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Thien-Khanh Tran a,b, Kuo-Feng Chiu b, Chiu-Yue Lin c, Hoang-Jyh Leu c,*
a
Faculty of Applied Sciences, Ton Duc Thang University, 19 Nguyen Huu Tho Street, Tan Phong Ward, District 7, Ho
Chi Minh City 70000, Viet Nam
b
Department of Material Science and Engineering, Feng Chia University, Taichung City 407, Taiwan
c
Green Energy Technology Research Group, Ton Duc Thang University, 19 Nguyen Huu Tho Street,
Tan Phong Ward, District 7, Ho Chi Minh City 70000, Viet Nam
Article history: Electrochemical processes have been known as a very efficient method for the industrial
Received 29 December 2016 wastewaters treatment, especially for the removal of heavy metal ions. In this work, we
Received in revised form would like to provide a method that not only effectively treats heavy metal ions but also
13 May 2017 carries out the process with a notable selectivity rate. An electrochemical cell with
Accepted 20 May 2017 conductive carbon fibers cloth cathode and Platinum coated titanium panel anode (5 5
Available online xxx cm), low voltage supply energy of 10 V, and pH value of 6.8 is designed to remove Coppers,
and Nickels out of the solutions contains Nickel Sulfate and Copper Sulfate (0.06 M).
Keywords: There are modifications applied to the electrode to improve its conductivity and
Electrochemical processes durability, the two factors that may effect directly on the efficiency of the whole process.
Differential pulse voltammetry The result we obtained shows a good and promising data with high removal efficiency (up
Cyclic voltammetry to 97%) during the 20 h working time. Together with the removal process, the properties of
Heavy metals removal electrode materials are also well investigated. With the conductive carbon cloth shows its
superiority, the electrochemical cell in this work become a very versatile system. In that
manner, we provide a system which is not only can treat the wastewater, but also creating
energies such as hydrogen and oxygen, collecting of heavy metals in hydroxide form, and
can be easily improved to a continuous process with higher efficiency and larger
application.
Furthermore, the affection of electrode arrangement is carefully studied and revealed
its properties, providing a chance applying the method to actual industrial purpose. With a
close, medium and far distance of the two electrodes we arrange, the result of removal
heavy metal ions is differently achieved (97, 96.5 and 71%). Technical problems appear
during the process seems to be minor and could be solved quickly by a simple solution
which will be described in the later part. However, a single effective process to treat the
wastewater we introduced here is just the beginning. A continuous system which can be
operated for a longer time, more effective and creating a decent amount of energies would
be welcome to investigate.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author.
E-mail address: huang-chihlu@tdt.edu.vn (H.-J. Leu).
http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
Introduction
Fig. 2 e CV measurement describes the electrical conductivity of the coated conductive carbon fiber cloth cathode and a SEM
photograph which indicates the cathodes coated surface.
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8 3
Fig. 4 e SEM image of the (a) coated conductive carbon fiber cloth cathode and (b) original conductive carbon cloth cathode.
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8 5
The reaction at cathode should be: coated a layer of conductive carbon ink on the surface of the
cloth. The use of carbon materials were based on their
mechanism of double layer capacitance [16e18]. It stored the
Cu2þ (aq) þ 2e / Cu (s) with E0 ¼ 0.340V. (3) charges electrochemically by reversible adsorption of the ion
into active material that are stable and possessing a high
accessible surface area [19].
Ni2þ (aq) þ 2e / Ni (s) with E0 ¼ 0.257V. (4) The porous structure of the conductive carbon cloth is
expected to facilitate the diffusion of electrolyte into the
electrode material and provide more channels for the ions
The Hydrogen gas obtained at Cathode due to the reaction: transportation. The carbon ink solution also improves the
3H2O þ 3e / 2H2 (g) þ 3OH (5) connections between the fibers of the cloth. Fig. 2 shows the
cyclic voltammetry (CV) measurement result of the conduc-
The element with higher reduction potential has a ten-
tivity of the coated conductive carbon fiber cloth cathode,
dency to gain an electron and be reduced by the oxidation
together with a SEM photograph which described the coated
process. Due to the more positive standard reduction potential
surface of the material.
value, copper would be treated and removed out of the solu-
During the process, the coated cathode contributes a
tion before nickel. As the treatment proceeds, hydrogen and
greater electrochemical performance and much better dura-
oxygen can be collected at cathode and anode after a few
bility in comparison with the original one. The performance of
minutes.
