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Journal of

Materials Chemistry A
PAPER

Reduced graphene oxide intercalated Co2C or


Co4N nanoparticles as an ecient and durable fuel
Cite this: J. Mater. Chem. A, 2017, 5,
2972 cell catalyst for oxygen reduction
Mayilvel Dinesh Meganathan,a Shun Mao,*b Taizhong Huang*a and Guoxin Suna

Research on catalysis for fuel cells is extremely important to enhance the sluggish oxygen reduction reaction
(ORR) using heterogeneous catalyst materials. In this work, cobalt carbide (Co2C) and cobalt nitride (Co4N)
nanoparticles were intercalated with reduced graphene oxide (rGO) sheets through heteroatom doping
and utilized for the ORR in alkaline fuel cells, in which rGO acted as a catalyst support. Cyclic voltammetry
results indicated that the ORR half-wave potentials of Co2C/rGO and Co4N/rGO were found to be
Received 10th November 2016
Accepted 15th January 2017
0.095 V and 0.118 V, respectively. Chronoamperometric studies revealed the excellent catalytic stability
of the prepared catalysts. The reaction kinetics study showed that Co2C/rGO and Co4N/rGO pursued a 4e
DOI: 10.1039/c6ta09729d
(four electron) oxygen reduction process. The catalytic activity and stability in alkaline electrolyte indicated
www.rsc.org/MaterialsA that Co2C/rGO and Co4N/rGO have great potential as alternatives to precious metal-based catalysts.

due to poor oxygen adsorption on the electrode, irreversibility of


Introduction oxygen, etc.1,3,6
Fuel cells are ecient and non-polluting power sources that Normally, the ORR in fuel cells is rather slow because of the
have been in practice for over ve decades. Initially, fuel cells high overpotential and stacking of OH ions at the cathode.
were utilized in space vehicles. Later, they came to be used in Moreover, the durability of the ORR is critical to the eciency of
portable power generation, electronic devices and hybrid elec- the fuel cell, which is mainly aected by the degradation of
tric vehicles, because of their high energy density, rapid start- active sites.7 Thus, ORR is the backbone to the performance of
up, lack of emissions, environmental friendliness, low opera- the fuel cell. The ORR mechanism strongly depends on the
tive temperature, etc.13 Fuel cell devices generate electricity cathode material and the electrolyte. The electron kinetics of
through electrochemical energy conversion between the anode the ORR are more favourable in alkaline medium, because of its
(like hydrogen, methanol, ethanol, etc.) and cathode (air/oxygen high ionic mobility property.8,9 In alkaline electrolytes, the ORR
from the atmosphere). Generally, ions move from the anode or involves both 4e reduction (O2 to OH) and 2e reduction (O2
cathode of the fuel cell to the other side of the electrolyte; to H2O2) processes. Normally, platinum (Pt), ruthenium (Rh),
whereas electrons liberated from the anode ow through the gold (Au) etc., are considered as the most ecient catalysts for
external circuit and reach the cathode.4 Among the fuel cell fast ORR kinetics, four electron transfer mechanism and low
types, alkaline fuel cells are ecient and have high power overpotential. However, these catalysts have some drawbacks
density and low operative temperature, which are useful in such as high cost, poor stability, agglomeration during the
portable devices and hybrid electric vehicles. In alkaline fuel reactions and rare sources. Also, CO poisoning for Pt-based
cells, alkaline electrolytes such as potassium hydroxide, sodium catalysts could degrade the fuel cell performance.6,10,11 To
hydroxide, etc., are preferred, due to their low-cost, high solu- attain maximum energy capacity in fuel cells, oxygen reduction
bility, low corrosivity and high ionic conductivity.5 Nevertheless, should happen through the 4e reduction process, because the
there are some disadvantages at the air cathode in fuel cells, like 2e reduction process results in the production of hydrogen
high overpotential, sluggish oxygen reduction reaction (ORR) peroxide (H2O2), which leads to performance degradation in
fuel cells.12
a
School of Chemistry and Chemical Engineering, University of Jinan, 336 West Road of
The demand for non-precious, low-cost and highly durable
Nanxinzhuang, Jinan, Shandong, 250022, China. E-mail: chm_huangtz@ujn.edu.cn electrocatalysts to improve the ORR kinetics and catalytic
b
State Key Laboratory of Pollution Control and Resource Reuse, College of stability is urgent. Carbon-based materials like graphene,
Environmental Science and Engineering, Tongji University, 1239 Siping Road, fullerenes, activated carbon, etc., are used for electrocatalysis.
Shanghai, 200092, China. E-mail: shunmao@tongji.edu.cn For the past decade, graphene-related research has been
Electronic supplementary information (ESI) available: Scanning electron
encouraged more, because of its high conductivity, mechanical
microscope images, energy dispersive spectra, elemental mapping data, XPS
spectra and catalytic activity comparison with other related catalysts. See DOI:
strength, large surface area, chemical stability, etc. At the same
10.1039/c6ta09729d time, heteroatom-doped carbon materials are considered as

