Electrochimica Acta 75 (2012) 71–79

Contents lists available at SciVerse ScienceDirect

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

Electrochemically functional graphene nanostructure and layer-by-layer

nanocomposite incorporating adsorption of electroactive methylene blue
Dongdong Zhang a,c , Lei Fu b,c,∗∗ , Lei Liao c , Boya Dai c , Rui Zou a , Chengxiao Zhang a,∗
a
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, PR China
b
College of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, PR China
c
Center for Nanochemistry (CNC), Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, PR China

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

Article history: This paper describes preparation and characterization of electrochemically functional graphene nano-
Received 15 February 2012 structure incorporating adsorption of electroactive methylene blue (MB) dye onto graphene and
Received in revised form 17 April 2012 nanocomposite assembled using layer-by-layer of graphene with MB on solid substrates. UV–visible spec-
Accepted 19 April 2012
troscopy, FT-IR spectroscopy, Raman spectroscopy and electrochemistry for systematical characterization
Available online 27 April 2012
of the MB adsorption onto graphene reveal the formation of a MB/graphene adsorptive nanostructure
through ␲–␲ stacking and hydrophobic interactions. Compared with MB adsorbed onto a graphene
Keywords:
oxide (GO) modified electrode and MB adsorbed onto a GC electrode, MB adsorbed onto a graphene
Graphene
Nanocomposite
modified electrode exhibits a good stability and distinct electrochemical properties. Additionally, MB
Adsorption adsorbed onto graphene can improve the water-disperse ability of graphene. Furthermore, scanning
Layer-by-layer electron microscopy, UV–vis-NIR spectroscopy and electrochemistry demonstrated that directly layer-
Electrochemistry by-layer assembling of MB and graphene was an excellent route to prepare a functional nanocomposite
on different solid substrates including silica plate, quartz slide and glassy carbon electrode. The excellent
electroactivity and the high stability of electrochemically functional graphene nanostructure and the lay-
ered nanocomposite are envisaged to make them very useful electrochemically functional nanomaterials
for practical development of electronic devices such as biosensors and photovoltaic cells.
© 2012 Published by Elsevier Ltd.

1. Introduction increasing interest is being focused on exploring the functional

Graphene has received considerable attention since it was
discovered by Geim and co-workers in 2004 [1] due to its
unique physical and chemical properties and powerful poten-
tial applications in synthesizing nanocomposite [2–5], fabricating
microelectrical devices [6–9] and lithium ion batteries [10]. Nowa-
days, in the investigation of graphene, one increasing interest is
being focused on developing novel methods of graphene prepara-
tion such as mechanical [1,11] and liquid-phase [12,13] exfoliation
of graphite crystals, epitaxial growth on silicon carbide [14] or
ruthenium [15], chemical vapor deposition of hydrocarbons over
metal catalysts [16,17], and chemical routes reduction of graphene
oxide [18,19]. Among these, the latter route by chemical treatment
of natural graphite is most promising for fabricating graphene in
large quantities for industrial applications, as graphite is naturally
abundant and chemical treatment is convenient [2]. And another
∗ Corresponding author. Tel.: +86 29 85303825; fax: +86 29 85307567.
∗∗ Corresponding author at: College of Chemistry and Molecular Science, Wuhan
University, Wuhan 430072, PR China. Tel: +86 27 68762119; fax: +86 27 68762119.
E-mail addresses: leifu@whu.edu.cn (L. Fu), cxzhang@snnu.edu.cn (C. Zhang).
nanostructures of graphene with novel properties through a cova-
lent or noncovalent interaction e.g., with biomolecules [20–22],
metal nanoparticles [4,5] or polymeric modification [23,24], and
expanding graphene applications. To this end, many strategies for
functional graphene nanostructures have been proposed to gener-
ate a large variety of new nanostructures with excellent functions
which are very attractive for practical applications. For example,
the noncovalent adsorption of biomolecules, such as DNA, enzymes
and proteins, onto the graphene created a lot of novel graphene-
based nanostructures consisting of biorecognition units, offering
an efficient route to bioelectronic nanodevices, e.g., biosensors and
bioelectronics [21,22].
The development of the preparation methods for functional
graphene becomes one of the important issues, particularly in the
increasing availability of synthetic graphene approaches, because
the direct dispersion of hydrophobic graphene in water is prone to
forming agglomerates irreversibly. It is known that graphene is rel-
atively difficult to be dispersed in water or organic solvents owing
to its poor solubility and strong aggregation in solutions. Much
effort has been devoted to disperse graphene sheets in water by uti-
lizing the electrostatic repulsion of negatively charged carboxylic
or sulfonic groups on the graphene surface [25,26] and to create

