40 kV. The morphology of the
samples was characterized by scanning electronic microscopy (SEM,
JSM-7800F) and transmission electron microscopy (TEM, FEI, Tecnai
G2F30). TGA was conducted on an SDT Q600 thermoanalyzer under
air. Contact angle was measured on LAUDOR scientific LSA60 surface
analyser.
2.3. Electrochemical characterization
The electrochemical performance of the samples was evaluated by a
Pine potentiostat in a three-electrode electrochemical cell. A graphite
rod was employed as a counter electrode. The reference electrode was a
Ag/AgCl electrode in 0.5 M H2SO4 solution. The working electrode was
made by dripping the catalyst ink on a 5 mm diameter glass carbon
(GC) disk to form a thin-film layer. The catalyst ink was prepared by
weighting 5 mg of the samples and then dispersing in 2 mL of ethanol
plus 30 μL of 5 wt% Nafion® solution (DuPont, USA) in an ultrasonic
bath for 10 min. After that, 20 μL of aliquots was pipetted on the GC
disk and dried naturally. A stable cyclic voltammogram (CV) curve with
J. Liu, et al.
Fig. 2. TEM images of FLGP-A-B (a–c), FLGP-B-A (d–f), FLGP-A (g–i), and FLGP-B (j–l).
a scan rate of 10 mV s−1 was recorded after surface clean by potential
scanning between −0.17–0.93 V vs. Ag/AgCl in a nitrogen saturated
0.5 M H2SO4 electrolyte. The scan rate was kept at 100 mV s−1. The
electrochemical performance on the oxygen reduction reaction were
performed in an oxygen saturated 0.5 M H2SO4 solution at a scanning
rate of 10 mV s−1.
2.4. Sing cell fabrication and testing
The membrane electrode assemblies (MEAs) were made using the
procedure as follows [25]. Briefly, the catalyst ink was prepared by
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Progress in Natural Science: Materials International 30 (2020) 846–854
ultrasonically blending Pt/FLGP catalysts with a Nafion solution and
ethanol for 2 h. The catalyst ink was sprayed onto the cathode side of
the membrane (Nafion 212) till the Pt loading reaching to 0.4 mg cm−2.
The anode catalyst layer was prepared by spraying the ink consisting of
40%Pt/C-JM with Nafion solution and ethanol. The Pt loading was kept
at 0.05 mg cm−2. The MEAs were fabricated by sandwiching the cat­
alyst-coated membranes between two prefabricated gas diffusion layer
(GDL) (Torry carbon paper, 10 wt% poly-tetrafluoroethylene), and then
hot pressing together at 130 °C under 0.1 MPa for 1 min. The control
MEAs were fabricated using 40%Pt/C-JM catalyst on both electrodes.
The Pt loading in the anode and the cathode were controlled at 0.05
J. Liu, et al.
Fig. 3. Physical characterization of Pt/FLGP-A-B catalyst. XRD patterns (a), TEM (b–c) and HRTEM images (d). The insert of (c) is the corresponding diameter
distribution of Pt NPs. The insert of (d) is the SAED of Pt NPs.
and 0.4 mg cm−2, respectively. The active area of the single-cell was
4 cm2. The operation temperature of the single cell was 50 °C. The
anode side was fed with 100% humidified H2 with a flow rate of
100 mL min−1 and the cathode side was fed with 100% humidified O2
with a flow rate of 200 mL min−1.
3. Results and discussion
The wettability of the few layered graphene is dependent on the
carbon precursors adopted in the CVD process. As depicted in Fig. 1,
Mg2(OH)2CO3 was firstly synthesized via a hydrothermal method,
which was then decomposed into MgO to act as the template and the
catalyst for the formation of few layered graphene. Catalyzed by MgO,
carbon precursors split and carbon atoms grow into graphenes
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[21,26,27]. The hydrophilic/phobic property of the obtained carbon
could be modulated by changing the carbon precursors. To obtain a
hydrophilic graphene surface, acetonitrile was chosen as the precursor
to generate nitrogen-doped few layered graphene catalyzed by the MgO
template in the process of CVD. Subsequently, benzene was chosen as
the carbon precursor to continuously form hydrophobic few layered
graphene surface outside. After etching the templates, a Janus FLGP of
an inner hydrophilic graphene wall (nitrogen-doped) and an outer hy­
drophobic graphene wall (un-doped) was obtained. Similar graphene
double-tubes have been recently reported for the application in lithium-
ion batteries [28]. It has been well demonstrated that the inner tube of
the nitrogen-doped graphene is hydrophilic while the outer tube of the
non-doped graphene is hydrophobic. Pt colloid was prepared by a
polyol reduction method and deposited on the Janus FLGP, denoted as
J. Liu, et al.
Fig. 4. TEM images of Pt/FLGP-B-A (a–b), Pt/FLGP-A (d–e), Pt/FLGP-B (g–h) and the corresponding histograms of Pt particle size distribution (c, f, i).
Pt/FLGP-A-B. For comparison, FLGP with inner hydrophobic graphene
wall and outer hydrophilic graphene wall was also synthesized, and
loaded Pt nanoparticles, labeled as Pt/FLGP-A-B. The merely hydro­
philic or hydrophobic FLGP supported Pt nanoparticles were denoted as
Pt/FLGP-A and Pt/FLGP-B, respectively.
