Thin Solid Films 534 (2013) 572–576

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Thin Solid Films

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Polyethyleneimine-functionalized graphene and its layer-by-layer assembly with

Prussian blue
Changsheng Shan a, Lingnan Wang a, Dongxue Han a,⁎, Fenghua Li a, Qixian Zhang a, Xindong Zhang b, Li Niu a
a
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
b
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, 2699 Qianjin Street, Changchun 130012, PR China

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

Article history: The polyethyleneimine (PEI)-functionalized graphene, which showed excellent dispersibility in water, has
Received 28 May 2012 been simply synthesized in an alkaline solution. The graphene sheets played an important role as connector
Received in revised form 1 February 2013 to assemble the active amino groups in PEI. This composite provided a positive environment for further
Accepted 1 February 2013
functionalization. As an example, a [Prussian blue (PB)/PEI–graphene]n multilayer film has been constructed
Available online 16 February 2013
through layer-by-layer complexation method. The resulting [PB/PEI–graphene]n multilayer film demonstrat-
Keywords:
ed preferable electrochromic property and excellent electrocatalysis towards H2O2, which showed promising
Polyethyleneimine potential application in electrochemical sensing.
Graphene © 2013 Elsevier B.V. All rights reserved.
Prussian blue
Layer-by-layer complexation
Electrocatalysis

1. Introduction of the potential application in separation, sensing, optical and electronic

Graphene, a single layer of carbon atoms in a closely packed honey-
comb two-dimensional lattice, has attracted a tremendous amount of
attention recently [1–4]. Due to its unique electronic, mechanical, and
thermal properties [5,6], graphene has been extensively applied in
many fields, such as battery [7], field-effect transistors [8], ultrasensitive
sensors [9] and electromechanical resonators [10]. However, graphene
tends to form irreversible agglomerates through strong π–π stacking
and van der Waals interaction. So the prevention of aggregation for
graphene sheets is of particular importance because most of the unique
properties are only associated with individual sheets [11]. Some
methods containing covalent and noncovalent functionalization of
graphene have been applied to obtain dispersed graphene in water or
organic solvent [12–16]. But synthesis of water-soluble graphene is
still a challenge and research hotspot. Polyethyleneimine (PEI, structure
shown in Fig. 1) is a water-soluble polymer with amine groups in the
molecular backbone, which provides a positive charged structure in
the acid solution. Due to its active amine groups, PEI can react with
other materials with some certain active groups, such as carboxyl or
epoxy groups. These properties of PEI make it an ideal candidate for
the modification of graphene and further extend its application.
Layer-by-layer (LBL) assembly is concerned as a powerful and versa-
tile method for the preparation of functional ultrathin films. In the re-
cent decade, the functional film has attracted much attention because
devices, etc. [17–20]. It has been reported that various materials, such as
charged polyelectrolyte, nanoparticles, carbon nanotubes, Prussian blue
(PB) and polyoxometalate, have been assembled into functional com-
posite films [21–24]. It is noticeable that PB is a kind of poly-nuclear
and mixed-valent iron cyanide complex which possess repeating unit
of Fe(III)[Fe(II)–(CN)6] (FeIIIHCFII) [25,26]. This compound has been
employed in electrochromic devices [27,28] and electrochemical bio-
sensors [29,30] due to its excellent electrochromic and electrocatalytical
properties [31].
Here the PEI was grafted covalently onto graphene sheets via the
nucleophilic ring-opening reaction between the amine groups in PEI
and epoxy groups of graphene oxide. Since it was positively charged
and had an excellent dispersibility in water, the resulting PEI-grafted
graphene could assemble with other negatively charged materials by
electrostatic interaction to obtain ultrathin composite films with special
properties. As an example, a [PB/PEI–graphene]n multilayer film was
constructed by layer-by-layer complexation method. Furthermore,
this obtained [PB/PEI–graphene]n multilayer film exhibited excellent
electrochromic property and preferable electrocatalysis towards H2O2,
which showed a promising prospect for application in electrochemical
sensing.
2. Experimental section
2.1. Materials

⁎ Corresponding author. Tel.: +86 431 85262425; fax: +86 431 8526 2800. Graphite, hydrazine solution (50 wt.%) and ammonia solution
E-mail address: dxhan@ciac.jl.cn (D. Han). (28 wt.%) were purchased from Sinopharm Chemical Reagent Co., Ltd.

