Desalination 336 (2014) 64–71

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Optimization of the operational parameters for desalination with

response surface methodology during a capacitive deionization process
Yan Zhao, Xiao-min Hu ⁎, Bin-hui Jiang, Liang Li
School of Resources and Civil Engineering, Northeastern University, Shenyang 110819, China

H I G H L I G H T S

• Optimization of experimental parameters was carried out by BBD with RSM.

• The equivalent circuit for the CDI system was analyzed by EIS from Nyquist plot.
• Cell voltage, salt concentration and flow rate are key parameters of optimization.
• The response surface model with R2 = 0.9945 and p-value b 0.0001 is highly significant.
• The maximum electrosorption capacity of 10.53 mg/g was obtained after optimization.

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

Article history: The performance of capacitive deionization (CDI) and the effects of various operational parameters in CDI exper-
Received 22 October 2013 iments were investigated for desalination on activated carbon electrodes. The pore size distribution determined
Received in revised form 2 December 2013 using density functional theory showed that the carbon electrode materials used in this study contained some
Accepted 21 December 2013
mesopores that could reduce the electric double-layer overlapping effect. From a Nyquist plot derived from elec-
Available online 23 January 2014
trochemical impedance spectroscopy, the equivalent circuit and impedance for the CDI system were analyzed,
Keywords:
and the specific capacitance of the electrodes was approximately 71.05 F/g. Optimization of the operational con-
Electrosorption ditions under the main experimental parameters, including the cell voltage (1.2–1.6 V), initial NaCl concentra-
Capacitive deionization tion (200–1000 mg/l) and flow rate (10–40 ml/min), was performed by Box–Behnken design with response
Electrochemical impedance spectroscopy surface methodology. A quadratic polynomial model was properly fit to the experimental data with a determina-
Response surface methodology tion coefficient (R2) of 0.9945 and a p-value b0.0001. The analysis of variance for the quadratic model demon-
Box–Behnken design strated that the model was highly significant and reliable. The predicted maximum electrosorption capacity
(10.67 mg/g) was given under the optimal conditions consisting of a cell voltage, initial NaCl concentration
and flow rate of 1.57 V, 1000 mg/l and 25 ml/min, respectively, in accordance with the results of the validation
experiments.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction solutions. However, some drawbacks, such as high energy consumption,

The shortage of fresh water has been a crucial problem around the
world due to population and economic growth, which cause large-
scale exploitation and contamination of natural water resources by in-
dustry, agriculture and urbanization [1,2]. More than 96.5% of water re-
sources are salty, whereas only 0.26% of all water resources can be
utilized by people as fresh water. Therefore, the desalination process is
an efficient method to produce purified or fresh water to resolve the se-
vere crisis of water resource shortages [3]. Conventional desalination
technologies, including multi-stage flash evaporation (MSF), multi-
effect distillation (MED), reverse osmosis (RO), electrodialysis (ED)
and ion exchange (IE), are used to remove ionic species from aqueous
⁎ Corresponding author. Tel./fax: +86 24 83689128.
E-mail address: hxmin_jj@163.com (X. Hu).
intensive cost, large membrane investment and fouling, exist in these
technologies [4–6]. Capacitive deionization (CDI), an emerging and
promising electrochemical desalination technology, which is available
for the removal of ions from brackish water, seawater, groundwater
and even wastewater, has attracted more and more attention due to
its typical advantages, such as energy-efficiency, no need for high-
pressure pumps and expensive membranes, low cost and no secondary
pollution, compared with other aforementioned technologies [7–10].
CDI works at a relatively low operating voltage (0.8–2.0 V) for the
removal of ions in solution by electrostatic forces [1,3,5]. When an elec-
trical voltage is applied to electrodes, usually made of highly porous car-
bon materials, cations and anions from the feed solution migrate to the
oppositely charged electrodes and are held in the electrical double layer
formed on the surface between the electrodes and the bulk solution
until the electrodes are saturated with ions [11]. Then, regeneration of