2972 | J. Mater. Chem. A, 2017, 5, 29722980 This journal is The Royal Society of Chemistry 2017
Paper Journal of Materials Chemistry A

potential alternatives for Pt towards the ORR.13 Amazingly, Experimental methods


graphene contains a unique feature as a supporting platform to
catalysts, compared to other carbonaceous materials such as Preparation of Co3O4/GO
carbon nanotubes, carbon black, nanoporous gold leaf, etc.14 Initially, graphene oxide (GO) solution was prepared through
Graphene can hold the catalytic nanoparticles closely using its a modied Hummers method.23 0.07 g of cobalt nitrate
matrix structure and reduce the oxidation of the catalyst (Co(NO3)2$6H2O, 98.2%) and 0.015 g of ammonium nitrate
materials, particularly for the ORR. Additionally, vacancy sites (NH4NO3, 99.5%) were mixed in 30 ml of DI water. Then, 3.5 ml
in the catalyst can be achieved through high-level hetero-atom of the prepared GO (6 mg ml1) liquid ink was added into the
doping in the graphitic lattice through ammonia annealing, mixture solution. Stirring was started gently in the mixture
nitrogen plasma etching, ion irradiation, etc.,8 oering solution at room temperature. Aer 10 minutes, 25 ml of conc.
outstanding electrocatalytic activities. In heteroatom-doped ammonia (29% pure) was added dropwise with the help of ink
carbonaceous materials, the presence of nitrogen imparts ller into the mixture solution under constant stirring. The
a high positive charge on adjacent carbon atoms, which solution was stirred for additional 10 minutes and then trans-
increases the number of active ORR sites and makes the cata- ferred to a Petri dish and kept in a hot air oven at 80  C for 14
lytic kinetics similar to those of commercial Pt/C.2,6,10,1520 These hours. The obtained precipitate was completely washed with
characteristics made graphene play a signicant role in elec- ethanol and then fully dried at 80  C. The nal black coloured
trocatalysis for energy conversion and storage devices.21 powder contains a composite of cobalt oxide and graphene
Researchers have investigated numerous ORR catalysts of oxide (Co3O4/GO).30
transitional metal oxides, metal carbides, and metal nitrides.11
In general, transitional metals have incomplete outermost d
orbitals, so electrons can be easily accepted/given for electro- Preparation of Co2C/rGO and Co4N/rGO catalysts
chemical reactions. Metal oxides, such as FeOx, NiO, Co3O4, and The as-obtained Co3O4/GO was moved to a ceramic crucible and
Mn3O4, have shown good electrocatalytic activity and excellent kept inside the hollow glass tube of a tubular furnace. Then,
stability for the ORR. Similarly, metal carbides and metal ammonia (NH3) gas was fed and the heating rate of the furnace
nitrides also showed good catalytic activity and stability for the was set at 15  C min1. The maximum set temperature of 400  C
ORR.22,23 Transitional metal carbides oer high electrocatalytic was maintained for 5 hours with an endless ow of gaseous
activity and excellent stability towards the ORR due to the NH3.30 Aer that, the furnace was gradually cooled to room
excellent synergistic eect between the carbides and metals.24,25 temperature and then the gaseous ammonia ow was stopped.
