i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

High efficiency platinum nanoparticles based on

carbon quantum dot and its application for oxygen
reduction reaction

Karim Kakaei*
Department of Physical Chemistry and Nano Chemistry, Faculty of Science, University of Maragheh,
P.O. Box. 55181-83111, Maragheh, Iran

article info abstracts

Article history: Carbon quantum dots (CQDs) are synthesized by one pot electrochemical method using
Received 6 December 2016 small molecule and applied as the support materials for platinum (Pt) catalysts. The effect
Received in revised form of CQD on the catalytic activity and stability of the supported Pt catalysts for oxygen
9 January 2017 reduction reaction is investigated for the first time. The as-prepared Pt/CQD nano-
Accepted 12 January 2017 composites has been carefully characterized by spectroscopic and electrochemical tech-
Available online 2 February 2017 niques. X-ray diffractometer and tunneling electron microscopy techniques are employed
to study the crystallite size. X-ray photoelectron spectroscopy revealed that Pt deposited to
Keywords: CQD.
Carbon quantum dot The electrochemical behavior, characterized by oxygen reduction reaction onset po-
Electro synthesis tentials, electrochemical active surface area, cyclic voltammetry stability (1000 cycles) and
Platinum nanoparticles charge transfer resistance is attributed to the strong interaction between the nanosize
Oxygen reduction reaction platinum particles and the CQDs composite, which induces modulation in the electronic
structure of the platinum clusters.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

supports such as carbon nanostructured are generally used to

Introduction decrease the load of Pt and Pt alloy nanoparticles with
improved stability and enhanced activity [10e12]. Conse-
Platinum is a key electro-catalyst in fuel cells due to its high quently, the seeking and developing novel catalyst supports is
oxygen reduction reaction (ORR) capability at the cathode and an effective approach to increase catalytic activity. Recently,
fuel oxidation (e.g., methanol and hydrogen) at anode side carbonaceous materials, such as carbon black, carbon meso-
[1e3]. porous, multi-walled carbon nanotubes (MWCNTs), carbon
High dispersed noble Pt nanoparticles are commonly used nanofibers (CNFs), reduced graphene oxide (RGO) and so on,
as anode and cathode catalysts for fuel cells (FCs) [4e6]. are usually used as supports for ORR [13e17].
However, its high price, poor Pt utilization, inferior durability In recent years a great interest has been carried out on the
and limited availability in environment hinder its using in FCs carbon application as electrode materials due to their acces-
[7e9]. To decrease the Pt amount at the anode and cathode sibility, facile processability, excellent conductivity, ease of
sides of FCs and enhance the catalytic activity, the conductive

* Fax: þ98 41 37276066.

E-mail addresses: [email protected], [email protected].
http://dx.doi.org/10.1016/j.ijhydene.2017.01.057
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
11606 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3

functionalization, and relatively low cost [18]. They are electrode. The ethanol was converted into CQDs after
chemically stable in various solutions such as strongly acidic electrochemical carbonization.
or basic and can use in a different temperatures. Also well-
established physical and chemical technique allow to syn- Electrochemical measurements
thesis materials with a high surface area and a controlled
pores distribution that estimate the electrode/electrolyte Electrochemical technique such as linear sweep voltammetry
interface for application in energy storage and electronic (LSV), cyclic voltammetry (CV), electrochemical impedance
device. spectroscopy (EIS) and chronoamperometry (CA) tests were
Up to date, very few researcher studies the CQD-containing measured by potentiostat-galvanostat (VSP300) in a standard
metal electrocatalyst for ORR or methanol oxidation reaction three-electrode cell under ambient condition. The working
(MOR) except for two recent new reference that they were electrode was made from the Pt/CQD or standard Pt/C cata-
noticed during operation which demonstrate Pt-CQD/RGO is lysts (E-TEC) and Nafion as a binder. Typically, a mixture
ultra-efficient performance towards MOR [19] or the Pt depo- containing of 0.2 mg of a certain catalyst dispersed in 100 mL of
sition on N-doped CQD/CNT hybrid is more active for MOR water and 100 mL of a 0.5 wt % Nafion solution were homog-
than only on CNT [20]. On the other hand, the most of reported enized by sonication for 10 min at ambient conditions. The
fuel cell electrocatalysts used GQD as Pt-free electrocatalysts above-prepared catalyst ink was dropped onto a polished
[21e23] or Pt based on GQD [24,25] in ORR. Because the inti- glassy carbon electrode and dried at room temperature before
mate electronic interactions between Pt nanoparticles and electrochemical measurement. For ORR measurements,
nanosized GQDs show the dissociative adsorption of oxygen an aqueous solution of HClO4 or H2SO4 was used as the elec-
and binding reaction intermediates on the Pt surface [24]. CQD trolyte. N2 or O2 was used to purge the solution to achieve the
carries abundant oxygen groups [26] on its surface and pro- O2e free or O2-saturated electrolyte solution. The rotating disk
vides a considerable active sites to help the performance of Pt electrode (RDE) method was employed to investigate the ORR
catalysts to ORR. kinetics with a rotating speed of 225e2500 rpm.
In this study, for the first time based on our knowledge, we
have synthesized the CQDs by electrochemical method and Characterization
also investigated the effects of CQDs as a catalyst support on
the electrocatalytic activity of Pt nanoparticles for ORR in Transmission electron microscope (TEM) was used to conduct
acidic media. the TEM images. Raman spectra were measured with a 532 nm
excitation laser. X-ray diffraction (XRD) patterns were recor-
ded on an advance diffractometer with a Cu Ka radiation. A
Experimental section Zeiss Dual-Beam FESEM system was applied to take the
scanning electron microscopy (SEM).
Preparation of CQD

