international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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CVD graphene supported cobalt (II) phthalocyanine

as cathode electrocatalyst for PEM fuel cells

Sumeyye Dursun a, R. Gultekin Akay a, M. Suha Yazici b,*

a
Department of Chemical Engineering, Kocaeli University, Kocaeli, Turkey
b
TUBITAK Marmara Research Center, Energy Institute, 41470, Gebze, Kocaeli, Turkey

highlights graphical abstract

CoPc/CVD graphene electrode is

developed for acid electrolytes.

Electrochemical activity of CoPc/
CVD graphene proceeds with less
than 4-electron.

Heat treatment of CoPc/Graphene
at 800  C gives the best polariza-
tion response.

CoPc/Graphene has lower perfor-
mance compare to CoPc/C and Pt/
C electrocatalyst.

article info abstract

Article history: For the first time, CVD graphene supported cobalt (II) phthalocyanine (CoPc) is investigated
Received 28 October 2019 as a possible catalyst to replace Pt cathode in polymer electrolyte membrane (PEM) fuel
Received in revised form cells. Impregnation method is utilized for the synthesis of CVD graphene supported CoPc
22 March 2020 catalyst. Higher heat-treatment temperatures for CoPc/CVD graphene mixtures have
Accepted 21 April 2020 resulted with better electrochemical activity and stability. 5% Co/CoPc-G electrode
Available online xxx compare to 9.3% Co/CoPc-G for 0.3 mg Co/cm2 loading has resulted reduced voltage-current
characteristics due to kinetic and mass transfer limitations. Operational parameters are
Keywords: evaluated resulting maximum power density of 186 mW/cm2 with 9.3Co%/CoPc-Graphene,
CVD graphene 25-psi backpressure, 100% RH and 80  C operational temperature.
Cobal phthalocyanine © 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Oxygen reduction
Fuel cell