0040-6090/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2013.02.011
 C. Shan et al. / Thin Solid Films 534 (2013) 572–576
Polyethyleneimine (Mw = 25,000, PEI) was obtained from Aldrich. Dial-
ysis membrane (MWCO 10,000) was purchased from Sino-American
Biotechnology Co. Ltd. FeCl2·4H2O, K3Fe(CN)6 and hydrogen peroxide
solution (30 wt.%) were obtained from Beijing Chemical Reagent
(Beijing, China). All the other reagents were of analytical grade and
used as received. The double-distilled water filtered using an ultrafiltra-
tion system (Millipore system, >18 MΩ cm) was employed for prepar-
ing all the aqueous solutions.
2.2. Instruments
UV–vis absorption spectra of PEI-grafted graphene were collected
in aqueous solution using a CARY 500 Scan UV/vis/NIR spectropho-
tometer. Fourier transform infrared (FTIR) spectroscopy was recorded
on a Bruker Vertex 70 spectrometer (4 cm −1). Tapping-mode atomic
force microscopy (AFM) imaging was performed on a Digital Instru-
ments multimode microscope controlled by Nanoscope IIIa apparatus
(Digital Instruments, Santa Barbara, CA) equipped with a J scanner.
The X-ray photoelectron spectroscopy (XPS) analysis was carried
out on a Thermo ESCALAB 250 X-ray photo-electron spectrometer
(Al (Kα) X-ray, 1486.6 eV). The bonding energy of C1s with 284.6 eV
was used as reference for energy scale. The software Avantage 4.15
attached on this XPS instrument was used for peak fitting. Electro-
chemical measurements were performed using a conventional three-
electrode cell with a platinum wire as auxiliary electrode and an Ag|
AgCl (saturated KCl) as reference electrode on a CHI 660 Electrochemi-
cal Workstation (CHI, USA). And the working electrodes were modified
indium tin oxide (ITO) electrodes.
2.3. Synthesis of PEI-functionalized graphene
Graphene oxides (Fig. 1A) were synthesized from graphite powder
via a modified Hummers method [32]. As shown in Fig. 1, the PEI-
functionalized graphene (Fig. 1B) was prepared by vigorously stirring
a mixture containing 8 mg graphene oxides, 40 mg PEI, and 15 mg
KOH in 15 mL H2O at 80 °C for 24 h. Then, 2 mL of 1 M NaBH4 solution
was added into the mixture and the reaction solution was kept at
80 °C for 2 h. Finally, the resulting PEI–graphene was collected by cen-
trifugation and washed adequately with distilled water for several
times to remove the impurities and the excess physically adsorbent
PEI.
Fig. 1. Schematic diagram of synthesis of PEI-functionalized graphene.
573
2.4. Preparation of [PB/PEI–graphene]n multilayer film
PB nanoparticles were synthesized according to the previous
report [27]. A FeCl2 aqueous solution (50 mL, 0.01 M) was added
dropwise to a 50 mL 0.05 M K3Fe(CN)6 solution containing 0.05 M
KCl. After stirring for 12 h, the resulting solution was dialyzed by a
dialysis membrane with double-distilled water for 4 days.
[PB/PEI–graphene]n multilayer film was prepared via a layer-
by-layer complexation method. The ITO substrate was cleaned by
ultrasonication in a series of solvents: acetone, 10% KOH in ethanol
and distilled water for 20 min each time. And the layer-by-layer assem-
bly process was performed as following: first, the cleaned ITO substrate
was immersed in a poly(diallyldimethylammonium chloride) (PDDA)
solution (2 mg/mL) for 20 min to form a positively charged surface
and then washed with water for three times. Second, the PDDA modi-
fied substrate was soaked into the PB solution for 20 min and rinsed
with water for three times. Third, the substrate was immersed in
2 mg/mL of PEI–graphene solution for 20 min and also rinsed with
water for three times. Finally, the ITO/PDDA/[PB/PEI–graphene]n multi-
layer film was obtained by repeating the second and third procedures.
As control experiment, the preparation of ITO/PDDA/[PB/PEI]n mul-
tilayer film was similar to that of ITO/PDDA/[PB/PEI–graphene]n film
except using 1 mg/mL PEI aqueous solution instead of PEI–graphene
solution.
3. Results and discussion
3.1. Characterization of PEI-functionalized graphene
Fig. 1 illustrated the reaction mechanism of PEI–graphene compos-
ite, which showed a covalent grafting process of PEI to the graphene
sheets through the nucleophilic ring-opening reaction of epoxy groups
in graphene oxide with the amino groups in PEI.
The formation of PEI-functionalized graphene was confirmed by
UV–vis absorption spectroscopy (Fig. 2A). The UV–vis absorption spec-
tra of graphene oxide (Curve a) and PEI (Curve b) solution showed ab-
sorption peaks at 230 nm and 191 nm, respectively. After the formation
