Colloids and Surfaces A: Physicochem. Eng.

Aspects 461 (2014) 133141

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Naon based nanocomposite membranes with improved electric

and protonic conduction
Adina Boldeiu a , Eugeniu Vasile b , Raluca Gavrila a , Monica Simion a , Antonio Radoi a ,
Alina Matei a , Iuliana Mihalache a , Razvan Pascu a , Mihaela Kusko a,
a

National Institute for Research and Development in Microtechnology (IMT-Bucharest), 126A Erou Iancu Nicolae Str., 077190 Bucharest, Romania
University Politechnica of Bucharest, Faculty of Applied Chemistry and Material Science, Department of Science and Engineering of Oxidic Materials and
Nanomaterials, 011061 Bucharest, Romania
b

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

A nanocomposite membrane was

obtained based on Naon with
PtNPGNPDDA/PSS multilayers.
Charge transport characteristics (EIS)
were analyzed during the assembling
process.
Improved nanocomposite multilayer
structures with simultaneously proton and electron conduction.

a r t i c l e

i n f o

Article history:
Received 16 May 2014
Received in revised form 14 July 2014
Accepted 26 July 2014
Available online 4 August 2014
Keywords:
Layer-by-layer
Platinum nanoparticles
Polymer-modied graphene
Nanocomposite material
Charge transport

a b s t r a c t
In this work, a stable aqueous dispersion solution of polymer-modied graphene was prepared by in situ
reduction with ethylene glycol from graphene nanosheets (GNs) in the presence of poly (diallyldimethylammonium chloride) (PDDA), in order to obtain a (PtNPsGNsPDDA) nanocomposite material, where
Pt nanoparticles (PtNPs) with a narrow size distribution of 24 nm uniformly decorates GNs, being both
embedded into the PDDA. The multilayer lms consisting of this new nanocomposite material and a common negatively charged polyelectrolyte (PSS) were fabricated on Naon NRE 212 membrane applying
the versatile layer-by-layer (LbL) self-assembly technique. Both morpho-structural (HR-TEM, FEG-SEM,
AFM, UVvis spectroscopy, ATR-IR spectroscopy, ELS) and charge transport characteristics (EIS) were
analyzed during the assembling process showing that the new nanocomposite membrane presents an
improved electrical conduction without a major alteration of the protonic one. The results may open new
areas of applications, from proton exchange membrane fuel cells to biosensors.
2014 Elsevier B.V. All rights reserved.

1. Introduction
The layer-by-layer self-assembly (LbL) based on electrostatic
interactions represents a simple and versatile nanofabrication technique widely used to build three dimensional ultrathin multilayer

Corresponding author. Tel.: +40 21 269 07 68.

E-mail address: mihaela.kusko@imt.ro (M. Kusko).
http://dx.doi.org/10.1016/j.colsurfa.2014.07.041
0927-7757/ 2014 Elsevier B.V. All rights reserved.

lms [1] or even more complicated structures, such as patterned

colloidal crystals [2]. One of the rst applications was in fabrication of direct methanol fuel cells (DMFC), as an efcient solution to
mitigate the common problem of methanol crossover. Accordingly,
novel multilayer membranes with low methanol permeability
and satisfactory proton conductivity were reported, based on sulfonated polyimide copolymers [3,4], poly(arylene ether sulfone)s
[5,6], poly(ether ether ketones) [7] or sulfonated-poly(arylene
ether ketone)s [8,9]. Encouraging results related to the use of Naon

134

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

and, more recently, multilayer membranes based on Naon have

been also reported in biosensor domain. It was shown that using
Naon nanocomposite membrane as outer membrane, the electrochemical biosensor performances were improved, in terms of both
protection and extension of the sensor response linearity [1012].
However, the negative effect of the polyelectrolyte bilayer
presence on the Naon membrane conductivity [13] remains an
unsolved issue. Different approaches have been proposed, including addition of metallic nanoparticles (i.e. Pt [14]) and alloys (i.e.
PtSn [15], PtRu [16,17]) or multi-walled carbon nanotubes [18]
inside of one of the polyelectrolytes. The platinum nanoparticle size
control represents a key parameter for the fuel cell electrochemical and methanol oxidation [19], which dispersed on the Naon
surface blocks the methanol cross-over [20].
Graphene is a two dimensional nanomaterial with a monolayer
of carbon atoms packed in a honeycomb lattice. Recently, it has
become one of the most studied material due to its noteworthy
properties, such as large surface area, high conductivity, excellent
electrochemical stability and good mechanical stiffness [2325].
Graphene has applications in many critical areas, including energy
conversion, sensors, solar cells, storage devices [21,22].
During the last years, an intensive research activity has been
done in order to develop uniform and stable functional nanocomposites based on graphene nanosheets (GNs). Part of these studies
aimed to nd efcient methods to reduce the aggregation phenomenon by covalent or non-covalent functionalization with
different molecules [2628]. Taking into consideration that modication of the graphenes carbon hybridization from sp2 to
sp3 leads to unwanted alteration or destruction of the basic
electronic properties of graphene [29], the functionalization by
non-covalent interactions with polymers, biomolecules or small
aromatic molecules become preferable [3032].
It has been shown that the presence of noble metal nanoparticles and graphene leads to an improved catalytic performance for
methanol electrooxidation in alkaline medium [33], as well as the
interfacial properties between catalyst and electrolyte [34], which
represent signicant improvements for several electrochemical
applications, and in particular for the fuel cells area. In this regard,
PtNPs supported on the GNs revealed to be less susceptible to CO
poisoning than those deposited onto traditional carbon supports
[35].
However, without a stabilizer, besides the natural tendency to
agglomerate, graphene nanosheets are known to be hydrophobic,
and thus, the nanoparticles deposition requires careful choice of
reaction media [36]. A simple approach to solve this issue may
be a preliminary functionalization with polyelectrolytes, which
are adsorbed on the graphenes surface, preventing aggregation
[37]. In the last years, it has been demonstrated the benecial role
of the positively charged polyelectrolyte poly (diallyldimethylammonium chloride) PDDA in graphene functionalization,
exhibiting good conductivity, biocompatibility and even electrocatalytic activity for oxygen reduction [38,39]. Based on these proven
properties, in this study, PDDA would be appropriate for functionalization of graphene via interactions, providing in the same
time active sites for reduction of the platinum precursor.
Going further toward layer-by-layer self-assembling on Naon
membrane using Pt modied graphene inside of the polyelectrolyte based multilayers, the reported studies in the area of direct
methanol fuel cells as well as biosensors are focused particularly
on the improvements of electrocatalytic activity for methanol oxidation [40,41] or biodetection for glucose [42]. In this context, an
insightful analysis of the nanocomposite membrane conductivity
is necessary. Furthermore, the presence of Pt and GN nanollers
provides the premise [43,44] to investigate the nanocomposite
capacity to conduct simultaneously electrons and protons, achieving in-depth data about their individual contributions.