* Corresponding author.
E-mail address: suha.yazici@tubitak.gov.tr (M.S. Yazici).
https://doi.org/10.1016/j.ijhydene.2020.04.168
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
Slow kinetics of oxygen reduction reaction (ORR) in acid
electrolytes and fuel cells require large amount of Pt catalyst
to be used [1]. Earlier work of Jasinski and later Jahnke showed
ability of transition metal (TM) phthalocyanines and porphy-
rins to reduce oxygen has led to research on fuel cell cathode
electrocatalysts [2,3]. Hence, many studies have investigated
non-precious metal catalysts, including metal macrocycle,
chalcogenides, oxides and nitrides, as potential catalysts for
oxygen reduction [4e8]. Porphyrin and phthalocyanine
structures are such that four nitrogen atoms (N4) surrounds a
central transition metal (TM) forming electron sharing d-band
and electron delocalizing N4 matrix [9]. This makes TM-N4
structures different from other catalyst in terms of their
transition metal-nitrogen coordination [10].
Heat treatment of cobalt phthalocyanine (CoPc) above 700  C
increases stability and activity in acid and alkali electrolytes for
ORR [11,12]. Both pyrolyzed and unpyrolyzed carbon-supported
copper phthalocyanine (CuPc/C) nano-catalyst were examined
for ORR [13]. Heat-treatment at 800  C improved ORR activity of
the catalyst with an onset potential of 0.10 V and a half-wave
potential of 0.05 V in alkaline electrolyte. Higher heat treat-
ment temperatures for NiPc/C catalyst resulted higher number
of electron transfer in 0.1 M KOH [14]. However, electrocatalytic
activity of transition metal centered phthalocyanines was
reduced in the following order: Fe2þ >Co2þ >Mn2þ > Ni2þ >Cu2þ
[14]. For this reason, CoPc and FePc were the most investigated
catalysts for ORR in alkaline electrolytes.
Various catalyst supports (carbon black, nanotubes and
graphene) have been studied for TM-N4 macrocycle materials in
order to create p- p interactions between carbon and transition
metal N4-macrocycles [15]. While ORR on carbon-supported Fe
phthalocyanine (FePc/C) proceeded with 4e pathway, ORR on
CoPc/C proceeded with 2e and more stable in 0.1 M NaOH
electrolyte [16]. FePc supported on carbon nanoribbon reported
showing higher ORR activity than the commercial Pt electro-
catalyst in alkaline solution [17]. FePc supported on carbon black
was studied in alkaline and acidic media for ORR. While the best
activity in acid medium was achieved at 800  C with E1/2 of 0.72 V,
the best activity in alkaline medium was achieved at 500  C with
E1/2 of 0.925 V [18]. CoPc adsorbed on carbon black (CB) and multi
walled carbon nanotube (MWCNT) was investigated in alkaline
media. The peak power density of CoPc/CB, CoPc/MWCNTs
were found as 55, 35 mW/cm2 respectively for H2eO2 in alkali
fuel cell [19]. 4% Co phthalocyanines supported on carbon black
(CoPc/CB) were studied in PEM fuel cell giving maximum power
density of 40 mW/cm2 [8]. When Co, Mn and Fe phthalocyanines
supported on N-modified activated carbon were evaluated for
oxygen reduction reaction in 0.1 M HClO4, heat treatment at
800  C incorporated metals into carbon structure with graphitic-
N groups giving maximum current density in the following
order: FePc > CoPc > MnPc [20]. Similar analysis with multi-
walled carbon nanotubes resulted with oxidized multiwall car-
bon nanotubes giving the highest current density and number of
electrons in acidic and alkaline electrolytes [21]. CoPc supported
on multiwalled carbon nanotube was studied in 0.5 M H2SO4
with different heat treatment temperatures resulting best oxy-
gen reduction activity at 550  C [22].
Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
In particular, graphene as a catalyst support has attracted
interest in oxygen reduction reaction due to superior proper-
ties. FePc and CoPh on reduced graphene oxide (rGO) were
highly active for ORR in 0.1 M KOH electrolyte [23]. Unpyr-
olysed FePc supported on N-doped graphene (FePc/N-G) gave
higher oxygen reduction activity in an alkaline electrolyte [24].
Cobalt phthalocyanine on 3D graphene prepared by coal tar
pitch was investigated for oxygen reduction reaction in 0.1 M
KOH solution giving 3.9 electron at 0.65 V [25]. FePc supported
on N-doped graphene (FePc/N-G) gave 4-electron process
(n ¼ 4) for ORR in alkaline media [26]. CoPc, and FePc adsorbed
on graphite was studied for ORR. While FePc demonstrated 4-
electron reduction process, Co showed 2-electron process for
ORR in alkaline media [27].
With a few exception, most of the oxygen reduction ac-
tivities of CoPc in the literature were in alkali (KOH) electrolyte
and graphene used in those measurements were chemically
modified using Hummers’ method. Electrochemical charac-
terizations were, most of the time, limited to three-electrode
measurements. There is little understanding about fuel cell
behavior of these catalysts. In this research, CVD graphene
supported Co phthalocyanine (CoPc) was studied, for the first
time, as an oxygen reduction catalyst in acid electrolytes and
as a cathode electrode for PEM fuel cells.
Experimental
Chemicals
Cobalt (II) phthalocyanine (93%, TCI America) was used as
received and dissolved in tetrahydrofuran (THF, 99.9%,
Merck). Sulfuric acid (H2SO4, %95, Sigma Aldrich) was used for
membrane treatment and nitric acid (HNO3, 65%, Sigma
Aldrich) was used for graphene processing. Nafion® XL
membrane was purchased from Ion Power. Platinum on
Vulcan (20% Pt/C, Alfa Aesar) and Nafion solution (5 wt%) were
purchased from Alfa Aesar. Gas diffusion layer (GDL) for
catalyst loading was Sigracet 29BC carbon paper from SGL
Carbon. Gasses with 99.99 purity was used in all experiments.
Preparation of graphene supported CoPc
Details for the production and characterization of CVD gra-
phene was previously described [28]. Graphene was grown on
porous nickel substrate by chemical vapor deposition (CVD) at
1000  C with methane (CH4) as carbon source. After 5 min CH4
flow, furnace was cooled rapidly to allow growth of graphene.
Continuous phase, porous graphene was obtained by etching
away nickel foam using 30% nitric acid solution and washing
with distilled water. For electrode preparation, CoPc was dis-
solved in THF and mixed with graphene. Approximately,
13 mg, 40 mg and 100 mg graphene were mixed with 200 mg,
200 mg and 100 mg CoPc in order to obtain 9.3% Co, 8.3% Co
and 5% Co content respectively. Mixture was stirred at room
temperature and ultrasonicated for 2 h. After ultrasonication
process, catalyst mixture was dried at 80  C. Resulting CVD
graphene supported CoPc catalyst was pyrolyzed at 500  C,
650  C and 800  C under Ar gas for 2 h. Schematics of electrode
preparation is given in Fig. 1.
 international journal of hydrogen energy xxx (xxxx) xxx 3

