Beruflich Dokumente
Kultur Dokumente
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 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
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A. Boldeiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 133141
135
136
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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.
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.
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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
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
100
Zimg (k
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
120
80
40
(1)
p
p
10
No of bilayers
(b)
Electronic conductivity (mS/cm)
=k
(a)
139
10
el
l
el
l
1E-3
t
t
el
el
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.
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