0011-9164/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2013.12.024
 Y. Zhao et al. / Desalination 336 (2014) 64–71
the electrodes is performed by opening the circuit or applying a reverse
voltage, and the adsorbed ions are released into the bulk solution [12].
The system again removes ions from the feed water once the electrodes
are regenerated.
One of the key parameters for commercial realization of CDI is the
salt adsorption capacity of the carbon electrodes, which strongly de-
pends on the pore structure, specific surface area, electronic conductiv-
ity and electrochemical stability of electrode materials [13]. Recently,
carbon materials, such as activated carbon, carbon nanotubes (CNT),
carbon aerogel, graphene and ordered mesoporous carbon (OMC),
have been focused on studying the electrosorption process as carbon
electrodes [14–19]. The pore structure and pore size distribution of elec-
trode materials have been seen as crucial factors affecting the
electrosorption capacity. Although microporous carbon materials
(b2 nm) can result in a larger surface area, they do not contribute to
greater ion adsorption capacity due to electric double-layer (EDL) over-
lapping [20]. Some researchers have confirmed that carbon electrode
materials with some mesopores (2–50 nm) will benefit the removal
of ions [14]. C. Tsouris et al. and Linda Zou et al. developed self-
assembled ordered mesoporous carbon electrode materials with a reg-
ular mesoporous arrangement, narrow pore size distribution, chemical
inertness and high conductivity to avoid EDL overlapping effects during
CDI processes [19,20]. However, operational parameters, such as cell
voltage or initial solution concentration, which significantly affect the
ion removal efficiency and electrosorption capacity, are also key factors
in attaining the commercial application of CDI technology. M. Mossad
has studied the CDI performance under various operational conditions
(feed solution temperature, feed solution TDS and flow rate) [7]. How-
ever, few studies have reported the interactive and synthetic effects of
the operational conditions on the CDI process.
Response surface methodology (RSM), defined as a useful statistic
method with synthetic experiment-designed and mathematical model-
ing, includes some experiment-designed approaches, such as central
composite design (CCD), Box–Behnken design (BBD) and Doehlert Ma-
trix (DM). Among these approaches, BBD made up of three interlocking
22 factorial designs with several points is one of the most common
spherical and revolving response surface methodology designs [21,22].
Although response surface methodology is often used for designing ex-
periments, building models and deciding optimum conditions in many
physical, biological and chemical experimental processes [23–25], opti-
mizing the experimental parameters of the electrosorption process has
not been reported previously.
The objective of this study is to investigate the characteristics and
performance of developed activated carbon electrodes, optimize various
electrosorption operational parameters and enhance the ion removal
efficiency and sorption capacity for further large-scale application de-
velopment of this desalination technique. To discuss the performance
and mechanism of electrosorption, the pore size distribution of
electrode materials was obtained using density functional theory
(DFT) method, and the equivalent circuit for the CDI unit was tested
by electrochemical impedance spectroscopy (EIS). In addition, the
electrosorption capacity under different operational conditions of pa-
rameters (including applied voltage, initial NaCl concentration and
flow rate) was investigated by Box–Behnken design with RSM.
2. Materials and methods
2.1. Fabrication and preparation of carbon electrodes
Powdered activated carbon supplied by Yihuan Carbon Co., Ltd
(Fuzhou, China) was used as the electrode material of CDI for desalina-
tion. The carbon electrodes were prepared by casting a slurry of porous