of PEI–graphene, its absorption peaks (Curve c) occurred at 268 nm and
192 nm, which were corresponding to the absorptions of graphene
and PEI components, respectively. Moreover, compared with pristine
graphene oxide, the absorption of graphene content in PEI–graphene
was observed to redshift from 230 nm to 268 nm, which suggested
that the electronic conjugation within graphene sheets has been
574 C. Shan et al. / Thin Solid Films 534 (2013) 572–576
Fig. 2. (A) UV–vis absorption spectra of PEI (a), graphene oxide (b) and PEI–graphene
(c) in water; (inset: snapshots of graphene oxide and PEI–graphene in water.); and
(B) FTIR spectra of graphene oxide (upper), PEI (middle) and PEI–graphene (lower).
restored after reaction. In addition, the changing of solution color before
and after reaction (from brown to dark, shown in the inset of Fig. 2A)
also revealed the reduction of graphene oxide. At the concentration
of 2 mg/mL, the PEI–graphene aqueous solution is very stable and no
distinct precipitate was observed in the dispersion even after several
months' storage. Such excellent dispersibility of this composite makes
it very favorable for further application.
The FTIR spectroscopy also confirmed the formation of PEI–
graphene (Fig. 2B). The spectrum of graphene oxide revealed the pres-
ence of O\H (νO\H at 3235 cm −1), C_O (νC_O at 1730 cm −1), C_C
(νC_C at 1620 cm −1) and C\O (νC\O at 1129 cm −1). After reduction,
the disappearance of characteristic peaks of oxide-containing groups
in PEI–graphene indicated that graphene oxide has been reduced to
graphene. And the spectrum of PEI–graphene exhibited the feature
absorption of PEI. This demonstrated that PEI has been grafted onto
graphene sheet. It is noticeable that the presence of free NH3+ groups
(νN\H at 3294 cm−1 in free NH3+ groups) will play a key role for the fur-
ther functionalization and application of PEI–graphene nanocomposite.
The formation of PEI-functionalized graphene has also been proved
by XPS, which is considered as an effective tool to characterize the
removal of the oxygen groups [16,33]. As shown in Fig. 3A, the XPS
spectrum of graphene oxide mainly showed the C1s and O1s peaks.
Compared to graphene oxide, PEI–graphene exhibited a N1s peak in
XPS spectrum, which indicated the presence of PEI component in the
resulting PEI–graphene composite. The C1s XPS spectrum of PEI–
graphene also showed a significant decrease in signals at ca. 286.8 eV
and 288.4 eV compared to that of graphene oxide. This indicated the
Fig. 3. (A) XPS of graphene oxides (up) and PEI–graphene (down) (peaks of Si were
attributed to silicon wafer as a substrate); and (B) the C1s XPS spectra of graphene
oxide (up) and pristine graphene (down).
loss of C\O and C_O functionalities (Fig. 3B) in graphene oxide. More-
over, there were two additional absorbance peaks that appeared at
285.3 eV and 285.9 eV corresponding to the carbon element in the
C\NH2 and C\N bonds respectively [34]. The above results suggested
that graphene has been functionalized by PEI through free \NH2
groups. In addition, the respective decreasing of molar ratio for O to C
from 0.367 (graphene oxide) to 0.177 (PEI–graphene), and the presence
of nitrogen (16.47 at.%) in the PEI–graphene (data not shown here), also
proved the formation of PEI–graphene.
AFM images revealed the presence of isolated graphitic sheets in
graphene oxide and PEI–graphene composite, respectively (Fig. 4).
The exfoliated graphene oxides with the average lateral dimensions of
several hundreds of nanometers and thickness of 1.1 nm were observed
in Fig. 4A. After the final reduction step, the thickness of graphene–PEI
was observed to distribute from 2.4 to 3.0 nm (Fig. 4B). The increase
of the thickness for PEI–graphene should originate from the coverage
of PEI on both sides of the graphene sheets.
Due to the excellent dispersibility of PEI–graphene and existing of
active amino groups in the molecular backbone, this composite will fea-
sibly become a perfect candidate for constructing nanocomposites with
attractive properties. And these corresponding nanocomposites might
be expected into kinds of potential application, such as energy, catalysis,
biology and medicine, etc. As an example, the [PB/PEI–graphene]n
multilayer film has been assembled by the electrostatic layer-by-layer
assembly method. PB nanoparticles with good electrochromic and
electrocatalytical properties, were synthesized according to the previ-
ous report [27]. The electrochromic principle of PB was performed as
 C. Shan et al. / Thin Solid Films 534 (2013) 572–576 575

