158 Journal of the Chinese Chemical Society, 2009, 56, 158-163

Electropolymerization of Methylene Blue on Carbon Ionic Liquid Electrode

and Its Electrocatalysis to 3,4-Dihydroxybenzoic Acid

Rui-Jun Zhao ( ), Qiang Jiang ( ),

Wei Sun* ( ) and Kui Jiao ( )
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology,
Qingdao 266042, P. R. China

In this paper an ionic liquid modified carbon paste electrode (CILE) was prepared and methylene blue
(MB) was electropolymerized on the CILE by using the cyclic voltammetric technique in the potential
range from -1.0 V to 0.8 V (vs. SCE). A stable polymer film was obtained and exhibited a pair of redox
peaks. The morphology and characteristics of poly(methylene blue) (PMB) film was studied by the tech-
niques such as scanning electron microscopy and electrochemical impedance spectroscopy. This PMB
modified CILE (PMB/CILE) showed excellent electrocatalytic response to 3,4-dihydroxybenzoic acid
with the increase of the electrochemical responses. The oxidation peak current had a linear relationship
with 3,4-dihydroxybenzoic acid concentration in the range of 5.0 ´ 10-4 ~ 3.0 ´ 10-2 mol L-1 and the detec-
tion limit was 1.72 ´ 10-4 mol L-1 (3s).

Keywords: Methylene blue; 3,4-Dihydroxybenzoic acid; Ionic liquid modified carbon paste elec-
trode; Electropolymerization; Electrocatalysis.