Herein, we obtained a method to fabricate in one-pot synthesis

a nanocomposite material where Pt nanoparticles and graphene
nanosheets were embedded into a positively charged polyelectrolyte PDDA. Moreover, we showed that this method leads to
signicant improvements regarding morphological and structural
characteristics. The obtained PtNPs have a narrow size distribution around 24 nm, fullling the most important requirement for
efcient catalysts, and uniformly decorate the PDDA functionalized graphene nanosheets. The resulting nanocomposite material
was then used to obtain a multilayered structure on Naon NRE
212 membrane by applying the versatile LbL self-assembly technique using a common negatively charged polyelectrolyte (PSS).
Both morpho-structural and charge transport characteristics were
analyzed during the assembling process showing that the new
nanocomposite membrane presents an improved electrical conduction without a major alteration of the protonic one, This
attribute opens new areas of applications, from proton exchange
membrane fuel cells to biosensors. Therefore, PtNPGNPDDA/PSS
multilayers assembled on Naon NRE 212 were able to promote,
the conduction of both electrons and protons, exhibiting mixed
electronic and ionic conduction in parallel.
2. Materials and methods
2.1. Materials
Hexachloroplatinic acid (H2 PtCl6 8 wt.% solution in water),
ethylene glycol, (EG 99.8%, anhydrous), poly (diallyldimethylammonium chloride) (PDDA, 200,000350,000 MW, 20 wt.% in water),
poly (sodium styrene sulphonate) (PSS, 200,000 MW 30 wt.% in
water), sodium chloride, hydrochloric acid, sodium hydroxide
and Naon NRE 212 membrane, 50 m in thickness were from
SigmaAldrich, Germany. Graphene nanosheets solution (50 mg/l)
was from NanoIntegris, USA (PuresheetsTM Quattro).
2.2. Synthesis procedures
2.2.1. Preparation of the platinum nanoparticles decorated
graphene nanosheets
A homogeneous dispersion of PDDA functionalized graphene
nanosheets (GNs) was prepared by mixing equal volumes (10 mL) of
GNs (50 mg/l) and PDDA (20 mM), and further subjected to an ultrasonication process during 1 h. The poly(diallyldimethylammonium
chloride) solution was prepared in an increased ionic strength environment containing 0.5 M NaCl, since PDDA has the tendency to
adopt a linear shape when is solubilized in low ionic strength
solutions, and it is becoming coiled when the ionic strength is
increased [45]. Based on our previous results, we adjusted the pH
of this solution to pH = 4.5 [46]. A certain volume (10 mL) of the
prepared dispersion (GNsPDDA) was added to a mixture containing 20 mL of ethylene glycol (EG) and 1 mL of 0.2 M water based
hexachloroplatinic acid solution (H2 PtCl6 ), under continuous stirring (600 rpm) and heating (40 C). After 1 h, the pH of solution was
adjusted to 11.0 using a 6 M NaOH solution and then increasing
the reaction temperature up to 130 C, during 4 h, under nitrogen
atmosphere. The obtained nanocomposite, PtNPsGNsPDDA, was
allowed to cool off and then was centrifuged at 900 rpm for 30 min.
The obtained precipitate was re-dispersed in 10 mL of deionized
water and centrifuged again in order to eliminate the unreacted
precursors. Finally, the precipitate was re-dispersed in 10 mL of
deionized water, sonicated during 30 min and then further used.
2.2.2. Preparation of the self-assembled nanocomposite on Naon
membrane
Naon contains both hydrophobic and hydrophilic regions,
ascribed to the polyethylene backbone and sulphonic groups,

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

respectively [47]. Methanol cross-over regime is governed by the

hydrophilic regions, in Naon based proton exchange membrane,
thus controlling hydrophilic areas in order to stop the methanol
cross-over through the protonated Naon membrane is a desiderate for many researchers. The presence of anionic sulphonic groups
on membrane surface makes possible the electrostatic interactions
between Naon and a positively charged polyelectrolyte.
The as received Naon NRE 212 membrane was pre-cleaned in
3% (v/v) H2 O2 , during 30 min at 80 C, washed in deionized water
(DI), boiled in 5 M HCl solution for 30 min at 80 C, plenty rinsed
with DI, boiled again in 1 M H2 SO4 water based solution during
30 min at 80 C and nally rinsed with DI. The activated Naon
membrane was immersed in the PtNPsGNsPDDA nanocomposite solution during 15 min, followed by rinsing with DI and drying
in a nitrogen ow. The positively charged thin lm on the Naon
membrane self-assembled with its negatively counterpart, i.e. poly
(sodium styrene sulphonate), starting from a 20 mM PSS solution
prepared in 0.5 M NaCl solution (pH = 8.0) for another 15 min. This
procedure was continued alternatively, until the desired number
of bilayers was obtained.
Additionally, in order to see the inuence of the graphene
nanosheets decorated with platinum nanoparticles on the Naon
membrane conductivity, a standard self-assembled nanocomposite
membrane was prepared using Naon NRE 212 membrane, PDDA
and PSS solutions, except the use of graphene nanosheets and platinum nanoparticles.