0013-4686/$ – see front matter © 2012 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.electacta.2012.04.074
72 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79
electrochemically functional graphene nanostructure by utilizing
noncovalent interaction between graphene and aromatic com-
pounds. It is reported that the ␲–␲ stacking interaction between
flat graphite and aromatic compounds, e.g., methylene blue (MB),
essentially results in a stable adsorption of such kind of compounds
on the graphitic surface [27,28]. Mao and co-workers [28] reported
that the adsorption of MB onto the single-wall carbon nanotubes
(CNTs) essentially makes the formed nanostructure disperse into
water. Compared with the CNTs consisting of seamlessly rolled-up
graphene sheets of carbon, graphene (the flat graphite) possesses a
long-range ␲-conjugation structure with a highly flat hydrophobic
surface [29]. These unique properties of the graphene essentially
allow graphene to facilely interact with some organic compounds,
such as (polynuclear) aromatic compounds, in particular, through
␲–␲ electronic and hydrophobic interactions and thus to form
new nanostructures [28,30–32]. Additionally, MB possessing good
electrochemical properties has been widely used for basic electro-
chemical studies and applications, i.e., electrocatalysis, solar cells,
and biosensors [33–35]. Recently, Wu and co-workers reported
the graphene thin films grafted with MB used as electrocatalytic
electrode for the oxidation of ␤-nicotinamide adenine dinucleo-
tide [36]. And Xia and co-workers studied the kinetic process of the
adsorption of MB onto graphene and indicated that the graphene
is a good adsorbent for the adsorption of MB [37]. More recently,
Du and co-workers reported an electrochemical immunosensor for
the detection of protsate specific antigen using a nanocomposite
film of graphene sheets-MB-chitosan as electrode material [38].
They introduced chitosan as dispersant to solve the leakage prob-
lem of MB/graphene composite on the modified electrode surface.
And Wang and co-workers reported a label-free electrochemi-
cal aptasensor for peptide detection by physically adsorbing the
aptamer onto the conductive film on ITO electrode. The conductive
film was layer-by-layer assembled on the basis of the electro-
static interaction between MB/positive charged polyelectrolyte
[poly(diallyldimethylammonium chloride)] and negative charged
polyelectrolyte [poly(sodium 4-styrenesuifonate)]/graphene [39].
However, the systematical study up on adsorptive property,
the electrochemical property and water-disperse ability of
MB/graphene nanostructure have not yet been reported. Further-
more, the preparation and characterization of electrochemically
functional graphene nanocomposite assembled directly using
layer-by-layer of graphene with MB also has not been reported.
With the foregoing insights of electrochemically functional
graphene nanocomposite in mind, in this work, we here proposed,
a new method for preparing electrochemically functional graphene
nanocomposite through layer-by-layer directly assembling of MB
and graphene on different solid substrate. In this paper, the MB/RGO
nanostructure was systematically characterized by UV–visible, FT-
IR spectroscopy, Raman spectroscopy and electrochemistry. The
layered (MB/RGO)n nanocomposite on the solid substrates were
characterized by scanning electron microscopy, UV–vis–NIR spec-
troscopy and electrochemistry. And the properties of prepared
graphene nanocomposite, including adsorption, stability, water-
disperse ability and electrochemistry, are presented.
2. Experimental
2.1. Materials and apparatus
MB (structure shown in Scheme 1) was purchased from Bei-
jing Chemical Company (Beijing, China). Other chemicals were of
analytical grade or higher and used without further purification.
Aqueous solutions were prepared with doubly distilled water.
Electrochemical measurements were carried out with a
computer-controlled CHI760A electrochemical analyzer (CHI,
Scheme 1. Methylene blue adsorption onto graphene surface and its chemical struc-
ture.
Austin, USA) in a conventional and two-compartment cell. Bare
and modified glassy carbon (GC) electrodes were used as a work-
ing electrode and a platinum spiral wire as a counter electrode. All
potentials were referred to a KCl-saturated calomel electrode (SCE).
A 0.10 M phosphate buffer (pH 7.0) was used as a supporting elec-
trolyte. The electrolyte was deoxygenated by purging pure nitrogen
into the solution for about 30 min and nitrogen gas was kept flowing
over the solution during the electrochemical measurements.
Ultraviolet–visible (UV–vis) spectra and
ultraviolet–visible–near-infrared (UV–vis–NIR) spectra were
recorded with a Lambda 950 UV–visible spectrophotometer
(Perkin Elmer, America). Fourier transform infrared (FT-IR)
measurements were performed with a System 2000 infrared spec-
trometer (Perkin Elmer, America). Raman spectra were obtained on
a HR800 Raman spectrometer (Horiba, France). Scanning electron
microscopic (SEM) images were obtained using a S4800 cold field
emission scanning microscopes (Hitachi, Japan).
2.2. Preparation and characterization of MB/RGO nanostructure
Graphene oxide (GO) was prepared from graphite powders
following the method described by Hummers [40]. Then the chem-
ical reduction with hydrazine led to blank aqueous suspension of
reduced graphene oxide (RGO) [18]. The obtained GO was dispersed
in ammonia solution (28 wt%) to yield a yellow–brown suspen-
sion (0.5 mg mL−1 ). MB (20 ␮M) aqueous solution and hydrazine
hydrate (35 wt%) were added into the yellow–brown suspension,
and the resultant mixture was ultrasonicated at 95 ◦ C for 1 h until it
became clear with no observed particulate matter and then filtered.
The precipitation was washed with a copious volume of deion-
ized water and dried by continuous N2 flow for about 10 h to form
MB/RGO nanostructure [32]. This nanostructure was dispersed in
water (0.1 mg mL−1 ) as MB/RGO dispersion for subsequent experi-
ments.
The prepared MB/RGO nanostructure was dispersed in dis-
tilled water for UV–vis spectroscopic measurements, pressed into
a KBr pellet for FT-IR measurements, dispersed onto a silica wafer
for Raman spectroscopic measurements, and confined onto a
GC electrode for electrochemical measurements, respectively. For
electrochemical measurements, the GC electrodes were first pol-
ished with emery paper (#2000), 0.1 ␮m and 0.05 ␮m alumina
slurry on chamois leather, then cleaned under bath sonication for
5 min, and finally thoroughly rinsed with distilled water. The low
density and high density RGO modified electrodes were prepared
by coating 10 ␮L of 0.01 mg mL−1 and 0.1 mg mL−1 RGO aqueous
solution onto GC electrode, respectively (denoted as L-RGO/GC and
H-RGO/GC, hereafter). The modified MB/RGO/GC electrodes were
also prepared by immersing the L-RGO/GC and H-RGO/GC modified
electrodes into 0.1 M phosphate buffer (pH 7.0) containing 2.0 ␮M
 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79 73

