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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

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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-

The zinc–air batteries (ZABs) and alkaline fuel cells (AFCs) are
considered as ideal power sources for future portable and vehicle
devices due to their high theoretical specific energy, low cost and
environmental friendliness [1–3]. However, further improvements
in their key materials as well as their performance are needed for
commercial applications. The sluggish kinetics of the oxygen reduc-
tion reaction (ORR) at the air cathode is considered as one of the
major problems for ZABs and AFCs which is urgently demanded
to be resolved [2,4]. Previous studies have already demonstrated
that oxygen at the cathode in alkaline media can be reduced by
two pathways: the two-electron and four-electron processes [5–9].
The two-electron pathway is recognized as an inefficient process
because of the intermediate (HO2 − ) with lower electron density
(only two electrons per oxygen molecule). The platinum (Pt) is
the most common and efficient catalyst used in the ORR pro-
cess with the four-electron pathway as the dominating reaction
process. But the high cost and scarcity of Pt limit its large-scale
application in the commercialized batteries. So preparation of an
alternative catalyst material with low cost and high electrochem-
ical catalytic activity toward the ORR in the alkaline medium
is urgently needed. Various catalysts have been investigated to
∗ Corresponding authors. Tel.: +86 24 2399 8320; fax: +86 24 2388 0201.
E-mail addresses: yuanhang1988@yeah.net (Y. Cheng), xzfan@imr.ac.cn (X. Fan),
cwyan@imr.ac.cn (C. Yan).
way during the ORR, such as noble metals [5–13], metal oxides
[14–16] and carbon based nanomaterials [17–19]. Among these
catalytic materials studied before, the Ag or Ag/C is supposed to
be a competitive material to replace the Pt due to its relative low
cost and high activity toward the ORR in alkaline medium [20–26].
However, the performances of Ag based catalysts are affected by
the agglomeration of the Ag nanoparticles and the electrochemi-
cal corrosion of the catalyst supports, which needs to be further
studied.
Recently, Tammeveski et al. deposited Ag nanoparticles
(15 nm) directly on a MWCNT-decorated glassy carbon electrode
(AgNP/MWCNT/GC) by sputter-deposition. The AgNP/MWCNT/GC
shows a high ORR electrocatalytic activity for the ORR in alkaline
media and is active for the reduction of HO2 − [27]. However, in this
paper, the modified multi-walled carbon nanotubes (m-MWCNTs)
with high electric conductivity and chemical stability in the alka-
line electrolyte were employed as the host materials to support the
Ag nanoparticles. Furthermore, in order to eliminate toxic reagents
[26,28] and produce dispersed Ag nanoparticles, a facile in situ
method using the sodium borohydride (NaBH4 ) aqueous solution
as the reductant was conducted to prepare the Ag/m-MWCNTs
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
a very promising way to produce Ag or other metal nanoparti-
cles/carbon composite catalysts toward the ORR in the alkaline
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
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.
2.3. Deposition of Ag nanoparticles
Ag nanoparticles were loaded on m-MWCNTs by an in situ
growth method using NaBH4 as reductant [29]. The procedure is
briefly introduced as following: 60 mg m-MWCNTs were added
into 60 mL deionized water and ultrasonically dispersed homoge-
neously, followed by adding 2.4 mL of 100 mM AgNO3 and 2.4 mL of
100 mM sodium citrate solution. The resulting solution was quickly
mixed by magnetic stirring vigorously in an ice/water bath. The
reduction reaction was carried out by introducing 4.6 mL of 300 mM
NaBH4 aqueous solution slowly to the above solution. After that, the
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
with deionized water and ethanol, and dried in a vacuum oven at
80 ◦ C overnight before collection. The loading of Ag on m-MWCNTs
is about 30 wt.%.
2.4. Physical characterization
X-ray diffraction (XRD) studies were performed using Cu K␣
( = 0.154 nm) radiation on an X’Pert PRO instrument operating
at 40 kV and a current of 40 mA at room temperature. Trans-
mission electron microscopy (TEM), high resolution transmission
electron microscopy (HRTEM) and energy dispersive X-ray spec-
troscopy (EDS) were observed on a JEOL JEM-2100F operated at an
accelerating voltage of 200 kV. X-ray photoelectron spectroscopy
(XPS) was employed using a monochromatic Al K␣ radiation at
1486.6 eV employing ESCALAB250 surface analysis system. The
specific surface area (BET) was determined by nitrogen adsorp-
tion measurement at 77 K with the instrument of Micromeritics
ASAP2020.