Apparently, nitrogen-doped catalysts (metalnitrogencarbon) The Co2C/rGO catalytic material was collected as a black
are believed to be one of the most promising non-noble metal powdered material and then ground well.
electrocatalysts for the ORR, particularly in alkaline medium Similarly, Co4N/rGO was prepared from Co3O4/GO that
because of their high electron conductivity, durability, electron reacted with NH3 gas at 700  C in the tubular furnace.31 During
modulation and inhibition towards oxygen. Co-based ORR this preparation, the temperature of the furnace reached 300  C
catalysts have been widely studied. Liang et al., discussed the in 40 minutes and then the heating was maintained for the next
electrocatalytic behaviour of Co3O4 on nitrogen-doped reduced 30 minutes. Sequentially, the furnace temperature was
mildly oxidized graphene oxide (N-rmGO), which exhibited high increased from 300  C to 450  C in 200 minutes and then from
catalytic performance in both the ORR and oxygen evolution 450  C to 700  C in 180 minutes. At 700  C the heating was
reaction (OER) in alkaline solutions. The catalytic activity was maintained for 2 hours and then the temperature of the tubular
high due to the doped nitrogen and strong synergistic eect furnace was gradually cooled down to room temperature. The
between Co and rmGO.26,27 Likewise, cobalt sulphide embedded Co4N/rGO black colored powder was obtained and ne ground
on nitrogen-doped carbon exhibited excellent ORR catalytic using a mortar.32,33
activity as a Pt-free heterogeneous catalyst.28,29
In this work, the electrocatalytic activities of Co2C/rGO and
Co4N/rGO for oxygen reduction in alkaline electrolyte were Structure characterizations
studied. Both of the prepared electrocatalysts have hetero- X-ray diraction (XRD) patterns were obtained and the dirac-
atoms, which enrich the ORR sites and oxygen reduction tion data were collected between 10 and 80 (2q) using a Bruker
performance. To the best of our knowledge, Co2C/rGO and D8 advanced X-ray diractometer with Cu-Ka radiation (l
Co4N/rGO have never been adopted as the electrocatalyst for 1.5418 A). The morphology of the catalysts was examined using
the ORR in alkaline medium. The electrocatalytic activity and scanning electron microscopy (SEM), energy dispersive spectra
durability of the obtained catalysts were investigated in alka- (EDS) and elemental mapping techniques using a Hitachi (S-
line medium. Additionally, the number of electrons trans- 4800) scanning electron microscope. Transmission electron
ferred and hydrogen peroxide production during the oxygen microscopy (TEM) and selected area electron diraction (SAED)
reduction reaction were calculated. The purpose of this studies were conducted using a Tecnai (20 U-TWIN) trans-
research is to reveal a highly active ORR catalyst through the mission electron microscope. The elemental binding energies
comparative study of the electrocatalytic performance between of the obtained catalysts were detected using a Perkin Elmer
Co2C/rGO and Co4N/rGO. (PHI5300) X-ray photoelectron spectrometer with Mg Ka radia-
tion. The Raman spectra of Co2C/rGO and Co4N/rGO were