Electrode and MEA preparation
CoPc/G powder with 5 wt% Nafion and water were ultrasoni-
cally mixed to prepare electrocatalyst ink. A drop of (9 ml) ink
was placed on glassy carbon electrode for rotating disc elec-
trode (RDE) measurements. Fuel cell electrode was prepared
by having 0.3 wt% Co loading with 9.3% Co, 8.3% Co and 5% Co
on CoPc/G catalyst mixture on a 29BC carbon paper. This
electrode was used on the cathode side of the fuel cell. For the
anode side, 20 wt% Pt/C mixture was used to prepare
0.4 mg Pt/cm2 loaded catalyst ink with the same procedure on
29BC carbon paper. Nafion-XL membrane was hot pressed
with cathode and anode electrodes at 110  C using a pressure
of 100 kg/cm2 for 3 min forming MEA for fuel cell tests.
Physical characterization
crystallographic properties and phase orientation of the
catalyst structures.
Electrochemical measurement
RDE analyses were performed using Gamry Reference 3000
Potentiostat, RDE360 rotating disc electrode system. Ink
deposited glassy carbon electrode connected to the rotating
disc system was used as working electrode. Pt wire was used
as counter and calomel electrode containing 3 M KCl solution
was used as reference electrode. Linear sweep voltammetry
was routinely used to characterize ORR performance of the
catalyst. Fuel cell measurements were carried out with
Scribner fuel cell test station at different temperatures, pres-
sures and humidity levels.

Structural morphologies of the catalysts were characterized Results and discussion

using thermogravimetric analyzer (TGA STA 449 F3 Jupiter),
scanning electron microscopy (SEM-JSM6335-F Oxford In-
struments AZTEC-EDS) and transmission electron microscopy
(TEM-JEOL 2100 HRTEM). X-Ray Diffraction method (XRD-
PANalytical X’pert Pro MPD) was used to investigate the
CoPc may show different catalytic response under different
temperatures due to presence of nitrogen (N) in its structure.
Main pyrolysis products of CoPc were reported as cyanogens
(CN)2, hydrogen cyanide (HCN), benzonitrile (C6H5CN), and
phthalonitrile (C6H4(CN)2) [29]. Thermogravimetric response

Fig. 1 e Schematics of CoPc/Graphene catalyst/electrode preparation process.

Fig. 2 e (a) Thermogravimetric response of cobalt phthalocyanine under argon with temperature ramp of 20  C/min and (b)
XRD pattern of CoPc, CoPc-500, CoPc-800, CoPc/G-500 and CoPc/G-800.

Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 3 e At different magnifications, SEM images of CoPc/G (a,b) before heat-treatment, (c,d) after 800  C heat-treatment and
(e,f) TEM images after 800  C heat-treatment.