Fig. 2 shows the TEM images of the FLGP samples. For all the FLGP
samples, they exhibit the similar hieratical structures of graphene na­
nospheres (GNPs) parasite on graphene nanotubes (GNTs). The average
diameter of GNPs is around 500 nm, and the GNTs are of about 0.2 μm
in width and 10 μm in length. From the enlarged TEM images, the few
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Progress in Natural Science: Materials International 30 (2020) 846–854
layered porous graphene structure of the samples could be clearly vi­
sualized. The thickness of graphene layer is about 10 nm for FLGP-A-B
and FLGP-B-A, and 5 nm for FLGP-A and FLGP-B. It is reasonable that
the graphene layer became thicker for FLGP-A-B and FLGP- B-A, which
was experienced twice CVD processes.
The XRD patterns of the Pt/FLGP samples are presented in Fig. 3a.
The broad peak located at around 25° is ascribed to the graphite (002)
diffraction index of FLGP, suggesting FLGP is of amorphous carbon
structure. The Pt nanoparticles could be evidenced by the diffraction
peak at around 40° assigned to Pt (111) planes. The TEM images of Pt/
J. Liu, et al.
Fig. 5. Contact angles of water droplets on Pt/FLGP-A-B (a), Pt/FLGP-B-A (b),
Pt/FLGP-A (c) and Pt/FLGP-B (d).
FLGP-A-B are shown in Fig. 3b–d. It can be seen that the FLGP-A-B
retains the hieratical nanosphere and nanotube in morphology with
porous graphene layers as the scaffold, where Pt nanoparticles are
distributed uniformly. The average diameter of the Pt NPs in Pt/FLGP-
A-B is about 1.88 nm. As shown from the HRTEM image of Pt/FLGP-A-B
in Fig. 3d, the interplanar distance in the Pt NP is 0.23 nm, which is
attributed to the Pt (111) plane. The inset of Fig. 3d exhibits the se­
lected area electron diffraction (SAED) of Pt/FLGP-A-B, confirming the
formation of face centered cubic phase of Pt. The morphology and
distribution of Pt NPs in the counterpart samples are also characterized
by TEM and shown in Fig. 4. Pt NPs dispersed evenly on the FLGP
support. The average diameter of the Pt NPs in the Pt/FLGP-B-A, Pt/
FLGP-A and Pt/FLGP-B were 1.84 nm, 2.03 nm and 1.97 nm, respec­
tively. The above results suggest that the support has little influence on
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Progress in Natural Science: Materials International 30 (2020) 846–854
the dispersion of the Pt NPs, which provides a chance to study the effect
of the graphene supports on the cathodic performance.
The wettability of Pt/FLGP-A-B, Pt/FLGP-B-A, Pt/FLGP-A and Pt/
FLGP-B were reflected by the contact angles, as shown in Fig. 5. The
contact angle of Pt/FLGP-A-B and Pt/FLGP-B is 128° and 124.8°, re­
spectively, which is much higher than that of Pt/FLGP-B-A (89.6°) and
Pt/FLGP-A (91.6°). It is reasonable and expected, because for Pt/FLGP-
A-B and Pt/FLGP-B, the outer wall of the support is non-doped gra­
phene, which is hydrophobic; in contrast, Pt/FLGP-B-A and Pt/FLGP-A
with an outer wall of N-doped graphene, which is hydrophilic. The
relatively hydrophobic CCL is expected to avoid the water flooding of in
cathode and could be able to maintain good water balance during op­
eration of the PEMFC.