the two cathodes was compared base on their properties of
In this work, platinum coated titanium panel anode is
durability and electrical conductivity. Fig. 3 indicate the cyclic
proven itself as an excellent electrode. Not only providing a
voltammetry (CV) result of the coated conductive carbon fiber
significant electrical conductivity but also shows its superior
cloth cathode and the original one.
durability. It is clear that we can carry on the treatment longer
It is clear to see that the coated sample is a more advanced
without the fear of destroying the electrode and decreasing of
material, which is providing a larger electrical conductivity
electrochemical performance. Different from conventional
area. Not only that, the coated conductive carbon fiber cloth
electrochemical processes, platinum does not join in the
cathode sample is densely packed with the enhanced carbon
reduction reaction (It is required a very large current to reduce
ink layer, randomly oriented to form a macroscopically open
platinum), thus so, the reaction happens at the anode is a
structure that offers a better accessibility to the electrolyte, as
simple process of water electrolysis.
SEM photograph described it in Fig. 4.
There are reasons behind the choice of conductive carbon
ink solution as a reinforcing material. However, the idea of
The reaction at anode should be: 2H2O (aq) / O2 (g) þ 4Hþ
providing a low cost material which is strong, durable and can
(aq) þ 4e (6)
be reused several times is promised. The fact that explains the
advance of the coated sample over the original one is related
Accordingly, maintaining and improving the quality of
to the increasing of hydrophilicity gained from suitable sur-
cathode should be the only task that matter. The results from
face treatment applied to the material. The thickness of the
such previous works of Naohide [12], Kobya [13] and Kashe-
coated conductive carbon layer can be controlled by adjusting
fialasl [14] indicated that the current density determines both
the immersion time and the concentration of the bath
coagulant dosage and bubble generation rate not only that,
solution.
the solution mixing and mass transfer at the electrodes were
also influenced [15]. In that manner, charge loading value is
Effect of the electrode arrangements
the primary factor affects the efficiency of the whole process,
and the parameter itself was affected by a cathodic and anodic
The heavy metal contained a solution in this work was made
reaction, which depends on the performance of the electrode.
with a total volume of 500 mL which is included 0.06 M of
Therefore, every improvement to extend the cathodic reduc-
copper sulfate and 0.06 M nickel sulfate. Accordingly, the total
tion, in this case, can be considered as an alternative factor.
amount of solid heavy metals should be 3.9 g (2 g of copper and
1.9 g of nickel). Table 1 provides the details of the solution
Effects of electrode material
before treatment; the mixture is carefully made and then
stored for 24 h before use. Differential pulse voltammetry
We design an electrochemical cell possessed a cathode of
(DPV) is used to investigate the heavy metals concentration in
conductive carbon fiber cloth, and the anode of platinum
the solution after 10 h and 20 h treatment while the energy
coated titanium panel was prepared to treat heavy metal
dispersed x-ray spectroscopy (EDS) is used to measure the
contained solution. While the platinum coated material is
collected heavy metals on the surface of the coated conduc-
proven itself to be a very excellent anode, the conductive
tive carbon cloth, due to the reduction happened at the
carbon fiber cloth is seemed to have needed more attention for
cathode.
improvement. To advance the performance of the cathode, we
Fig. 6 e The result of DPV and EDS measurements of (a) 10 h of treatment sample and (b) 20 h of treatment sample at far
range arrangement of electrodes, (c) 10 h of treatment and (d) 20 h treatment using medium arrangement, (e) 10 h of
treatment and (f) 20 h treatment using close arrangement setup.
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8
During the process, experiments were carried out with signal using DPV result after 10 h treatment with far
similar conditions accepts for the arrangement of the two arrangement electrode setup as an example.
electrodes. Samples were drawn after 10 h and 20 h for As it was described in Fig. 5, the distance between the ex-
investigating the result on heavy metal concentration in wet pected peaks to the background indicates the concentration of
phase and collected solids. The decreasing of heavy metals in the element at which that peak represents. Therefore, a1, a2, a3
the solution can be clarified by analyzing the DPV result. and a4 apparently represent for the concentration of copper in
Theories of voltammetry explain that the signal peak in the the original solution (a1), copper in treated solution (a2), nickel
DPV result represents the concentration of elements and in the original solution (a3) and nickel in the treated solution
species inside the solution. According to that fact, indicating (a4). The result obtained from DPV measurement can only
the relationship of the peak signal obtained from DPV mea- show the change of the heavy metal concentration in the so-
surement and the treatment time should also describe the lution but cannot indicate which metal is treated before the
decreasing of heavy metals concentration in the solution. The other one. Therefore, EDS results on the collected metals are
signal peak depends on its heights and can be calculated attached and show the behavior of the removal process which
easily by measuring the distance from the expected peak to is copper treated before nickel, due to its more positive
the background line in the DPV result chart. Following that reduction potential. Fig. 6 shows the result of DPV measure-
manner, Fig. 5 will show us how to acquire the peak height ment together with EDS result for the whole process.