The charge transport in the nanocomposite structures was

investigated using a Princeton Applied Research Model PARSTAT
2273 potentiostat/galvanostat/FRA by electrochemical impedance
spectroscopy (EIS) method. ZSimpWin 3.21 software package was
used to analyze data. All conductivity values reported in this work
correspond to the average of two membrane samples.
3. Results and discussion
3.1. Characterization of the graphene nanosheets decorated with
platinum nanoparticles
Fig. 1(a) presents a typical micrograph revealing quite well dispersed graphene nanosheets decorated with spheroid like platinum
nanoparticles. The EDX spectrum inset of Fig. 1(a) conrms

2.3. Instrumental analyses

High resolution transmission electron microscopy has been used
to investigate the morphology, geometrical size, shape, and nanostructure of platinum nanoparticles from the PtNPsGNsPDDA
structure. These analyses have been performed using a TECNAI F30
G2 S-TWIN microscope operated at 300 kV with EDX and EELS facilities, very small amounts of samples being deposited on a TEM
copper grid covered with a thin amorphous carbon lm with holes.
Selected area electron diffraction (SAED) analysis was also performed.
An atomic force microscope, NTEGRA Aura NT-MDT (NT-MDT
Co., Russia), was also, used to observe the structure of the new platinum nanoparticles which decorate the graphene nanosheets. The
AFM samples were prepared by immersing clean 1 cm2 silicon supports for 5 min into the solution containing the PtNPsGNsPDDA
nanocomposite, and dried at room temperature.
The stability of the platinum based nanocomposites in very step
of the process was checked using Beckman Coulter DelsaTM Nano
Instrument utilizing Electrophoretic Light Spectroscopy (ELS). Particles were illuminated by a dual 30 mW laser diode, producing
time-dependent uctuations in the intensity of laser light. The
scattered light is collected at 15 for zeta potential measurements
(diluted concentration samples), and then is measured by a highly
sensitive detector.
Field Emission Gun Scanning Electron Microscopy (FEG-SEM) a
Nova NanoSEM 630 (FEI Company, USA) workstation with a resolution of 1.8 nm @ 3 kV was used to analyze the morphology
and the thickness of the resulting multilayer membrane samples.
Before measurements, the prepared nanocomposite membranes
were frozen using nitrogen and then cut-off in order to obtain
accurate cross-section images.
The growth of the self-assembled multilayers of polyelectrolytes
on Naon was studied by room temperature UVvis spectroscopy
using a U-0080D bio-spectrophotometer from Hitachi High Technologies. Attenuated total reection infrared absorption spectroscopy
was used to investigate the successful preparation of the multilayered nanocomposite membrane, recording spectra in the range of
4000 and 520 cm1 on Tensor 27 (Bruker Optics, USA).

135

Fig. 1. HR-TEM images of the PtNPsGNsPDDA nanocomposite.

136

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

on one hand the presence of the platinum and some oxygen elements. On the other hand, the presence of the Na and Cl ions in
EDX pattern is due to the existence of the counter ions from the
PDDA. The HR-TEM image Fig. 1(b) reveals both the nanoparticle crystallinity and the distribution of their sizes. Furthermore, the
selected area electron diffraction (SAED) analysis identied crystalline planes [(1 1 1), (2 0 0), (2 2 0) and (3 1 1)], all attributed to
face-centered-cubic platinum lattice upper-right corner inset of
Fig. 1(b). The diameter distribution of PtNPs is presented in the
bottom-right corner inset of Fig. 1(b), and shows a relatively narrow size distribution ranging from 2 nm to 5.5 nm with an average
diameter of 3.4 0.3 nm.
The AFM images of the graphene sheets before and after decoration with PtNPs are presented in Fig. 2. Accordingly, the starting
material contains exfoliated graphene sheets with the average lateral dimension of 517 nm and thickness of 1.32 nm Fig. 2(a). After
the in situ synthesis of the PtNPsGNsPDDA nanocomposite, an
increase of the thickness up to 2.55 nm was observed Fig. 2(b).
Going further, the resulting dispersion stability was analyzed
using the electrophoretic light scattering (ELS) method by zeta
potential () measurements. Briey, when an electric eld is
applied across a sample in a cell, charged particles suspended in the
medium are attracted toward the electrode of opposite charge. This
movement called electrophoresis produces the light uctuations,
whose frequency is proportional with its velocity. Accordingly, 
potential can be estimated by measuring the velocity of the particles using HelmholtzSmoluchowski equation which gives the
relationship between the velocity and the amount of the particles
surface charge [48,49]. Therefore, the zeta potential measurement
of the GNs suspension in water gives a value of 35.92 mV, which
indicate a very good stability of the dispersion. The functionalization of GNs with polyelectrolyte produces a relevant shift in
zeta potential, the  value becoming positive (+21.00 mV), which
certies the successful preparation of the GNsPDDA composite. Thus, the functionalized graphene nanosheets provide a good
distribution of sites for the negatively charged [PtCl6 ]2 ions of
the Pt precursor. These ions are bound via electrostatic forces to
the functionalized graphene, leading to an improved uniformity
of PtNPs distribution. This hypothesis was conrmed by the zeta
potential value of +31.10 mV indicating that the in situ reduction
was achieved, with a very good stability of the PtNPsGNsPDDA
dispersion. In the absence of polyelectrolyte, the measured zeta
potential of PtNPsGNs was 15.35 mV, demonstrating the important role of PDDA: facilitates the preparation of a good dispersion
of nanoparticles with regular shape and diameter and stabilization
of the nanocomposite.
3.2. Characterization of the self-assembled nanocomposite on
Naon membrane
Assembling of the multilayer nanocomposite structures was
monitored by microscopic and spectroscopic techniques, such as
scanning electron microscopy (SEM), UVvis spectroscopy and
Fourier transform infrared spectroscopy (FTIR).
3.2.1. Morphological characterization of the multilayered
nanocomposite membranes
SEM analyses of the membrane cross-section reveal
the successfully achievement of the self-assembled layers
PtNPsGNsPDDA/PSS on Naon membrane. The images
obtained after assembling 4 and 10 bilayers, respectively, are
presented in Fig. 3. As it can be observed, the thickness of the
resulting membrane is around 158 nm when 4 bilayers were
deposited Fig. 3(a), and become 399 nm after 10 bilayers
assemblage Fig. 3(b), leading to the mean value of one bilayer

Fig. 2. AFM images for: (a) graphene nanosheetsGNs; and (b) PtNPsGNsPDDA
nanocomposite.

thickness to be around 40 nm, as it results from both sample

analyses.
3.2.2. UV-spectroscopy
The UVvis spectra of pristine protonated Naon membrane and
after the successive assembling of 2, 4, 6, 8, 10 bilayers of PDDA/PSS
are presented in Fig. 4(a), which reveals very well the absorbance

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

1,4

137

228 nm

(a)

10 bL

Absorbance (a.u.)

1,2
1,0

8 bL

0,8
6 bL
0,6
4 bL
0,4
2 bL
0,2
Naf
0,0
220

240

260

280

300

320

Wavelength (nm)
0.30
Absorbance at 253 nm
R=0.9861
SD=0.00637

(b)

0.25

288 nm

Absorbance (a.u.)

