Desalination and Water Treatment
www.deswater.com
215 (2021) 69–79
March
doi: 10.5004/dwt.2021.26809
Design and synthesis of two novel carbon aerogels using citric and tartaric
acids as catalysts for continuous water desalination
Mohammadreza Alipoura, Mohamadreza Massoudinejada,*, Daryoush Sanaeia,
Hassan Rasoulzadehb,*, Mostafa Hadeic
a
Department of Environmental Health Engineering, School of Public Health and Safety, Shahid Beheshti University of Medical Sciences,
Tehran, Islamic Republic of Iran, Tel. +982122432040-1; emails: massoudi2010@yahoo.com/massoudi@sbmu.ac.ir (M. Massoudinejad),
mreza.aalipour@gmail.com (M. Alipour), daryss2572@gmail.com (D. Sanaei)
b
Department of Environmental Health Engineering, Student Research Committee, School of Public Health and Safety, Shahid Beheshti
University of Medical Sciences, Tehran, Iran, Tel. +989147715780; emails: Hasanrseng@gmail.com/Hrasoulzadeh@sbmu.ac.ir
c
Department of Environmental Health Engineering, School of Health, Tehran University of Medical Sciences, Tehran, Iran,
email: mostafa.hadei@gmail.com
Received 7 April 2020; Accepted 13 November 2020
abstract
This study aimed to find the best capacitive deionization (CD) carbon electrode without supercritical drying by preparing two different types of carbon aerogels with citric (CA) and tartaric (CAS)
acid catalysts. Both electrodes were prepared by the short sol–gel process through vacuum drying
and pyrolysis with CO2. The structure, pore size characterization, and electrosorption behavior of
electrodes were characterized by scanning electron microscopy (SEM), N2 adsorption–desorption
isotherms, and cyclic voltammetry (CV), respectively. SEM results showed highly porous, smooth,
and homogeneous structures without any cracks in both aerogels; however, the two aerogels
showed different pore structures. Analysis of the Brunauer–Emmett–Teller surface area also proved
no difference between CA and CAS in specific surface area (819 and 636 m2 g–1, respectively). But
the proportion of mesoporosity was higher in CD than CAS; so, CD outperformed CAS. CV also
showed better capacitive behavior than CAS since CAS needed more potential. The performance of
CD was considered in different concentrations of NaCl aqueous solutions (range: 200–1,000 mg L–1)
and at various applied voltages (range: 0.8–2 V). Besides, results revealed that salt-adsorption for
CA and CAS in optimum NaCl concentration of 250 mg L–1 and applied voltage of 2 V was 22.4 and
12.8 mg g–1, respectively.
Keywords: Carbon aerogel; Citric and tartaric acids; Brackish water; Desalination
1. Introduction
Developing desalination technologies is a certain requirement even in water-rich countries due to the increasing
rate of population growth, industrialization, as well as a
shortage of freshwater. For the last decades, reverse osmosis (RO) [1], Thermal technologies [2] and ion-exchange
(IX) [3] membrane technologies have been the most widely
used methods for generating drinking water from the sea
and brackish water. RO and thermal technology have been
commonly played the main role in producing freshwater,
particularly in the Persian Gulf countries [4,5]. These two
processes require higher energy consumption and operational costs [6]. Compared to these two techniques, control
capacitive deionization (CD) has reduced the cost of energy
consumption because of low scaling and fouling. It has also
* Corresponding authors.
1944-3994/1944-3986 © 2021 Desalination Publications. All rights reserved.
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M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
been shown to be easy to deploy, operate, and maintain
[7–9]. CD is an attractive safe (low-pressure and low-voltage) and adequate electrochemical process for brackish
water desalination that has received great attention over the
past years [10].
