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Modified multi-walled carbon nanotube/Ag


nanoparticle composite catalyst for the oxygen
reduction reaction in alkaline solution

ARTICLE in ELECTROCHIMICA ACTA · NOVEMBER 2013


Impact Factor: 4.5 · DOI: 10.1016/j.electacta.2013.08.034

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Electrochimica Acta 111 (2013) 635–641

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Modified multi-walled carbon nanotube/Ag nanoparticle composite


catalyst for the oxygen reduction reaction in alkaline solution
Yuanhang Cheng, Wenyue Li, Xinzhuang Fan ∗ , Jianguo Liu, Weiguo Xu, Chuanwei Yan ∗
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

a r t i c l e i n f o a b s t r a c t

Article history: The modified multi-walled carbon nanotubes (m-MWCNTs)/Ag composite catalyst (Ag/m-MWCNTs)
Received 2 May 2013 is prepared successfully by a facile in situ growth method. The physicochemical properties of Ag/m-
Received in revised form 3 August 2013 MWCNTs are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray
Accepted 5 August 2013
photoelectron spectroscopy (XPS) and electrochemical measurements. The results demonstrate that the
Available online 19 August 2013
dispersed Ag nanoparticles are anchored on the surface of m-MWCNTs with a mean diameter about
10.6 nm. The as-prepared Ag/m-MWCNTs catalyst shows high electrocatalytic activity toward the oxy-
Keywords:
gen reduction reaction (ORR) in alkaline media. The ORR is dominated by four-electron pathway in the
Silver nanoparticles
Multi-walled carbon nanotubes
limiting diffusion zone, which is similar to the commercial Pt/C catalyst. The high catalytic activity of
Electrocatalyst the Ag/m-MWCNTs can ascribe to the dispersed Ag nanoparticles on the m-MWCNTs which not only
Oxygen reduction reaction facilitate the ORR process, but also may promote the decomposition or further reduction of HO2 − formed
Alkaline solution at the surfaces of the MWCNTs.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction improve the kinetics and the proportion of four-electron path-


way during the ORR, such as noble metals [5–13], metal oxides
The zinc–air batteries (ZABs) and alkaline fuel cells (AFCs) are [14–16] and carbon based nanomaterials [17–19]. Among these
considered as ideal power sources for future portable and vehicle catalytic materials studied before, the Ag or Ag/C is supposed to
devices due to their high theoretical specific energy, low cost and be a competitive material to replace the Pt due to its relative low
environmental friendliness [1–3]. However, further improvements cost and high activity toward the ORR in alkaline medium [20–26].
in their key materials as well as their performance are needed for However, the performances of Ag based catalysts are affected by
commercial applications. The sluggish kinetics of the oxygen reduc- the agglomeration of the Ag nanoparticles and the electrochemi-
tion reaction (ORR) at the air cathode is considered as one of the cal corrosion of the catalyst supports, which needs to be further
major problems for ZABs and AFCs which is urgently demanded studied.
to be resolved [2,4]. Previous studies have already demonstrated Recently, Tammeveski et al. deposited Ag nanoparticles
that oxygen at the cathode in alkaline media can be reduced by (15 nm) directly on a MWCNT-decorated glassy carbon electrode
two pathways: the two-electron and four-electron processes [5–9]. (AgNP/MWCNT/GC) by sputter-deposition. The AgNP/MWCNT/GC
The two-electron pathway is recognized as an inefficient process shows a high ORR electrocatalytic activity for the ORR in alkaline
because of the intermediate (HO2 − ) with lower electron density media and is active for the reduction of HO2 − [27]. However, in this
(only two electrons per oxygen molecule). The platinum (Pt) is paper, the modified multi-walled carbon nanotubes (m-MWCNTs)
the most common and efficient catalyst used in the ORR pro- with high electric conductivity and chemical stability in the alka-
cess with the four-electron pathway as the dominating reaction line electrolyte were employed as the host materials to support the
process. But the high cost and scarcity of Pt limit its large-scale Ag nanoparticles. Furthermore, in order to eliminate toxic reagents
application in the commercialized batteries. So preparation of an [26,28] and produce dispersed Ag nanoparticles, a facile in situ
alternative catalyst material with low cost and high electrochem- method using the sodium borohydride (NaBH4 ) aqueous solution
ical catalytic activity toward the ORR in the alkaline medium as the reductant was conducted to prepare the Ag/m-MWCNTs
is urgently needed. Various catalysts have been investigated to composite catalyst. The Ag nanoparticles are dispersed on the sur-
faces of the m-MWCNTs with high electrochemical catalytic activity
toward the ORR process. The simple but efficient method presents
∗ Corresponding authors. Tel.: +86 24 2399 8320; fax: +86 24 2388 0201. a very promising way to produce Ag or other metal nanoparti-
E-mail addresses: yuanhang1988@yeah.net (Y. Cheng), xzfan@imr.ac.cn (X. Fan), cles/carbon composite catalysts toward the ORR in the alkaline
cwyan@imr.ac.cn (C. Yan). medium.

