Journal of Industrial and Engineering Chemistry 21 (2015) 787–791

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Journal of Industrial and Engineering Chemistry

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Electrochemical decolorization of Methylene blue at Pt electrode in KCl

solution for environmental remediation
M.A. Hasnat a,*, Jamil A. Safwan a, M. Shariful Islam a, Zidnia Rahman a,
Mohammad Razaul Karim a, Talha J. Pirzada b, Ahmed Jalal Samed a,
Mohammed M. Rahman c,*
a
Department of Chemistry, Graduate School of Physical Sciences, Shahjalal University of Science and Technology, Sylhet 3114, Bangladesh
b
Department of Mechanical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK
c
Chemistry department & Center of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203,
Jeddah 21589, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Article history: Electrochemical decolorization of Methylene blue (MB) molecules was studied at Pt electrode in
Received 1 December 2013 presence of KNO3 and KCl as the supporting electrolytes under acidic condition. The KNO3 electrolyte
Received in revised form 7 April 2014 displayed MB decolorization effect, where MB molecules exhibited two redox peaks at 0.48 V and
Accepted 9 April 2014
0.34 V, respectively, in cyclic voltammogram (CV). The features of redox couples indicated the
Available online 19 April 2014
dimerization of MB molecules. In this simple preparation technique, a less amount of sample loading was
required, and the method displayed high efficiency toward decolorization of MB dye. This report
Keywords:
indicates the possibility for improving the quality of wastewater discharged from textile and other
Methylene blue
Pt electrode
industries.
Bleaching ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Cyclic voltammetry reserved.
Chronoamperometry

Introduction coagulation and biological treatment followed by activated carbon

adsorption. However, these processes are not sustainable as the
Methylene blue is a heterocyclic aromatic compound with the high volume of hazardous sludge is still difficult to dispose. In
molecular formula C16H18N3SCl. It has many uses in a range of addition, dye stuff are slowly decolourized by conventional
diverse fields, such as biology and chemistry. Usually these dye biological wastewater treatment and may be toxic to the
molecules are not easily degraded [1]. The N-riched aromatic microorganisms incurred in the treatment plants. Hence, much
compounds are often toxic and may upshot the formation of attention has been paid to explore alternative oxidation methods
aromatic amines, which are harmful for human organs belonging such as ozonation, photocatalytic oxidation, and electrochemical
to the carcinogenic and/or mutagenic agents. Besides, the practical oxidation [1–11]. The potential application of electrochemical
usage of reactive dyes is growing up hastily and instigating various technologies for wastewater treatment is benefiting from advan-
problems in the ecosystem as they are nonbiodegradable. Since tages such as versatility, environmental compatibility and cost
wastewater from textile industries has harmful environmental and effectiveness. As a result, electrochemistry offers promising
ecological impact, therefore the effluents are required to be treated approaches for the anticipation of pollution problems in the
before being discharged into the environment. The conventional processes industry and the feasibility of electrochemical conver-
processes for textile wastewater treatment include chemical sion/destruction of organic substrates in wastewater has attracted
much attention since pioneering studies to the present days [12].
In the recent years, electrochemical oxidation has been extensively
used as conceivable alternatives for the degradation of toxic
* Corresponding authors at: King Abdulaziz University, Chemistry Department & organic compounds to simpler molecules and even to CO2 and H2O
Center of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, molecules [8–15].
Hai Al-Jamea, Jeddah 21589 80203, Saudi Arabia.
Tel.: +966 59 642 1830/+88 0821 715752; fax: +966 026 95 2292/+88 0821 715752.
Methylene blue (Fig. 1), a cationic dye belonging to thiazine
E-mail addresses: [email protected], [email protected] (M.A. Hasnat), family, is widely used as photo-sensitizers and redox mediators in
[email protected], [email protected] (M.M. Rahman). electrocatalytic systems [14]. Many attempts have been taken to

http://dx.doi.org/10.1016/j.jiec.2014.04.013
1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
[(Fig._1)TD$IG]
788 [(Fig._2)TD$IG]
M.A. Hasnat et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 787–791

200

100

0
Fig. 1. Molecular structure of Methylene blue in aqueous solution.

Current / μA
-100
investigate the electrochemical behavior of MB molecules in the
aqueous medium using various electrodes such as mercury [15– -200
20], platinum [21], gold [22] and graphite [23]. It is well known 50 mVs-1
200 mVs-1
that organic compound degradation in aqueous media through 500 mVs
-1

electrochemical oxidation processes depends on several influential -300

factors such as, pH, temperature, electrolyte concentration and

electric current density. The objective of this study is to examine -400
the effect of applied potential on bleaching/decolorization of MB+ -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
at an ordinary polycrystalline Pt electrode in the presence of KCl E / V vs. Ag/AgCl (sat. KCl)
supporting electrolyte.
Fig. 2. Cyclic voltammograms of MB+ (2  104 M) at scan rates of 50, 200 and
Experimental 500 mV s1 recorded in 0.5 M KCl at pH of 2.