The electrochemical preparation of CQDs was performed by Results and discussion

electrochemical carbonization of low-molecular-weight
alcohols as reported by Zhang et al. [27] a two-electrode Physical characteristics of Pt/CQD
electrochemical cell. The electrolyte of the electro-
chemical process was prepared by mixing ethanol/H2O Fig. 1 demonstrates the XRD features of Pt/CQD. there are five
(100 mL; volume ratio ¼ 99.5:0.5) with appropriate amount main peaks at 2W ¼ 26 , 39.8 , 47.2 , 67.8 , and 81.2 which
(0.2e0.5 g) of NaOH, by using two Pt sheets as the working correspond to the C (002) and Pt (111), Pt (200), Pt (220) and Pt
and auxiliary electrodes and an Ag/AgCl as the reference (311) planes, respectively, indicating that the metallic Pt

Fig. 1 e XRD patterns of Pt/CQD.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3 11607

nanoparticles are formed after being reduced. We notice that 10 nm thick and, thus, are transparent under electron irradi-
the C (002) peak of Pt/CQD at 26 is broadened, because of the ation. The electron diffraction pattern from an area-selected
decreased delocalization of the carbon system. of the wall of honeycomb shows gray rings with spots, indi-
The crystallite size parameter was calculated using the cating that the CQDs within the honeycomb structure still
Scherer equation [28,29] for the (002) peak of CQDs and (111) remain the crystalline in nature after deposition of Pt nano-
for Pt on Pt/CQD yielding values of 9 and 4 nm. particles. Also this fig. displays that Pt nanoparticles as
Raman spectroscopy is a suitable and powerful tool to observed as black dots are remarkably well dispersed on the
investigate the structure of CQDs-based materials. Fig. 2 il- surface of Pt/CQD nanocomposites and no obvious aggrega-
lustrates the Raman spectra for graphite and CQDs. In the tions are detected. The EDX spectra of the Pt/CQD catalyst is
Raman spectra, two obvious peaks for the G and D band can be presented in Fig. 3c and d. It is obvious from this profile that
observed. the Pt/CQD catalyst is composed of carbon, oxygen and Pt.
As observed in this figure, two strong bands are located at The surface chemical state of Pt/CQD and Pt/C catalysts
1522.5 cm1 (G band) and 1135.7 cm1 (D band) for CQD while were investigated by X-ray photoelectron spectroscopy
the G band at 1593.1 cm1 and the D band at 1330 cm1 is (XPS). Fig. 4 represents the full XPS spectra and high-
related to of graphite powder. The D band is due to the resolution XPS spectra for Pt4f of Pt/CQD and Pt/C cata-
breathing mode of the k -point phonons of A1g symmetry and lysts. From Fig. 4a, it is found that the characteristic peaks of
the G band is related to the first-order scattering of the E2g Pt4f, C1s, and O1s are appeared at the binding energies of 72,
phonons. The shift of D band is proportional to the inverse of 285 and 575 eV, indicating the presence of Pt, C, and O ele-
the grain size. Another index, the intensity ratio of D and G ments in the electro-catalysts. While according the XPS
bands (I (D)/I (G)) is used as a ration to evaluate the property of spectra for Pt4f of Pt/CQD and Pt/C catalysts shown in Fig. 4b,
graphitization or disorders of defective on the crystalline each XPS profile of Pt4f region can be deconvoluted into two
graphite. Compared with graphite, the I (D)/I (G) of CQD is pairs of doublet peaks. The peaks at 70.0e71.9 eV and
drastically increased from 0.2 to 0.9, which is due to the in- 74.3e76.0 eV belong to metallic Pt (0), and the peaks at
crease of the disordered structure in the CQD structure. 71.0e73 eV and 74.2e76.6 eV are related to Pt (II) [30,31].
Fig. 3a and b shows the TEM images of the CQD and plat- Obviously, a positive shift occurs in XPS spectra of Pt4f in Pt/
inum reduced on CQD (Pt/CQD) assembled honeycomb CQD catalyst. This suggests that there is an enhanced
structures of the CQDs. The CQD honeycomb walls are ca. interaction between Pt nanoparticles and CQD support