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.08.034
636 Y. Cheng et al. / Electrochimica Acta 111 (2013) 635–641

Fig. 1. TEM images of (a) p-MWCNTs, (b) m-MWCNTs, (c and d) Ag/m-MWCNTs (inset: HRTEM image of Ag/m-MWCNTs), (e) particle diameter distribution of Ag/m-MWCNTs,
and (f) EDS element analysis of the Ag/m-MWCNT.
Y. Cheng et al. / Electrochimica Acta 111 (2013) 635–641 637

2. Experimental

2.1. Materials

The pristine multi-walled carbon nanotubes (p-MWCNTs)


were purchased from Shenzhen Nanotech Port Co. Ltd. Silver
nitrate (AgNO3 ), sodium citrate and NaBH4 were purchased from
Sinopharm Chemical Reagent Co., Ltd. and all the chemical reagents
were analytical grade. The commercial 20% Pt catalyst supported on
Vulcan XC-72 (20% Pt/C) was purchased from Alfa Aesar (Johnson
Matthey Company, Tianjin, China).

2.2. Modification of MWCNTs

The p-MWCNTs were oxidized at room temperature by reflux-


ing in a mixed solution of H2 SO4 and HNO3 (3:1, v/v) for 6 h
in order to eliminate the impurities and increase the content of
hydrophilic oxygen functional groups on their surface. Afterwards,
the m-MWCNTs were filtered and washed with deionized water
extensively to pH = 7 and then dried at 80 ◦ C overnight before use. Fig. 2. XRD patterns of the p-MWCNTs, m-MWCNTs and Ag/m-MWCNTs.