carbon powder and polyvinylidene fluoride (PVDF, M.W = 275,000,
Sigma-Aldrich) binder in dimethylacetamide (DMAc) solution to the
graphite plate collector (60 × 80 mm) followed by stirring for 12 h to
guarantee homogeneity [2,11]. The coating carbon mixture was dried in
65
a 60 °C oven for 4 h and in a 60 °C vacuum oven for 2 h to form the car-
bon electrodes with a weight of approximately 1.5 g and no remaining
organic solvents. The thickness of the electrodes was approximately
0.22 mm and the PVDF polymer accounted for 10 wt.% of the carbon
electrode after drying.
2.2. CDI experimental apparatus and methods
CDI experiments were conducted in a continuous system that
consisted of a CDI unit cell, a DC power supply, a conductivity meter, a
peristaltic pump and a power meter, as depicted in Fig. 1. The CDI unit
cell was made of a couple of activated carbon electrodes adjacent to
the Plexiglas support plates, which were separated by a spacer with a
2 mm thickness for solution flow. The NaCl (AR, Kermel) electrolyte so-
lution was continuously pumped into the cell using a peristaltic pump
(Loner BT100) at different flow rates (10, 25 and 40 ml/min). A 50 ml
NaCl solution with different initial concentrations (200, 600 and
1000 mg/l) was prepared with deionized water. The given voltage of
1.2, 1.6 or 2.0 V was applied to the two activated carbon electrodes
using a DC power supply (WYJ2A30V, Pingguo). Each experiment was
conducted until the conductivity in the solution was almost constant
and stable-state conditions were obtained. The changes of the NaCl con-
centration in the solution and the actual energy consumption under the
optimum operational conditions of the system were monitored by a
conductivity meter (Professional Plus, YSI) and power meter (NORMA
4000CN, FLUKE), respectively.
The electrosorption capacity (Q, mg/g carbon) is calculated as the
following equation (Eq. (1)) [2]:
ðC 0 −C e Þ  V NaCl
Q¼ ð1Þ
m
where C0 and Ce are the initial and equilibrium concentrations (mg/l),
respectively, VNaCl is the solution volume (ml) and m is the mass of
the activated carbon electrodes (g). The concentrations of the NaCl elec-
trolytes were also determined by the conductivity meter due to the pro-
portional relationship between the NaCl concentration and the
conductivity in solution at a constant temperature (25 °C), and the cor-
responding concentration could be obtained through a calibration curve
made prior to the experiments.
2.3. Characterization of the carbon electrodes
The carbon electrode materials were characterized by nitrogen ad-
sorption at 77 K, and the specific surface area was measured using
Brunauer–Emmett–Teller (BET) method from the nitrogen adsorption/
desorption data at a relative pressure of p/p0 = 0.99 by a full-
automatic surface area and porosity analyzer (QUADRASORB SI,
Quantachrome Inc.). Furthermore, the pore size distributions were cal-
culated by the Density Functional Theory (DFT) method with a NLDFT
equilibrium calculation model in the 0–1 relative pressure range provid-
ed by NOVAwin2 version 2.1 from Quantachrome Instruments [26]. The
carbon samples were degassed under vacuum at 423 K for 6 h prior to
the nitrogen adsorption.
The equivalent circuit for the CDI system and the specific capacitance
of carbon electrodes were measured by electrochemical impedance spec-
troscopy (EIS) using a CHI660D electrochemical workstation (Beijing
Huatianpuke Technology Co., Ltd) with a three-electrode cell system
composed of a saturated calomel electrode (SCE) as the reference elec-
trode, a Pt electrode as the counter electrode and a working electrode
with an apparent diameter of 1 cm carbon coating electrode in a 1 M
NaCl solution at room temperature. The scanning frequency range was
from 100 kHz to 10 mHz with 5 mV amplitude and 0 V electrical levels.
66
Fig. 1. Schematic diagram of the electrosorption equipment for the CDI process.
2.4. Experimental designs of response surface methodology