INTRODUCTION advantages of ILs such as negligible vapor pressure, wide

Electropolymerization is a powerful tool in the devel-
opment of modified electrodes with the advantage of selec-
tive modification of multi-layer electrodes that couldn’t be
obtained by the usual method; it also can change the prop-
erties of polymers. The polymers got from electropoly-
merization show some unique properties that are peculiar
to the corresponding monomer. Many conducting poly-
mers, such as polyaniline, 1 polypyrrole, 2 and polythio-
phene, 3 have received a great deal of interest since they
have high conductivity, high redox reversibility and high
stability. Different electroactive dyes can also be electro-
polymerized on the electrode surface and the thus polymers
formed exhibit excellent applications in electroanalysis
and bioelectrochemistry. For example, Hianik4 et al. elec-
tropolymerized phenothiazine dyes onto a glassy carbon
electrode and used it as a DNA biosensor for a DNA aptamer
specific to human a-thrombin. Yang5 et al. prepared poly
(safranine T) films on a graphite electrode and investigated
the electrocatalytic effect on dopamine. Zhou6 et al. elec-
tropolymerized nile blue on a glassy carbon electrode for
the amperometric determination of hemoglobin.
Carbon ionic liquid electrode (CILE), which is made
of graphite powder and different kinds of ionic liquids
(ILs), has aroused great interest in recent years. Due to the
potential windows, good ionic conductivity, extraction and
catalytic ability, CILE has shown many specific character-
istics including simple preparation procedure, wide poten-
tial windows, high rates of electron transfer and good anti-
fouling ability. ILs can act not only as binders to connect
graphite powder, but also as inherent catalysts present on
the electrode surface. The direct electrochemistry of elec-
troactive molecules such as proteins and ssDNA has been
achieved on CILE.7-10 Maliki11 et al. also electrodeposited
Pd nanoparticles on CILE, which showed good electrocat-
alytic ability for dopamine and ascorbic acid.
In this paper, methylene blue (MB) was electropoly-
merized on the surface of CILE. MB is a kind of electro-
active cationic dye and has been extensively used as an in-
dicator and mediator in the field of bioelectrochemis-
try.12-14 A sensor for hemoglobin based on poly(methylene
blue) (PMB) electrodeposited on a glassy carbon electrode
has also been reported. 15 To our knowledge, no reports
have described the electropolymerization of MB on the sur-
face of CILE. The conditions for electropolymerization
were optimized and the PMB modified CILE was charac-
terized by cyclic voltammetry (CV), electrochemical im-
pedance spectroscopy (EIS) and scanning electron micros-
copy (SEM). The electrocatalytic behaviors for 3,4-dihy-
Poly(methylene blue) on CILE and Its Electrocatalysis
droxybenzoic acid (3,4-DHBA) were further investigated
on PMB/CILE. 3,4-DHBA, a kind of phenolic compound
which is present principally in fruits, legumes, nuts and
vegetables, has functions such as antioxidition, lowering
blood pressure and anti-cancer effects. 3,4-DHBA is also
used as an intermediate chemical in the preparation of dyes
and medicines. Several analytical methods have been used
for the determination of 3,4-DHBA, such as high perfor-
mance liquid chromatography with UV detection or fluo-
rimetric detection,16,17 flow injection analysis,18 capillary
electrophoresis, 19 GC-MS, 20 chemiluminescence 21 and
electrochemistry.22,23 Up to now, methods based on poly-
mer modified carbon ionic liquid electrode have not been
reported for the study of 3,4-DHBA. The experimental
results indicated that the fabricated PMB/CILE showed
good electrocatalytic ability for the oxidation of 3,4-
DHBA.
EXPERIMENTAL SECTION
Apparatus and reagents
A LK2005 electrochemical workstation (Tianjin
Lanlike Instrument, China) was used for all the electro-
chemical experiments with a traditional three-electrode
system composed of a CILE or PMB/CILE as working
electrode, a platinum wire as auxiliary electrode and a satu-
rated calomel electrode (SCE) as reference electrode.
Scanning electron microscopy (SEM) was obtained on a
JSM-6700F scanning electron microscope (Japan Electron
Company).
Methylene blue (MB, Shanghai Reagent Company),
1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]
BF 4, Hangzhou Chemer Chemical Limited Company),
3,4-dihydroxybenzoic acid (3,4-DHBA, Shanghai Kefeng
Chemical Reagent Limited Company) and graphite powder
(average particle size 30 mm, Shanghai Colloid Chemical
Plant) were used as received. 0.1 mol L-1 phosphate buffer
solution (PBS) was used as the supporting electrolyte. All
the other chemicals were of analytical reagent grade, and
double-distilled water was used in all experiments.
Preparation of polymer modified electrode
The CILE was prepared as follows: 1.6 g of graphite
powder, 100 mL of [EMIM]BF4 and 400 mL of liquid paraf-
fin were mixed in a mortar by hand until a homogeneous
paste was obtained. The prepared carbon paste was tightly
packed into a glass tube and a copper wire was introduced
into the other end for the electrical contact. Prior to use, the
surface of the well-prepared electrode was smoothed on a
J. Chin. Chem. Soc., Vol. 56, No. 1, 2009 159
weighing paper. For MB polymerization, the CILE was im-
mersed into 0.1 mol L-1 pH 7.0 PBS containing 1.0 mmol
L-1 MB and 0.1 mol L-1 KCl. The cyclic voltammetry was
performed between the potential range from -1.0 V and 0.8
V for 50 cycles with a scan rate of 50 mV s-1. An electrode
with electropolymerized layers was rinsed with PBS, dis-
tilled water and dried at room temperature.
RESULTS AND DISCUSSION
Electropolymerization of methylene blue on CILE
The solution for the electrolysis consisted of 1.0
mmol L-1 MB, 0.1 mol L-1 pH 7.0 PBS and 0.1 mol L-1 KCl.
Fig. 1 shows the cyclic voltammograms of polymer film
growth in electrolytic solution. From the first cycle it can
be seen that a pair of well-defined redox peaks was ob-
tained with the anodic peak and cathodic peak appearing at
-0.28 V and -0.20 V, respectively, which was attributed to
the oxidation and reduction of MB. With the increased
number of potential cycles, a new pair of redox peaks was
obtained with the anodic peak and cathodic peak at 0.0 V
and -0.45 V, respectively, and the currents of the new peaks
increased. The result indicated that the polymer film was
formed on the CILE and its thickness increased with the
number of potential cycles. According to reference 24,
electropolymerization of MB is due to the oxidative con-
densation of aromatic phenothiazine fragments and partial
demethylation of dimethylamino side groups. In this paper
CILE was used as the basal electrode for the polymeriza-
Fig. 1. Cyclic voltammograms of MB electropolyme-
rization in a mixture solution of 1.0 mmol L-1
MB and 0.1 mol L-1 KCl in 0.1 mol L-1 PBS with
a scan rate of 50 mV s-1.
160 J. Chin. Chem. Soc., Vol. 56, No. 1, 2009 Zhao et al.