2.3. Deposition of Ag nanoparticles vs. NHE) reference electrode and a modified GCE working elec-
trode, was utilized to perform the electrochemical measurement
Ag nanoparticles were loaded on m-MWCNTs by an in situ on a CHI 730C electrochemical Analyzer (Chenhua, China). Cyclic
growth method using NaBH4 as reductant [29]. The procedure is voltammetry (CV) tests were measured in the nitrogen saturated
briefly introduced as following: 60 mg m-MWCNTs were added and oxygen saturated 0.1 M KOH aqueous solutions at a sweep rate
into 60 mL deionized water and ultrasonically dispersed homoge- of 100 mV s−1 from 0.2 V to −1 V, respectively. The rotating disk
neously, followed by adding 2.4 mL of 100 mM AgNO3 and 2.4 mL of electrode (RDE) voltammetry was also carried out in the 0.1 M KOH
100 mM sodium citrate solution. The resulting solution was quickly aqueous solution saturated with oxygen at a scan rate of 10 mV s−1
mixed by magnetic stirring vigorously in an ice/water bath. The from 0.2 V to −1 V at various rotating speeds from 400 rpm to
reduction reaction was carried out by introducing 4.6 mL of 300 mM 2000 rpm by a Pine bipotentiostat RDE setup (Pine Instrument Com-
NaBH4 aqueous solution slowly to the above solution. After that, the pany, USA) combined with the CHI 730C electrochemical Analyzer.
solution was kept in the ice/water bath for 5 h and aged at room
temperature for 19 h. Finally, the products were filtered, washed 3. Results and discussion
with deionized water and ethanol, and dried in a vacuum oven at
80 ◦ C overnight before collection. The loading of Ag on m-MWCNTs Fig. 1 shows the surface morphologies of p-MWCNTs, m-
is about 30 wt.%. MWCNTs and as prepared Ag/m-MWCNTs. For the p-MWCNTs
(Fig. 1a), plenty of nanotubes tangle together with some impurities
2.4. Physical characterization (such as catalysts and amorphous carbon) clinging on them. The
amount of impurities and tangling nanotubes decrease markedly
X-ray diffraction (XRD) studies were performed using Cu K␣ due to the oxidation process by the strong mixed acids, as shown
( = 0.154 nm) radiation on an X’Pert PRO instrument operating in Fig. 1b. The modification process also produces more active sites
at 40 kV and a current of 40 mA at room temperature. Trans- for the deposition of Ag nanoparticles because of the increasing spe-
mission electron microscopy (TEM), high resolution transmission cific surface areas (the BET specific surface areas for m-MWCNTs is
electron microscopy (HRTEM) and energy dispersive X-ray spec- about 234 m2 g−1 , which is higher than the value of 149.8 m2 g−1
troscopy (EDS) were observed on a JEOL JEM-2100F operated at an for p-MWCNTs) and surface oxygen functional groups. The typical
accelerating voltage of 200 kV. X-ray photoelectron spectroscopy TEM images of Ag/m-MWCNTs (Fig. 1c and d) illustrate that most
(XPS) was employed using a monochromatic Al K␣ radiation at of the m-MWCNTs surfaces are coupled with the sphere-shaped
1486.6 eV employing ESCALAB250 surface analysis system. The Ag nanoparticles. The Ag nanoparticles distribute on the surfaces
specific surface area (BET) was determined by nitrogen adsorp- of m-MWCNTs with the diameters ranging from 5 to 15 nm (Fig. 1e),
tion measurement at 77 K with the instrument of Micromeritics besides some large nanoparticles (pointed by red arrows in Fig. 1c
ASAP2020. and d). The mean diameter (dmean ) of Ag nanoparticles which is
about 10.6 nm is calculated by Eq. (1) [5,30]. The EDS of Ag/m-
MWCNTs reveals the presence of element C and Ag, the two peaks
2.5. Electrochemical measurements
located at 800–900 keV are attributed to the Cu substrate material
used for TEM observation (Fig. 1f).
The surface of the glassy carbon electrode (GCE, diameter:
 3
5 mm) was polished to a mirror finish using 0.3 ␮m alumina fd
slurries. After alumina polishing, the electrode was ultrasonically dmean =  i i2 (1)
fi di
cleaned in deionized water for 5 min. Catalyst ink was prepared by
ultrasonically dispersing 4 mg Ag/m-MWCNTs in 4 mL 0.05% Nafion where fi is the fraction of nanoparticles with diameter di .
ethanol solution. Then 10 ␮L of the catalyst ink was dropped on the The XRD patterns of p-MWCNTs, m-MWCNTs and the as-
surface of the polished GCE using a microinjector and dried at 80 ◦ C prepared Ag/m-MWCNTs are shown in Fig. 2. The peaks at 2 = 26◦ ,
for 12 h before the electrochemical measurement. 43.1◦ , 53.8◦ and 78.2◦ in the patterns of p-MWCNTs and m-
A standard three-electrode system, which is composed of a Pt MWCNTs can be attributed to the characteristic diffraction peaks of
sheet counter electrode, a saturated calomel electrode (SCE, 0.245 V (0 0 2), (1 0 0), (0 0 4) and (1 1 0) lattice plane of graphite structure
638 Y. Cheng et al. / Electrochimica Acta 111 (2013) 635–641