The Box–Behnken design (BBD) was used to optimize the experi-
mental conditions of the NaCl desalination on activated carbon elec-
trodes under response surface methodology in the CDI experiments.
Based on the preliminary single-factor experiments, three main factors
affecting the electrosorption efficiency, including the cell voltage (X1),
initial NaCl concentration (X2) and flow rate (X3), were chosen to imple-
ment the three factors and three levels experimental plan of seventeen
points (five central points) at the request of the Box–Behnken design,
and the response was the electrosorption capacity (Q). The variables
and levels of the BBD experimental design are given in Table 1. In addi-
tion, Table 2 demonstrates the response surface design arrangement
and actual experimental design matrix. The experimental results were
analyzed using the determination coefficient (R2) with Design-Expert
8.0 software (Stat-Ease, Inc.).
3. Results and discussion
3.1. Pore structure and size distribution of electrode materials
The performance of a CDI system has close ties with the specific sur-
face area and pore size distribution of the carbon electrode materials
(see Fig. 2). The BET specific surface area was 1770 m2/g, and the total
pore volume reached 1.02 cm3/g. Although micropores accounted for
a large portion of the pore size distribution, some mesopores which
were among 2.0–2.5 nm still existed in the pores of the carbon materials
and the volume distribution ratio of mesopores to total volume was ap-
proximately 35%. Micropores are an inherent pore structure of raw ma-
terials that can form electrical double layer whose thickness depends
mainly on the electrolyte concentration and affect the capacitance and
surface area, whereas many micropores also result in strong EDL over-
lapping [20,27]. Mesopores are shaped during the production process
Table 1
Factors, levels and codes of variables for the Box–Behnken design.
Variables Units Code Level values
Cell voltage (A) V X1 −1, 0, 1
Initial concentration of NaCl (B) mg/l X2 −1, 0, 1
Flow rate (C) ml/min X3 −1, 0, 1
Y. Zhao et al. / Desalination 336 (2014) 64–71
of activated carbon and both form the electrical double layer and convey
ions from the bulk solution to the inner electrodes. Therefore,
mesopores not only weaken the EDL overlapping effect and reduce dif-
fusion resistance to accelerate the movement of ions, but they also in-
crease the electrosorption capacity [14,19,20]. Therefore, the pore
structure of the electrode materials used in this study was a great ad-
vantage to remove ions by electrosorption.
3.2. Electrochemical impedance spectroscopy analysis
The alternating current impedance technique is an important meth-
od to study kinetics of electrode processes and superficial phenomena
[5]. The Nyquist plot (see Fig. 3) from electrochemical impedance spec-
troscopy is able to determine the proper equivalent circuit and mecha-
nism of the electrode system depicted real (abscissa X-axis, Z′) and
imaginary (ordinate Y-axis, Z″) at different frequencies (10 mHz–
1000 Hz).
At higher frequencies, the diffusing process minimally affects the
electrode process and concentration polarization will not occur. There-
fore, the Warburg impedance that represents a resistance for mass
transfer can be neglected, and the Nyquist plot of CDI cell can be ana-
lyzed by the equivalent circuit shown in Fig. 4A. The impedance (Z) of
the electrochemical system, except the Warburg impedance was de-
fined as follows (Eq. (2)) [28]:
!
2
RP ωRP C d
Z ðωÞ ¼ RE þ −j ð2Þ
1 þ ω 2 RP 2 C d 2 1 þ ω2 RP 2 C d 2
where RE is the equivalent resistance of the electrolyte solution and
carbon electrodes, RP is the polarization resistance, Cd is the double
layer capacitance, and ω is the angular frequency of the applied ac-
signal, ω = 2πf (f is the frequency, Hz). At relatively high frequency
(ω2 R2P C2d N N 1), the total impedance (Z) becomes the following
equation (Eq. (3)) [28]:
 