tion. CILE had been demonstrated to have advantages such
as wide potential windows, high rates of electron transfer
and good anti-fouling ability. A layer of ILs also formed on
the surface of CILE, which had inherent catalytic ability.
As indicated in reference 25, the presence of IL in the car-
bon paste electrode exhibited not only the high adherence
of graphite particles, but also the p-electron interaction of
the layers of the ionic liquids with the p-electron system of
graphite. So the presence of IL as modifier in the carbon
paste electrode provided an inherent catalytic interface for
MB polymerization to take place.
The optimal conditions for the growth of PMB were
investigated. Electropolymerization of MB requires a high
potential for the irreversible oxidation of the monomer. If
the potential is too high, over-oxidation of the polymer will
take place. So the potential range was optimized and the re-
dox peak currents of PMB reached the maximum in the po-
tential range from -1.0 V to 0.8 V. The redox peak currents
of PMB increased with the increase in number of the poten-
tial cycles. But when the number of potential cycles was up
to 50, there were no obvious increases of the redox peak
currents. From the experiments it was found that the redox
peak currents of PMB decreased with the increase of scan
rate in the range from 30 mV s-1 to 200 mV s-1. After con-
sidering the factor of time in experiments, the number of
potential cycles and scan rate were selected as 50 and 50
mV s-1, respectively.
Surface morphologies of modified electrodes
Scanning electron microscopy (SEM) was used to
characterize and compare the morphology of different
kinds of modified electrodes. Fig. 3 compared the morpho-
logical features of the CILE and PMB/CILE. The SEM im-
age of CILE was uniform and no separated carbon layers
could be observed (Fig. 3a). Since [EMIM]BF4 was a hy-
drophilic ionic liquid with higher viscosity, it could fill into
the layer of graphite powder and bridge the isolated carbon
flask, so a flat surface could be obtained. Fig. 3b shows a
SEM image of PMB/CILE with porous, loose, multi-layer
composite films topography. The significant differences in
the surface structure of the two electrodes exhibited that the
methylene blue was successfully electropolymerized on
the surface of CILE.
Electrochemical impedance spectroscopy of modified
electrode
The interfacial characteristic of PMB/CILE was stud-
ied by electrochemical impedance spectroscopy (EIS) in a

Cyclic voltammograms of modified electrodes in

buffer solution
The cyclic voltammograms of modified electrodes in
pH 7.0 PBS were further investigated with the results
shown in Fig. 2. Curves a and b were that of CPE and CILE
in PBS; no electrochemical response appeared with a little Fig. 2. Cyclic voltammograms of (a) CPE, (b) CILE,
increase of the background current, which may be due to (c) PMB/CPE and (d) PMB/CILE in pH 7.0
that the addition of IL affected the capacitance of the elec- PBS with the scan rate of 50 mV s-1.
trode. Curve d was that of PMB/CILE in PBS with a pair of
redox peaks appeared, which was due to the oxidation and
reduction of PMB on the electrode surface. The electro-
polymerization of MB on the traditional carbon paste elec-
trode was also carried out and the cyclic voltammogram of
PMB/CPE in PBS is shown as curve c. It can be seen that a
pair of rather broad redox peaks appeared with a small elec-
trochemical response. The experimental results testified to
the superiority of CILE to CPE, indicating the addition of
IL facilitated the electron transfer between PMB and elec- Fig. 3. Surface morphologies of CILE (a) and PMB/
trode. CILE (b).
Poly(methylene blue) on CILE and Its Electrocatalysis
0.1 mol L-1 KCl solution containing the redox couples of
1.0 mmol L-1 K4Fe(CN)6 and 1.0 mmol L-1 K3Fe(CN)6 at
the applied potential of 0.0 V (vs. SCE). The applied per-
turbation amplitude was 5 mV and the frequencies swept
from 105 to 0.05 Hz. In EIS the semicircle diameter is equal
to the electron transfer resistance (Ret), which is related to
the electron transfer kinetics of the redox probe at the sur-
face of the electrode. Fig. 4 records the electrochemical
impedance spectra of CILE (curve a) and PMB/CILE
(curve b). It could be seen that on CILE a flat semicircle
was produced at a high frequency with the R et value of
3000 W, which showed that the electrode/solution surface
was difficult for the electron transfer. While on PMB/CILE
a straight line was produced (curve b), indicating that the
electron transfer process was controlled by a mass trans-
port finite-diffusion at low frequency. The results showed
that the PMB film exhibited good conductivity and in-
creased the ability of the electron transfer at the electrode/
solution surface.
Electrochemical behaviors of 3,4-DHBA on PMB/
CILE
Fig. 5 shows cyclic voltammograms of 1.0 mmol L-1
3,4-DHBA in 0.1 mol L-1 PBS (pH 7.0) on CILE and PMB/
CILE, respectively. A pair of quasi-reversible redox peaks
Fig. 4. Electrochemical impedance spectroscopy of
CILE (a) and PMB/CILE (b) in a 0.1 mol L -1
KCl solution containing the redox couple of 1.0
mmol L -1 K 4 Fe(CN) 6 and 1.0 mmol L -1
K3Fe(CN)6 with the applied perturbation ampli-
tude as 5 mV and the frequencies swept from
105 to 0.05 Hz.
J. Chin. Chem. Soc., Vol. 56, No. 1, 2009 161
at the surface of CILE was produced with the anodic peak
potential and the cathodic peak potential appearing at 0.537
V and 0.0 V. The peak-to-peak separation (DEp) was 537
mV (vs. SCE). While on the surface of PMB/CILE, a pair
of well-defined quasi-reversible redox peaks appeared
with the increased currents and the decrease of peak-to-
peak separation. The anodic peak potential and the cath-
odic peak potential appeared at 0.261 V and 0.184 V, re-
spectively, with the DEp value of 77 mV. It is wellknown
that the increase of peak current and the decrease of over-
potential are the characteristics of electrocatalytic reac-
tions. The experimental results testified to the superiority
of PMB/CILE over CILE, indicating that PMB film on the
surface of the electrode increased the ability of electron
transfer at the interface of electrode/solution and catalyzed
the redox reaction of 3,4-DHBA. The interaction mecha-
nism may be that the anodic groups -N(CH 3) 2+ of PMB
bind the cathodic groups -COO - of 3,4-DHBA with the
electrostatic interaction and then increase the speed of elec-
tron transfer rate.
Fig. 6 shows cyclic voltammograms of 3,4-DHBA on
the PMB/CILE with different scan rates (u) in the 0.1 mol
L-1 pH 7.0 PBS. It can be seen that the redox peak currents
increased with the increase of scan rate in the range from 10
mV s-1 to 100 mV s-1. The relationship of redox peak cur-
rents (Ip) of 3,4-DHBA and scan rate were plotted and
good linear relationships were got with the linear regres-
sion equations as Ipa (mA) = 7.247 + 0.460 u (V s-1) (n = 10,
Fig. 5. Cyclic voltammograms of 3,4-DHBA on CILE
(a) and PMB/CILE (b) with the scan rate of 50
mV s-1 in pH 7.0 PBS.
162 J. Chin. Chem. Soc., Vol. 56, No. 1, 2009 Zhao et al.