A CD cell consists of a pair of porous carbon electrodes,
a dielectric separator between the electrodes to preserve
the paired electrode from electrical short circuits, and current collectors. By applying the electric field by charging
voltage between two electrodes, electrical double layers
(EDLs) are formed near the electrode and ionic species with
an electric charge move to the oppositely charged electrode
and are adsorbed. This is known as the electro-sorption
process [11]. Thus, for the CD technique, the material
and surface area of the electrode are keys to remove ionic
constituents from water.
In literature, the effect of electrode type and various
carbon materials (graphene [12], activated carbons (AC)
[13], carbon nanotubes (CNT) [14], carbon aerogels (CA),
(e.g., cryogel, xerogel, and metal oxide doped aerogels),
and carbon composites such as ordered-mesopores carbon
[15,16]) respectively used in CD cells and in the electrode for
deionization performance have been investigated. Among
the aforementioned materials, CA with high salt adsorption and electrical conductivity has been considered an
ideal electrode for CD [17]. According to previous studies,
there are two methods for improving the CA sol–gel and
drying process: (1) to decrease polymerization time, and (2)
to use ambient drying [18,19]. The preparation of carbon
aerogel with acid catalysts accelerates the polymerization
in the sol–gel process; hence, we utilized citric and tartaric
acids to catalyze the gelling process with no super-critical
step and solvent exchange for drying.
Recently, major advances have been made in the flow of
feed water to the electrodes for CD cells such as flow-through
electrodes [20], flow-between electrodes [21], Fluidized
bed electrodes [22], hybrid capacitive deionization (CDI)
and desalination battery [23]. These architectural developments for cells have occurred when CD techniques and
large-scale CDI desalination modules started to be applied
more around the world. However, flow-between electrodes
are the most commonly used architectural cells in CD [24].
In this work, we proposed carbon aerogel electrodes consisting of a cationic and anionic capturing electrode appropriate for ion selectivity with different electrode materials. The
main aim of the study was to evaluate the CD performance
of the developed electrode via vacuum drying for investigating the influence of different charging voltages on NaCl
solution during the operation conditions. We also evaluated
the efficacy of CD performance in laboratory-scale tests.
2. Materials and methods
2.1. Materials
Resorcinol (R) >99% and an aqueous solution of formaldehyde (F) (37%wet, with 10% methanol) were supplied
from Merck, Germany. Ethanol and acetone (pure, technical
grade) solutions were also purchased from Sigma Aldrich,
Germany. Further, citric and tartaric acids (C, 1.0 N; standardized solution) were obtained from Merck, Germany.
Besides, for carbon aerogels synthesis, deionized water (W)
and sealable containers for gelation (200 mL, polypropylene
with screw cap) were used.
2.2. Synthesis of organic gels, drying and pyrolysis
In this study, the molar ratios used for the synthesis of resorcinol–formaldehyde gels were 0.5, 250, and
0.02 for R:F, R:C, and R:W, respectively. For each sample,
resorcinol was dissolved in deionized water at room temperature (23°C–25°C). Then, aqueous formaldehyde was
added gradually and the solutions were stirred for 10 min
to obtain homogeneous solutions. Tartaric and citric acid
1N were added to the solutions as catalysts until their pH
was fixed at 3.5 and 5.5, respectively and the resulting suspension was stirred for another 20 min at 600 rpm by a
magnetic stirrer. Then, the resulting colorless solution was
divided between two sealable polypropylene containers.
At gelation time of RF aerogels, samples with citric acid
(CA) and tartaric acid (CAS) were put in an oven for 2 and
1 h, respectively at 95°C. After polymerization, without any
solvent exchange, the gels and just two times washing with
ethanol and acetone, cut to defined size (1 cm × 4 cm × 3 cm)
and dried at –0.04 MPa and 110°C in a vacuum drying
chamber (OV-12, Jiao Tech, Seoul, Korea) for 24 h. After
3 h, the carbon aerogels were provided by carbonizing
at 950°C in an inert atmosphere of CO2 gas.