(JCPDS card No. 41-1487), respectively. In the pattern of Ag/m- different modified GCEs, linear sweep voltammetry (LSV) mea-
MWCNTs, besides the (0 0 2) graphite lattice plane diffraction peak, surements were performed on a RDE in O2 -saturated 0.1 M KOH
the newly presented five peaks located at 2 = 38.1◦ , 44.3◦ , 64.4◦ , aqueous solution at a scan rate of 10 mV s−1 with various rotat-
71.5◦ , and 81.5◦ correspond to the (1 1 1), (2 0 0), (2 2 0), (3 1 1), ing speeds from 400 rpm to 2000 rpm. For the Ag/m-MWCNTs, the
and (2 2 2) planes of Ag crystals, respectively, demonstrating that limiting diffusion current density increases with increasing rotat-
these Ag nanoparticles have a typical face centered cubic (fcc) struc- ing rate (Fig. 5a), and the onset potential for ORR is at about −0.05 V
ture (JCPDS card No. 04-0783). No characteristic diffraction peak of (inset in Fig. 5a). The n values per oxygen molecule during the
Ag2 O, AgO or other silver oxides appears in the pattern. On the basis ORR process at different modified GCEs were calculated by the
of the results of XRD characterization, it also indicates that Ag/m- Koutecky–Levich (K-L) equation as follows [38,39].
MWCNTs catalyst was successfully prepared by this in situ growth −1
method. The mean size of Ag particles is about 15.2 nm calculated j−1 = jK−1 + jL−1 = jK−1 + (Bω1/2 ) (2)
from the (1 1 1) plane diffraction peak of Ag crystal by the Scherrer
equation [31], identifying with the TEM results. B = 0.62nFCO (DO )2/3 −1/6 (3)
The XPS spectra of the p-MWCNTs, m-MWCNTs and Ag/m-
MWCNTs are shown in Fig. 3. The oxygen content on the surface of where j is the measured current density, jK is kinetic current density
the m-MWCNTs is about 14.04%, which is much higher than that of and jL is limiting diffusion current density, ω is the rotation rate of
the p-MWCNTs (2.32%), indicating that oxygen-containing species the electrode, n is the overall number of electrons transferred dur-
are successfully introduced on the surface of m-MWCNTs after the ing the ORR process, F is the Faraday constant (F = 96,485 C mol−1 ),
purification process. The high-resolution C1s spectrum of the p- CO is the bulk concentration of O2 (CO = 1.2 × 10−6 mol cm−3 ),
MWCNTs (Fig. 3b) and m-MWCNTs (Fig. 3c) are deconvoluted to DO is the diffusion coefficient of O2 in the 0.1 M KOH solution
determine the type and content of the surface oxygen functional (DO = 1.9 × 10−5 cm2 s−1 ),  is the kinetic viscosity of the electrolyte
groups [32]. As presented in Fig. 3b, the main peaks at 284.6 eV ( = 0.01 cm2 s−1 ) [39–41].
and 285.9 eV correspond to the carbon in graphite ( C C ) and For the Ag/m-MWCNT, the K-L plots (j−1 vs. w−1/2 ) exhibited a
hydroxyl functional groups ( C OH), respectively. An additional good linearity with an almost constant slope at potentials ranging
peak at 289.1 eV assigned to the carbon in carboxyl functional from −0.4 V to −0.9 V (Fig. 5b). According to Eqs. (2) and (3), the n
groups ( COOH) can be resolved after the oxidation process. The values at different potentials were displayed as an inset in Fig. 5b.
increased surface oxygen functional groups especially the COOH These n values are all close to 4.0 in the range of potentials from
make the m-MWCNTs more hydrophilic and provide more favorite −0.4 V to −0.9 V and the average n value for ORR is calculated to
nucleation sites for the growth of Ag nanoparticles (the Ag ions be 3.80, revealing the four-electron pathway is the main reaction
can easily attach to the surface of the CNTs because of the elec- process with the H2 O as the product, which is comparable with
trostatic interaction with the oxygen functional groups) than the Pt based catalyst [5,8,13,30]. The average electron transfer number
p-MWCNTs. In the core-level spectrum of Ag (Fig. 3d), peaks at for ORR on p-MWCNTs and m-MWCNTs modified GCEs were also
368 eV and 374 eV correspond to the Ag 3d5/2 and Ag 3d3/2 , respec- calculated which is about 1.89 and 1.99, respectively, indicating a
tively. The spin-orbit splitting of the 3d doublet is 6 eV, which is two-electron pathway toward the ORR, which is in good agreement