of CoPc under argon atmosphere was given in Fig. 2a. CoPc
catalyst was heated from room temperature to 950  C. Three
stable regions were observed before sudden weight losses
took place (100, 600 and 750  C). Heat treatment temperatures
for the catalyst samples were selected as 500  C, 650  C and
800  C where major weight losses took place before or after.
Sharp weight loss after 600  C may indicate starting decom-
position of CoeN4 structure. At 800  C, original CoPc structure,
where Co was surrounded by N-atoms, mostly decomposed
and new structure with Co, oxides and CeN structures were
believed to be formed.
Fig. 2b shows x-ray diffraction pattern for plain CoPc and
CoPc/G at different heat-treatment temperatures. Plain CoPc
showed various peaks for different phases and structures of
CoPc. Heat-treatment of CoPc at 800  C resulted with main
peaks corresponding to Co structure at 44 (Co(111) and 52
(Co(200)). After CVD graphene addition (CoPc/G), similar XRD
pattern was obtained at 500  C with smaller magnitude. This
indicated presence of graphene could prevent significant
decomposition of CoPc structure (CoN4). This was not the case
at 800  C where intensities and positions of the CoPc/G
diffraction lines were suppressed and some disappeared.
Main graphite peak was observed at 26 as carbon C (002).
SEM and TEM were utilized to characterize structure of the
plain and heat-treated CoPc/G. Fig. 3 shows SEM images at two
different magnification for 5 wt% CoPc nanoparticles sup-
ported on graphene before (Fig. 3a and 3b) and after (Fig. 3c
and 3d) heat treatment at 800  C. As seen from the pictures,
particles were nicely dispersed on graphene support and
becoming more dense with heat treatment. TEM images in

Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3e and 3f suggested wide dispersion of Co and compo-
nents on graphene with particle sizes ranging from a few nm
to 50 nm in sizes.
To gain information about ORR activity of CoPc/G (9.3% Co),
linear sweep voltammetry (LSV) measurements at 20 mV/s
scan rate were conducted by RDE approach under different
rotation rate (400, 900 and 1600 rpm) in oxygen-saturated
electrolyte of 0.5 M H2SO4 (Fig. 4). Oxygen reduction peak
was clearly seen with samples heat-treated at 800  C (Fig. 4a).
Open circuit voltage (OCV) was in the range of 0.5e0.6 V (vs.
SCE) indicating oxygen reduction reaction may proceed
through formation of hydrogen peroxide (H2O2).
Influence of the pyrolysis temperature on the fuel cell
performance of CoPc/G catalyst was studied with samples
not heat-treated and heat-treated at 500  C, 650  C and
800  C. Fuel cell tests were performed at 80  C, relative hu-
midity of 100% and 25-psi backpressure (Fig. 5). Thermal
treatment of CoPc/G catalyst mixture has resulted with
higher fuel cell performance. Best polarization current
densities were obtained at 800  C treatment while no elec-
trocatalytic activity was observed with CoPc/G mixture heat-

O2 þ 2Hþ þ 2e- ¼ H2O2 E¼0.695 V (SHE) (1)

Mass activity within 100 mV from OCV is given in Fig. 4b.

Heat-treatment at 800  C has resulted better OCV and activity
compare to 600  C sample. Analysis conducted by using
Koutecky-Levich equations had resulted low number of elec-
tron transfer strongly suggesting H2O2 formation with cobalt
catalyst. The number of electrons for CoPc/G electrodes were
calculated as 2.7, 0.75, and 0.1 for 800  C, 650  C and 500  C
heat-treated samples respectively (Fig. 4d). Number of elec-
tron transfer became better with higher heat treatment tem-
peratures. Zagal et al. examined CoPc supported on graphite
for ORR and the reaction proceeded by 2-electron process [27].
Similarly, CoPc supported on carbon black has resulted 1.4 to Fig. 5 e Polarization curves for heat-treated samples of
2.4 electrons and cobalt (II) tetra-tert-butylphthalocyanine CoPc/G cathode.
(Co(Bu)Pc) on MWCNT with 2.83 electrons for ORR [16,21].

Fig. 4 e Linear sweep voltammetry of CoPc/G catalyst heat-treated at (a) 800  C (b) Mass activity (c) Koutecky-Levich plots, (d)
Number of electrons calculated.

Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
6 international journal of hydrogen energy xxx (xxxx) xxx

treated at 500  C or below. Sample heat-treated at 650  C was
kinetically limited giving low current. As confirmed with
XRD data, CoPc structure was intact at 500  C heat-
treatment. After this temperature structure started to
decompose to form some CoeN (not dissociated), Co and
oxides, and CeN structures. In fact, this decomposition was
needed for electrocatalyst to work.
Müller et al. investigated CoPc on carbon black by XPS
analysis. Co content and performance increased with 800  C
heat treatment according to their XPS results and fuel cell
data. The highest power density was obtained as 186 mW/cm2
with 800  C heat-treated samples [12]. Truong et al. studied
CoPc supported on carbon black (CB) and multi walled carbon
nanotube (MWCNT). Peak power density of 55, 35 mW/cm2
was achieved by CoPc/CB and CoPc/MWCNT respectively with
AEMFC [19]. It was obvious from these results that CoPc/G
reported in this research provided better polarization data
compare to literature presented above. However, performance
of the catalyst was still low compare to Pt/C catalyst/support
combination.
First, effect of operational temperature on the polarization
was evaluated (Fig. 6a). Fuel cell polarization for cells operated
at 60  C and 80  C were similar at kinetic region up to 200 mA/
cm2 current density. From ohmic to mass transfer limited
region, 50 mV polarization difference was measured at
600 mA/cm2 for 60  C and 80  C. Higher temperature was
favorable for mass transfer region.
Co supported by CB and MWCNT had reached maximum
power density with 4 wt% Co catalysts [19]. The effect of Co
content in the CoPc/G mixture was studied by changing Co
amount in the CoPc/G mixture from 5% to 9.3% Co. Increasing
cobalt content of the catalyst mixture while keeping the
loading constant at 0.3 mg Co/cm2, gave increased fuel cell
performance (Fig. 6b). Highest Co content of 9.3% in the
catalyst mixture was very close to the theoretical value of
10.3% Co for CoPc (C32H16CoN8: MW: 571.5 g/mol). As the gra-
phene amount in the electrode layer was increased, voltage-
current characteristics were reduced due to kinetic and
mass transfer limitations.
Back pressure effect on fuel cell polarization performance
for 9.3% Co mixture at 80  C, 100% RH and 0.3 mgCo/cm2
loading was shown in Fig. 6c. Lowest voltage-current charac-
teristics were obtained when the cell was not pressurized. As
back pressure was applied, kinetic and mass transfer limita-
tions were overcome and higher current density values were
reached.
Similarly, impact of humidification on the fuel cell per-
formance was presented in Fig. 6d. CoPc/G was performing
better at full hydration of the membrane. Humidification
levels lower than 100% resulted lower performance in the
order of 66% and 42%. However, drop from 100% to 42% was
not that significant. Dry operation was not considered since
voltage drop was very sharp even at very low current
densities.
Impact of operational parameters on catalyst mass ac-
tivity was evaluated at different Co/CoPc-G ratios (Fig. 7a)
and at different back pressures (Fig. 7b). Voltage levels were
very low at high current values. When 1 A/mgCo was
analyzed, there was more than 100 mV voltage difference
between low and high parameters (catalyst loading and

Fig. 6 e Polarization response of CoPc/G cathode at (a) different cell temperatures, (b) different Co/CoPc-G ratios, (c) different
back pressures and (d) different humidification levels.

Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 7 e Catalyst mass activity at (a) different Co/CoPc-G ratios, (b) different back pressures.
back-pressure). However, It is necessary to get to at least
0.5 V levels with high loadings for being able to use CoPc as
cathode.
Conclusions
Impregnation method was applied for the synthesis of CVD
graphene supported Cobalt (II) phthalocyanine (CoPc) catalyst
to be used in PEM fuel cell cathodes. Low open circuit voltage
at three-electrode configuration (0.7e0.8 V vs. SHE) and fuel
cell measurements (0.85 V) indicates oxygen reduction reac-
tion may proceed through formation of hydrogen peroxide
(H2O2). Heat-treatment at 800  C for CoPc/CVD graphene
mixtures have resulted with better electrochemical activity
and stability. While applying backpressure improved fuel cell
performance, CVD graphene displayed blocking effect on the
cathode side of the fuel cell. High graphene ratio in the cata-
lyst (5% Co/CoPc-G) caused agglomeration and resulted in
reduced voltage-current characteristics due to mass transfer
limitations. Operational parameters provided maximum
power density of 186 mW/cm2 with 9.3Co%/CoPc-Graphene
(0.3 mg Co/cm2 loading), 25-psi backpressure, 100% RH and
80  C operational temperature. CoPc with CVD graphene as an
electrocatalyst has resulted lower performance compare to
CoPc with carbon support and conventional Pt catalyst.
Acknowledgement
The authors would like to acknowledge financial support
provided by The Scientific and Technological Research
Council of Turkey (TUBITAK) through 1003 program under
contract # 215M302.
references
[1] Rabis A, Rodriguez P, Thomas J, Schmidt TJ. Electrocatalysis
for polymer electrolyte fuel cells: recent achievements and
future challenges. ACS Catal 2012;2:864e90.
Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
7
[2] Jasinski R. A new fuel cell cathode catalyst. Nature
1964;201:1212e3.
[3] Jahnke HG, Schonborn MF, Zimmerman C. Organic dyestuffs
as catalysts for fuel cells. Top Curr Chem 1975;61:133.
[4] Liu D, Long Y. Superior catalytic activity of electrochemically
reduced graphene oxide supported iron phthalocyanines
toward oxygen reduction reaction. ACS Appl Mater
Interfaces 2015;7(43):24063e8.
[5] Gao M-R, Jiang J, Yu S-H. Catalysis: solution-based synthesis
and design of late transition metal chalcogenide materials
for oxygen reduction reaction (ORR). Small 2012;8(1):13e27.
[6] Liang Y, Wang H, Diao P, Chang W, Hong G, Li Y, Gong M,
Xie L, Zhou J, Wang J, Regier TZ, Wei F, Dai H. Oxygen
reduction electrocatalyst based on strongly coupled cobalt
oxide nanocrystals and carbon nanotubes. J Am Chem Soc
2012;134:15849e57.
[7] Varga T, Va
sa