Fig. 2 e Raman spectra of graphite and CQD.

11608 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3

Fig. 3 e Typical TEM image of (a) CQD and (b) Pt/CQD (c and d) EDX spectra for Pt/CQD catalyst.

Fig. 4 e (a) XPS survey spectra of Pt/CQD and Pt/C catalysts and high resolution XPS spectra for (b) Pt4f.

compared to that between Pt nanoparticles and C support electro-catalysts at room temperature in N2e saturated 0.5 M
[31], which may be beneficial for improving the electro- H2SO4 solution at a scan rate of 50 mV s1. This Figure display
chemical catalytic activity and stability. On the other hand two distinctive potential regions related to the electrochemi-
the binding energy of Pt4f in all Pt/CQD is higher than Pt4f in cally under-potential deposited hydrogen (Hupd) desorption/
Pt/C catalyst, indicating the interaction existed in Pt nano- adsorption processes between 0 and -0.3 V and the formation
particles and CQD support is stronger than that existed in Pt and reduction of PtOH and PtO layer beyond 0.45e0.9 V at
nanoparticles and carbon Vulcan support. forward and 0.65e0.2 at reverse scan. The electrochemically
active surface area (EASA) of Pt/CQD and Pt/C electrodes were
Electrochemical characteristics of Pt/CQD calculated by using the columbic charge for hydrogen
desorption, an assumed value of 210 mCcm2 for the oxidation
The CV of the Pt/CQD composite was compared with the of adsorbed atomic hydrogen on a smooth Pt surface by the
commercial Pt/C catalyst. Fig. 5a shows the CV curves for the following formula [28,32]:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3 11609

Fig. 5 e CVs of (a) Pt/CQD and Pt/C electrodes in the 0.5 M H2SO4 at Scan rate: 50 mV s¡1 and after 100th cycle (b) Comparing
long term stability of Pt/C at 100th and 1000th cycle and (c) Comparing long term stability of Pt/CQD at 100th and 1000th cycle.

where E is the measured experimental potential, E0 is the

 2 equilibrium potential for ORR, b is the tafel slope, Io is the
m QðmC=cm2 Þ
EASA ¼ (1) exchange current density, a is the electron transfer coeffi-
g 21ðmC=cm Þplatinum loadingðg=cm2 Þ
2