1 1
Z ðωÞ≅RE þ −j ≅RE : ð3Þ
Factor values ω 2 RP C d 2 ωC d
1.2, 1.6, 2.0
200, 600, 1000 The impedance at high frequency ranges approximately equates to
10, 25, 40
the equivalent series resistance (ESR) of the CDI system; namely, the
 Y. Zhao et al. / Desalination 336 (2014) 64–71 67

Table 2
Response surface design arrangement and experimental results for electrosorption.

Numbers X1: Potential X2: Initial NaCl concentration X3: Flow rate Electrosorption capacity (mg/g)
(V) (mg/l) (ml/min)
Actual value Predicted value

1 1.20 200.00 25.00 2.61 2.32

2 2.00 200.00 25.00 2.05 1.89
3 1.20 1000.00 25.00 8.62 8.78
4 2.00 1000.00 25.00 7.83 8.12
5 1.20 600.00 10.00 4.53 4.57
6 2.00 600.00 10.00 4.02 3.93
7 1.20 600.00 40.00 4.22 4.31
8 2.00 600.00 40.00 3.92 3.88
9 1.60 200.00 10.00 3.15 3.40
10 1.60 1000.00 10.00 9.95 9.75
11 1.60 200.00 40.00 3.05 3.25
12 1.60 1000.00 40.00 9.84 9.59
13 1.60 600.00 25.00 7.48 7.36
14 1.60 600.00 25.00 7.02 7.36
15 1.60 600.00 25.00 7.44 7.36
16 1.60 600.00 25.00 7.42 7.36
17 1.60 600.00 25.00 7.45 7.36

resistances of the electrolyte solution and carbon electrode are the main
cause for the faradaic processes in the CDI unit cell. Furthermore, the re-
sistance of the electrolyte solution is inversely proportional to the con-
centration of ions in solution, which means that the total resistance of
the CDI system decreases as the concentration of the ionic species in
electrolyte solution increases, and the current of the CDI process will in-
crease if the cell voltage remains unchanged.
At lower frequency ranges, the Warburg impedance (W) cannot be
ignored because the effect of diffusion on the electrode process becomes
important, and the polarization resistance (RP) and double layer capac-
itance (Cd) are more pronounced when the frequencies approach lower
ranges due to concentration polarization [28,29]. The equivalent circuit
for the CDI system at low frequencies is shown in Fig. 4B. As the frequen-
cy decreases gradually, the ac-signal can attain and utilize more inner
surface sites of the carbon electrode, and the charging for the CDI system
is mostly done, which results in a higher capacitance due to the Helm-
holtz plane formed between the carbon electrode and the electrolyte so-
lution. At very low frequency ranges, the capacitance remains almost
constant once the CDI system is charged completely and the Nyquist
plot contains a linear slope. Then, the specific capacitance of the carbon
electrode (C) can be obtained from the imaginary part (Z″) of the
Nyquist plot, according to Eq. (4) [29]:
1 and the insignificant lack of fit (p-value N 0.05).
C¼
m  ω  jZ}j
where ω is the angular frequency of the ac-signal, and m is the mea-
sured mass of the carbon electrode. Accordingly, the specific capaci-
tance of the carbon electrode can be calculated as 71.05 F/g at a
frequency of 10 mHz, from Fig. 3.
3.3. Response surface model building and analysis for electrosorption
3.3.1. Building and fitting of the quadratic polynomial model
To study the interactive effects of different experimental parameters
on the ion removal efficiency, the values of three key independent var-
iables (X), the measured response values (Y) and the experimental re-
sults of desalination on activated carbon coating electrodes by
electrosorption are shown in Tables 1 and 2 (Section 2.4).
Linear, two factor interaction (2FI), quadratic and cubic models
were used to fit the experimental data to obtain the regression equa-
tions in the present work. Three different tests, including the se-
quential model sum of squares, lack of fit tests and model summary
statistics, were performed to determine the accordance and avail-
ability of the various models, the summary results are given in
Table 3. The cubic model proved to be aliased, and the quadratic
model was found to be appropriate for further studies due to the higher
order polynomial, significant additional terms (p-value b 0.05), the
maximum “Adjusted R-Squared” and “Predicted R-Squared” values,
ð4Þ

2.5
900 10 coated carbon electrode
Adsorbed volume(cm3/g)

850

2.0 800

8
dV/dr/(cm3/nm/g)

750

700
1.5 650 Adsorption
-Z"/ohm

Desorption
600 6
550
1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure(P/P0)
4
0.5