2.3. Cell preparation and lab bench-scale CD
Each aerogel sheet had an approximate density of
0.5 g cm–3. The aerogel sheets were then connected to titanium sheets as a current collector by a copper conductive
adhesive. Next, the bonding areas of the electrode and titanium plate were covered with silicone adhesive to prevent
the oxidation of the copper adhesive by air. As presented
(Fig. S1), a current collector was connected to the copper
wire by double-ended alligator electric cables to provide a
connection to a DC power supply for stabilizing and changing the voltage. Accordingly to Fig. 1a, the CD cell consists
of a pair of an electrode placed in a Plexiglas housing by
bolts and nuts and the distance between the electrodes was
adjusted to 3 mm. As shown in Fig. 1b, the diagrammatic
sketch of the CD test, the lab-scale system includes a digital conductivity meter, peristaltic pump, power supply, and
CD unit. NaCl solutions experimented during this work was
obtained from the equation and calibration curve derived
from seven tests presented (Fig. S2). Synthetic NaCl solutions employed as feed flow with a rate of 50 ml min–1 was
fed into a CD. The conductivities of these brackish solutions
(200, 500 and 1,000 µS cm–1) and the treated water samples
were measured by conductivity meter in one cycle. In the
present study, the specific electrosorption capacity was
defined as Eq. (1) [25]:
mg (Ci − C e ) V
=
m
g
(1)
where Ci and Ce are the initial and final concentrations, respectively, V is the volume of the saline solution,
and m is the quantity of carbon electrode.
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
2.4. Characterization
The surface structure and morphology of the carbon
aerogels were analyzed by scanning electron microscopy
(SEM, SU3500 Hitachi, Japan). The surface area, porevolume, and pore size distributions were estimated by
using the Brunauer–Emmett–Teller (BET) and Barrett–
Joyner–Halenda (BJH) methods, respectively. The t-plot
analysis was also used to analyze the mesopores area
as well as microspores volumes. Raman Spectrometer
(MultiRAM, Bruker Company, USA) of both carbon electrodes were analyzed in a range of wavelengths from 500
to 3,500 cm with an argon-ion laser. Moreover, to analyze
the composition and chemistry of the electrodes, the X-ray
photoelectron spectroscopy (XPS) was applied with an Al
X-rays micro-focused monochromator (K-alpha, Thermo
Fisher Scientific Company, USA). The electrosorption was
also carried out at room temperature and cyclic voltammetry (CV) was measured at various scan rates in the potential range from –0.8 V to 0.2 V in 1 M NaCl. Furthermore,
electrical specific conductance was measured for both CA
and CAS by using the four-point probe method (DEP-02,
SES Instruments & Pvt. Ltd., India). Also, Ag/AgCl (Silver/
Silver Chloride Electrode, 3.5 M KCl) and platinum were
used as reference electrode and counter electrode, respectively. Besides, the specific capacitance was calculated from
the CV curves on the basis of the following equation [26]:
C=
Q
∆Vm
(2)
where Q is the average charge, m is the mass of active material in grams, ΔV is the potential window, and C (F g–1) is the
specific capacitance.
3. Results and discussion
3.1. SEM morphologies of carbon aerogel samples
Figs. 2a and b show the SEM micrographs of the CA
and CAS. As can be seen, both carbon aerogels have highly
(a)
71
porous and three-dimensional network structures. Because
of the high velocity of sol–gel at the low pH in the polymerization process, aggregation of monomers occurred and
large microspheres particles with homogenous size were
shaped, which is obvious at a magnification of Figs. 2a and
b. The acid-catalyzed sol–gel particles have a thin neck,
which can be related to the effects of the short aging time
and nucleophilic attack of acid-catalyst [27,28]. However,
the release of carbon dioxide gas due to acid decomposition
at low temperatures can lead to the formation of the microspore [18]. The resultant CA and CAS aerogels exhibited a
strong particle network with large mesopores and no volume
shrinkage microstructure, respectively. Fig. 2a shows the
large mesopores and microspores, while in Fig. 2b several
mesopores can be observed at the surface of the CAS.