(low concentration) and 20 ␮M (high concentration) MB for 90 min,

respectively (denoted as L-MB/RGO/GC and H-MB/RGO/GC). The
as-prepared MB/RGO/GC electrodes were thoroughly rinsed with
water to remove the nonadsorbed MB. For comparison, GO/GC
electrodes were prepared with the same procedure as that for the
RGO/GC electrode. MB was adsorbed onto bare GC and GO/GC elec-
trodes by immersing the electrodes into 20 ␮M MB for 90 min and
the resulting electrodes (denoted as MB/GC and MB/GO/GC) were
rinsed with water. Cyclic voltammetric measurements were per-
formed with the all MB/RGO/GC, MB/GO/GC and MB/GC modified
electrodes.

2.3. Preparation and characterization of (MB/RGO)n

nanocomposite

(MB/RGO)n nanocomposite was layer-by-layer assembled onto

a silica plate for SEM characterization. The silica plates were
Fig. 1. UV spectra of MB (dashed curve), RGO (dotted curve) and MB/RGO adsorptive
treated by immersing the plates into piranha solution (vol% 3:1 nanostructure (solid curve) in water.
concentrated H2 SO4 and 30 wt% H2 O2 ) for 10 min at 50 ◦ C (Cau-
tion: piranha solution reacts violently with organics). After being
rinsed with water and dried with N2 , the treated plates were then
immersed in 0.1 mg mL−1 RGO dispersion solution for 5 min to
form a RGO layer onto the surface of the treated silica plates.
The RGO-coated plates were immersed into 20 ␮M MB solution
for 5 min. Layer-by-layer stepwise assembling of the MB/RGO
bilayer onto the pretreated (no any positively or negatively charged
base layer) silica plates was conducted by alternately repeat-
ing these two procedures. During each assembling interval, the
plates were rinsed with water to remove the excess materials
and dried with N2 bubbling. The formed multilayer nanocomp-
site was referred to as (MB/RGO)n . A Quartz slide was used as
the substrate to layer-by-layer assembled of the nanostructure for
UV–vis–NIR characterization. The treatment of the quartz slide and
the layer-by-layer assembling of the (MB/RGO)n nanocomposite
were conducted with the same procedures as those for the silica
plates. For electrochemical characterization, a GC electrode was
used for layer-by-layer assembling of the (MB/RGO)n multilayer Fig. 2. FT-IR spectra of MB (dashed curve), RGO (dotted curve), and MB/RGO adsorp-
nanocomposite with the same procedures as those for the silica tive nanostructure (solid curve).
plates.
246 nm disappear, and the sharp adsorption peaks at 663 nm and
3. Results and discussion 292 nm are changed to two wide adsorption peaks, respectively,
and the peak at 663 nm was shifted to 650 nm, after its adsorp-
3.1. Characterization of MB/RGO nanostructure tion onto the RGO. These suggest that the adsorption MB molecule
onto the graphene is MB monomer and there is a lack of MB dimer
The preparation and characterization of MB/RGO nanostructure and aggregation of MB molecules. The results are in accord with
is a basis of (MB/RGO)n nanocomposite, therefore, the system- that reported for adsorption of MB onto graphene [36]. However,
atically study about adsorptive property of MB onto RGO and
water-disperse ability of MB/RGO nanostructure were first per-
formed to insight of (MB/RGO)n nanocomposite.

3.1.1. Spectroscopic characterization of MB/RGO

The formation of a MB/RGO nanostructure was studied with
UV–vis spectroscopy. As shown in Fig. 1, the UV–vis spectrum of
the RGO dispersed in water shows an absorption peak at 263 nm
(dotted curve). This result is in accord with that reported [32]. The
spectrum of MB in aqueous solution displays a strong absorbance
at 663 nm and 292 nm (dashed curve), which are characteristic
absorbance peaks of the MB monomer in aqueous solution. The
shoulders at 617 nm and 246 nm are ascribed to the absorbance
of the MB dimer in aqueous solution [28,41]. The spectrum of
the MB/RGO (solid curve) displays two wide absorption peaks in
the range from 220 nm to 310 nm and from 580 nm to 700 nm.
Moreover, a close inspection of the spectrum of MB and MB/RGO
adsorptive nanostructure reveals that there is a change in the spec-
trum of MB after its adsorption onto the RGO. For example, two Fig. 3. Raman spectra of MB (dashed curve), RGO (dotted curve), and MB/RGO
absorption peaks of MB dimer in aqueous solution at 617 and adsorptive nanostructure (solid curve).
74 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79