2
0.0

1 2 3 4 5 6 0
Pore diameter (nm) 0 1 2 3 4 5 6 7 8 9 10
Z'/ohm
Fig. 2. DFT pore size distribution and nitrogen adsorption/desorption isotherm of the acti-
vated carbon electrode materials. Fig. 3. Nyquist plot for the EIS of the activated carbon electrode at 10 mHz–1000 Hz.
68 Y. Zhao et al. / Desalination 336 (2014) 64–71
Fig. 4. Equivalent circuit for the CDI system based on the electrochemical impedance
spectra: (A). at high frequencies and (B) at low frequencies.
The final quadratic equation in terms of coded factors regarding an
empirical relationship between the value of electrosorption capacity
and the value of tested parameters according to the experimental re-
sults obtained by software Design-Expert 8.0 is given in Eq. (5):
Y ¼ 7:36−0:27X 1 þ 3:17X 2 −0:077X 3 −0:058X 1 X 2 þ 0:053X 1 X 3
2 2 2 ð5Þ
−0:0025X 2 X 3 −2:20X 1 þ 0:12X 2 −0:98X 3
where Y is the response, namely, the value of electrosorption capacity;
X1, X2, X3 are the coded values of the main impact factors: cell voltage,
initial NaCl concentration and flow rate.
3.3.2. ANOVA and diagnostics of response surface quadratic model
Analysis of variance (ANOVA) is a statistical technique that divides
general variance into each component part and is used to test the statis-
tical significance of the average variance among two or more samples
[22]. The results of the ANOVA for this response surface quadratic equa-
tion are shown in Table 4. The significance of each coefficient was deter-
mined by the F-values and p-values, where a higher F-value and a lower
p-value represented greater significance [25]. From Table 4, it is ob-
served that the main effects of the variables were highly significant
(p b 0.0001) compared to the interactive effects of these variables.
The F-value (139.68) with a low probability value (p b 0.0001, less
than 0.05) provided high significance for the regression model. Further-
more, values of “Prob N F” less than 0.05 indicated that the model terms
were significant, so X1, X2, X21 and X23 were significant model terms due to
their low p-values in this case. The “Lack of Fit p-value” of 0.1062
(N0.05) implied that the lack of fit was not significant and that the
model fits well. The goodness of the fitting model was also evaluated
by the multiple correlation coefficient (R2 = 0.9945), which revealed
that this regression was statistically significant and only 0.55% of the
total variance was not explained by the model. The “Pred R-Squared”
of 0.9313 was in reasonable agreement with the “Adj R-Squared” of
0.9873. Additionally, a relatively lower value of the coefficient of vari-
ance (C.V = 4.92%) reflected better accuracy and reliability of the
electrosorption experiments.
The data and model need to be diagnosed by checking the normality
of the residuals with the normal probability plot of the studentized re-
siduals (see Fig. 5). From Fig. 5, the data points tended to be close to a
straight line and were closely consistent with the theoretical distribu-
tion, supporting the conclusion that the model building and the results
of the ANOVA were reasonable and adequate [25].
Table 3
Summary of the tests of the model adequacy.
Source Sequential Lack of fit Adjusted Predicted
p-value p-value R-Squared R-Squared
Linear 0.0003 0.0004 0.6995 0.5839
2FI 0.9997 0.0002 0.6097 0.1416
Quadratic b0.0001 0.1062 0.9873 0.9313
Cubic 0.1062 0.9945
3.4. Effect and interaction of the main parameters on the electrosorption
capacity
The experiments were conducted by varying the key experimental
parameters under various conditions of cell voltage, initial NaCl concen-