cient, na is the electron transfer number, F is the Faraday's

constant (96,485 C/mol), T is the temperature (K), and R rep-
Value of 85 and 55 m2/g are obtained for Pt/CQD and Pt/C resents the universal gas constant (8.314 J/mol K) [34]. The
catalysts by measuring the charge collected in the Hupd calculated Tafel slope of the Pt/CQD and Pt/C were
adsorption/desorption region. It should be noted that the 108 mV dec1 and 115 mV dec1, respectively. The exchange
value of double layer is corrected as reported in previous
current density of Pt/CQD was 9  109 A/cm2 and for Pt/C
work [33]. Accelerated degradation tests (ADTs) were per-
was 6:02  109 A/cm2. It was clearly showed that the onset
formed by cycling the catalysts in H2SO4 solution at a sweep
potential of Pt/CQD was 0.87 V (versus Ag/AgCl), which was
rate of 50mVs1 to compare the EASA during potential
very higher to that of commercial Pt/C catalyst (0.76 V versus
cycling. Fig. 5b and c shows the 100th and 1000th CV curves
Ag/AgCl). Fig. 5 also revealed that the current density (I) at
for the Pt/CQD and Pt/C catalysts. After cycling, the CV
peak of Pt/CQD reaches up to 12.1 mA/cm2. However, the
measurements showed an increase of 55% in EASA for Pt/ current density at peak potentials of Pt/C was only about
CQD. However, Pt/C catalyst displayed a loss of 45% in EASA 7.8 mA/cm2, which was only %60 of that of Pt/CQD electro-
after 1000th cycle. catalyst.
Fig. 6 displayed the polarization tests of Pt/CQD and Pt/C The durability of the Pt/CQD and Pt/C for ORR is inves-
electrodes for ORR. It could be observed that the polarization tigated by continuous chronoamperometric measurements
voltage linearly changed with the logI. The ORR kinetic pa-
at 0.5 V vs Ag/AgCl in an O2-saturated 0.1 M HClO4 electro-
rameters can calculate according to the following Tafel
lyte (Fig. 7a). After the reaction for 21,000 s, the Pt/CQD and
formula (2) and (3):
Pt/C catalysts show different levels of performance atten-
uation with 89.4%, and 81.6% of the relative current per-
h ¼ E0  E ¼ blogðIO Þ þ blogðIk Þ (2)
sisted in acidic media. On the other hand, the current
density of Pt/CQD catalyst has smaller loss, and the loss was
2:303RT
b¼ (3) only 10.6% in acidic medium. However, the Pt/C catalyst
ð1  aÞna F
current density has a much superior loss, and the current

Fig. 6 e LSV curves of Pt/CQD and Pt/C electrocatalysts with and without O2-saturated 0.1 M HClO4 media at a scan speed of
10 mVs¡1.
11610 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3

Fig. 7 e (a) Currentetime chronoamperometric response of Pt/CQD and Pt/C at 0.5 Vin O2-saturated 0.1 M HClO4 media (b)
Nyquist plots for Pt/CQD and Pt/C in the range of 100 kHz to 100 mHz at 0.4 V (c) Schematic representation of the equivalent
circuit for both catalysts. Rs: electrolyte resistance, R1: electrode intrinsic resistance, R2: charge transfer resistance and CPE:
constant-phase element.

loss reaches 18.4% in acidic medium due to the sur- Fig. 7b represented a representative Nyquist diagram of EIS
face oxidization, particle dissolution/aggregation/oswald test for ORR on the Pt/CQD and Pt/C catalysts in the 0.1 M
ripening over time, and weak interactions with carbon HClO4 solution. The Nyquist plots of ORR showed one semi-
support [35]. The above results reveal that the Pt/CQD circle in the high frequency region that associated with the
catalyst indeed possesses excellent durability, which may intrinsic resistance. And the half circle in the low frequency
be a promising candidate as cathode catalyst to replace region was related to kinetic polarization [36e38]. Fig. 7c was
commercial Pt/C for fuel cells. the module equivalent circuit compatible with the Nyquist

Fig. 8 e (a) LSV curves for Pt/C catalyst on a glass carbon by RDE at rotation rates of 225e2500 rpm in 0.1 M HClO4 media (b)
The corresponding Koutecky¡Levich (KeL) plots at different potentials in 0.1 M HClO4 media.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3 11611

Fig. 9 e (a) LSV curves for Pt/CQD catalyst on a glass carbon by RDE at rotation rates of 225e2500 rpm in 0.1 M HClO4 media
(b) The corresponding Koutecky¡Levich (KeL) plots at different potentials in 0.1 M HClO4 media.