3.2. Pore characteristics of CA and CAS
The porous property of CA and CAS were investigated
by low-temperature N2 adsorption–desorption tests. The N2
adsorption–desorption isotherms and the Barrett–Joyner–
Halenda methods used for the pore size distribution of CA
and CAS are shown in Figs. 2c and d, respectively. The isotherms of CA and CAS can be classified as type I and IV,
according to the International Union of Pure and Applied
Chemistry classification. Fig. 3a shows hysteresis loops
at relative pressures higher than 0.7 for CA indicating the
presence of a large quantity of mesopores, while CAS has
the main microspores structure with no mesopores area.
This is presumably due to the poor structure of CAS, which
caused some mesopores to collapse to other pores during
pyrolization [27]. Therefore, we can claim that the presence
of both mesopores and microspores in an ideal carbon material is required for appropriate CD performance. Mesopores
can provide proper transport for ions to the surface of
carbon material to developing the electric double layer,
while microspores with many channels are suitable for
permeation of electrolyte [29]. CA in Fig. 2c shows a microspores structure and predominant mesopores with competent pore size distributions that play an essential role in the
ideal CD process. Also, curves (c) and (d) in Fig. 2 indicate
(b)
Fig. 1. (a) A cell and electrodes for capacitive deionization and (b) flow schematic of CD pilot-scale experiment system.
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M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
(c)
(d)
Fig. 2. SEM images of (a) CA, (b) CAS, (c) N2 adsorption–desorption isotherms and (d) BJH pore size distribution of CA and CAS.
that the CAS produced by vacuum drying had microspores
structure with approximately 819 m2 g–1 specific area while
having an unfavorable pore size distributions. Table 1 presents the BET specific surface area and Pore properties of
CA and CAS.
In the CD process, one of the removal characteristics is
typically related to the radius of hydrated ions with ionic
conductivity, which is 0.35 nm and 50.1 S cm2 mol–1 for Na
and 0.33 nm with 76.3 S cm2 mol–1 for Cl, respectively [30].
As shown in Table 1, the average pore diameters for CA
and CAS are 6.5 and 1.5 nm, respectively, so that the largest
pores of CA and a small part of CAS pores are larger than the
ionic radius.
3.3. XPS and Raman spectra characterization of carbon electrodes
In the current work, to further characterization of electrode structure, Raman spectroscopy was performed for both
CA and CAS (Fig. S3). Two particular emerged peaks in each
graph correspond to the D and G bands. Revealed D bands
in CA and CAS at around 1,355 and 1,340 cm–1, respectively
was related to the disordered carbon structure. The G band
in CA and CAS observed at about 1,585 and 1,570 cm–1 was
attributed to the graphitic composition of samples. In addition, 2D-bands for CA and CAS at 2,800 cm–1 are illustrated
Table 1
Pore characteristic of CA and CAS aerogels
2
–1
SBET (m g )
rp peak (nm)
Vp (cm3 g–1)
Vtotal (cm3 g–1)
Average pore diameter (nm)
CA
CAS
819
7.98
0.96
164
6.5
636
1.29
0.02
146
1.5
in Fig. S3. In spectroscopy, due to 2D-bands, the high-temperature of pyrolysis with CO2 caused graphite structure as
it was expected.
Towards a better understanding of elemental composition and the overall electronic structure, the main compositions of electrodes were analyzed by XPS. The curves of
both CA and CAS are shown in Fig. 3. As shown, the particular components in both electrodes are oxygen and carbon.