tration and flow rate of 1.2 to 2.0 V, 200 to 1000 mg/l and 10 to 40 ml/
min, respectively. The results are shown in Fig. 6. Fig. 6A reflects the 3D
response surface plot showing the effect of the cell voltage and the ini-
tial NaCl concentration on the electrosorption capacity at a constant
flow rate of 25 ml/min in the CDI system. Accordingly, the effect of
the cell voltage and flow rate on the electrosorption capacity at the spe-
cial initial NaCl concentration of 600 mg/l, and the effect of the initial
NaCl concentration and flow rate on the electrosorption capacity at
the special voltage of 1.6 V were also observed in the 3D response sur-
face graphs of Fig. 6B and C, respectively.
From Fig. 6A and B, it was found that at any settled value of flow rate
or NaCl concentration, the electrosorption capacity had a linear increase
as the applied voltage rose to a limited value and then decreased until it
reached 2.0 V, which can be explained by the theoretically higher volt-
ages inducing stronger electrostatic forces and thicker EDL, so the
electrosorption capacity should increase with the enhancement of the
cell voltage, whereas the electrochemical redox reaction could occur
once the applied voltage exceeded a certain value [30]. For example,
when the applied voltage is greater than 1.6 V, the redox of ions in solu-
tion can generate the following oxidation-reduction reaction at the elec-
trodes during the CDI process. The possible reduction reactions that
dissolved oxygen is to undergo at the cathode under acidic and alkaline
conditions are shown below:
þ − θ
pHb7 : O2 þ 2H þ 2e →H 2 O2 ; ϕ ¼ 0:6945V ð6Þ
− − − θ
pHN7 : O2 þ H 2 O þ 2e →HO2 þ OH ; ϕ ¼ −0:146V ð7Þ
and then at the anode, the oxidation of Cl− is conducted based on the
following reaction:
− θ
2Cl →Cl2 þ 2e; ϕ ¼ 1:360V: ð8Þ
Also, another reaction concerning the disproportionation of chlorine
followed [29]:
Cl2 þ H 2 O→HCl þ HOCl: ð9Þ
In the CDI experiments, all the reactions mentioned above not only
resulted in a decrease of the NaCl removal efficiency and a decrease in
the electrosorption capacity but also caused a series of problems be-
cause of the change of the pH in the solution, such as the production
of scale on the electrode surface and the erosion of the electrodes.
Higher cell voltages demand more energy consumption, so the control
of the cell voltage was crucial to avoid the occurrence of electrochemical
reactions and minimize power consumption.
Fig. 6A and C demonstrate the effect of the initial NaCl concentration
on the electrosorption capacity at any fixed voltage or flow rate. The
electrosorption capacity increased gradually with an increase of the initial
NaCl concentration ranging from 200 to 1000 mg/l, which was a result of
the growing diffuse double-layer capacity that depended mainly on the
electrolyte solution concentration according to Gouy–Chapman–Stern
theory [31], and the active sites such as surface functional groups of the
adsorbent (carbon electrode materials) could be in contact with more
salt ions along with the increase of the initial NaCl concentration. More-
Remark over, the sorption rates and current density would be strengthened due
to the decrease in the electrolyte resistance with the increase of the
solution concentration [28]. Therefore, the process of electrosorption
would be performed more sufficiently and efficiently. The growth rate
Suggested of electrosorption capacity became slow when the concentration of
Aliased
NaCl was above 800 mg/l, meaning that the adsorption capacity of the
 Y. Zhao et al. / Desalination 336 (2014) 64–71 69

