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