This journal is The Royal Society of Chemistry 2017 J. Mater. Chem. A, 2017, 5, 29722980 | 2973
Journal of Materials Chemistry A Paper

collected using a Renishaw inVia spectrometer with 532 nm


laser excitation.

Electrochemical measurements
The electrochemical tests of the prepared Co2C/rGO and Co4N/
rGO catalysts were conducted using a CHI 760D electrochemical
workstation. Cyclic voltammetry (CV), linear sweep voltammetry
(LSV) and electrochemical impedance spectroscopy (EIS), and
Tafel and chronoamperometric tests were conducted using
a three-electrode cell setup (glassy carbon disk-working,
platinum-counter and Ag/AgCl-reference) in 0.1 M KOH
(potassium hydroxide) electrolyte solution. The potential
window range between 0.2 V and 0.8 V was maintained during
the half-cell electrochemical tests. Ar (argon) and O2 (oxygen)
gases were bubbled for 1 hour each into 0.1 M KOH electrolyte
for the saturated electrolyte. At rst, CV curves were recorded in
Ar-saturated electrolyte at a sweeping rate of 20 mV s1. Aer
that, O2 was bubbled into the electrolyte solution and then CVs
were recorded again. Simultaneously, electrochemical tests like
LSV, EIS, Tafel and chronoamperometry were also conducted in
an O2-saturated 0.1 M KOH electrolyte. Likewise, a rotating ring
disk electrode (RRDE) 3A electrode was used for rotating disk
electrode (RDE) and RRDE tests in Ar and O2-saturated 0.1 M
KOH solution at various rotating speeds. In the RDE test, CV
curves were recorded rst in Ar-saturated 0.1 M KOH. Then in
O2-saturated 0.1 M KOH, the CV test was conducted rst and
then LSV data were recorded at a rotating speed range between Fig. 1 (a) XRD patterns of Co2C/rGO and Co4N/rGO and (b) Raman
100 rpm and 1600 rpm. In the RRDE test, electrochemical spectra of Co2C/rGO and Co4N/rGO.
testing was carried out at a rotating speed of 1600 rpm of the
RRDE ring disk electrode. Here, catalyst ink was prepared as
follows, 5 mg of the obtained catalyst (either Co2C/rGO or Co4N/ temperature and a long period of nitridation during the prep-
rGO at once) powder was mixed with 50 ml of Naon and 450 ml aration process.
of DI water (18.25 MU cm) and then the mixture was sonicated Fig. 1b shows the Raman spectra of Co2C/rGO and Co4N/
for 40 minutes. 5 ml of the as-prepared catalyst ink was pipetted rGO. For Co2C/rGO, D and G bands are obtained at 1333.57
on glassy carbon and RDE disk electrodes for electrochemical cm1 and 1595.77 cm1, respectively. The intensity ratio of ID/IG
tests. 10 ml of the catalyst ink was utilised for RRDE tests for Co2C/rGO is 1.29, which implies the intensity of D is above
because of the large disk electrode area. All the working elec- that of G due to the defects, partial disorder of the graphite
trodes were sequentially washed and sonicated well in aqueous lattice and low degree of graphitization that typically occurs in
ethanol and DI water before catalyst ink loading. GO and rGO.34 Likewise, D and G bands are observed at 1330.29
cm1 and 1583.75 cm1, respectively, for Co4N/rGO. The
intensity ratio of ID/IG for Co4N/rGO is 1.33. Additionally, small
Results and discussion peaks are observed at 1676.06 cm1 and 1824.11 cm1, which
The XRD patterns of Co2C/rGO and Co4N/rGO are shown in conrms the presence of C]N and C]C in the prepared Co4N/
Fig. 1a. For both Co2C/rGO and Co4N/rGO, the diraction peak rGO electrocatalyst.35 The small peak at 668.24 cm1 is raised
at around 26.7 is indexed to the (002) facets of carbon, which due to the signicant contribution of nitrogen36 during the
can be attributed to rGO. The sharp XRD peaks of Co2C/rGO nitridation process.
denote its crystalline property. The peaks at 36.97 (101), 41.2 Fig. S1a (ESI) shows an SEM image of Co2C/rGO. It is clearly
(020), 42.5 (111), 45.93 (210) and 56.71 (121) are indexed to seen that Co2C particles with various sizes are deposited on the
the Co2C nanoparticles, corresponding to the JCPDS 65-1457.30 rGO sheet.30 During the Co2C/rGO synthesis, a lot of cobalt ions
The sharp peak at 31.66 (220) is from cobalt oxide (Co3O4) due coupled with carbons in the GO sheet. The SEM image shows
to the short nitridation treatment on Co3O4/GO and a mild peak solid evidence that the rGO sheet is the platform for expansion
at 22.44 is from carbonoxygen in rGO. For Co4N/rGO, and support of the Co2C particles. Fig. S1be shows the
diraction peaks at 44.05 (111), 51.12 (200), and 75.37 (220) elemental mapping of cobalt (Co), carbon (C) and oxygen (O) in
were assigned to Co4N (JCPDS 01-1259), which indicates the Co2C/rGO and silicon (Si) from the substrate, in which carbon
good crystalline nature of the Co4N nanoparticles.33 The sharp has 21.63 wt%, cobalt has 1.60 wt% and oxygen has 4.35 wt%.
peaks in the Co4N/rGO diraction pattern are due to a rise in The signal of oxygen can be attributed to the physisorption of