2.5. Electrochemical measurements
The surface of the glassy carbon electrode (GCE, diameter:
5 mm) was polished to a mirror finish using 0.3 ␮m alumina
slurries. After alumina polishing, the electrode was ultrasonically
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
ethanol solution. Then 10 ␮L of the catalyst ink was dropped on the
surface of the polished GCE using a microinjector and dried at 80 ◦ C
for 12 h before the electrochemical measurement.
A standard three-electrode system, which is composed of a Pt
sheet counter electrode, a saturated calomel electrode (SCE, 0.245 V
637
Fig. 2. XRD patterns of the p-MWCNTs, m-MWCNTs and Ag/m-MWCNTs.
vs. NHE) reference electrode and a modified GCE working elec-
trode, was utilized to perform the electrochemical measurement
on a CHI 730C electrochemical Analyzer (Chenhua, China). Cyclic
voltammetry (CV) tests were measured in the nitrogen saturated
and oxygen saturated 0.1 M KOH aqueous solutions at a sweep rate
of 100 mV s−1 from 0.2 V to −1 V, respectively. The rotating disk
electrode (RDE) voltammetry was also carried out in the 0.1 M KOH
aqueous solution saturated with oxygen at a scan rate of 10 mV s−1
from 0.2 V to −1 V at various rotating speeds from 400 rpm to
2000 rpm by a Pine bipotentiostat RDE setup (Pine Instrument Com-
pany, USA) combined with the CHI 730C electrochemical Analyzer.
3. Results and discussion
Fig. 1 shows the surface morphologies of p-MWCNTs, m-
MWCNTs and as prepared Ag/m-MWCNTs. For the p-MWCNTs
(Fig. 1a), plenty of nanotubes tangle together with some impurities
(such as catalysts and amorphous carbon) clinging on them. The
amount of impurities and tangling nanotubes decrease markedly
due to the oxidation process by the strong mixed acids, as shown
in Fig. 1b. The modification process also produces more active sites
for the deposition of Ag nanoparticles because of the increasing spe-
cific surface areas (the BET specific surface areas for m-MWCNTs is
about 234 m2 g−1 , which is higher than the value of 149.8 m2 g−1
for p-MWCNTs) and surface oxygen functional groups. The typical
TEM images of Ag/m-MWCNTs (Fig. 1c and d) illustrate that most
of the m-MWCNTs surfaces are coupled with the sphere-shaped
Ag nanoparticles. The Ag nanoparticles distribute on the surfaces
of m-MWCNTs with the diameters ranging from 5 to 15 nm (Fig. 1e),
besides some large nanoparticles (pointed by red arrows in Fig. 1c
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
located at 800–900 keV are attributed to the Cu substrate material
used for TEM observation (Fig. 1f).
 3
fd
dmean =  i i2 (1)
fi di
where fi is the fraction of nanoparticles with diameter di .
The XRD patterns of p-MWCNTs, m-MWCNTs and the as-
prepared Ag/m-MWCNTs are shown in Fig. 2. The peaks at 2 = 26◦ ,
43.1◦ , 53.8◦ and 78.2◦ in the patterns of p-MWCNTs and m-
MWCNTs can be attributed to the characteristic diffraction peaks of
(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-
MWCNTs, besides the (0 0 2) graphite lattice plane diffraction peak,
the newly presented five peaks located at 2 = 38.1◦ , 44.3◦ , 64.4◦ ,
71.5◦ , and 81.5◦ correspond to the (1 1 1), (2 0 0), (2 2 0), (3 1 1),
and (2 2 2) planes of Ag crystals, respectively, demonstrating that
these Ag nanoparticles have a typical face centered cubic (fcc) struc-
ture (JCPDS card No. 04-0783). No characteristic diffraction peak of
Ag2 O, AgO or other silver oxides appears in the pattern. On the basis
of the results of XRD characterization, it also indicates that Ag/m-
MWCNTs catalyst was successfully prepared by this in situ growth
method. The mean size of Ag particles is about 15.2 nm calculated
from the (1 1 1) plane diffraction peak of Ag crystal by the Scherrer
equation [31], identifying with the TEM results.