Fig. 4. Cyclic voltammograms obtained at the L-RGO/GC and H-RGO/GC modified electrodes in 0.1 M phosphate buffer containing 2.0 ␮M (Panel A) and 20 ␮M (Panel C) MB,
respectively. The electrode was immersed into MB solution for 2, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70 and 80 min (from inner to outer). Scan rate: 50 mV s−1 . And Cyclic
voltammograms at the L-RGO/GC (Panel B solid line), L-MB/RGO/GC (Panel B dotted line), H-RGO/GC (Panel D solid line) and H-MB/RGO/GC (Panel D dotted line) modified
electrodes in 0.1 M phosphate buffer in the absence of MB, respectively. The MB/RGO/GC electrode was prepared by immersing the RGO/GC electrode into MB solution for
90 min. Scan rate: 100 mV s−1 .

they are different from that reported for adsorption of MB onto
graphite [41] or carbon nanotubes [28]. Furthermore, they are
maybe attributed to the fact that the interaction between MB and
graphene is stronger than that between MB and graphite as well as
between MB and carbon nanotubes.
Fig. 2 shows the FT-IR spectra of MB, RGO and MB/RGO. The
FT-IR spectrum of RGO (dotted curve) presents that C O stretch-
ing vibrations at 1060 cm−1 and C OH stretching vibrations at
1220 cm−1 , which are caused by remaining carboxyl groups even
after hydrazine reduction [18]. The FT-IR spectrum of MB (dashed
curve) exhibits its ring stretch at 1603 cm−1 , the symmetric stretch
of C N at 1398 cm−1 , and symmetric deformation of CH3 at
1354 cm−1 [28]. Similar to the conclusion drawn from the UV–vis
spectra (Fig. 1), the adsorption of MB onto the RGO was also
substantial, based on the FT-IR spectra, since the characteristic
spectrum of MB/RGO (solid curve) was changed clearly comparison
of the spectrum of RGO.
Fig. 3 shows the Raman spectra of MB (dashed curve), RGO (dot-
ted curve) and MB/RGO (solid curve). The Raman spectrum for RGO
sheet exhibits the regular two wide peaks, corresponding to the D-
band line (∼1340 cm−1 ) and the G-band line (∼1590 cm−1 ) (dotted
curve). The most intense peaks in the MB spectra are the ring stretch
(v CC) at 1618 cm−l , the symmetric and asymmetric CN stretches
(vsym CN and vasym CN) at 1390 and 1430 cm−l , respectively [42,43]
(dashed curve). After the adsorption of MB onto the RGO, the Raman
spectra of MB/RGO displays similar to that of MB, which appears a
wide peak at ∼1340 cm−1 and a wide peak at ∼1600 cm−1 merges
with the ring stretch (v CC) peak of MB at 1618 cm−l (solid curve).
Additionally, from the Raman spectra in Fig. 3, it can be seen that
the characteristic spectrum of MB (dashed curve) is in accord with
the characteristic spectrum of the adsorptive adduct (solid curve).
This further demonstrates that MB/RGO nanostructure is formed.
The spectroscopic studies above demonstrated that a functional
MB/RGO nanostructure was formed. Furthermore, the observed
changes in the UV–vis and FTIR spectra that are generally consis-
tent with electron donor–acceptor interaction suggest that a ␲–␲
stacking interaction is involved in the structure-associated inter-
actions between MB and RGO. These can be further confirmed by
electrochemistry, as described below.
3.1.2. Electrochemical characterization of MB/RGO on GC
electrode
Fig. 4 displays cyclic voltammograms (CVs) of L-RGO/GC mod-
ified electrode immersed into 0.1 M PBS containing 2.0 ␮M MB
 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79 75

Fig. 5. Cyclic voltammograms of MB/RGO/GC (A), MB/GO/GC (B), and MB/GC (C) electrodes in 0.1 M phosphate buffer. Dotted and dashed curves represent the voltammograms
of first and 100th cycles, and solid curves represent the voltammograms of the electrodes without MB adsorption. Scan rate, 100 mV s−1 . (D) The ratio of the anodic current
recorded in successive cycles to the first cycle at the MB/RGO/GC (), MB/GO/GC (), and MB/GC (•) electrodes in phosphate buffer. Scan rate, 100 mV s−1 .