Methylene blue (MB+) (BDH, England), KCl and KNO3 (BDH,

England), were used without further purification in our experi- experimental condition. For this dye, the anodic peak current
ments. All of the solutions were prepared using Millipore Milli-Q was lower than that of the cathodic peak current at all scan
water (resistivity > 18.2 MV1) and total organics was lower than rates. It was also noticed that the cathodic to anodic peak
3 ppb. An electrochemical workstation (CH Instrument series) was current ratio was increased considerably with the increase of
used to carry out all the electrochemical measurements. All the scan rate. This kind of observation is an undisputed indication of
experiments were conducted at room temperature (23 8C) and involvement of some chemical steps followed by electrochemi-
under N2-atmosphere in a conventional three-electrode cell. cal electron transfers at the cathodic peak potential. In the
In case of voltammetric experiments, a three electrode literature, this behavior has been exploited to be the reversible
cylindrical cell was used as reactor, which was furnished with a dimer of dye molecules in solution after the cathodic scan [25].
Pt working electrode (geometric surface area, 0.0314 cm2), a Pt However, when the recording of the CVs was performed
counter electrode (1.0 cm2) and a KCl saturated Ag/AgCl reference between 0.6 V and +0.6 V, the peak currents were gradually
electrode. Hence all of the current densities will be quoted on the lost (CVs not shown). After 20th cycle at 10.0 mV s1 scan rate, a
basis of geometric area of electrode and the potential will be clear bleaching/decolorization of MB+ solution was noticed even
quoted with respect to Ag/AgCl reference electrode. In case of by visual inspection. In order to confirm the decolorization,
electrolysis, a 4.0 cm2 Pt electrode was used as working electrode. spectral analysis of the solution was carried out.
Before experiment, Pt working electrodes was cleaned by flame Fig. 3 shows the UV–visible absorption bands of MB+ solution
annealing processes followed by washing with deionized water. In before and after recording cyclic voltammograms. The MB
case of each experiment, 20 mL solution was taken in the molecules show maximum absorption at 665 nm, which is
electrochemical cell. Electrodes were supported by a Teflon- gradually decreased and removed finally with the increase of
holder, which was dipped into the solution. Before switching on cycle numbers. After cycling 20 times, the absorption peak reached
the electrochemical device, the reactor was allowed for 5 min to to the minimum value, and corresponded to the complete
attain an equilibrium state. A specific rest potential was also set for
[(Fig._3)TD$IG]
30s before commencing the scan. The absorption spectral 1.2
measurements were made on a JASCO Model 550 UV–visible 0th Cycle
spectrophotometer. The required FTIR analysis was performed 10μM MB
using SHIMADZU IR spectrometer(Model No-dxp 400) in the form 1.0

of KBr pellet.
0.8
Results and discussion
Absorbance

0.6 5th Cycle

Cyclic voltammetry

Cyclic voltammograms (CVs) of 2  104 M MB+ solution in 0.4 15th Cycle

0.5 M KCl recorded between 0.1 and 0.7 V and at three
different scan rates 50, 200 and 500 mV s1 are displayed in
0.2
Fig. 2 at pH of 2. At lower pH (<2.2), two redox peaks are seen at
0.48 V and 0.34 V at a scan rate of 50 mV s1. Such behavior 20th Cycle

of MB molecules has also been reported over thionine modified 0.0

400 500 600 700 800
zeolite electrode [24]. In case of reversible voltammetry, the
peak positions are independent of scan rates. However, in the Wave length / nm
present case, the anodic to cathodic peak separation (DE) is
Fig. 3. Influence of voltammetric scan number on UV–visible spectra of MB
140 mV at 50 mV s1, and this became larger with the increase (15  106 M) molecules at the counter electrode compartment. 20 mL, scan rate
of scan rate. Such a behavior of CVs suggests that MB molecules 25 mV s1, scan range 0.6 V and +0.6 V, supporting electrolyte: 0.5 M KCl, pH: 2,
undergo quasi-reversible electrochemical processes under the room temperature.
 [(Fig._5)TD$IG]
M.A. Hasnat et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 787–791 789

bleaching/decolorization. Non appearance of any any new 1.4

absorption band in the UV–visible regions suggests that the 0min

10μM MB
decolorization was resulted from the degradation of MB molecules. 1.2

This decolorization behavior can be explained by the mecha-

nism of hypochlorite generation. Since decolorization behavior 1.0
was observed when the electrode potential was maintained at