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
the m-MWCNTs is about 14.04%, which is much higher than that of
the p-MWCNTs (2.32%), indicating that oxygen-containing species
are successfully introduced on the surface of m-MWCNTs after the
purification process. The high-resolution C1s spectrum of the p-
MWCNTs (Fig. 3b) and m-MWCNTs (Fig. 3c) are deconvoluted to
determine the type and content of the surface oxygen functional
groups [32]. As presented in Fig. 3b, the main peaks at 284.6 eV
and 285.9 eV correspond to the carbon in graphite ( C C ) and
hydroxyl functional groups ( C OH), respectively. An additional
peak at 289.1 eV assigned to the carbon in carboxyl functional
groups ( COOH) can be resolved after the oxidation process. The
increased surface oxygen functional groups especially the COOH
make the m-MWCNTs more hydrophilic and provide more favorite
nucleation sites for the growth of Ag nanoparticles (the Ag ions
can easily attach to the surface of the CNTs because of the elec-
trostatic interaction with the oxygen functional groups) than the
p-MWCNTs. In the core-level spectrum of Ag (Fig. 3d), peaks at
368 eV and 374 eV correspond to the Ag 3d5/2 and Ag 3d3/2 , respec-
tively. The spin-orbit splitting of the 3d doublet is 6 eV, which is
characteristic to silver in metallic form (Ag0 ) [33]. No peaks of Ag
3d in Ag2 O, AgO or other silver oxides is observed, suggesting the Ag
nanoparticles are stable in the atmosphere, which is in accordance
with the XRD results.
CV tests were employed to investigate the electrocatalytic activ-
ity of Ag/m-MWCNTs toward the ORR in 0.1 M KOH aqueous
solution. Fig. 4a shows the CV curves of ORR on the Ag/m-MWCNTs
modified GCE in 0.1 M KOH aqueous solution saturated with nitro-
gen and oxygen, respectively. The peaks at 0.123 V in the two CV
curves result from the reduction of silver oxides formed at the
beginning of the CV test when the potential is positive [34,35].
A new peak for Ag/m-MWCNTs in the O2 saturated electrolyte is
observed at −0.341 V with a current density of −1.77 mA cm−2 com-
pared with the curve in the N2 saturated solution, suggesting this
reduction peak contributed by the ORR. CV curves for the ORR at dif-
ferent modified GCEs in 0.1 M KOH solution saturated with O2 are
shown in Fig. 4b. The small reduction peak is observed on the bare
GCE till the potential reaches at −0.545 V, indicating its low cat-
alytic activity toward the ORR, which identifies with other previous
results [36,37]. The ORR peak of the p-MWCNTs and m-MWCNTs
modified GCEs appear at −0.450 and −0.376 V, respectively, more
negative than that of the Ag/m-MWCNTs modified GCE, suggesting
less overpotential (reaction activation energy) is needed to trigger
the ORR on the composite catalyst. Moreover, the ORR peak current
density of Ag/m-MWCNTs modified GCE (−1.77 mA cm−2 ) is much
higher than that of the p-MWCNTs modified GCE (0.64 mA cm−2 )
and m-MWCNTs modified GCE (−1.03 mA cm−2 ). The results of CV
tests suggest that the Ag/m-MWCNTs composite has high elec-
trocatalytic activity toward the ORR due to the Ag nanoparticles
modification process.
To gain a further insight into the ORR process and evalu-
ate the transferred electron number (n) per oxygen molecule at
different modified GCEs, linear sweep voltammetry (LSV) mea-
surements were performed on a RDE in O2 -saturated 0.1 M KOH
aqueous solution at a scan rate of 10 mV s−1 with various rotat-
ing speeds from 400 rpm to 2000 rpm. For the Ag/m-MWCNTs, the
limiting diffusion current density increases with increasing rotat-
ing rate (Fig. 5a), and the onset potential for ORR is at about −0.05 V
(inset in Fig. 5a). The n values per oxygen molecule during the
ORR process at different modified GCEs were calculated by the
Koutecky–Levich (K-L) equation as follows [38,39].
−1
j−1 = jK−1 + jL−1 = jK−1 + (Bω1/2 ) (2)
B = 0.62nFCO (DO )2/3 −1/6 (3)
where j is the measured current density, jK is kinetic current density
and jL is limiting diffusion current density, ω is the rotation rate of
the electrode, n is the overall number of electrons transferred dur-
ing the ORR process, F is the Faraday constant (F = 96,485 C mol−1 ),
CO is the bulk concentration of O2 (CO = 1.2 × 10−6 mol cm−3 ),
DO is the diffusion coefficient of O2 in the 0.1 M KOH solution
(DO = 1.9 × 10−5 cm2 s−1 ),  is the kinetic viscosity of the electrolyte
( = 0.01 cm2 s−1 ) [39–41].
For the Ag/m-MWCNT, the K-L plots (j−1 vs. w−1/2 ) exhibited a
good linearity with an almost constant slope at potentials ranging
from −0.4 V to −0.9 V (Fig. 5b). According to Eqs. (2) and (3), the n
values at different potentials were displayed as an inset in Fig. 5b.
These n values are all close to 4.0 in the range of potentials from
−0.4 V to −0.9 V and the average n value for ORR is calculated to
be 3.80, revealing the four-electron pathway is the main reaction
process with the H2 O as the product, which is comparable with
Pt based catalyst [5,8,13,30]. The average electron transfer number
for ORR on p-MWCNTs and m-MWCNTs modified GCEs were also
calculated which is about 1.89 and 1.99, respectively, indicating a
two-electron pathway toward the ORR, which is in good agreement
with previous studies [42,43].