g = 0.997) and Ipc(mA) = 10.051 + 0.329 u (V s-1) (n = 10, g 2.3RT

Epa = E 0' + log u
= 0.993), respectively, which illustrated a surface-con- (1 - a ) nF
trolled redox process. The peak-to-peak separation also in-
log k s = a log(1 - a ) + (1 - a ) log a
creased with the scan rate, indicating the electrode process
turned to be more irreversible. RT a (1 - a ) nFDEp
- log
The electrochemical parameters of 3,4-DHBA on the nFu 2.3RT
PMB/CILE were estimated with the following Laviron’s
where a is the charge transfer coefficient, n is the number
equations:26
of electrons transferred and ks is the electron transfer rate
2.3RT constant. The relationships of redox peak potentials with
Epc = E 0' - log u
anF lnu were Epa(V) = 0.380 + 0.028 lnu (n = 8, g = 0.995) and
Epc(V) = 0.129 - 0.021 lnu (n = 8, g = 0.990). According to
the above equations, the values of a, n and ks were calcu-
lated as 0.57, 2.1 and 0.423 s-1, respectively. The ks value
indicated a quasi-reversible redox process of 3,4-DHBA at
the surface of PMB/CILE.
Fig. 7(A) shows the cyclic voltammgrams of PMB/
CILE at different concentrations of 3,4-DHBA. With the
increase of 3,4-DHBA concentration, the redox peak cur-
rents increased gradually. A linear relationship could be es-
tablished between the oxidation peak current and the con-
centration of 3,4-DHBA in the range of 5.0 ´ 10-4 to 3.0 ´
10-2 mol L-1 (Fig. 7B). The linear regression equation was
calculated as Ipa(mA) = 25.33 + 33.55C (mmol L-1) (n = 13,
g = 0.998) with a detection limit of 1.72 ´ 10-4 mol L-1 (3s).