solution (Panel A) and H-RGO/GC modified electrode immersed into
0.1 M PBS containing 20 ␮M MB solution (Panel C) with increas-
ing time. As Fig. 4A shows, one pair of redox peaks is observed
at −0.26 V of oxidation peak potential and at −0.30 V of reduc-
tion peak potential. It is attributed to the electrochemical redox
process of leuco MB adsorbed on the surface of the L-RGO/GC mod-
ified electrode [44]. This is supported by the CV (Panel B) in which
such a redox wave is still clearly observed when the L-MB/RGO/GC
modified electrode is re-cycled in the pure phosphate buffer in
the absence of MB. The potential separation (Ep ) (Panel A) for
all time is ∼40 mV although both oxidation peak potential (Epa )
and reduction peak potential (Epc ) positively shifts ∼10 mV with
prolonging the time for immersing the electrode into low concen-
tration of MB solution. This small Ep indicates that the adsorbed
intermediate appears to be more easily reduced than the MB [44].
It is also seen that the oxidation peak current at −0.26 V and the
reduction peak current at −0.30 V obviously increase with pro-
longing the time for immersing the electrode into MB solution
until being saturated state (∼60 min). This suggests the contin-
uous adsorption and growth of MB onto the graphene on GC
electrode arise. These results indicate that MB is adsorbed on L-
MB/RGO and electrochemically functional graphene nanostructure
is obtained.
From Fig. 4C at H-RGO/GC electrode immersed in a high con-
centration of MB solution, it is seen that one pair of redox peaks is
observed at Epa = −0.26 V and at Epc = −0.32 V when the immersing
time is less than 3 min, while both Epa and Epc positively shift and
the potential separation change wider from 62 mV to 133 mV with
prolonging the time for immersing the electrode into the solution
with a high concentration of MB. Two pairs of redox waves appears,
respectively, at Epa = −0.12 V and Epc = −0.24 V, at Epa = −0.17 V and
Epc = −0.30 V when the immersing time is longer than 60 min. In
these two pairs of redox waves, the former wave at Epa = −0.12 V
and Epc = −0.24 V is ascribed to the redox process of solution-phase
MB at the graphene, while the latter wave at Epa = −0.17 V and
Epc = −0.30 V is attributed to the redox process of MB itself adsorbed
onto the graphene. This is supported by the CV (Panel D) in which
the former wave at −0.12 V was mostly disappeared but the latter
wave at −0.17 V was still clearly observed when the H-MB/RGO/GC
modified electrode is re-cycled in the pure phosphate buffer in the
absence of MB. Additionally, it can be seen that the oxidation peak
currents at H-RGO/GC electrode immersed into the solution with a
high concentration of MB (Fig. 4C) are about 15-folds higher than
that at L-RGO/GC electrode immersed into the solution with a low
concentration of MB (Fig. 4A) after the same immersing time. This
is attributed to the fact that a high equilibrium adsorption capacity
76 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79

Fig. 6. Cyclic voltammograms and the plots of peak currents and potentials of anodic and cathodic versus scan rate or scan rate square root obtained at the L-MB/RGO/GC
(A and B) and H-MB/RGO/GC (C and D) modified electrodes in 0.1 M phosphate buffer. Scan rate (from inner to outer), 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, and
500 mV s−1 . Line a and b are the plots of peak currents, and line c and d are the plots of peak potentials versus scan rate or logarithmic of scan rate.