10 bL
0.20

8 bL

270 nm
258 nm

0.15

6 bL

253 nm

4 bL
228 nm

0.10

2 bL
0.05
Naf
0.00
220

240

260

280

300

320

Wavelength (nm)
Fig. 4. UV-absorbance spectra for the self-assembled multilayers membranes with
210 bilayers of PDDA/PSS (a) and PtNPsGNsPDDA/PSS (b).
Fig. 3. Cross-sectional SEM pictures of 4 (a) and 10 (b) bilayers of self-assembled
PtNPsGNsPDDA/PSS.

increasing when more bilayers are added. This behavior is better

observed in the inset graph from Fig. 4(a), where the absorbance
from 228 nm, characteristic to the sodium ion from the negative
polyelectrolyte is represented as function of number of assembled
bilayers. The cationic polyelectrolyte is transparent in the UV measured domain. The plot demonstrates that the 228 nm absorbance
increases practically linear, indicating a quite uniform amount of
polyelectrolytes deposited on Naon membrane [50,51].
In the case of the multilayers membranes where
PtNPsGNsPDDA nanocomposite was used instead of bare
PDDA, the UV spectra recorded after different bilayer assembling
steps are overlaid in Fig. 4(b), where a similar trend is observed.
While the 253 nm absorbance, ascribed to PSS, is dominant, the
absorbance from 228 nm is perceptible only as a very small shoulder, becoming more visible as from the 8th bilayer. The absorbance
from 258 nm, which increase more evident starting with the 6th
bilayer can be assigned to graphene nanosheets, indicating their
successful embedding into the multilayer lms [41]. In order to
have a better image of the multilayered lm thickness increment,
the inset graph from Fig. 4(b) depicts the absorbance variation
from 253 nm with the number of bilayers. It is also, presented
a broad spectrum from 280 to approximately 300 nm with a
maximum around 288 nm, assigned to the electronic conjugation

from graphene nanosheets [52]. The small absorbance peak around

270 nm can be assigned * transitions of aromatic C C bonds
present in the structure of graphene nanosheets.

3.2.3. Attenuated total reection infrared spectroscopy (ATR-IR)

Attenuated total reection infrared absorption spectra of the
prepared nanocomposite membranes with 2, 4 and 8 bilayers of
PtNPsGNsPDDA/PSS are presented in Fig. 5. The presence of the
Naon substrate inside the multilayer structure is conrmed by
the bands from 1230 and 1147 cm1 , assigned to the CF2 stretching vibration. Also, the peak observed at 980 cm1 is due to the
symmetric stretching of C O C bonds from Naon membrane,
and its absorbance intensity increases with the number of bilayers.
A peak at 1640 cm1 assigned to stretching double C C from the
aromatic ring of the anionic polyelectrolyte, PSS, can be observed in
spectra, its intensity increasing with deposited bilayers. The small
peak from 1320 cm1 , more intense in the case of the 8th bilayer,
may be assigned to the C H bond from CH3 group of the polycationic polymer used to functionalize the graphene nanosheets. The
decreasing band values in transmittance by increasing the bilayers
number observed at 1060 cm1 are associated with SO3 stretching vibration from the negative PSS polyelectrolyte [53]. The small
bands from 810 cm1 and the intense ones from 630 cm1 , assigned

138

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

1.0

70

0.9
1640

60

1320
0.8

50

1032

810

Zimg (k

Transmitance (%)

through-plane measurements

80

980

0.7
1060

30

2 bLs
4 bLs
8 bLs

10

630

1210
1147

1800

Nafion + bilayers (PDDA+Pt+GN)/PSS

10 bLs
8 bLs
6 bLs
4 bLs
2 bLs
Nafion + bilayers PDDA/PSS
10 bLs
8 bLs
6 bLs
4 bLs
2 bLs

20

0.6

0.5

40

1600

1400

1200

1000

800

50

100

600

150

200

250

Zre (k

-1

Wavenumber (cm )
in-plane measurements

120

Fig. 5. ATR-IR pattern of the nanocomposite membrane with 2, 4 and 8 bilayers of

PtNPsGNsPDDA/PSS.

100

to symmetrical O H bond deformation, are more evidenced as the

number of bilayers increases [54].

Fig. 6. Schematic representation of through-plane (a) and in-plane (b) conductivity

measurement systems.

Zimg (k

3.2.4. Electrochemical impedance spectroscopy measurements

The inuence of graphene nanosheets and the charge kinetics in multilayer nanocomposite structures were evaluated by
two-probe electrochemical impedance spectroscopy, which is
well-established diagnostic and modeling method, widely used in
characterization of protonic membranes. Both, through-plane and
in-plane measurements were realized using custom-made connection systems, schematic presented in Fig. 6. Therefore, while in
the rst case Fig. 6(a) the membranes previously equilibrated
with water were placed between two square (1 cm2 ) copper plated
electrodes, for the second type of measurements Fig. 6(b) the
membranes were placed on two striped copper plated electrodes
distanced at 1 cm and on the top a simple plastic sheet is put in
order to uniformly press the entire assembly.
The impedance spectroscopy measurements were done at 25 C,
in the range of 0.1 Hz100 kHz, by applying an alternative voltage
of 10 mV, at open circuit potential. The through-plane and in-plane
Nyquist plots of membrane subjected of layer-by-layer assembly
process with polyelectrolytes with and without graphene and Pt
nanoparticles are presented in Fig. 7.
Both types of measurements, through-plane and in-plane
showed that the charge transfer resistance signicantly decreased
when the conductive nanoelements (PtNPs and GNs) were added

80

60
Nafion + bilayers (PDDA+Pt+GN)/PSS
10 bLs
8 bLs
6 bLs
4 bLs
2 bLs
Nafion + bilayers PDDA/PSS
10 bLs
8 bLs
6 bLs
4 bLs
2 bLs

40

20

0
0

100

200

300

400

Zre (k
Fig. 7. Through-plane (a) and in-plane (b) Nyquist plots of membrane after different
number of polyelectrolyte bilayers with and without graphene and Pt nanoparticles.