2974 | J. Mater. Chem. A, 2017, 5, 29722980 This journal is The Royal Society of Chemistry 2017
Paper Journal of Materials Chemistry A

oxygen from the environment. Fig. S1f shows the EDS spec- oxidation doping by nitrides. Fig. 2e shows a HRTEM image
trum that matches with the elemental mapping data, in which of Co4N/rGO. The crystal lattice spacing in cobalt nitride is
carbon has a high-intensity peak at 0.3 keV and oxygen has 0.1515 nm, which corresponds to the (111) facet of Co4N.37 The
a peak at 0.55 keV. Cobalt has three peaks at dierent intensi- SAED pattern for Co4N/rGO is shown as an inset in Fig. 2e. The
ties at 0.8 keV (Co 2p3/2), 6.9 keV (Co 2p1/2) and 7.6 keV (Co 3s). perfect hexagonal patterns are the typical patterns of rGO. The
Likewise, Fig. S2a (ESI) shows the SEM image of Co4N/rGO, wide spread of Co4N nanoparticles in Co4N/rGO is clearly evi-
in which the rGO sheets are clearly shown and the corre- denced in Fig. 2f, in which 61% of the particles have a size range
sponding elemental mappings of Co, C, N and O for Co4N/rGO of 540 nm and 30% of the particles are between 4080 nm. The
are shown in Fig. S2be, respectively. The weight percentage Co4N nanoparticles have a smaller size compared with the Co2C
of Co, C, N and O are 36.35 wt%, 31.46 wt%, 14.48 wt% and nanoparticles, which have a better crystal structure and excel-
17.78 wt%, respectively. An SEM image of Co4N/rGO of larger lent atomic alignments.
magnication is shown in Fig. S2f, in which the morphology of Fig. S3a (ESI) shows an XPS spectrum of Co2C/rGO, which
the cobalt nitride is dierent from that of cobalt carbide. The contains peaks for Co 2p3, C 1s, O 1s, OKLL and CoLMM. This
Co4N particles are well blended and intercalated with the rGO spectrum indicates the presence of cobalt, carbon and oxygen in
sheet through the longer period of nitridation. Fig. S2g shows Co2C/rGO. High resolution XPS spectra of Co, C and O are
the corresponding EDS spectrum of Co4N/rGO. In addition to C, shown in Fig. S3bd, respectively. In Fig. S3b, the high
O, and Co signals, nitrogen has been registered at 0.45 keV, intense peak at 782.9 eV corresponds to Co 2p3/2 and the other
which conrms the present of nitrogen in Co4N/rGO. peaks at 798.8 eV and 779.6 eV belong to Co 2p1/2 and CoC.38
Fig. 2a shows a TEM image of Co2C/rGO. The captured TEM The peaks for Co 2p3/2 and Co 2p1/2 are due to the presence of
image clearly shows that rGO has a nanosheet morphology with Co.39 In addition, the CoC peak has been raised because of the
Co2C nanoparticles of dierent sizes incorporated on its cobalt carbide formation. Fig. S3c shows the binding energies
surface. Fig. 2b shows a HRTEM image of the Co2C/rGO sample. of C 1s (285.3 eV), CCo (283 eV) and C]O (286.8 eV).38 The C 1s
The crystal lattice spacing of 0.264 nm corresponds to the (111) carbon peak is due to rGO. The peak at 283 eV is caused by the
facet of Co2C. The inset in Fig. 2b is the SAED pattern of Co2C/ cobaltcarbon bond. At 286.8 eV, a mild peak is seen for strong
rGO, in which the orientations of Co2C and rGO are projected. binding between carbon and oxygen. The binding energies of
Fig. 2c shows the size distribution of the Co2C nanoparticles, in oxygen are shown in Fig. S3d. At 531.3 eV, a peak rise for O 1s
which particles with a size around 2575 nm dominate in the may be due to oxygen presence in rGO. Similarly, the O]C bond
catalysts. Fig. 2d shows a TEM image of the Co4N/rGO sample, energy is determined to be 533.3 eV through the strong coupling
and a lot of Co4N particles are distributed well on the rGO sheet. of oxygen with carbon.
In contrast, in Co4N/rGO the agglomeration of Co4N nano- Fig. S4a (ESI) shows the XPS spectrum of Co4N/rGO. The
particles is much less than that of Co2C/rGO due to the anti- binding energies have risen due to Co 3p, Co 2p3, C 1s, N 1s, O

Fig. 2 (a) TEM, (b) HRTEM with SAED pattern (inset) and (c) particle size distributions of Co2C/rGO. (d) TEM, (e) HRTEM with SAED pattern (inset)
and (f) particle size distributions of Co4N/rGO.