To obtain the electrochemical active surface area (ECSA) of Pt/FLGP
catalyst, the cyclic voltammograms (CV) of Pt/FLGP catalysts in ni­
trogen-saturated 0.5 M H2SO4 with a scan rate of 10 mV s−1 were firstly
recorded. As shown in Fig. 6a, the ECSA of the Pt/FLGP catalysts were
estimated from integrating the charge of hydrogen underpotential de­
position area and the values are listed in Table S1. Pt/FLGP-A-B catalyst
exhibited a high ECSA of 67.1 m2 g−1, while the Pt/FLGP-B catalyst had
the lowest ECSA of 33.1 m2 g-1. The result demonstrates that biphilicity
of FLGP allows the aqueous electrolyte to infiltrate the inner hydro­
philic graphene surface and provides a highway for proton transfer,
thus leading to the enlargement of ECSA. From the ORR polarization
curves shown in Fig. 6b, it can be seen that all the Pt/FLGP samples
exhibit almost identical catalytic activity for the ORR in the low over­
potential region (0.9–0.7 V vs. Ag/AgCl). The similar capability to in­
itiate the ORR clearly demonstrates that the active center in the Pt/
FLGP was the same in the aqueous electrolyte. However, in the mass-
diffusion-limiting potential region, the ORR limiting current was a little
different, i.e., Pt/FLGP-A-B and Pt/PLGP-B with the hydrophobic sur­
face showed slight higher ORR limiting currents, as compared to the
other two with the hydrophilic surface. This is probably due to the
expedited oxygen transfer from the electrolyte to the hydrophobic
catalyst surface across the interface. To further explore the effect of the
surface characteristics on the activity of Pt/FLGP based electrode in a
real PEMFC where a three-phase boundary was crucial to insure good
performance, single cells with the Pt/FLGP as the cathodic electro­
catalysts were assembled and tested. The discharging curves are dis­
played in Fig. 6c. All the Pt/FLGP based cells show an open circuit
voltage above 0.99 V. The best performance was obtained using the
Janus FLGP with inner hydrophilic surface and outer hydrophobic
surface (FLGP-A-B) as the support, and the peak power density reach up
to 632 mW cm−2 under the operating temperature (50 °C). In contrast,
the single cells with Pt/FLGP-B-A, Pt/FLGP-B and Pt/FLGP-A as the
cathode catalysts show inferior performance, with the peak power
density of 565 mW cm−2, 296 mW cm−2 and 223 mW cm−2, respec­
tively. It is clear that by properly designing the support of Janus
wettability, the peak power density of the PEMFC increases by nearly
two-folds and three-folds, as compared to those with either hydro­
phobic or hydrophilic supports. Fig. 6d is the electrochemical im­
pedance spectra (EIS) of the PEMFC with the Pt/FLGP catalysts at a
discharging current density of 1000 mA cm−2. The curves are fitted and
an equivalent circuit is shown in Fig. S3. The corresponding fitting
parameters are listed in Table S1. The first arc represents charge re­
sistance, which increases in the sequence of Pt/FLGP-A-B
J. Liu, et al. Progress in Natural Science: Materials International 30 (2020) 846–854

Fig. 6. Electrochemical characterization of Pt/FLGP catalysts. CV curves (a) and ORR polarization curves (b) was tested in 0.5 M H2SO4 electrolyte with a scan rate of
10 mV s−1. The rotating rate was 1600 rpm, H2–O2 single cell performance was at operation temperature of 50 °C (c) and the corresponding impedance spectroscopy
at a discharging current density of 1000 mA cm−2 (d). The insert of (d) is the enlarged view for selected overlapped curves.

(0.030 Ω) = Pt/FLGP-A (0.030 Ω) < Pt/FLGP-B-A (0.036 Ω) < Pt/
FLGP-B (0.045 Ω). The larger charge transfer resistance of the cell based
on Pt/FLGP-B suggests the poor capability of Pt/FLGP-B electrode in
building effective three phase boundary. In addition, the mass transfer
resistance is reflected by the second arc in the impedance curves. The
absence of the second semi-circle responding to the mass transfer on the
Pt/FLGP-A-B electrode at large discharging current density confirms the
superior mass transport capability. On the contrary, the fuel cell based
on whether Pt/FLGP-A or Pt/FLGP-B show severe mass transfer re­
sistance, resulting to inferior performance. It should be noted here that
the catalyst layer of the Pt/FLGP based electrode is much thicker than a
conventional Pt/C electrode, as measured in Fig. S2, so even a high
oxygen flow rate of 200 ml min−1 was set at the cathodes, a con­
siderable mass transfer resistance remains for the Pt/FLGP-A or Pt/
FLGP-B based electrode. Specifically, as illustrated in Fig. 7, the sur­
faces of Pt/FLGP-B-A electrode and Pt/FLGP-A electrode are hydro­
philic, which are thus prone to be flooded and increase the oxygen mass
transfer resistance. In regard of the Pt/FLGP-B electrode, the water
flooding issue may be mitigated due to the hydrophobic surface.
However, the Pt NP surface that inaccessible to the Nafion ionomer
becomes dead area. On the contrary, the Pt/FLGP-A-B could not only
mitigate water flooding with the help of the outer hydrophobic surface,
but also provide continuous proton pathway through the porous inner
hydrophilic walls, which facilitate the construction of three phase
boundary and maintain efficient mass transportation.
4. Conclusions
A novel strategy to develop a Janus FLGP with asymmetric wett­
ability by varying the carbon precursors in the CVD process is reported.
Using the Janus FLGP supported Pt with asymmetric wettability as the
cathode of a PEMFC, a peak power density of 632 mW cm−2 is
achieved, which is almost two-folds of hydrophobic FLGP and 3-folds of
hydrophilic FLGP based cathode, respectively. The enhanced perfor­
mance can be ascribed to the well-construction of three-phase boundary
in the anti-flooding cathode, leading to enlarged electrochemical active
surface area and facilitated mass transfer.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.

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J. Liu, et al.
Fig. 7. Schematic diagram of triple phase boundary in electrodes constructed by Pt/FLGP-A-B (a), Pt/FLGP-B-A (b), Pt/FLGP-A (c) and Pt/FLGP/B (d).
Acknowledgements
This work is supported by the National Science Foundation of China
(21776146, 21805156), the Key Research and Development Project of
Shandong Province (2019JZZY020809), International Science and
Technology Cooperation Programme, China (2016YFE0125700) and
Taishan Scholar Program of Shandong Province (ts201712046).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.pnsc.2020.1319.
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