plot, where Rs is the electrolyte resistance, R1 is the electrode is the bulk concentration of O2 in the electrolyte [41]. The cor-
intrinsic resistance, R2 is the charge transfer resistance, and responding curves are plotted for different potentials in Figs. 8b
Q1 and Q2 (constant-phase elements) represent the double- and 9b insets. The n value for Pt/CQD and Pt/C were derived to
layer capacitances distributed between the ohmic and be 3.80e4.05 and 3.85e4.15 over the potential range from
faradic processes, respectively. Based on the simulated 0.0e0.3 V, reflecting a four electron process for both electrodes.
equivalent circuit, it could be obtained that the ohmic resis-
tance Rs is 4.3U and reaction resistance R1of oxygen reduction
on Pt/CQD and Pt/C are 9.2 and 20.9 U respectively.
Conclusions
Linear sweep voltammetry (LSVs) were performed to gain
insight into the ORR activity of deposited Pt based on elec-
A facile, efficient and general electrochemical method was
trochemically synthetic CQD and the standard Pt/C electro
developed for constructing of carbon quantum dot and then
catalysts using rotating disk electrode (RDE). Figs. 8a and 9a
decorated using platinum nanoparticles with large surface
illustrates the LSV tests of ORR at various rotation speeds on
area. After decorating Pt nanoparticles, the obtained Pt/CQD
the Pt/C and Pt/CQD at the same mass loading content in 0.1 M
catalyst displays excellent catalytic activity and durability for
HClO4 media at room temperature, respectively. It was obvi-
ORR. Noticeably, the binary Pt/CQD catalyst exhibits the best
ously seen that the limiting current density increases with
electrocatalytic performance compared to Pt/C catalyst. This
increasing rotation rate for each catalysts, which should be
improved performance is due to its large specific surface area
induced by the increasing diffusion of oxygen on the electrode
and strong interaction between Pt and carbon quantum dot
surface. The kinetics of ORR was investigated according to the
that allows faster reduction of the O2 and excellent electron
KouteckyeLevich equation (4) [39e41]:
transfer property of Pt/CQD catalyst. The confinement effect
1 1 1 1 1 of carbon quantum dot existed in Pt/CQD catalyst can effec-
¼ þ ¼ þ (4) tively inhibit the aggregation of Pt nanoparticles during the
I IL IK Bu1=2 IK
operation process, thereby resulting in an enhanced stability.
where I is the measured current density,IK and IL are the ki-
Our work provide an effective and robust route to design
netic- and the diffusion-limiting current densities at a
carbon quantum dot with various metal, which can used as
particular voltage, u is the electrode rotation rate in rad/s
the support for proton exchange membrane fuel cells.
(u ¼ 2p N/60, N is the linear rotation speed); B could be
calculated from the slope of the KeL (inset panels in Figs. 8b
and 9b) based on the following equation (5):
Acknowledgments
B ¼ 0:62nFC0 ðD0 Þ2=3 w1=6 (5)

where n is the overall number of electron transfer, F is the This work was supported by the Fuel cell Steering Committee,
Faraday constant, D0 is the diffusion coefficient of O2 in the SANA, Iranian Nano Technology Initiative Council and East
electrolyte, w is the kinematic viscosity of the electrolyte, and C0 Azarbaijan Science and Technology Park (EASTP).
11612 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3