occurs at H-RGO/GC electrode in a high concentration of MB [37].
All these results indicate that the electroactive MB can be adsorbed
onto the graphene, forming an electrochemically functional nano-
structure. Both the electrodes surface property of low density and
high density MB/RGO/GC modified electrodes were further studied
later.
The interactions between graphene and MB and stability of
MB/RGO nanostructure were investigated by comparing the elec-
trochemical behaviors of MB adsorbed onto RGO, GO and GC,
respectively. Fig. 5 shows the typical CVs (1st and 100th cycle)
obtained at the MB/RGO/GC (A), MB/GO/GC (B), and MB/GC (C) elec-
trodes in 0.1 M PBS. Compared with the CVs (1st and 100th cycle)
in Fig. 5B and C, the CV in 1st cycle scan at the MB/RGO/GC in Fig. 5A
coincides with that in 100th cycle scan and the oxidation peak cur-
rent (64.4 ␮A) in Fig. 5A is higher than that (49.2 ␮A) in Fig. 5B and
much higher than that (0.9 ␮A) in Fig. 5C. This indicates that the
adsorption density of MB onto RGO is higher than that onto GO
and much higher than that onto GC. Furthermore, from Fig. 5D, it is
clearly seen that the ratios (in /i1 ) obtained at the MB/RGO/GC keeps
a constant while the ratios (in /i1 ) at the MB/GO/GC and the MB/GC
almost lineally decrease with a increasing of cycle scan numbers.
This indicates that the stability of MB/RGO nanocomposite is higher
than that of MB/GO and much higher than that of MB/GC. The inter-
acting force of MB-RGO is stronger than that of MB-GO, attributed to
the fact that there are a lot of hydrophilic groups, i.e., OH, COOH
and epoxides in the surface of GO, led to decreasing hydrophobic
interaction. The interacting force of MB-RGO is much stronger than
that of MB–GC, attributed to the fact that there are no sp2 carbons in
the surface of GC, led to decreasing ␲–␲ stacking interaction. This
demonstrated again that the ␲–␲ interaction is a major interaction
and the hydrophobic interaction is a minor interaction between MB
and the RGO. The proposed patter for MB adsorption onto graphene
is showed in Scheme 1. Such a high stability of electrochemically
functional nanostructure is believed to be very useful for practi-
cal applications, e.g., electrocatalysis, biosensors, and photovoltaic
cells.
Fig. 6A and C depict the cyclic voltammograms of L-MB/RGO/GC
modified electrode (A) and H-MB/RGO/GC modified electrode (C)
in phosphate buffer in the range of the scan rates from 10 to
500 mV s−1 . The data in Fig. 6B and D were abstracted from Fig. 6A
and C. From line a and b in Fig. 6B, it can be seen that the oxi-
dation peak currents linearly increase with the scan rates while
the reduction peak currents linearly decrease with the scan rates.
And the peak potentials are nearly unchanged with increasing the
scan rates. This indicates that the electrochemical process at the
L-MB/RGO/GC electrode is a surface-confined process with a fast
electron transfer [45] and is in accord with Langmuir adsorption.
From Fig. 6D (line a and b), it can be seen that both the absolute val-
ues of the oxidation and reduction peak currents are linear increase
with increasing the scan rates. And from Fig. 6D (line c and d), it can
be seen that both the absolute values of the oxidation and reduction
peak potentials are increase with logarithmic of the scan rates, and
 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79
Fig. 7. Photographs of RGO dispersion in aqueous solution stayed for 1 month after
ultrasonication. (a) 0.1 mg mL−1 RGO; (b) 0.5 mg mL−1 RGO; (c) 0.5 mg mL−1 MB/RGO
and (d) 1.0 mg mL−1 MB/RGO.
keeps a nearly constant in low scan rates and linearly increase in
high scan rates. This indicates that the electrochemical process at
the H-MB/RGO/GC electrode is a surface-confined process with rel-
atively slow electron transfer [46,47]. All these results suggest that
the different electrochemical behaviors of MB/RGO nanostructures
can be easily controlled by changing the concentrations of graphene
and MB.
3.1.3. Disperse ability of MB/RGO in water
Fig. 7 shows the photographs of the dispersion RGO and pre-
pared MB/RGO nanocomposite into water stayed for 1 month after
ultrasonication. Compared with photograph (a), aggregation in
photograph (b) is clearly observed even if a low concentration of
MB-free RGO. Importantly, the appreciable aggregation in photo-
graph (c and d) is not observed even if in a high concentration of
MB/RGO. This indicates that MB adsorbed onto RGO can enhance
Fig. 8. SEM images of (MB/RGO)n multilayer nanocomposite assembled onto silica wafer. (a) n = 1, (b) n = 3, (c) n = 5, and (d) n = 5 in a larger magnified.
77
the dispersion amount and stability of RGO in water at least ten
folds. This is attributed to the fact that MB adsorbed onto RGO has
positively charge groups and thus has a fine hydrophilicity, which
increases the repellence in separated graphene sheets. This sug-
gests that adsorption of MB onto RGO is a promising route to an
electrochemically functional graphene nanostructure with a good
disperse ability.
3.2. Characterization of (MB/RGO)n nanocomposite
(MB/RGO)n nanocomposite prepared by the protocol described