As we explained in Fig. 5, the follows Fig. 7 is helpful in
describing the relationship between the treatment time and
the concentration of the heavy metals. It is clear to see the
concentration of Copper and Nickels are significantly
decreased after 10 h of treatment, and the decreasing rate
becomes slower until the removal finishes.
According to the reduction at the cathode, the heavy
metals solid gathers at the cathode and form a layer on its
Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e8 7
surface. Those heavy metal solids were carefully collected, after about 10 h of treatment with the close arrangement
dried and stored for 24 h before measured and analyzed by setup.
EDS. The result of removal efficiency of the process would be
decided after comparing the weight of the collected solids
with the original amount listed in Table 2. In that manner, the Conclusion
result we obtained should be described in Table 2. It is
reasonable to see the total removal efficiency rate of all the In this work, we successfully treated a solution contains
work is very high with most of the copper removed. nickel salts and copper salts with a high removal efficiency.
The work provides a method to remove the heavy metals with
Discussion and future work an expected order, effective against heavy metals, simple and
less need for the chemical. Furthermore, our experiments
The process of heavy metal removal results in a superb were not only profitable by saving the initial investment fee
treatment efficiency which is successful removes 95% of but also producing energy during its process. The collected
coppers out of the solution. However, the removal efficiency of gasses (hydrogen and oxygen) can be put into a proper appli-
nickel is not as we expected and still need more time to cation or return to the system as a secondary power supply
improve, due to the complex mechanism of electrochemical while solids we get from the cathode can also be stored and
reactions in aqueous phase [19]. Under the affection of elec- clean for the refinery process. However, the main purpose of
tricity and long stored time of solution, there are some un- this work is about wastewater treatment, and the amount of
desired reactions happened which are sometimes put the gasses we acquired during the process is not much as we
process into the problem of wasting energy or unstable. The expected.
issues of electricity can be explained by the affection of the The selection of current density significantly affects the
charge loading to the electrochemical treatment. The charge charge loading value and should be made with other optimal
loading value is affected by the supply of current density to parameters such as pH value, temperature, system design,
the electrochemical cell, which determines the number of flow rate and working time. The relationship between the
positive ions released from the respective electrode. There- distance between the electrode and the charge loading is
fore, the performance of the two electrodes plays a significant apparently affecting the removal efficiency of the work, so
role during the process. By adjusting the space between the that, it should be carefully managed. However, the sludge
two electrodes and applying modifications on the cathode, we created after the treatment process may put a stress to all the
found that with the range of 2.5e5 cm distance of cathode and recycle technologies, at which have to deal with a combina-
anode should be the optimum conditions for carrying out the tion of metals, hydroxides, and organic compounds. A larger
removal process. Nevertheless, to finish the removal process system can be built based on the set up of the electrochemical
with high efficiency is one thing, and makes the process works cell we provide in this work and that ideas should be worth to
with our expected removal orders should be a very different carry out for a larger application, stronger durability, contin-
story. Therefore, we would like to recommend a longer uous process, saving energies together with producing it and
treatment time combined with a reasonable adjusting of the of course higher removal efficiency of heavy metals.
electrode space during the process should be an idea. In
comparison with other works such as Nanseu-Nikki [20],
Kabdash [21] and Safaei [22], the electrochemical method
Acknowledgement
shows a very high efficiency for metal removal process; most
of the case provides the result of 95e99% heavy metals
All of the experiments were carried out at the laboratory of the
removed. However, the problem of cost effective is always
Green Energy Development Center, Feng Chia University,
appeared as an obstacle to the revolution of the process, due
Taiwan. Measurements and further analysis were performed
to the high initial investment and expensive electricity supply.
at the Instrument Center and Material Science and Engineer-
In that manner, a supply energy source from the solar system
ing Department of Feng Chia University (FCU).
and using cheap materials such as conductive carbon fiber
cloth should be very helpful for the further application of
electrochemical methods. references
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process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156
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Please cite this article in press as: Tran T-K, et al., Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.156