together with PDDA, suggesting the improvement of charge transport properties of the multilayer membrane. Hence, the injected
charges can be transferred more rapidly through the graphene
nanosheets in the PtNPsGNsPDDA nanocomposite lm. Moreover, since the impedance arcs are just about the real axis in the low
frequency regions, an electronic conduction can be identied [55],
where the negative inuence of assembling dielectric polymeric
bilayers [39] is reduced, being observed only a two-fold increasing
of the charge transfer resistance comparing with ve-fold increasing when the polyelectrolytes are not doped. The Bode plots, both
absolute value of impedance (|Z|) and phase angle () as a function
of frequency support this behavior as well, a slight decrease of the
phase angle accompanied with a signicant narrowing and shifts
toward low frequency values being observed, indicating that the
new systems deviate from the case of pure capacitance and have
faster electron transfer rates [33,56].
An equivalent circuit type Rbm (R1 Q1 ) (R2 Q2 ) is proposed to
model the EIS diagrams and to calculate the conductivity of the
nanocomposite membranes, taking into account the presence of the
new created interfaces [57] and being shown in Fig. S1 (see Supplementary Information). In the equivalent circuit we had a resistance
in series with parallel combinations of charge transfer resistance
(Ri ) and the constant phase element (Qi ). The constant phase elements represent non-ideal capacitors of capacity Ci and roughness
factor i , where takes values between 0 and 1, an value of 1

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

Rbm the bulk membrane resistance used to calculate the protonic

conductivity;
(R2 Q2 ) parallel combination of charge transfer resistance of the
membrane (R2 ) and the constant phase element (Q2 ) representing
the electrode double layer, respectively;
(R3 Q3 ) parallel combination of charge transfer resistance (R3 )
and constant phase element (Q3 ) assigned to the interfaces of the
boundary layers.
Concerning the proton conductivity, which is a crucial criterion
for evaluating fuel cell performance as well as the practicability of
novel PEM materials, it was calculated from equation:
1
Rbm

120

80

Nafion + bLs (PDDA+Pt+GN/PSS)

Nafion + bLs (PDDA)/PSS

40

(1)

where:  is the proton conductivity, k is the cell constant which

varies depending on the type of measurements and Rbm is the
measured bulk resistance value, determined from the Nyquist plot
intercepts on real axis at high frequencies.
Therefore, for the through-plane set-up, ktp is d/A, where d is
the membrane thickness (0.005 cm) and A is the area of electrodes
(1 cm2 ) and, respectively, for the in-plane set-up, kip is L/Am , where
L is the length parallel to the ion ow (in this study the distance
between electrodes is 1 cm), and Am is the membrane section area
(Am = dl, where d is the membrane thickness, l is the length of electrodes covered with membrane 0.8 cm). Therefore, while for the
in-plane conductivity measurements the cell constant kip takes
larger values 000000050 cm1 for bare Naon and 220 cm1 when
the Naon is assembled with 10 bilayers, for the through-plane setup, the ktp is signicant smaller, between 0.005 and 0.006 cm1 ,
depending also on the membrane thickness modication after each
step of bilayers assembling. Consequently, the rst type of measurements should provide a greater accuracy because the bulk
membrane contribution is dominant in the measured impedances,
but a lot of information about the impedance contributions from
the interfacial regions are missing [58].
The proton conductivity of LbL self-assembled PDDA
with/without GNs-PtNPs and PSS polyelectrolytes on Naon 212,
measured both through-plane and in-plane is presented in Fig. 8(a).
First of all, the conductance anisotropy of the Naon membrane
can be observed, this behavior being in accordance to the previous
reports [59], due to the orientation of both Naon chains and ionic
clusters at the interface. The conductivity of Naon 212 membrane
decreases gradually with the increase on the number of PDDA/PSS
bilayers, a more accentuated decrease rate being observed for
the perpendicular one. In the case of replacing the PDDA with
a nanocomposite where conductive nanoelements are added,
although the contribution toward enhancement of proton conductivity by GNs in wet membranes is not signicant, mainly due to
presence of large number of water molecules with hydrogen bonding capability, the decreasing rate is diminished, being rather slow.
Furthermore a stabilization of the conductivity at values around
41 2 mS/cm in-plane and 2.3 0.1 mS/cm through-plane is
evident after ca. 5 bilayers, and this behavior is related to the incorporation of the conducting elements in the multilayer structures.
In terms of the proton conductivity loss, it can be dened as:
( Naon  Naon+bilayers / Naon ) 100.
The presence of Pt3 Sn alloy particles in PAH/PSS bilayers
assembled on Naon led to a reduction from 82% to 74% after
deposition of 10 bilayers [60]. After a similar number of bilayers of PDDA with GNPtNP llers and PSS, a signicant reduction
of the proton conductivity loss was achieved for the throughplane conductivity, from 70% for (PDDA/PSS)10 /Naon to 48% for

p
p

Nafion + bLs (PDDA+Pt+GN/PSS)

Nafion + bLs (PDDA)/PSS

10

No of bilayers

(b)
Electronic conductivity (mS/cm)

=k

(a)

Protonic conductivity (mS/cm)

represents perfectly smooth surface. These circuit elements have

the following meaning for our analyzed systems:

139

10

el
l
el
l

Nafion + bLs (PDDA+Pt+GN/PSS)

Nafion + bLs (PDDA)/PSS

1E-3
t
t

el
el

Nafion + bLs (PDDA+Pt+GN/PSS)

Nafion + bLs (PDDA)/PSS

1E-4

10

No of bilayers
Fig. 8. Through-plane and in-plane protonic (a) and electronic (b) conductivities as
function of the number of self-assembled bilayers.

((PDDA + Pt + GN)/PSS)10 /Naon. Accordingly, if for the reference

samples after assembling of 10 bilayers of polyelectrolytes without
GNsPtNPs the proton conductivity decreases from 4.62 mS/cm to
1.4 mS/cm, their addition leads to a signicant improvement of this
value which becomes 70 times larger, specically 2.4 mS/cm. This
performance is due to the good dispersion of PtNPs on graphene
which gives an easy access of ions to the catalytic active sites,
facilitating the proton diffusion and mass transport [61].
Furthermore, a secondary conductive path, the electronic one,
was evidenced and the results of the electronic conductivity are
presented in Fig. 8(b) as function of the number of assembled bilayers. It is clearly observable that while the simple polyelectrolyte
assembling determine a signicant decrease of the electronic
conductivity, up to orders of magnitude, the presence of the conductive elements inside PDDA leads to constant improvement of
the corresponding values, which demonstrate that this secondary
conduction path become non-negligible. In Fig. S2 (see Supplementary Information) are presented the plots of through-plane and
in-plane of the electrical conductivities as function of the number
of self-assembled bilayers of PDDA/PSS and (PDDA + Pt + GN)/PSS,
respectively. The plots clearly demonstrate the opposite behavior of the electrical conductivity after successive assembling of the
polyelectrolytes when the GNsPtNPs are added. Accordingly, on
one hand, the electrical conductivity successively decreases after
each assembling step of (PDDA/PSS) bilayers, reaching two orders