in Section 2.3 were characterized by SEM, UV–vis–NIR spec-
troscopy and electrochemistry. Fig. 8 displays typical SEM images
of (MB/RGO)n multilayer films assembled by layer-by-layer on a sil-
ica wafer. RGO was first immersed-coated on the silica wafer and
then MB was adsorbed on RGO/Si, to form (MB/RGO)n (n = 1) first
layer. From Fig. 8(a), (b) and (c), it can be seen that the nanocom-
posite are isolated and the ratio of dark tones, which are the phase
of the MB/RGO nanocomposite, obviously increase with increasing
assembled layers from 1 to 5. And from Figure 8(d), the size of the
nanocomposite is about micron grade.
In order to confirm the formation of the (MB/RGO)n multilayer,
the UV–vis–NIR absorption spectra of (MB/RGO)n (n = 1∼5) multi-
layer nanostructure assembled onto quartz slide were recorded, as
shown in Fig. 9. The UV–vis–NIR spectra of (MB/RGO)n multilayer
nanostructure assembled onto quartz slide are difference from the
spectrum of the MB/RGO dispersed in water (see Fig. 1), but they
are similar to that in aqueous MB solution, which displays a strong
absorption peak at 666 ± 2 nm and 290 ± 1 nm, and the shoulders at
625 ± 5 nm and 247 ± 2 nm. Furthermore, in Fig. 9, the absorbance
in the range from 220 nm to 320 nm is stronger than that in the
range from 520 nm to 720 nm, and the absorption in the all scanned
wavelength increases. All these are maybe attributed to the absorp-
tion peak of RGO at 263 nm and with strong absorption in the all
scanned wavelength (Fig. 1 dotted curve). Most importantly, all val-
ues of the absorbance are found to clearly increase with the growth
of the films and the amplitude is linear with the layer number (inset
78 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79
Fig. 9. UV–vis–NIR spectra of (MB/RGO)n multilayer nanocomposite assembled
onto quartz slide. Inset, absorbance at 247 ± 2 nm, 290 ± 1 nm, 625 ± 52 nm and
666 ± 2 nm versus the number of the adsorption cycles.
in Fig. 9). This indicates that the loading of the MB/RGO in each layer
almost is same and further confirms the layer-by-layer assembling
of the MB/RGO nanostructure into a functional nanocomposite with
the stepwise assembling process.
Furthermore, the (MB/RGO)n multilayer nanocomposite assem-
bled onto a GC electrode was investigated by electrochemistry.
Fig. 10 displays cyclic voltammograms of (MB/RGO)n /GC electrodes
(from n = 1 to n = 5) in 0.1 M phosphate buffer. As shown in Fig. 10, a
pair of redox peaks appears at the formal potential of −0.25 V. The
peak currents of these redox peaks clearly increase with increas-
ing the layer number of (MB/RGO)n assembled onto a GC electrode
and are linear with the layer number (inset, line a, line b). These
are reflective of the loading of MB and RGO in each layer onto GC
electrodes and demonstrate that layer-by-layer assembling of MB
and graphene is an excellent route to prepare an electrochemically
functional nanocomposite on a solid substrate.
Comparison of cyclic voltammograms obtained at the L-RGO/GC
electrodes in 0.1 M phosphate buffer containing 2.0 ␮M MB
(Fig. 4A), the layered (MB/RGO)n nanocomposite possesses almost
Fig. 10. Cyclic voltammograms of the (MB/RGO)n multilayer nanocomposite assem-
bled onto GC electrode in 0.1 M phosphate buffer. Inset plots of anodic Faradaic peak
current at −0.20 V (a) and current measured at 0 V (b) versus the number of the
adsorption cycles. Scan rate, 100 mV s−1 .
Fig. 11. Cyclic voltammograms of the first (Dashed line) and the 120th (Solid line)
cycle at (MB/RGO)5 /GC modified electrode in 0.1 M phosphate buffer. Scan rate,
100 mV s−1 .
the same electrochemical properties as MB/RGO nanostructure,
e.g., the same formal potential and the small peak potential sep-
aration. This indicates that as-prepared nanocomposite retain
their properties. Fig. 11 displays CVs (1st and 120th cycle) at
a (MB/RGO)5 /GC modified electrode in 0.1 M phosphate buffer.
The CV of 120th potential scanning is nearly the same as of 1st
potential scanning. This is indicates that as-assembled (MB/RGO)5
nanocomposite has a satisfactory electrochemical stability and
the electrochemical stability is even greater than that of MB/RGO
monolayer nanostructure.
4. Conclusion
We here demonstrated that MB, a polynuclear aromatic elec-
troactive dye, can be stably adsorbed onto the graphene to prepare
an electrochemically functional MB/RGO nanostructure and multi-
layer (MB/RGO)n nanocomposite. Firstly, UV–visible, Raman and
IR spectroscopic and voltammetric results substantially support
evident that the interaction between MB and the RGO is domi-
nated by the ␲–␲ stacking interaction rather than the hydrophobic
interaction. The formed MB/RGO adsorptive nanostructure exhibits
good stability and electrochemical properties that are distinct from
those of MB adsorbed onto GO and GC electrodes. Additionally, the
adsorption of MB onto the RGO is found to improve the disperse
ability of RGO nanostructure into water and to facilitate layer-by-
layer of the prepared electrochemically functional nanostructure
into a nanocomposite on the solid substrates. This work provides
a convenient preparation method for electrochemically func-