characteristic to silver in metallic form (Ag0 ) [33]. No peaks of Ag with previous studies [42,43].
3d in Ag2 O, AgO or other silver oxides is observed, suggesting the Ag For the purpose of further comparing the ORR electrocatalytic
nanoparticles are stable in the atmosphere, which is in accordance activity of Ag/m-MWCNTs, p-MWCNTs, m-MWCNTs and commer-
with the XRD results. cial 20% Pt/C, the different modified RDEs were investigated in 0.1 M
CV tests were employed to investigate the electrocatalytic activ- KOH aqueous solution saturated with oxygen at a rotating rate of
ity of Ag/m-MWCNTs toward the ORR in 0.1 M KOH aqueous 1200 rpm (Fig. 5c). It is obvious that the Ag/m-MWCNTs catalyst
solution. Fig. 4a shows the CV curves of ORR on the Ag/m-MWCNTs displays a more positive onset potential (−0.05 V) and a higher
modified GCE in 0.1 M KOH aqueous solution saturated with nitro- limiting diffusion current density toward the ORR than those of
gen and oxygen, respectively. The peaks at 0.123 V in the two CV the p-MWCNTs and m-MWCNTs catalysts. The superior catalytic
curves result from the reduction of silver oxides formed at the activity of Ag/m-MWCNTs could be contributed to the combination
beginning of the CV test when the potential is positive [34,35]. of the electrochemical activity of the dispersed Ag nanoparticles
A new peak for Ag/m-MWCNTs in the O2 saturated electrolyte is attached on the surface of m-MWCNTs and unique properties of m-
observed at −0.341 V with a current density of −1.77 mA cm−2 com- MWCNTs. Furthermore, it has been reported that Ag can promote
pared with the curve in the N2 saturated solution, suggesting this the decomposition or further reduction of HO2 − formed at the sur-
reduction peak contributed by the ORR. CV curves for the ORR at dif- faces of the m-MWCNTs [2,27], which facilitate the ORR process in
ferent modified GCEs in 0.1 M KOH solution saturated with O2 are alkaline media. As is shown, the LSV curves of Ag/m-MWCNTs and
shown in Fig. 4b. The small reduction peak is observed on the bare commercial 20% Pt/C both show a single-step wide platform. The
GCE till the potential reaches at −0.545 V, indicating its low cat- Pt/C catalysts show higher limiting diffusion current and more pos-
alytic activity toward the ORR, which identifies with other previous itive ORR onset potential than Ag/m-MWCNTs. The mass activity
results [36,37]. The ORR peak of the p-MWCNTs and m-MWCNTs (MA) [44,45] of the ORR was calculated for further comparison. The
modified GCEs appear at −0.450 and −0.376 V, respectively, more MA of 20% Pt/C (the average particle size of Pt is about 2.8 nm) and
negative than that of the Ag/m-MWCNTs modified GCE, suggesting Ag/m-MWCNTs (the average particle size of Ag is about 10.6 nm)
less overpotential (reaction activation energy) is needed to trigger at −0.3 V (1200 rpm) is 394.9 mA mg−1 Pt and 111.3 mA mg−1 Ag,
the ORR on the composite catalyst. Moreover, the ORR peak current respectively. Although the electrocatalytic activity toward the ORR
density of Ag/m-MWCNTs modified GCE (−1.77 mA cm−2 ) is much of 20% Pt/C is higher than that of Ag/m-MWCNTs composite, the
higher than that of the p-MWCNTs modified GCE (0.64 mA cm−2 ) Ag/m-MWCNTs would have a great potential to be an alternative
and m-MWCNTs modified GCE (−1.03 mA cm−2 ). The results of CV electrocatalyst toward the ORR in the alkaline aqueous solution
tests suggest that the Ag/m-MWCNTs composite has high elec- considering its much lower cost.
trocatalytic activity toward the ORR due to the Ag nanoparticles Damjanovic et al. reported that the Tafel slope values of ORR on
modification process. Pt catalysts in alkaline solution can be used to evaluate the ORR
To gain a further insight into the ORR process and evalu- kinetics and the oxygen adsorption mechanism [46]. The adsorp-
ate the transferred electron number (n) per oxygen molecule at tion condition of molecular oxygen on the Pt catalysts surface
Y. Cheng et al. / Electrochimica Acta 111 (2013) 635–641 639