140

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141

of magnitude lower values after 10 bilayers, from 14.2 mS/cm to

0.56 mS/cm in-plane and from 3.7 S/cm to 0.0035 S/cm throughplane, respectively. On the other hand, the samples containing
bilayers of (PDDA + Pt + GN)/PSS show an enhancement of the
conductivity, from 14.2 mS/cm to 42 mS/cm in-plane and from
3.7 S/cm to 4.4 S/cm through-plane, respectively.
The increase in electrical conductivity can be also partially
responsible for improvement of the protonic transport, because
a better electrically conductive structure promotes the motion of
ions through the multilayer structure when an electric eld is
applied [62].
Moreover, the values of the electronic conductivities are still
at the same order of magnitude with protonic conductivities,
being comparable with those obtained when vertically aligned carbon nanotube columns [63] or reduced graphene oxide [64] were
directly embedded in a Naon matrix to improve the electrical conduction. It is remarkable also that these values of the electronic
conductivities obtained for the ((PDDA + Pt + GN)/PSS)n /Naon
membranes where obtained from the measurements made on
hydrated membrane, where the electronic conduction is diminished due to the presence of water molecules.
4. Conclusions
In summary, graphene was functionally modied with PDDA
and then, decorated with small and uniform platinum nanoparticles of 3.4 0.4 nm, in situ synthesized by hexachloroplatinic
acid reduction with ethylene glycol. After that, nanocomposite ((PDDA + Pt + GN)/PSS)n -Naon membranes were prepared by
LbL self-assembly technique and analyzed by comparison with
corresponding reference ((PDDA)/PSS)n -Naon membranes using
different microscopic and spectroscopic techniques. The UVvis, as
well as ATR-IR spectroscopies conrmed the successful assembling
of the polyelectrolytes regular or with nanollers on the Naon
membrane.
The impedance spectroscopy measurements revealed interesting conduction properties of the novel membrane obtained using
additional conductive PtNPsGNs nanollers. Accordingly, both
through-plane and in-plane analyses were realized to investigate
their inuence on the conduction properties of the resulting multilayer structures. First of all, it was shown that the variation of
the charge transfer resistances signicantly decreased after similar steps of the polyelectrolyte assembling process when the
PtNPsGNs nanollers are present, suggesting an improvement
of the charge transport properties. Accordingly, on one hand, the
decreasing of protonic conduction slows down, achieving a preservation of the conductivity after 5 bilayers. On the other hand,
integration of the conducting llers in the multilayer structures
leads to generation of an equally important secondary conduction path, the electronic one, which becomes non-negligible.
Consequently, it was demonstrated that the nanocomposite
((PDDA + Pt + GN)/PSS)n -Naon membranes are capable of simultaneously conducting protons and electrons, which represents an
advantage for development of further applications.
Acknowledgement
This work was supported by CNCSUEFISCDI Romania, under
the project number PNII-PCCA1-004/2012.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2014.07.041.