CONCLUSION
Fig. 6. Cyclic voltammograms of 3,4-DHBA on PMB/ Electrochemical polymerization of methylene blue
CILE with different scan rates (from 1 to 8: 10, on the surface of the carbon ionic liquid electrode was per-
30, 50, 60, 70, 80, 90,100 mV s-1). formed and the properties of the resulting films were inves-

Fig. 7. (A) Cyclic voltammograms of different concentrations of 3,4-DHBA on PMB/CILE in pH 7.0 PBS (from 1 to 7: 0.5,
0.8, 0.9, 1.0, 1.2, 1.5, 1.8 mmol L-1); (B) The calibration curve between oxidative peak currents with 3,4-DHBA con-
centrations.
Poly(methylene blue) on CILE and Its Electrocatalysis
tigated. The experimental results of SEM and EIS exhib-
ited that methylene blue was polymerized on the surface of
the electrode. The polymer film on the electrode showed
good electrocatalytic ability for 3,4-dihydroxybenzoic
acid. The linear relationship of the oxidation peak current
and the concentration was obtained with the concentration
range from 5.0 ´ 10-4 to 3.0 ´ 10-2 mol L-1.
ACKNOWLEDGEMENTS
We are grateful for the financial support of the Na-
tional Natural Science Foundation of China (Nos.
20405008, 20635020) and the Doctoral Foundation of
QUST (0022125).
Received August 4, 2008.
REFERENCES
1. Maeikienè, R.; Malinauskas, A. Electrochim. Acta 1999, 41,
1587.
2. Genies, E.-M.; Bidan, G.; Diaz, A.-F. J. Electroanal. Chem.
1999, 149, 101.
3. Tanaka, K.; Shichiri, T.; Yamabe, T. Synth. Met. 1986, 16,
207.
4. Evtugyn, G.-A.; Porfireva, A.-V.; Hianik, T.; Cheburova,
M.-S.; Budnikov, H.-C. Electroanalysis 2008, 20, 1300.
5. Yang, Q.-X.; Zhang, M.-F.; Li, G.-B.; Zhang, Y. Chinese J.
Anal. Lab. 2007, 26, 72.
6. Zhou, D.-M.; Chen, H.-Y. Electroanalysis 1997, 9, 399.
7. Sun, W.; Wang, D.-D.; Gao, R.-F.; Jiao, K. Electrochem.
Commun. 2007, 9, 1159.
8. Sun, W.; Gao, R.-F.; Jiao, K. J. Phys. Chem. B 2007, 111,
4560.
J. Chin. Chem. Soc., Vol. 56, No. 1, 2009 163
9. Sun, W.; Li, X.-Q.; Jiao, K. J. Chin. Chem. Soc. 2008, 55(5),
1074.
10. Sun, W.; Li, Y.-Z.; Yang, M.-X.; Liu, S.-F.; Jiao, K. Electro-
chem. Commun. 2008, 10, 298.
11. Safavi, A.; Maleki, N.; Tajabadi, F.; Farjami, E. Electro-
chem. Commun. 2007, 9, 1963.
12. Yang, J.; Yang, T.; Feng, Y.-Y.; Jiao, K. Anal. Biochem.
2007, 365, 24.
13. Karyakin, A.-A.; Karyakina, E.-E.; Schuhmann, W.; Schmidt,
H.-L. Electroanalysis 1994, 6, 821.
14. Tonlé, I.-K.; Ngameni, E.; Tcheumi, H.-L.; Tchiéda, V.;
Carteret, C.; Walcarius, A. Talanta 2008, 74, 489.
15. Brett, C.-M.; Inzelt, G.; Kertesz, V. Anal. Chim. Acta 1999,
385, 119.
16. Garcia-Parrilla, M.-C.; Camacho, M.-L.; Heredia, F.-J.;
Troncoso, A.-M. Food Chem. 1994, 50, 313.
17. Lores, M.; Garicia, C.-M.; Cela, R. J. Chromatogr. A 1994,
683, 31.
18. Haghighi, B.; Gorton, L.; Ruzgas, T.; Jönsson, L.-J. Anal.
Chim. Acta 2003, 487, 3.
19. Deng, Y.; Wellons, A.; Bolla, D.; Krzyaniak, M.; Wylie, H.
J. Chromatogr. A 2003, 1013, 191.
20. Franca, A.; Nicola, D.; Panajotis, K.; Luciana, D.-G. J.
Agric. Food Chem. 1995, 43, 1802.
21. Xie, C.-G.; Li, H.-F. Chin. J. Metall. Anal. 2004, 24, 17.
22. Long, H.; Li, Y.-H. Chin. J. Anal. Lab. 1999, 18, 19.
23. Moghaddam, A.-B.; Kobarfard, F.; Davarani, S.-S.;
Nematollahi, D.; Shamsipur, M.; Fakhari, A.-R. J. Electro-
anal. Chem. 2006, 586, 161.
24. Karyakin, A.-A.; Karyakina, E.-E.; Schmidt, H.-L. Electro-
analysis 1999, 11, 149.
25. Maleki, N.; Safavi, A.; Tajabadi, F. Anal. Chem. 2006, 78,
3820.
26. Laviron, E. J. Electroanal. Chem. 1979, 101, 19.