Fig. 3. (a) XPS survey spectra of the p-MWCNTs, m-MWCNTs and Ag/m-MWCNTs, high-resolution of C1s spectrum for p-MWCNTs (b) and m-MWCNTs (c), and Ag 3d for the
Ag/m-MWCNTs (d).

changing from Temkin adsorption isotherm at low overpotential −0.076 V and −0.128 V, respectively. The existence of two Tafel
to Langmuir adsorption isotherm at high overpotential is taken slopes, similar to that of Pt catalysts, indicates that the adsorp-
to account for the changing of Tafel slope values of Pt catalysts tion condition of molecular oxygen on the Ag/m-MWCNTs catalysts
(from −0.06 V at low overpotential to −0.12 V at high overpo- is similar to that on the Pt catalysts. The ORR kinetics on Ag/m-
tential) [46–48]. As is shown in Fig. 5d, the Tafel slope values of MWCNTs in alkaline solution can be described by two steps similar
Ag/m-MWCNTs catalysts at the low and high overpotential are to Pt catalysts: the first step is the adsorption of O2 , and the

Fig. 4. (a) CV curves for ORR on Ag/m-MWCNTs modified GCE in 0.1 M KOH aqueous solution saturated with nitrogen and oxygen. (b) CVs for ORR on GCE, p-MWCNTs,
m-MWCNTs and Ag/m-MWCNTs modified GCEs in 0.1 M KOH aqueous solution saturated with oxygen at a scan rate of 100 mV s−1 .
640 Y. Cheng et al. / Electrochimica Acta 111 (2013) 635–641

Fig. 5. (a) RDE voltammograms of ORR on Ag/m-MWCNTs modified GCE in 0.1 M KOH aqueous solution saturated with oxygen at various rotation rates from 400 rpm to
2000 rpm. Scan rate: 10 mV s−1 . (b) Koutecky–Levich plots of Ag/m-MWCNTs modified GCE at different potentials from −0.4 V to −0.9 V. Inset: electron transfer number (n)
at different potentials from −0.4 V to −0.9 V. (c) RDE voltammograms of ORR on bare GCE, m-MWCNTs, Ag/m-MWCNTs and commercial 20% Pt/C modified GCEs in 0.1 M
KOH aqueous solution saturated with oxygen at a rotation rate of 1200 rpm. Scan rate: 10 mV s−1 . (d) Tafel plot for the ORR on Ag/m-MWCNTs modified GCE in 0.1 M KOH
(ω = 1200 rpm).

second step is the first charge-transfer reaction which is considered a promising ORR catalysts for AFCs and ZABs considering that Ag is
as the rate determining step [49,50]. In the other hand, accord- much cheaper than Pt.
ing to the Butler–Volmer equation (b = RT/˛nF) [5], a high Tafel
slope value means the less transfer coefficient ˛ and/or number Acknowledgements
of exchanged electrons n during the reaction at the same tem-
perature. So a lower Tafel slope value is desirable during the ORR This work is supported by National Basic Research 973 Program
procedure and a higher Tafel slope value indicates an inferior ORR of China (Grant No. 2006AA05Z255). Thanks to Miss Xiao Ling for
kinetics. By comparing the Tafel slope values of Ag/m-MWCNTs the amendment of this paper.
and Pt at low and high overpotential respectively, it is clear that
the ORR kinetics of Ag/m-MWCNTs is more sluggish than that of
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