This journal is The Royal Society of Chemistry 2017 J. Mater. Chem. A, 2017, 5, 29722980 | 2975
Journal of Materials Chemistry A Paper

1s, OKLL and CoLMM. Fig. S4b shows the binding energies of mA cm2 with a peak current potential of 0.155 V. This is due
carbon in Co4N/rGO, in which the spectra are similar to that of to the well sorted intermetallic alignment of Co4N/rGO
Co2C/rGO. The peak at 283.4 eV (C 1s) indicates the carbon-rich (annealing treatment with higher temperature) against the
catalytic material. The small peak at 285.6 eV (C]O) is caused disordered catalyst structure of Co2C/rGO, and there are more
by the bond of carbon and oxygen. The binding energies of active sites in Co4N/rGO for the ORR. This is also due to the
oxygen species are shown in Fig. S4c. Two peaks at 533.3 eV doped N atoms to the graphitic lattice, which improves the
and 531.2 eV that correspond to O]C and O 1s, respectively, are oxygen adsorption on the surface of Co4N/rGO.41 These two
detected. These peaks illustrated the binding of oxygen with factors lead to the higher reaction current of Co4N/rGO than
carbon in the obtained rGO-based catalyst. In Fig. S4d, the two that of Co2C/rGO in the ORR. Compared with other metal
peaks at 795.3 eV and 782 eV are caused by Co 2p1/2 and Co 2p3/ carbides or nitrides, the peak current density of Co4N/rGO is
2, respectively. In addition, a sharp peak is found at 779 eV (Co also good, e.g., higher than that of N-doped SiC/C.42 Fig. 3b
N), which indicates that cobalt is coupled with nitrogen (metal shows LSV curves of Co2C/rGO (black), Co4N/rGO (red) and Pt/C
nitride). Fig. S4e represents the binding energy spectra of (blue), in which both the prepared catalysts attained a higher
nitrogen. One strong peak at 389.8 eV (N 1s) and one mild peak current density than that of the Pt/C catalyst.
at 393.9 eV (NCo) are obtained.38 Fig. 3c and d show the Nyquist and bode plots, respectively,
Cyclic voltammetry results of Co2C/rGO and Co4N/rGO are of Co2C/rGO and Co4N/rGO. The equivalent circuit for the cor-
shown in Fig. 3a. The black and red thick lines represent the responding Nyquist plots is shown as an inset in Fig. 3c. R1 is
CVs of Co2C/rGO and Co4N/rGO that were obtained in O2- the ohmic resistance that occurs in the alkaline electrolyte,
saturated 0.1 M KOH, whereas the green and blue thin lines which restricts electron transfer from the electrolyte. The values
indicate the CV curves of Co2C/rGO and Co4N/rGO that were of R1 for Co2C/rGO and Co4N/rGO are 101.2 U and 126.9 U,
obtained in Ar-saturated 0.1 M KOH. For Co2C/rGO, the onset respectively. Likewise, the reaction resistance R2 (charge trans-
potential for oxygen reduction is 0.045 V and the half-wave fer) denotes the resistance of oxygen reduction. R2 values of
potential is obtained at 0.095 V.40 The peak current potential 1700 U and 1316 U are obtained for Co2C/rGO and Co4N/rGO,
is determined to be 0.135 V with a maximum current density respectively. The charge transfer resistance of Co4N/rGO is
of 2.21 mA cm2 for the ORR. Compared with Co2C/rGO, the smaller than that of Co2C/rGO, i.e., the electron conduction is
ORR onset potential of Co4N/rGO is found to be 0.088 V and highly favorable for oxygen reduction. Constant phase element
the half-wave potential is obtained at 0.118 V.40 Although the (CPE)43 values of 0.10127 and 0.00067 are obtained for Co2C/
onset potential of Co4N/rGO is negatively shied compared to rGO and Co4N/rGO, respectively. The capacitive parameters
Co2C/rGO, the maximum current density is increased to 2.76 from CPE denote that Co4N/rGO has a thin catalytic layer, which

Fig. 3 (a) Cyclic voltammograms in Ar- and O2-saturated 0.1 M KOH solution at a sweeping rate of 20 mV s1. (b) Linear sweep voltammograms
in O2-saturated 0.1 M KOH solution at a sweeping rate of 10 mV s1. (c) Nyquist plots with corresponding equivalent circuit (inset), (d) Bode plots,
(e) Tafel plots and (f) chronoamperometric results of Co2C/rGO and Co4N/rGO.