Fig. 4. AFM images of graphene oxide (A) and PEI–graphene (B).

following: the valence change of central iron ions in the crystal caused
the change in the energy of charge transfer oscillation, which changed
the color of the crystal as result.
The formation of PB nanoparticles was confirmed by UV–vis spec-
troscopy. The blue PB solution clearly showed a broad absorption peak
at 685 nm, which was attributed to the intervalence charge transfer
band of PB nanoparticles (data not shown here). The growth of LBL
self-assembled [PB/PEI–graphene]n can also be monitored by UV–vis
absorption spectroscopy. As shown in Fig. 5A, it was distinctly ob-
served that the adsorption peaks of multilayer film increased linearly
with the numbers of deposited PB/PEI–graphene bilayer with a corre-
lation coefficient of 0.997. The results indicated a very uniform growth
of the multilayer films. Therefore the amount of PB/PEI–graphene
composite film can be controlled simply by the alternate depositing
number of the bilayer.

3.2. Electrochemical properties of [PB/PEI–graphene]n films

The electrochemical and electrochromic properties of such [PB/PEI–

graphene]n multilayer films have been further investigated. Cyclic
voltammetry (CV) of ITO/[PB/PEI]10 and ITO/[PB/PEI–graphene]10 elec-
trode were performed in potassium hydrogen phthalate (0.1 M, pH=
4) at a scan rate of 10 mV/s (Fig. 5B). The ITO/[PB/PEI–graphene]10 elec-
trode demonstrated two typical redox characteristics of PB. The couple of
redox peaks located near 0.20 V was corresponding to the transformation
between PB and Prussian white, while the other pair of peaks located at
ca. 0.87 V was ascribed to the transformation between PB and Prussian
yellow. The peak-to-peak difference (ΔEp1) of redox peaks near 0.2 V
was about 120 mV, which was broader than those observed for the pris-
tine PB films in previous report [26]. This peak-broadening effect was at-
tributed to the existence of non-equivalent electrochemical sites by
Peerce and Bard [35]. However, the ΔEp1 at [PB/PEI–graphene]10 elec-
trode is narrower than ΔEp2 near 0.2 V at [PB/PEI]10 electrode. It might
be ascribed to the excellent electron transfer ability of graphene, which
can facilitate the electron transfer of PB. The thickness-dependent elec-
trochemical behavior of this [PB/PEI–graphene]n film was further investi-
gated. As shown in Fig. 5C, the redox peak current increased with
increasing number of the assembly bilayer. When n=1, the redox
peaks of PB in this film could hardly be observed, which indicated that
there is very little amount of PB in the first bilayer. The redox peak
of PB increased obviously with increasing number of bilayer when
n≥2. The linear increases of the reduced current (at ca. 0.2 V) to the
layer number (inset in Fig. 5C) indicated that similar amount of PB was
absorbed during each assembly. It was well consistent with the
above-described UV–vis absorption spectra (Fig. 5A).