tional MB/graphene nanostructure and layer-by-layer assembled
nanocomposite and valuable information of the MB/RGO nanocom-
posite properties, including adsorption, stability, water-disperse
ability and electrochemistry. It is expected that the prepared
functional MB/graphene nanostructure and layered (MB/RGO)n
nanocomposite will be very useful electrochemically functional
nanomaterials for practical development of electronic devices such
as biosensors and photovoltaic cells.
Acknowledgment
Financial supports from the National Science Foundations of
China (no.20975065, no.21027007).
 D. Zhang et al. / Electrochimica Acta 75 (2012) 71–79
References
[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Science 306 (2004) 666.
[2] X. Du, Z.Z. Yu, A. Dasari, J. Ma, M. Mo, Y. Meng, Y.W. Mai, Chemistry of Materials
20 (2008) 2066.
[3] D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu, C. Wang, L.V. Saraf, J. Zhang,
I.A. Aksay, J. Liu, ACS Nano 3 (2009) 907.
[4] K. Jasuja, V. Berry, ACS Nano 3 (2009) 2358.
[5] G. Goncalves, P.A.A.P. Marques, C.M. Granadeiro, H.I.S. Nogueira, M.K. Singh, J.
Gracio, Chemistry of Materials 21 (2009) 4796.
[6] K.S. Kim, Y. Zhao, H. Jang, S.Y. Lee, J.M. Kim, K.S. Kim, J.H. Ahn, P. Kim, J.Y. Choi,
B.H. Hong, Nature 457 (2009) 706.
[7] S. Pang, H.N. Tsao, X. Feng, K. Müllen, Advanced Materials 21 (2009) 3488.
[8] C. Di, D. Wei, G. Yu, Y. Liu, Y. Guo, D. Zhu, Advanced Materials 20 (2008) 3289.
[9] J.H. Chen, M. Ishigami, C. Jang, D.R. Hines, M.S. Fuhrer, E.D. Williams, Advanced
Materials 19 (2007) 3623.
[10] E. Yoo, J. Kim, E. Hosono, H. Zhou, T. Kudo, I. Honma, Nano Letters 8 (2008)
2277.
[11] K.S. Novoselov, Proceedings of the National Academy of Sciences of the United
States of America 102 (2005) 10451.
[12] C. Valles, C. Drummond, H. Saadaoui, C.A. Furtado, M. He, O. Roubeau, L. Ortolani,
M. Monthioux, A. Penicaud, Journal of the American Chemical Society 130
(2008) 15802.
[13] A.B. Bourlinos, V. Georgakilas, R. Zboril, T.A. Steriotis, A.K. Stubos, Small 5 (2009)
1841.
[14] C. Berger, Z. Song, X. Li, X. Wu, N. Brown, C. Naud, D. Mayou, T. Li, J. Hass, A.N.
Marchenkov, E.H. Conrad, P.N. First, W.A. Heer, Science 312 (2006) 1191.
[15] P.W. Sutter, J.I. Flege, E.A. Sutter, Nature Materials 7 (2008) 406.
[16] A. Reina, X. Jia, J. Ho, D. Nezich, H. Son, V. Bulovic, M.S. Dresselhaus, J. Kong,
Nano Letters 9 (2009) 30.
[17] X. Wang, H. You, F. Liu, M. Li, L. Wan, S. Li, Q. Li, Y. Xu, R. Tian, Z. Yu, D. Xiang, J.
Cheng, Chemical Vapor Deposition 15 (2009) 53.
[18] D. Li, M.B. Müller, S. Gilje, R.B. Kaner, G.G. Wallace, Nature Nanotechnology 3
(2008) 101.
[19] X. Fan, W. Peng, Y. Li, X. Li, S. Wang, G. Zhang, F. Zhang, Advanced Materials 20
(2008) 4490.
[20] T.H. Han, W.J. Lee, D.H. Lee, J.E. Kim, E.Y. Choi, S.O. Kim, Advanced Materials 22
(2010) 2060.
[21] C.H. Lu, H.H. Yang, C.L. Zhu, X. Chen, G.N. Chen, Angewandte Chemie Interna-
tional Edition 48 (2009) 4785.
79
[22] M. Zhou, Y. Zhai, S. Dong, Analytical Chemistry 81 (2009) 5603.
[23] H.J. Salavagione, M.n.A. Gomez, G. Martinez, Macromolecules 42 (2009)
6331.
[24] X. Zhou, T. Wu, B. Hu, G. Yang, B. Han, Chemical Communications 46 (2010)
3663.
[25] Y. Si, E.T. Samulski, Nano Letters 8 (2008) 1679.
[26] S. Stankovich, R.D. Piner, X. Chen, N. Wu, S.T. Nguyen, R.S. Ruoff, Journal of
Materials Chemistry 16 (2006) 155.
[27] H. Jaegfeldt, T. Kuwana, G. Johansson, Journal of the American Chemical Society
105 (1983) 1805.
[28] Y. Yan, M. Zhang, K. Gong, L. Su, Z. Guo, L. Mao, Chemistry of Materials 17 (2005)
3457.
[29] J.A. Matthew, C.T. Vincent, B.K. Richard, Chemical Reviews 110 (2010)
132.
[30] J. Zhang, J.K. Lee, Y. Wu, R.W. Murray, Nano Letters 3 (2003) 403.
[31] E.V. Basiuk, E.V. Rybak-Akimova, V.A. Basiuk, D. Acosta-Najarro, J.M. Saniger,
Nano Letters 2 (2002) 1249.
[32] H. Liu, J. Gao, M. Xue, N. Zhu, M. Zhang, T. Cao, Langmuir 25 (2009) 12006.
[33] S.B. Khoo, F. Chen, Analytical Chemistry 74 (2002) 5734.
[34] J. Huang, Z. Huang, Y. Yang, H. Zhu, T. Lian, Journal of the American Chemical
Society 132 (2010) 4858.
[35] D. Zhang, Y. Peng, H. Qi, Q. Gao, C. Zhang, Biosensors and Bioelectronics 25
(2010) 1088.
[36] D. Wang, Y. Li, P. Hasin, Y. Wu, Nano Research 4 (2011) 124.
[37] T. Liu, Y. Li, Q. Du, J. Sun, Y. Jiao, G. Yang, Z. Wang, Y. Xia, W. Zhang,
K. Wang, H. Zhu, D. Wu, Colloids and Surfaces B: Biointerfaces 90 (2012)
197.
[38] K. Mao, D. Wu, Y. Li, H. Ma, Z. Ni, H. Yu, C. Luo, Q. Wei, B. Du, Analytical Bio-
chemistry 422 (2012) 22.
[39] H. Qin, J. Liu, C. Chen, J.H. Wang, E. Wang, Analytica Chimica Acta 712 (2012)
127.
[40] W.S. Hummers, R.E. Offeman, Journal of the American Chemical Society 80
(1958) 1339.
[41] T. Sagara, K. Niki, Langmuir 9 (1993) 831.
[42] R.R. Naujok, R.V. Duevel, R.M. Corn, Langmuir 9 (1993) 1771.
[43] G.N. Xiao, S.Q. Man, Chemical Physics Letters 447 (2007) 305.
[44] R.H. Wopschall, I. Shain, Analytical Chemistry 39 (1967) 1527.
[45] A.J. Bard, L.R. Faulkner, Electrochemical methods, in: Fundamentals and Appli-
cations, 2nd ed., John Wiley & Sons, Inc, 2001.
[46] R.H. Wopschall, I. Shain, Analytical Chemistry 39 (1967) 1514.
[47] A.P. Brown, F.C. Anson, Analytical Chemistry 49 (1977) 1589.