For the purpose of further comparing the ORR electrocatalytic
activity of Ag/m-MWCNTs, p-MWCNTs, m-MWCNTs and commer-
cial 20% Pt/C, the different modified RDEs were investigated in 0.1 M
KOH aqueous solution saturated with oxygen at a rotating rate of
1200 rpm (Fig. 5c). It is obvious that the Ag/m-MWCNTs catalyst
displays a more positive onset potential (−0.05 V) and a higher
limiting diffusion current density toward the ORR than those of
the p-MWCNTs and m-MWCNTs catalysts. The superior catalytic
activity of Ag/m-MWCNTs could be contributed to the combination
of the electrochemical activity of the dispersed Ag nanoparticles
attached on the surface of m-MWCNTs and unique properties of m-
MWCNTs. Furthermore, it has been reported that Ag can promote
the decomposition or further reduction of HO2 − formed at the sur-
faces of the m-MWCNTs [2,27], which facilitate the ORR process in
alkaline media. As is shown, the LSV curves of Ag/m-MWCNTs and
commercial 20% Pt/C both show a single-step wide platform. The
Pt/C catalysts show higher limiting diffusion current and more pos-
itive ORR onset potential than Ag/m-MWCNTs. The mass activity
(MA) [44,45] of the ORR was calculated for further comparison. The
MA of 20% Pt/C (the average particle size of Pt is about 2.8 nm) and
Ag/m-MWCNTs (the average particle size of Ag is about 10.6 nm)
at −0.3 V (1200 rpm) is 394.9 mA mg−1 Pt and 111.3 mA mg−1 Ag,
respectively. Although the electrocatalytic activity toward the ORR
of 20% Pt/C is higher than that of Ag/m-MWCNTs composite, the
Ag/m-MWCNTs would have a great potential to be an alternative
electrocatalyst toward the ORR in the alkaline aqueous solution
considering its much lower cost.
Damjanovic et al. reported that the Tafel slope values of ORR on
Pt catalysts in alkaline solution can be used to evaluate the ORR
kinetics and the oxygen adsorption mechanism [46]. The adsorp-
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
to Langmuir adsorption isotherm at high overpotential is taken
to account for the changing of Tafel slope values of Pt catalysts
(from −0.06 V at low overpotential to −0.12 V at high overpo-
tential) [46–48]. As is shown in Fig. 5d, the Tafel slope values of
Ag/m-MWCNTs catalysts at the low and high overpotential are
−0.076 V and −0.128 V, respectively. The existence of two Tafel
slopes, similar to that of Pt catalysts, indicates that the adsorp-
tion condition of molecular oxygen on the Ag/m-MWCNTs catalysts
is similar to that on the Pt catalysts. The ORR kinetics on Ag/m-
MWCNTs in alkaline solution can be described by two steps similar
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
as the rate determining step [49,50]. In the other hand, accord-
ing to the Butler–Volmer equation (b = RT/˛nF) [5], a high Tafel
slope value means the less transfer coefficient ˛ and/or number
of exchanged electrons n during the reaction at the same tem-
perature. So a lower Tafel slope value is desirable during the ORR
procedure and a higher Tafel slope value indicates an inferior ORR
kinetics. By comparing the Tafel slope values of Ag/m-MWCNTs
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
Pt.
4. Conclusions
In summary, a facile environmentally friendly in situ growth
method was employed to prepare Ag/m-MWCNTs composite.
The Ag/m-MWCNTs catalyst shows high electrocatalytic activity
toward the ORR in alkaline electrolyte and the reduction process is
dominated by four-electron pathway. Tafel plot analysis of Ag/m-
MWCNTs indicates a similar oxygen adsorption mechanism and
kinetic steps on the Ag/m-MWCNTs compared to Pt based catalysts.
The high ORR activity of the Ag/m-MWCNTs could be attributed to
the high electrochemical activity of the dispersed Ag nanoparticles
on the surfaces of the m-MWCNTs which makes the oxygen easily
reduced during the cathodic process. Although the present perfor-
mance of the Ag/m-MWCNTs is not yet as good as the commercial
20% Pt/C catalysts, this Ag/m-MWCNTs composite is proved to be
a promising ORR catalysts for AFCs and ZABs considering that Ag is
much cheaper than Pt.
Acknowledgements
This work is supported by National Basic Research 973 Program
of China (Grant No. 2006AA05Z255). Thanks to Miss Xiao Ling for
the amendment of this paper.
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