references [18] Frackowiak E, Be guin F. Carbon materials for the

electrochemical storage of energy in capacitors. Carbon
2001;39:937e50.
[19] Hong T-Z, Xue Q, Yang Z-Y, Dong Y-P. Great-enhanced
[1] Sasaki K, Wang JX, Balasubramanian M, McBreen J, Uribe F,
performance of Pt nanoparticles by the unique carbon
Adzic RR. Ultra-low platinum content fuel cell anode
quantum dot/reduced graphene oxide hybrid supports
electrocatalyst with a long-term performance stability.
towards methanol electrochemical oxidation. J Power
Electrochim Acta 2004;49:3873e7.
Sources 2016;303:109e17.
[2] Thompson SD, Jordan LR, Forsyth M. Platinum
[20] Zhang J-J, Wang Z-B, Li C, Zhao L, Liu J, Zhang L-M, et al.
electrodeposition for polymer electrolyte membrane fuel
Multiwall-carbon nanotube modified by N-doped carbon
cells. Electrochim Acta 2001;46:1657e63.
quantum dots as Pt catalyst support for methanol
[3] Kakaei K, Zhiani M. A new method for manufacturing
electrooxidation. J Power Sources 2015;289:63e70.
graphene and electrochemical characteristic of graphene-
[21] Liu Y, Wu P. Graphene quantum dot hybrids as efficient
supported Pt nanoparticles in methanol oxidation. J Power
metal-free electrocatalyst for the oxygen reduction reaction.
Sources 2013;225:356e63.
ACS Appl Mater Interfaces 2013;5:3362e9.
[4] Wang Y, Chen KS, Mishler J, Cho SC, Adroher XC. A review of
[22] Kakaei K, Javan H, Khamforoush M, Zarei SA. Fabrication of
polymer electrolyte membrane fuel cells: Technology,
new gas diffusion electrode based on carbon quantum dot
applications, and needs on fundamental research. Appl
and its application for oxygen reduction reaction. Int J
Energy 2011;88:981e1007.
Hydrogen Energy 2016;41:14684e91.
[5] Li Y, Gao W, Ci L, Wang C, Ajayan PM. Catalytic performance
[23] Liu K, Song Y, Chen S. Oxygen reduction catalyzed by
of Pt nanoparticles on reduced graphene oxide for methanol
nanocomposites based on graphene quantum dots-
electro-oxidation. Carbon 2010;48:1124e30.
supported copper nanoparticles. Int J Hydrogen Energy 21
[6] Bokach D, ten Hoopen S, Muthuswamy N, Buan MEM,
January 2016;41(3):1559e67.
Rønning M. Nitrogen-doped carbon nanofiber catalyst for
[24] He G, Song Y, Liu K, Walter A, Chen S, Chen S. Oxygen
ORR in PEM fuel cell stack: performance, durability and
reduction catalyzed by platinum nanoparticles supported on
market application aspects. Int J Hydrogen Energy
graphene quantum dots. ACS Catal 2013;3:831e8.
2016;41:17616e30.
[25] Song Y, Chen S. Graphene quantum-dot-supported platinum
[7] Li F, Guo Y, Li R, Wu F, Liu Y, Sun X, et al. A facile method to
nanoparticles: defect-mediated electrocatalytic activity in
synthesize supported Pd-Au nanoparticles using graphene
oxygen reduction. ACS Appl Mater Interfaces
oxide as the reductant and their extremely high
2014;6:14050e60.
electrocatalytic activity for the electrooxidation of methanol
[26] Miao P, Han K, Tang Y, Wang B, Lin T, Cheng W. Recent
and ethanol. J Mater Chem A 2013;1:6579e87.
advances in carbon nanodots: synthesis, properties and
[8] Bing Y, Liu H, Zhang L, Ghosh D, Zhang J. Nanostructured Pt-
biomedical applications. Nanoscale 2015;7:1586e95.
alloy electrocatalysts for PEM fuel cell oxygen reduction
[27] Deng J, Lu Q, Mi N, Li H, Liu M, Xu M, et al. Electrochemical
reaction. Chem Soc Rev 2010;39:2184e202.
synthesis of carbon nanodots directly from alcohols. Chem e
[9] Alonso-Lemus IL, Rodriguez-Varela FJ, Figueroa-Torres MZ,
A Eur J 2014;20:4993e9.
Sanchez-Castro ME, Hernandez-Ramı́rez A, Lardizabal-
[28] Kakaei K, Rahimi A, Husseindoost S, Hamidi M, Javan H,
Gutierrez D, et al. Novel self-nitrogen-doped porous carbon
Balavandi A. Fabrication of PteCeO2 nanoparticles supported
from waste leather as highly active metal-free electrocatalyst
sulfonated reduced graphene oxide as an efficient
for the ORR. Int J Hydrogen Energy 2016;41:23409e16.
electrocatalyst for ethanol oxidation. Int J Hydrogen Energy
[10] Kakati N, Maiti J, Lee SH, Jee SH, Viswanathan B, Yoon YS.
2016;41:3861e9.
Anode catalysts for direct methanol fuel cells in acidic
[29] Gharibi H, Kakaei K, Zhiani M. Platinum nanoparticles
media: do we have any alternative for Pt or PteRu? Chem Rev
supported by a vulcan XC-72 and PANI doped with
2014;114:12397e429.
trifluoromethane sulfonic acid substrate as a new
[11] Zheng W, Suominen A, Tuominen A. Discussion on the
electrocatalyst for direct methanol fuel cells. J Phys Chem C
challenges of DMFC catalyst loading process for mass
2010;114:5233e40.
production. Energy Procedia 2012;28:78e87.
[30] Ma L, Zhao X, Si F, Liu C, Liao J, Liang L, et al. A comparative
[12] Xie J, Chen J, Li CM. Self-assembling reduced graphene
study of Pt/C and PteMoOx/C catalysts with various
quantum dots on hematite photoanode for passivating
compositions for methanol electro-oxidation. Electrochim
surface states toward significantly improved water splitting.
Acta 2010;55:9105e12.
Int J Hydrogen Energy 2017;42:7158e65.
[31] Yan Z, He G, Shen PK, Luo Z, Xie J, Chen M. MoC-graphite
[13] Huang H, Wang X. Recent progress on carbon-based support
composite as a Pt electrocatalyst support for highly active
materials for electrocatalysts of direct methanol fuel cells. J
methanol oxidation and oxygen reduction reaction. J Mater
Mater Chem A 2014;2:6266e91.
Chem A 2014;2:4014e22.
[14] Yuan W, Lu S, Xiang Y, Jiang SP. Pt-based nanoparticles on
[32] Karimi Shervedani R, Amini A, Moetamedi Sedeh N.
non-covalent functionalized carbon nanotubes as effective
Preparation of graphene/Nile blue nanostructure on glassy
electrocatalysts for proton exchange membrane fuel cells.
carbon electrode: decoration with platinum nanoparticles
RSC Adv 2014;4:46265e84.
and application for electro-oxidation of methanol. Int J
[15] Zhou X, Qiao J, Yang L, Zhang J. A review of graphene-based
Hydrogen Energy 2016;41:13459e68.
nanostructural materials for both catalyst supports and
[33] Gharibi H, Kakaei K, Zhiani M, Taghiabadi MM. Effect of
metal-free catalysts in PEM fuel cell oxygen reduction
polyaniline-doped trifluoromethane sulfonic acid nanofiber
reactions. Adv Energy Mater 2014;4. n/a-n/a.
composite film thickness on electrode for methanol
[16] Kakaei K, Gharibi H. Palladium nanoparticle catalysts
oxidation. Int J Hydrogen Energy 2011;36:13301e9.
synthesis on graphene in sodium dodecyl sulfate for oxygen
[34] Gharibi H, Zhiani M, Mirzaie RA, Kheirmand M, Entezami AA,
reduction reaction. Energy 2014;65:166e71.
Kakaei K, et al. Investigation of polyaniline impregnation on
[17] Antolini E. Graphene as a new carbon support for low-
the performance of gas diffusion electrode (GDE) in PEMFC
temperature fuel cell catalysts. Appl Catal B Environ
using binary of Nafion and polyaniline nanofiber. J Power
2012;123e124:52e68.
Sources 2006;157:703e8.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 1 1 6 0 5 e1 1 6 1 3 11613