Since PB has good electrocatalytic ability towards H2O2, the electro-
catalytic behavior of [PB/PEI–graphene]10 film towards H2O2 has also
been investigated. Fig. 6A showed CV graphs of [PB/PEI–graphene]10
and [PB/PEI]10 film modified electrode in the presence of 5 mM H2O2
in potassium hydrogen phthalate (0.1 M, pH = 4). Compared to [PB/
Fig. 5. (A) UV–vis absorption spectra of the deposited [PB/PEI–graphene]n multilayers
with different layers. Inset: a plot of absorbance vs. layer numbers. (B) Cyclic
voltammograms of [PB/PEI]10 (solid) and [PB/PEI–graphene]10 (dashed) multilayer
films on ITO electrode in potassium hydrogen phthalate (0.1 M, pH = 4) at a scan rate
of 10 mV/s. (C) Cyclic voltammograms of [PB/PEI–graphene]n multilayer films with
different numbers of bilayer (n = 1, 2, 4, 6, 10, 14, and 16) in potassium hydrogen
phthalate (0.1 M, pH = 4) at a scan rate of 10 mV/s. Inset: plot of reduced peak current
at ca. 0.2 V to bilayer number.
PEI]10, the [PB/PEI–graphene]10 modified electrode showed a more pos-
itive reductive potential, which could be attributed to the excellent elec-
tron transfer ability of graphene and thus facilitated the electrocatalysis
of H2O2 in the reaction system. In addition, the [PB/PEI–graphene]10
modified electrode had preferable transparency and demonstrated
excellent optical switching between Prussian white (low absorbance,
−0.2 V) and Prussian blue (high absorbance, 0.6 V), which was shown
in Fig. 6B. The results indicated that the [PB/PEI–graphene]10 electrode
showed good electrochromic property.
4. Conclusion
PEI functionalized graphene with excellent dispersion has been
synthesized. The graphene sheets played an important role as connec-
tor to assemble the active amino groups of PEI and provided a suitable
environment for further functionalization. As an example, a [PB/PEI–
graphene]n multilayer film was constructed using a layer-by-layer com-
plexation method. The resulting [PB/PEI–graphene]n multilayer film
showed excellent electrochromic property and good electrocatalysis
towards H2O2, which are promising for electrosensing applications.
576 C. Shan et al. / Thin Solid Films 534 (2013) 572–576
Fig. 6. (A) Cyclic voltammograms of [PB/PEI–graphene]10 multilayer (a) in N2-saturated
potassium hydrogen phthalate (0.1 M, pH=4), [PB/PEI–graphene]10 multilayer (b) and
[PB/PEI]10 multilayer (c) in the presence of 5 mM H2O2 in N2-saturated potassium hydro-
gen phthalate. Scan rate: 10 mV/s. (B) Spectroscopic monitoring of potential switching for
[PB/PEI–graphene]16 multilayer film immersed in a quiescent cuvette cell. Switching oc-
curred between −0.2 V (Prussian white, low absorbance) and 0.6 V (Prussian blue, high
absorbance).
Acknowledgment
The authors are most grateful to the NSFC, China (Nos. 21175130,
21205112 and 21105096), and the Department of Science and Tech-
nology of Jilin Province (Nos. 201215091 and 20120308) for their
financial support.
References