2976 | J. Mater. Chem. A, 2017, 5, 29722980 This journal is The Royal Society of Chemistry 2017
Paper Journal of Materials Chemistry A

can make charge transfer more easily than Co2C/rGO. Fig. 3d


shows bode plots, in which the maximum frequency of Co4N/
rGO was beyond that of Co2C/rGO, which implied that the
electrocatalytic reaction rate of Co4N/rGO is higher during the
ORR.25,44 Hence, EIS studies ensure that Co4N/rGO is more
active than Co2C/rGO for the ORR.
Fig. 3e shows Tafel plots of Co2C/rGO and Co4N/rGO. The
slopes were tted to the Tafel curves at the potential region (i.e.,
from 0.06 V to 0.12 V), where oxygen reduction occurred. A
Tafel slope of 372.93 mV per decade is obtained on the Co2C/
rGO catalyst. In contrast, Co4N/rGO oered a smaller slope of
203.59 mV per decade, which indicates that Co4N/rGO has
a higher activity than Co2C/rGO. The ORR kinetics can be found
using Tafels eqn (1):
2:303RT 2:303RT
h a b log i  log i0 log i (1)
anF anF
where R is the universal gas constant, T is the absolute
temperature in kelvin, F is Faradays constant, a is the charge
transfer coecient, n is the electron transfer coecient and i0 is
the exchange current density. From eqn (1), the electron
transfer coecient and exchange current density were calcu-
lated. The electron transfer coecient for Co2C/rGO is 0.31 and
for Co4N/rGO is 0.58, which is similar to that of PtFe/C (0.55).45
Meanwhile, the exchange current density of Co4N/rGO is 9.81 
106 A cm2, which is lower than that of Co2C/rGO (4.410  Fig. 4 Rotating disk electrode (RDE) results and corresponding KL
105 A cm2), and also approaches Pt/C (2.8  107 A cm2).45 lines (inset) of (a) Co2C/rGO and (b) Co4N/rGO.
This arms the fact that the electrocatalytic activity of Co4N/
rGO is higher than that of Co2C/rGO.
Fig. 3f shows the current retention of the two catalysts for a maximum at 2.89 mA cm2 for Co2C/rGO. The following
5000 seconds during the ORR. Co2C/rGO and Co4N/rGO main- KoutechyLevich eqn (2) is employed to determine the kinetics
tained 99.95% and 99.91% of their current, respectively, of electrons during the oxygen reduction reaction:
throughout the reaction time. Small current spikes occurred at 1 1 1 1 1
; (2)
the beginning of the test for both catalysts, which was due to the J JL JK Bu1=2 JK
initial activation of the catalyst, and the current became stabi-
where J is the measured current density, JK is the kinetic current
lized aerward. In contrast, Pt/C lost 84.2% and Cr2O3/rGO,
density and JL is the diusion limiting current density. The
FexN/N-graphene, CoN/C and WC lost 15.4%, 5%, 4% and
angular frequency u can be found out using u 2pN/60, where
3.3% activity in current aer 5000 seconds test.13,23,4547 The
N is the rotation speed of the working electrode. From the
stability results indicate that both electrocatalysts are stable
KoutechyLevich equation, B, the slope of the KL line, can be
during ORR tests. The chronoamperometric test also proved
written as the following eqn (3):
that the catalysts are durable in alkaline electrolyte. The good
durability is achieved due to a strong coupling eect between Co
B 0.62nFC0(D0)2/3w1/6, (3)
and C and the anti-oxide sites formation on the surface of the
electrocatalysts. The Pt/C catalyst current decays during the where n is the electron transfer number, F (96 485 C mol1) is
ORR due to fast formation of oxides over Pt and the solubility in the Faraday constant, D0 (1.9  105 cm2 S1) is the diusion
the electrolyte. Therefore, the prepared electrocatalysts are coecient of O2 in the electrolyte, w (0.01 cm2 S1) is the
longer lasting than Pt/C for electrochemical catalytic activities. kinematic viscosity and C0 (1.2  107 mol cm3) is the bulk
The electrocatalytic activity and electron kinetics of the ORR concentration of O2 in the solution.
for the prepared materials were further investigated using The electron transfer was found to be 3.9 for Co2C/rGO.
a rotating disk electrode. Fig. 4a shows the voltammogram Likewise, the kinetics of the electrons for Co4N/rGO is evalu-
curves recorded for Co2C/rGO during the RDE test and the inset ated from the RDE voltammograms and their corresponding
shows the corresponding KoutechyLevich plots for electron KL plots (inset) as shown in Fig. 4b. The cathodic half-wave
kinetics. The voltammogram curves were recorded at dierent potential is found to be 0.13 V with a corresponding current
rotating speeds. The half-wave potential of Co2C/rGO is density of 1.82 mA cm2. The number of electrons
observed at 0.19 V with an electrode rotation of 1600 rpm. The transferred at this potential is found to be 3.3. Hence, both of
half-wave potential shis negatively when the rotation speed the catalysts prove that 4e reduction happens at the ORR
decreases gradually. The limited current density reaches peak region. Similarly, the electron transfer number and