[35] Wei J, Hu Y, Wu Z, Liang Y, Leong S, Kong B, et al. A electrolyte additive in magnesium-air battery system. J
graphene-directed assembly route to hierarchically porous Power Sources 2015;276:32e8.
Co-Nx/C catalysts for high-performance oxygen reduction. J [39] Liang Y, Li Y, Wang H, Zhou J, Wang J, Regier T, et al. Co(3)
Mater Chem A 2015;3:16867e73. O(4) nanocrystals on graphene as a synergistic catalyst for
[36] Ehsani A, Vaziri-Rad A, Babaei F, Shiri HM. Electrosynthesis, oxygen reduction reaction. Nat Mater 2011;10:780e6.
optical modeling and electrocatalytic activity of Ni- [40] Kakaei K, Balavandi A. Synthesis of halogen-doped reduced
MWCNT-PT nanocomposite film. Electrochim Acta graphene oxide nanosheets as highly efficient metal-free
2015;159:140e8. electrocatalyst for oxygen reduction reaction. J Colloid
[37] Ehsani A, Mahjani MG, Jafarian M. Electrosynthesis of poly Interface Sci 2016;463:46e54.
ortho aminophenol films and nanoparticles: a comparative [41] Kakaei K, Balavandi A. Hierarchically porous fluorine-doped
study. Synth Met 2012;162:199e204. graphene as efficient metal-free electrocatalyst for oxygen
[38] Mayilvel Dinesh M, Saminathan K, Selvam M, Srither SR, reduction in gas diffusion electrode. J Colloid Interf Sci
Rajendran V, Kaler KVIS. Water soluble graphene as 2017;490:819e24.