Absorbance
positive value (+0.7 V), it was supposed that electrochemically 0.8
generated hypochlorite from chloride oxidation on the Pt surface
was responsible for the dye degradation. At positive potentials, 0.6
chloride ions are oxidized to form strong oxidizing species
hypochlorite [26,27] as per following reactions: 0.4

2Cl ! Cl2 þ 2e (1)

0.2
90 min
þ 
Cl2 þ H2 O ! HOCl þ H þ Cl (2)
0.0
400 500 600 700 800
HOCl ! Hþ þ OCl (3)
Wave length / nm
The OCl ion is a strong oxidizing agent which has the ability to
Fig. 5. Decolorization of MB (15  106 M) molecules in 0.5 M KNO3 solution at
degrade organic molecules through direct and indirect routes. It is
1.0 V. Pt electrode (4 cm2), volume 20 mL, pH  2, room temperature.
therefore, expected that MB molecules were degraded chemically
followed by electrochemical generation of OCl species at Pt
surface:
insignificant bleaching occurred both in the working and in
the counter electrode chambers in the potential range +0.1 V to
OCl þ MBþ ! Degradedproducts (4) +0.4 V irrespective of electrolyte used. The bleaching became
significant at higher potentials (>+0.6 V) in the working
electrode chamber in the presence of KCl. On the other hand,
Bulk electrolysis inconsequential decolorization was noticed in the presence of
nitrate ions. In order to figure out the dependency of potential
In order to rationalize the degradation mechanism, the bulk on bleaching of MB molecules in the presence of KCl, controlled
electrolysis was performed in the presence of 0.5 M KNO3 and potential electrolysis was carried out at the working electrode as
0.5 M KCl within the potential range between 0 and +1.5 V at pH 2. shown in Fig. 4. It was noticed that rapid bleaching processes took
The relative bleaching/decolorization performance was evaluated place at the working electrode chamber in the presence of KCl when
based on the assumption that MB molecules decayed exponen- the potential was exceeded + 0.6 V, which reached in a maxima at
tially following the first order reaction presented below: +1.0 V (k: 78.2  103 min1). At higher potentials than +1.0 V, the
½MBþ t ¼ ½MBþ o expðktÞ (5) rate constant was found to decrease, which might be because water
oxidation inhibited the hypochlorite formation. This effect was not
+
Here, [MB ]t is the concentration of MB molecules at time t, observed when KNO3 was used as supporting electrolyte in place of
[MB+]o the initial MB+ concentration and k the first order rate KCl. In the presence of KNO3, decolorization rate was sufficiently low
constant. In order to perform electrolysis of MB+ solution, a two throughout the potential range. This observation indicates that at
chamber reactor was used. Each of the chambers was equipped potentials higher than +0.6 V at the working electrode, hypoclorites
with 4 cm2 Pt electrode and the reference electrode was placed were generated that caused chemical oxidation of MB molecules in
in the working electrode chamber. It was observed that the presence of KCl.

[(Fig._4)TD$IG]
[(Fig._6)TD$IG]
90.0
165
%T
80.0
157.5
-1
Rate constant, k / 10 min

70.0 150
-3

142.5
60.0

135
50.0
127.5

40.0
120

30.0 112.5

105
20.0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
97.5
E/ V vs Ag,AgCl (sat. KCl)
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 40
Fig. 4. Influence of applied potential on decolorization rate of MB molecules. MB+ Methylene blue 1/cm
(15  106 M): 7 mL, scan rate: 25 mV s1, supporting electrolyte: 0.5 M KCl, pH: 2,
room temperature. Fig. 6. FTIR spectrum of Methylene blue.
[(Fig._7)TD$IG]
790 M.A. Hasnat et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 787–791

-0.5.0

-1.0.0

-2
Current density, j / mA cm
-1.5.0

-2.0.0

-2.5.0

-3.0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

Time, t /s
+ 6
Fig. 7. Chronoamperogram of MB (15  10 M) in 0.5 M KCl solution at variable step 0.7 V. Nucleation pulse 25.0 ms. pH: 2.0. Inset: Plot of Ic/Id versus t1/2 curve.