This journal is The Royal Society of Chemistry 2017 J. Mater. Chem. A, 2017, 5, 29722980 | 2977
Journal of Materials Chemistry A Paper

hydrogen peroxide content in the electrolyte were evaluated percentage of hydrogen peroxide species produced in the elec-
using RRDE (rotating ring disk electrode) tests using the eqn trolyte is expected to be 24.1% (minimum yield of hydrogen
(4) and (5), peroxide). The percentage of H2O2 increases when the electrode
4  Id potential shis to a more negative direction and the 2e
n ; (4) reduction process is enhanced. The RRDE test of Co4N/rGO is
Id Ir =N
shown in Fig. 5c. The disk current Id attained is 0.43 mA and Ir
Ir =N is almost negligible. As shown in Fig. 5d, the electron transfer
H2 O2 % 200  ; (5) number and H2O2 percentage were 3.3 and 32.5%, respectively,
Id Ir =N
for Co4N/rGO. It could be deduced that the 4e and 2e reac-
where Id is the disk current, Ir is the ring current and N is the tions coexist in the process of oxygen reduction in the range
geometrical current collection coecient of Pt in the RRDE as from 0.2 V to 0.8 V.
0.39. Fig. 5a shows the current delivered by the disk (Co2C/rGO) Fig. 6 shows a schematic representation of Co2C and Co4N
and ring (Pt). Usually, the ring current is negligible due to the nanoparticles on the rGO sheet, which denotes the 2e and 4e
low diusivity of metals. Fig. 5b shows the plots for electron oxygen reduction processes. For Co2C/rGO, up to the potential
transfer and hydrogen peroxide percentage on the Co2C/rGO of 0.33 V (the ORR region for Co), the 4e process was main-
electrode at 1600 rpm during the RRDE testing. The ORR tained to produce OH by reducing the oxygen in alkaline
reaction in aqueous alkaline electrolyte is generally written as electrolyte. Aer that potential region (0.33 V), the 2e process
follows:23 starts to move towards a more negative potential region, where
Direct 4e reaction, indirect/slow oxygen reduction occurs to yield hydrogen
peroxide.48 However, the 4e oxygen reduction process occurs
O2 + 2H2O + 4e / 4OH, (6)
up to 0.17 V (the ORR potential for commercial Pt/C is 0.1
V)45 for Co4N/rGO, i.e., the fast reduction of O2 to OH. This 4e
Indirect 2e reaction,
oxygen reduction at a potential similar to Pt/C is achieved by
O2 + 2H2O + 2e / 2OH + H2O2, (7) Co4N/rGO with the support of carbon and nitrogen, which
oered additional ORR sites and better catalytic activity.49,50
H2O2 + 2e / 2OH. (8) Table S1 (ESI) illustrates the merits of Co4N/rGO for the
ORR onset potential (Eon), peak current density (J), electron
transfer coecient and current retention compared with other
At a half-wave potential of 0.19 V, the calculated electron metal oxides, metal carbides and heterogeneous catalysts. The
transfer is 3.5, which suggests that the direct 4e oxygen calculated electron transfer coecient for Co4N/rGO is 0.58,
reduction reaction occurs as mentioned in eqn (6) and also the which is similar to that of PtFe/C (0.55).45 ORR catalysts such as

Fig. 5 Rotating ring disk electrode (RRDE) results at 1600 rpm and electron transfer number (n) & H2O2% of (a) and (b) Co2C/rGO and (c) and (d)
Co4N/rGO.

2978 | J. Mater. Chem. A, 2017, 5, 29722980 This journal is The Royal Society of Chemistry 2017
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2980 | J. Mater. Chem. A, 2017, 5, 29722980 This journal is The Royal Society of Chemistry 2017