rhelyi L, Ballai G, Haspel H, Oszko

A,
Kukovecz A,
et al. Noble-metal-free iron nitride/nitrogen-
doped graphene composite for the oxygen reduction
reaction. ACS Omega 2019;4:130e9.
[8] Erkan S. MSc. Thesis in chemical engineering. Ankara,
Turkey: Middle East Technical University; 2005.
[9] Tiwari BR, Noori MT, Ghangrekar MM. Carbon supported
nickel-phthalocyanine/MnOx as novel cathode catalyst for
microbial fuel cell application. Int J Hydrogen Energy
2017;42:23085e94.
[10] Lefevre M, Proietti E, Jaouen F, Dodelet JP. Iron-based
catalysts with improved oxygen reduction activity in
polymer electrolyte fuel cells. Science 2009;324:71e4.
[11] Osmieri L. Transition metalenitrogenecarbon (MeNeC)
catalysts for oxygen reduction reaction. Insights on
synthesis and performance in polymer electrolyte fuel cells.
ChemEngineering 2019;3(1):16.
[12] Müller K, Richter M, Friedrich D, Paloumpa I, Kramm UI,
Schmeißer D. Spectroscopic characterization of
CobaltePhthalocyanine electrocatalysts for fuel cell
applications. Solid State Ionics 2012;216:78e82.
[13] Ding L, Qiao J, Dai X, Zhang J, Zhang J, Tian B. Highly active
electrocatalysts for oxygen reduction from carbon-supported
copper-phthalocyanine synthesized by high temperature
treatment. Int J Hydrogen Energy 2012;37:14103e13.
[14] Ding L, Xin Q, Zhou X, Qiao J, Li H, Wang H. Electrochemical
behavior of nanostructured nickel phthalocyanine (NiPc/C)
for oxygen reduction reaction in alkaline media. J Appl
Electrochem 2013;43:43e51.
[15] Liu Y, Yue X, Li K, Qiao J, Wilkinson DP, Zhang J. PEM fuel cell
electrocatalysts based on transition metal macrocyclic
compounds. Coord Chem Rev 2016;315:153e77.
8 international journal of hydrogen energy xxx (xxxx) xxx
[16] Chen R, Li H, Chu D, Wang G. Unraveling oxygen reduction
reaction mechanisms on carbon-supported Fe-
phthalocyanine and Co-phthalocyanine catalysts in alkaline
solutions. J Phys Chem C 2009;113:20689e97.
[17] Chung DY, Kim MJ, Kang N, Yoo JM, Shin H, Kim OH. Low-
temperature and gram-scale synthesis of two-dimensional
FeeNeC carbon sheets for robust electrochemical oxygen
reduction reaction. Chem Mater 2017;29:2890e8.
[18] Zhang X, Chen C, Dong J, Wang RX, Wang Q, Zhou ZY.
Comparative study of the oxygen reduction reaction on
pyrolyzed FePc in acidic and alkaline media.
ChemElectroChem 2018;5(24):3946e52.
[19] Truong VM, Yang C-W, Yang H. Carbon black and multi-
walled carbon nanotube supported cobalt for anion
exchange membrane fuel cell. J Technol Innovat Renew
Energy 2018;7:1e6.
[20] Domı́nguez C, Pe
rez-Alonso F, Abdel Salam M, Go
mez de la
Fuente J, Al-Thabaiti S, Basahel S, Pen~ a M, Fierro J, Rojas S.
Effect of transition metal (M: Fe, Co or Mn) for the oxygen
reduction reaction with non-precious metal catalysts in acid
medium. Int J Hydrogen Energy 2014;39(10):5309e18.
[21] Morozan A, Campidelli S, Filoramo A, Jousselme B,
Palacin S. Catalytic activity of cobalt and iron
phthalocyanines or porphyrins supported on different
carbon nanotubes towards oxygen reduction reaction.
Carbon 2011;49:4839e47.
[22] Ramavathu LN, Maniam KK, Gopalram K, Chetty R. Effect of
pyrolysis temperature on cobalt phthalocyanine supported
on carbon nanotubes for oxygen reduction reaction. J Appl
Electrochem 2012;42:945e51.
Please cite this article as: Dursun S et al., CVD graphene supported cobalt (II) phthalocyanine as cathode electrocatalyst for PEM fuel
cells, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.04.168
[23] Kruusenberg I, Mondal J, Matisen L, Sammelselg V,
Tammeveski K. Oxygen reduction on graphene-supported
MN4 macrocycles in alkaline media. Electrochem Commun
2013;33:18e22.
[24] Komba N, Zhang G, Wei Q, Yang X, Prakash J, Chenitz R,
Rosei F, Sun S. Iron (II) phthalocyanine/N-doped graphene: a
highly efficient non-precious metal catalyst for oxygen
reduction. Int J Hydrogen Energy 2019;44:18103e14.
[25] Sun C, Li Z, Zhong X, Wang S, Yin X, Wang L. Three-
dimensional graphene-supported cobalt phthalocyanine as
advanced electrocatalysts for oxygen reduction reaction. J
Electrochem Soc 2018;165(2):24e31.
[26] Zhang C, Hao R, Yin H, Liu F, Hou Y. Iron phthalocyanine and
nitrogen-doped graphene composite as a novel non-precious
catalyst for the oxygen reduction reaction. Nanoscale
2012;4:7326e9.
[27] Zagal JH, Recioa FJ, Gutierreza CA, Zun ~ igaa C, Pa

eza MA,
Caro CA. Towards a unified way of comparing the
electrocatalytic activity MN4 macrocyclic metal catalysts for
O2reduction on the basis of the reversiblepotential of the
reaction. Electrochem Commun 2013;41:24e6.
[28] Yazici MS, Azder M, Salihoglu O. CVD grown graphene as
catalyst for acid electrolytes. Int J Hydrogen Energy
2018;43(23):10710e6.
[29] Achar BN, Lokesh KS, Fohlen GM, Mohan Kumar TM.
Characterization of cobalt phthalocyanine sheet polymer by
gas chromatography mass spectrometry on its pyrolysis
products. React Funct Polym 2005;63:63e9.