[1] M.J. Allen, V.C. Tung, R.B. Kaner, Chem. Rev. 110 (2010) 132.
[2] Y.Y. Shao, J. Wang, H. Wu, J. Liu, I.A. Aksay, Y.H. Lin, Electroanalysis 22 (2010) 1027.
[3] W. Choi, I. Lahiri, R. Seelaboyina, Y.S. Kang, Crit. Rev. Solid State Mater. Sci. 35
(2010) 52.
[4] K.P. Loh, Q.L. Bao, P.K. Ang, J.X. Yang, J. Mater. Chem. 20 (2010) 2277.
[5] A.K. Geim, K.S. Novoselov, Nat. Mater. 6 (2007) 183.
[6] X. Huang, Z.Y. Zeng, Z.X. Fan, J.Q. Liu, H. Zhang, Adv. Mater. 24 (2012) 5979.
[7] T. Cassagneau, J.H. Fendler, Adv. Mater. 10 (1998) 877.
[8] S. Gilje, S. Han, M. Wang, K.L. Wang, R.B. Kaner, Nano Lett. 7 (2007) 3394.
[9] F. Schedin, A.K. Geim, S.V. Morozov, E.W. Hill, P. Blake, M.I. Katsnelson, K.S.
Novoselov, Nat. Mater. 6 (2007) 652.
[10] J.S. Bunch, A.M. van der Zande, S.S. Verbridge, I.W. Frank, D.M. Tanenbaum, J.M.
Parpia, H.G. Craighead, P.L. McEuen, Science 315 (2007) 490.
[11] D. Li, M.B. Muller, S. Gilje, R.B. Kaner, G.G. Wallace, Nat. Nanotechnol. 3 (2008) 101.
[12] S. Niyogi, E. Bekyarova, M.E. Itkis, J.L. McWilliams, M.A. Hamon, R.C. Haddon,
J. Am. Chem. Soc. 128 (2006) 7720.
[13] Y. Si, E.T. Samulski, Nano Lett. 8 (2008) 1679.
[14] S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A. Stach,
R.D. Piner, S.T. Nguyen, R.S. Ruoff, Nature 442 (2006) 282.
[15] Y.X. Xu, H. Bai, G.W. Lu, C. Li, G.Q. Shi, J. Am. Chem. Soc. 130 (2008) 5856.
[16] S. Stankovich, R.D. Piner, X.Q. Chen, N.Q. Wu, S.T. Nguyen, R.S. Ruoff, J. Mater.
Chem. 16 (2006) 155.
[17] G. Decher, Science 277 (1997) 1232.
[18] P.T. Hammond, Adv. Mater. 16 (2004) 1271.
[19] Y. Ma, J. Sun, J. Shen, Chem. Mater. 19 (2007) 5058.
[20] X. Zhang, H. Chen, H.Y. Zhang, Chem. Commun. (2007) 1395.
[21] H. Paloniemi, M. Lukkarinen, T. Aaritalo, S. Areva, J. Leiro, M. Heinonen, K.
Haapakka, J. Lukkari, Langmuir 22 (2006) 74.
[22] B. Wang, R.N. Vyas, S. Shaik, Langmuir 23 (2007) 11120.
[23] B.Z. Wang, X.Y. Du, M.Q. Wang, W.L. Gong, J. Anzai, Electroanalysis 20 (2008) 1028.
[24] L. Wang, S.J. Guo, X.O. Hu, S. Dong, J. Colloids Surf., A 317 (2008) 394.
[25] R.E. Wilde, S.N. Ghosh, B.J. Marshall, Inorg. Chem. 9 (1970) 2512.
[26] D. Ellis, M. Eckhoff, V.D. Neff, J. Phys. Chem. 85 (1981) 1225.
[27] D.M. DeLongchamp, P.T. Hammond, Adv. Funct. Mater. 14 (2004) 224.
[28] R.J. Mortimer, C.P. Warren, J. Electroanal. Chem. 460 (1999) 263.
[29] J. Li, J.D. Qiu, J.J. Xu, H.Y. Chen, X.H. Xia, Adv. Funct. Mater. 17 (2007) 1574.
[30] D. Zhang, K. Zhang, Y.L. Yao, X.H. Xia, H.Y. Chen, Langmuir 20 (2004) 7303.
[31] D. Moscone, D. D'Ottavi, D. Compagnone, G. Palleschi, A. Amine, Anal. Chem. 73
(2001) 2529.
[32] W. Hummers, R. Offeman, J. Am. Chem. Soc. 80 (1958) 1339.
[33] M.J. McAllister, J.L. Li, D.H. Adamson, H.C. Schniepp, A.A. Abdala, J. Liu, M.
Herrera-Alonso, D.L. Milius, R. Car, R.K. Prud'homme, I.A. Aksay, Chem. Mater.
19 (2007) 4396.
[34] D.S. Everhart, C.N. Reilley, Anal. Chem. 53 (1981) 665.
[35] P.J. Peerce, A.J. Bard, J. Electroanal. Chem. 114 (1980) 89.