References
[1] G. Decher, Fuzzy nanoassemblies: toward layered polymeric multicomposites,
Science 277 (1997) 12321237.
[2] W. Li, B. Yang, D. Wang, Fabrication of colloidal crystals with dened and complex structures via layer-by-layer transfer, Langmuir 24 (2008) 1377213775.
[3] H. Bai, W.S.W. Ho, New poly(ethylene oxide) soft segment-containing
sulfonated polyimide copolymers for high temperature proton-exchange
membrane fuel cells, J. Membr. Sci. 313 (2008) 7585.
[4] K. Okamoto, Y. Yin, O. Yamada, N. Islam, T. Honda, T. Mishima, Y. Suto, K.
Tanaka, H. Kita, Methanol permeability and proton conductivity of sulfonated
co-polyimide membranes, J. Membr. Sci. 258 (2005) 115122.
[5] C. Wang, N. Li, D.W. Shin, S.Y. Lee, N.R. Kang, Y.M. Lee, M.D. Guiver, Fluorenebased poly(arylene ether sulfone)s containing clustered exible pendant
sulfonic acids as proton exchange membranes, Macromolecules 44 (2011)
72967306.
[6] G.L. Han, P.Y. Xu, Q.G. Ke Zhou, A.M. Zhang, Q.L. Zhu, Liu, Fluorene-containing
poly(arylene ether sulfone) block copolymers: synthesis, characterization and
application, J. Membr. Sci. 464 (2014) 7279.
[7] R.K. Nagarale, G.S. Gohil, V.K. Shahi, Sulfonated poly(ether ether
ketone)/polyaniline composite proton-exchange membrane, J. Membr.
Sci. 280 (2006) 389396.
[8] Y.S. Kim, F. Wang, M. Hickner, S. Mccartney, Y.T. Hong, W. Harrison, T.A.
Zawodzinski, J.E. Mcgrath, Effect of acidication treatment and morphological
stability of sulfonated poly(arylene ether sulfone) copolymer proton-exchange
membranes for fuel-cell use above 100 C, J. Polym. Sci. B: Polym. Phys. 41
(2013) 28162828.
[9] D. Xing, J. Kerres, Improved performance of sulfonated polyarylene ethers
for proton exchange membrane fuel cells, Polym. Adv. Technol. 17 (2006)
591597.
[10] X. Chen, X. Yan, K.A. Khor, B.K. Tay, Multilayer assembly of positively charged
polyelectrolyte and negatively charged glucose oxidase on a 3D Naon network
for detecting glucose, Biosens. Bioelectron. 22 (2007) 32563260.
[11] V. dos Santos, M. dos Santos, C.G. de Jesus, S.T. Fujiwara, J.R. Garcia, C.A. Pessa,
K. Wohnrath, The role of a layer-by-layer lm containing pt nanoparticle on
the performance of a glucose enzymatic biosensor, Int. J. Electrochem. Sci. 8
(2013) 1060110620.
[12] H. Wang, C. Zhou, J. Liang, H. Yu, F. Peng, An enhanced glucose biosensor
modied by Pt/sulfonated-MWCNTs with layer-by-layer technique, Int. J. Electrochem. Sci. 3 (2008) 11801185.
[13] H. Deligoz, S. Ylmazturk, M. Ylmazoglu, H. Damyan, The effect of selfassembled multilayer formation via LbL technique on thermomechanical and
transport properties of Naon 112 based composite membranes for PEM fuel
cells, J. Membr. Sci. 351 (2010) 131140.
[14] S.P. Jiang, Z. Liu, H.L. Tang, M. Pan, Synthesis and characterization of PDDAstabilized Pt nanoparticles for direct methanol fuel cells, Electrochim. Acta 51
(2006) 57215730.
[15] C.H. Lin, C.H. Wan, W. Wu, Suppressing methanol crossover with nanometersized Pt3 Sn particles self-assembled on a Naon membrane surface, Int. J.
Electrochem. Sci. 8 (2013) 82368251.
[16] C.H. Wan, M.T. Lin, Mitigating methanol crossover with self-assembled
Pt35 Ru65 catalyst on Naon surface, J. Power Sources 222 (2013) 470476.
[17] U.R. Filho, L.C. Battirola, J.F. Schneider, I.C.L. Torriani, G.T. Filho, Improvement
on direct ethanol fuel cell performance by using doped-Naon 117 membranes with Pt and PtRu nanoparticles, Int. J. Hydrogen Energy 38 (2013)
1206012068.
[18] H. Lin, W. Sun, C. Zhao, H. Na, Self-assembly of multiwall carbon nanotubes
on sulfonated poly(arylene ether ketone) as a proton exchange membrane, J.
Polym. Res. 20 (2013) 306.
[19] A.K. Roy, C.T. Hsieh, Pulse microwave-assisted synthesis of Pt nanoparticles
onto carbon nanotubes as electrocatalysts for proton exchange membrane fuel
cells, Electrochim. Acta 87 (2013) 6372.
[20] C.H. Wan, M.T. Lin, C.H. Lin, B.J. Su, Suppressing methanol crossover with a
deposited quaternary Pt-based catalyst on the Naon surface, Int. J. Hydrogen
Energy 39 (2014) 25162525.
[21] H.J. Choi, S.M. Jung, J.M. Seo, D.W. Chang, L. Dai, J.B. Baek, Graphene for energy
conversion and storage in fuel cells and supercapacitors, Nano Energy 1 (2012)
534551.
[22] J.A. Kim, T. Hwang, S.R. Dugasani, R. Amin, A. Kulkarni, S.H. Park, T. Kim,
Graphene based ber optic surface plasmon resonance for bio-chemical sensor
applications, Sens. Actuators B: Chem. 187 (2013) 426433.
[23] P. Yao, P. Chen, L. Jang, H. Zhao, H. Zhu, D. Zhou, W. Hu, B.H. Han, M. Liu,
Electric current induced reduction of graphene oxide and its application as
gap electrodes in organic photoswitching devices, Adv. Mater. 22 (2010)
50085012.
[24] S. Guo, S. Dong, Graphene nanosheet: synthesis, molecular engineering, thin
lm, hybrids, and energy and analytical applications, Chem. Soc. Rev. 40 (2011)
26442672.
[25] Y.H. Zhang, N. Zhang, Z.R. Tang, Y.J. Xu, Graphene transform a wide band gap
ZnS to a visible white light photocatalyst: the new role of graphene as a macromolecular photosensitizer, ACS Nano 6 (2012) 97779789.
[26] Y. Hu, K. Wang, Q. Zhang, F. Li, T. Wu, L. Niu, Decorated graphene sheets for
label-free DNA impedance biosensing, Biomaterials 33 (2012) 10971106.
[27] Y. Liu, Y. Huang, Y. Xie, Z. Yang, H. Huang, Q. Zhou, Preparation of highly dispersed CuPt nanoparticles on ionic-liquid-assisted graphene sheets for direct
methanol fuel cell, Chem. Eng. J. 197 (2012) 8087.

A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141
[28] X. Qi, K.Y. Pu, H. Li, X. Zhou, S. Wu, Q.-L. Fan, B. Liu, F. Boey, W. Huang, H. Zhang,
Amphiphilic graphene composites, Angew. Chem. Int. Ed. 49 (2010) 94269429.
[29] Y. Xue, H. Zhao, Z. Wu, X. Li, Y. He, Z. Yuan, The comparison of different gold
nanoparticles/graphene nanosheets hybrid nanocomposites in electrochemical performance and the construction of a sensitive uric acid electrochemical
sensor with novel hybrid nanocomposites, Biosens. Bioelectron. 29 (2011)
102108.
[30] C.X. Guo, L.Y. Zhang, J. Miao, J. Zhang, C.M. Li, DNA-functionalized graphene to
guide growth of highly active Pd nanocrystals as efcient electrocatalyst for
direct formic acid fuel cells, Adv. Eng. Mater. 3 (2013) 167171.
[31] M. Liu, Y. Duan, Y. Wang, Y. Zhao, Diazonium functionalization of graphene
nanosheets and impact response of aniline modied graphene/bismaleimide
nanocomposites, Mater. Des. 53 (2014) 466474.
[32] X. Chen, F.M. Yasin, P.K. Eggers, R.A. Boulos, X. Duan, R.N. Lamb, K.S. Iyer, C.L.
Raston, Non-covalently modied graphene supported ultrane nanoparticles
of palladium for hydrogen gas sensing, RSC Adv. 3 (2013) 32133217.
[33] Z. Yao, R. Yue, C. Zhai, F. Jiang, H. Wang, Y. Du, C. Wang, P. Yang, Electrochemical layer-by-layer fabrication of a novel three-dimensional Pt/graphene/carbon
ber electrode and its improved catalytic performance for methanol electrooxidation in alkaline medium, Int. J. Hydrogen Energy 38 (2013) 63686376.
[34] S. Liu, J. Wang, J. Zeng, J. Ou, Z. Li, X. Liu, S. Yang, Green electrochemical synthesis of Pt/graphene sheet nanocomposite lm and its electrocatalytic property,
J. Power Sources 195 (2010) 46284633.
[35] H.J. Huang, H.Q. Chen, D.P. Sun, X. Wang, Graphene nanoplatePt composite
as a high performance electrocatalyst for direct methanol fuel cells, J. Power
Sources 204 (2012) 4652.
[36] S.J. Guo, S.J. Dong, E.K. Wang, Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: facile synthesis and used as
an advanced nanoelectrocatalyst for methanol oxidation, ACS Nano 4 (2010)
547555.
[37] S. Zhang, Graphene decorated with PtAu alloy nanoparticles: facile synthesis
and promising application for formic acid oxidation, Chem. Mater. 23 (2011)
10791081.
[38] B.M. Luo, X.B. Yan, S. Xu, Q.J. Xue, Polyelectrolyte functionalization of graphene
nanosheets as support for platinum nanoparticles and their applications to
methanol oxidation, Electrochim. Acta 59 (2012) 424429.
[39] Y. Yu, Z. Chen, B. Zhang, X. Li, J. Pan, Selective and sensitive determination of
uric acid in the presence of ascorbic acid and dopamine by PDDA functionalized
graphene/graphite composite electrode, Talanta 112 (2013) 3136.
[40] J. Yang, Y. Zhou, L. Sun, N. Zhao, C. Zang, X. Cheng, Synthesis, characterization and optical property of graphene oxide lms, Appl. Surf. Sci. 258 (2012)
50565060.
[41] X. Huang, Z. Li, X. Zhang, X. He, S. Lin, Preparation of Pt/{PDDA-GN/PSS-GN}n
multilayer lms and their electrocatalytic activity regarding methanol oxidation, J. Colloid Interface Sci. 393 (2013) 300305.
[42] M.M. Barsan, M. David, M. Florescu, L. Tugulea, C.M.A. Brett, A new selfassembled layer-by-layer glucose biosensor based on chitosan biopolymer
entrapped enzyme with nitrogen doped graphene, Bioelectrochemisty 99
(2014) 4652.
[43] G. Inzelt, M. Pineri, J.W. Schultze, M.A. Vorotyntsev, Electron and proton conducting polymers: recent developments and prospects, Electrochim. Acta 45
(2000) 24032421.
[44] T.J. Wood, H.G. Andrews, R.L. Thompson, J.P.S. Badyal, Ion- and electronconducting platinumpolymer nanocomposite thin lms, ACS Appl. Mater.
Interfaces 4 (2012) 67476751.
[45] A.V. Dobrynina, M. Rubinstein, Theory of polyelectrolytes in solutions and at
surfaces, Prog. Polym. Sci. 30 (2005) 10491118.