Table 4
ANOVA for the response surface quadratic model in the BBD design.

Source Sum of squares df Mean square F-value p-Value Remark

Prob N F

Model 106.77 9 11.86 139.68 b0.0001 Significant

X1-cell voltages 0.58 1 0.58 6.87 0.0344
X2-initial concentration of NaCl 80.52 1 80.52 948.02 b0.0001
X3-flow rates 0.048 1 0.048 0.57 0.4765
X1X2 0.013 1 0.013 0.16 0.7049
X1X3 0.011 1 0.011 0.13 0.7293
X2X3 2.500E-005 1 2.500E-005 2.944E-004 0.9868
X21 20.47 1 20.47 240.98 b0.0001
X22 0.061 1 0.061 0.72 0.4252
X23 4.08 1 4.08 48.07 0.0002
Residual 0.59 7 0.085
Lack of Fit 0.45 3 0.15 4.02 0.1062 Not significant
Pure error 0.15 4 0.037
Cor total 107.37 16

Noted: R2 = 0.9945, adjusted R2 = 0.9873, predicted R2 = 0.9313, C.V. % = 4.92.

electrode materials might be close to saturation beyond 1000 mg/l of
NaCl concentration.
The effect of the flow rate on the electrosorption capacity at any
steady cell voltage or initial NaCl concentration is also shown in
Fig. 6B and C. The two figures show that the electrosorption capacity in-
creased with an increase of the flow rate up to a certain value, and then
the higher the flow rate was, the lower the electrosorption capacity ob-
tained. In the same conditions, more salt ions had access to the electrode
surfaces, and the sorption capacity of the activated carbon electrodes
would become saturated more rapidly with the increase in the flow
rate from the beginning [25]. However, the electrosorption capacity
began to drop as the flow rate continued to rise, due to less retention
time for the mass transfer inside the CDI cell [7]. In addition, the opti-
mum value of the flow rate, where the maximum electrosorption capac-
ity was obtained, was approximately 25 ml/min.
From all the three response surface plots between the experimental
parameters and the electrosorption capacity in Fig. 6 and the results of
the ANOVA for quadratic model in Table 4, it was found that the param-
eter of the initial NaCl concentration affected the electrosorption capac-
ity more than the other two parameters.
from the results of the Box–Behnken design under RSM, aimed at
attaining the maximum electrosorption capacity in preparation for fur-
ther commercial application. The maximum predicted value of the
electrosorption capacity obtained by the Box–Behnken design in this
case was 10.67 mg/g under the optimal level of various parameters of
cell voltage, initial NaCl concentration and flow rate of 1.57 V,
1000 mg/l and 25 ml/min, respectively. Furthermore, three repeated
validation experiments were implemented at the selected optimal
levels of the operational parameters, and the average values of the
electrosorption capacity obtained were 10.53 ± 0.21 mg/g, which
were among the 95% confidence intervals (10.25–11.08 mg/g) of the
predicted optimal value. The results revealed that the Box–Behnken de-
sign under RSM was a reliable and valuable method to optimize the
electrosorption process with regard to desalination on activated carbon
electrodes [22,23]. Additionally, the power consumption of the optimal
operational conditions was approximately 3.64 kWh/m3, relatively
lower than the energy consumption of other desalination technologies
in accordance with some reports [4,6,32].
4. Conclusion

3.5. Evaluation and validation of the optimal levels under RSM
The experimental conditions of desalination on activated carbon
electrodes in the CDI process were optimized using Eq. (5) derived
Fig. 5. Normal % probability plot of the internally studentized residuals.
This work investigated the electrosorption performance related to
desalination on activated carbon electrodes. A super-capacitance acti-
vated carbon with a BET-specific surface area of 1770 m2/g and some
ordered mesopores (2–2.5 nm) that can partially avoid the EDL over-
lapping effect was applied for CDI experiments.
The Box–Behnken design based on response surface methodology
(RSM) was used to examine the effect and interaction of three main
experimental parameters (cell voltage, initial NaCl concentration and
flow rate) on NaCl removal during the CDI process. A quadratic polynomi-
al model verified by the determination coefficient (R2 = 0.9945) fits the
experimental data with an F-value of 139.68 (p-value b 0.0001), which
indicated that the regression model was highly significant. The
electrosorption capacity gradually increased with the increase of the ini-
tial NaCl concentration ranging from 200 to 1000 mg/l until the sorption
capacity of the electrodes became saturated. Nevertheless, it first in-
creased and reached its summit when the cell voltage or the flow rate
rose to a certain value and then began to decrease as the applied voltage
or the flow rate continued to increase. The initial NaCl concentration has a
greater impact on the electrosorption capacity than the cell voltage and
flow rate. Accordingly, the optimal level of operational parameters
obtained by Design-Expert software included a cell voltage, initial NaCl
concentration and flow rate of 1.57 V, 1000 mg/l and 25 ml/min, respec-
tively. Under these conditions, the maximum electrosorption capacity of
three confirmation experiments was an average of 10.53 ± 0.21 mg/g,
which is within the confidence intervals of the predicted optimal value
(10.67 mg/g) of electrosorption capacity. The experimental results and
70 Y. Zhao et al. / Desalination 336 (2014) 64–71

Acknowledgments
A 11
city(mg/g)

10 This work was supported partly by the NSFC under Grant No.
9 51178088. It was also sponsored by the National Science & Technology
Pillar Program (2013BAB09B01) and the Program for Liaoning
8
representative office of the China Environment Protection Foundation
rption capa

7
(CEPF2011-123-1-6).

g/l)
6

(m
5

ation
Y: Electroso

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