Another set of electrolysis were also performed applying bond. However, all of these features were removed when the
negative potentials using KNO3 as supporting electrolyte. Howev- electrolysis was performed at +0.7 V. This FTIR disappearance,
er, at 1.0 V, MB molecules were decolorized moderately at the consistent with UV–visible spectral analysis, indicates that MB
working electrode (k: 7.5  103 min1) irrespective of electrolyte. molecules were disintegrated in the presence of KCl. In the other
The spectral changes (duration 90 min) of MB molecules, in the words, followed by hypochlorite action, MB molecules were
presence of KNO3, have been displayed in Fig. 5. The decrease of oxidized into numerous inorganic compounds, which might be
color at the working electrode at sufficiently high negative CO2, H2O, NO3, SO42 and so on.
potentials was obviously due to some heterogeneous electron
transfer reactions but which did not cause the breakdown of the Chronoamperometric study
MB molecules.
Finally, electrolyzed solution was analyzed using FTIR spec- In order to investigate the reason of bleaching at negative
troscopy. Several batch electrolysis experiments were performed potentials during BE experiments, chronoamperometric study was
using 30 mM MB+ at +0.7 V in the presence of 0.5 M KCl at working subsequently applied since this method is one of the best
electrode. After 40 min electrolysis, the electrolyzed solution was established technique and naturally fastest method to determine
collected for analysis. In this way, 60 ml electrolyzed solution was the number of heterogeneous electron transfer. Since KNO3 is also
collected and dried in a rotary evaporator to remove the solvent reduced at negative potentials [28] and may exceed the current of
under lower temperature (40.0–50.0 8C). After drying, FTIR MB+ adsorption/reduction therefore, the chronoampermetric
spectrum of the solid sample was recorded in the form of KBr experiments at variable negative potentials were carried out only
pellet. in the presence of KCl supporting electrolyte. In this regard, the
In the spectrum of MB+ (Fig. 6), several peaks are observed in counter electrode was separated from the working electrode using
the fingerprint region (from about 1500 to 500 cm1) with a sharp a membrane frit in order to avoid provable dye oxidation due to
peak at the region 1600 cm1 due to C5 5N and C5 5C double bond. formation of OCl species. The potential was varied by 50 mV
The broad peaks, for example, at 2250 cm1 are due to S5 5C5
5N steps starting from 0.3 V. The currents were sampled in every
[(Schem_1)TD$FIG]

Scheme 1. Mechanism of bleaching/decolorization of MB molecules onto Pt electrodes.

 M.A. Hasnat et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 787–791 791

25 ms. The features of diffusive currents were noticed at potentials Electrochemical bleaching of aromatic compounds like MB+ can
lower than 0.55 V, which is consistent with Fig. 2. As per Fig. 2, potentially be executed through chemical oxidation processes
the fast electron reactions were taken place at potentials lower followed by electrochemical approaches which might be adopted
than 0.48 V, where the reactions were diffusion controlled. Fig. 7 by the effluent treatment plants to degraded textile effluents with
shows the current transient at 0.7 V. The current transient shows high percentage of dye-destruction.
the hyperbolic decay of cathodic currents. The number of electron
(n) transfer was obtained by applying Cottrell’s equation: Acknowledgments
1=2 1=2
I ¼ nFAD C pt (6)
The authors are indebted to Prof. Masato Machida, Department
3
where, C is the bulk concentration (mol cm ), D of Chemical Engineering, Kumamoto University, Japan for his help.
(10.1  106 cm2 s1) [24], F the Faraday constant, A the Thanks to Dr. Aminul Haque (Chemistry Department, Jagannath
electrode area. From the slope of I versus t1/2 curve, the n was University, Bangladesh), Nahida Sharmin and Mr. Khairul Amin
determined to be 1.92 indicating that MB+ species were provably (Chemistry Department, SUST) for their cooperation. The authors
reduced to LMB (leoco—MB) by transferring two electrons: acknowledge UGC, Bangladesh for partial support (Grant No. 6(76)/
UGC/RSP/BKA/Chemistry (16)/2013/9844). Special thanks go
MBþ þ 2e þ Hþ ! LMB (7)
to Professor Muhammad Younus (Chemistry Department, SUST),
The formation of LMB might be the reason of bleaching at who inspired to install new electrochemical workstation
1.0 V during bulk electrolysis. Finally, electron exchange rate was (CH instrument series) in our lab.
determined at 0.7 V. At intermediate times (50–100 ms), the
current was dominated by the rate of the electron cross exchange
(Re) between the Pt redox sites and MB molecules. According to the References
method described in the literature [29], the rate of electron
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was calculated as per the following equation:
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