141

[46] A. Bragaru, M. Kusko, A. Radoi, M. Danila, M. Simion, F. Craciunoiu, R. Pascu,

I. Mihalache, T. Ignat, Microstructures and growth characteristics of polyelectrolytes on silicon using layer-by-layer assembly, Cent. Eur. J. Chem. 11 (2013)
205214.
[47] K.A. Mauritz, R.B. Moore, State of understanding of Naon, Chem. Rev. 104
(2004) 45354585.
[48] J. Jiang, G. Oberdrster, P. Biswas, Characterization of size, surface charge, and
agglomeration state of nanoparticle dispersions for toxicological studies, J.
Nanopart. Res. 11 (2009) 7789.
[49] M. Kosmulski, Surface Charging and Points of Zero Charge, CRC Press, Boca
Raton, FL, 2009.
[50] M. Yang, S. Lu, J. Lu, S.P. Jiang, Y. Xiang, Layer-by-layer self-assembly of
PDDA/PWA-Naon composite membranes for direct methanol fuel cells, Chem.
Commun. 46 (2010) 14341436.
[51] H. Deligoz, B. Tieke, QCM-D study of layer-by-layer assembly of polyelectrolyte
blend lms and their drug loading-release behavior, Colloids Surf. A: Physicochem. Eng. Aspects 441 (2014) 725736.
[52] D. Li, M.B. Muller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous dispersions of graphene nanosheets, Nat. Nanotechnol. 3 (2008) 101105.
[53] D. He, K. Cheng, H. Li, T. Peng, F. Xu, S. Mu, M. Pan, Highly active platinum
nanoparticles on graphene nanosheets with a signicant improvement in stability and CO tolerance, Langmuir 28 (2012) 39793986.
[54] M.C. Silva, F.H. Cristovan, R. Ruggiero, W.O. Cruz, A. Marletta, Near-infrared
emission of Nd-PSS lms, Braz. J. Phys. 36 (2006) 499500.
[55] V. Ijeri, L. Cappelletto, S. Bianco, M. Tortello, P. Spinelli, E. Tresso, Naon and
carbon nanotube nanocomposites for mixed proton and electron conduction,
J. Membr. Sci. 363 (2010) 265270.
[56] D. Sotta, J. Bernard, V. Sauvant-Moynot, Application of electrochemical
impedance spectroscopy to the study of ionic transport in polymer-based electrolytes, Prog. Org. Coat. 69 (2010) 207.
[57] S.M.R. Niya, M. Hoorfar, Study of proton exchange fuel cells using electrochemical impedance spectroscopy technique a review, J. Power Sources 240 (2013)
281293.
[58] T. Soboleva, Z. Xie, Z. Shi, E. Tsang, T. Navessin, S. Holdcroft, Investigation
of the through-plane impedance technique for evaluation of anisotropy of
proton conducting polymer membranes, J. Electroanal. Chem. 622 (2008)
145152.
[59] R.F. Silva, M. De Francesco, A. Pozio, Tangential and normal conductivities of
Naon membranes used in polymer electrolyte fuel cells, J. Power Sources
134 (2004) 1826.
[60] C.-H. Lin, C.-H. Wan, W. Wu, Suppressing methanol crossover with nanometersized Pt3 Sn particles self-assembled on a Naon membrane surface, Int. J.
Electrochem. Sci. 8 (2013) 82368251.
[61] L. Feng, G. Gao, P. Huang, X. Wang, C. Zhang, J. Zhang, S. Guo, D. Cui, Preparation
of PtAg alloy nanoisland/graphene hybrid composites and its high stability and
catalytic activity in methanol electro-oxidation, Nanoscale Res. Lett. 6 (2011)
551561.
[62] S. Liu, R. Montazami, Y. Liu, V. Jain, M. Lin, X. Zhou, J.R. Hein, Q.M. Zhang,
Inuence of the conductor network composites on the electromechanical
performance of ionic polymer conductor network composite actuators, Sens.
Actuators A: Phys. 157 (2010) 267275.
[63] M. Tortello, S. Bianco, V. Ijeri, P. Spinelli, E. Tresso, Naon membranes with
vertically aligned CNTs for mixed proton and electron conduction, J. Membr.
Sci. 415/416 (2012) 346352.
[64] B.A. Aragaw, W.-N. Su, J. Rick, B.-J. Hwang, Highly efcient synthesis of reduced
graphene oxideNaon nanocomposites with strong coupling for enhanced
proton and electron conduction, RSC Adv. 3 (2013) 2321223221.