The observed C1s spectrums in Fig. 3 include two peaks
for each carbon electrode at 287.5, 287, 288.5, and 287.4 eV
for CA and CAS, respectively. We found that these peaks
related to the carbon in CA and CAS occur principally as
C–O and C=O. The peaks at 284.8 and 285 eV were referred
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
73
Fig. 3. X-ray photoelectron spectra of carbon aerogel electrodes.
to the C=C bands in CA and CAS related to the graphitic
nature of samples shown as sp2 in Fig. 3. The peaks at 285.8
and 286.4 eV also indicated the C–C bands (sp3), which
were linked to the disordered structure of the samples.
As shown in Fig. 3, the O1s spectrums have three peaks at
534 and 533.8 eV as C=O, 535.7 eV and 536 eV as C–O, and
538 and 538.3 eV as O–C=O.
3.4. Capacitance measurements
Electrosorption characterization was measured at
room temperature in a typical four-electrode probe experiment performed for both CA and CAS electrode. As shown
in Figs. 4a and b, for obtaining the one current density,
CAS needs higher potential, while CA has better electrical conductivity behavior. The lower conductivity of
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M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
Fig. 4. (a and b) Electrical conductivity and the specific capacitance by scan rate of CA and CAS. (c and d) Cyclic voltammetry
of CA and CAS.
CAS was probably related to its Impenetrable structure.
The electrical conductivity for CA and CAS electrodes was
measured as 3.4 and 59 Sm–1, respectively. Furthermore, the
CV curves of the CA and CAS electrodes were measured
in 1 M NaCl solution with a potential of –0.8 to 0.2 V presented in Fig. 4. In this figure, the profiles of CA and CAS
curves achieved at scan rates ranged between 5–150 mVs–1
and 25–200 mVs–1, respectively. In Fig. 4c, it is evident that
at low scan rates (5, 10, and 25), the CV curves have an
elongated quadrilateral shape due to the pore structure of
CA through which the electrolyte can penetrate [31]. With
increasing electric current resistance in high scan rates,
the ohmic resistance changed the forming behavior of
EDL. Then, the curves became deformed to quasi-rectangular. Moreover, the curves were without any redox peaks
exhibiting the ideal capacitive performance [32]. This also
indicated the cations and anions adsorbed on the surface
area of CA via coulombic interaction [33]. According to
Fig. 4d, the typical CV curves of the CAS electrode displays a lower voltage range and is approximately less
rectangular in shape than the CA electrode. This, indeed,
suggested the inferior electrochemical behavior of CAS
electrode. Eventually, the values of specific capacitances
were 178 and 58 Fg–1 for CA and 149 and 36 Fg–1 for CAS
at 25 and 150 mVs–1 obtained from Eq. (2).
3.5. CD performance of electrodes
The CD behaviors of both carbon electrodes were evaluated by adjusting the applied voltage between 0.8–2 V and
the flow rate of solution at 50 ml min–1 at ambient temperature. The concentration of NaCl solution, as the feed stream
in all tests, was fixed at 200, 500 and 1,000 µS cm–1. During
each test, the carbon electrode was regenerated by replacing
the voltage of the electrode and cell rinsed with deionized
water. Besides, the timing of shifting voltage to discharging
and separating ions from electrodes was considered according to Fig. S4. Under the adsorption and desorption cycles,
a digital conductivity meter was used to control any fluctuations in the conductivity of the inlet and outlet stream.
Fig. 5a shows the effluent conductivity of the 200 µS cm–1
influent solution in both CA and CAS electrodes with
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
75
Fig. 5. Variation of NaCl concentration with the applied voltage for CA and CAS. (a) 200 µS cm–1 for CA, (b) 500 µS cm–1 for CA,
(c) 1,000 µS cm–1 for CA, (d) 200 µS cm–1 for CAS, (e) 500 µS cm–1 for CAS, and (f) 1,000 µS cm–1 for CAS.
76
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
different applied voltages and times. By using NaCl solution as the influent, when the applied voltage to the system
increased from 0.8 to 2 V, the NaCl concentration in effluent
quickly decreased over time. In all tests, CD cells including
CA and CAS electrodes were charged by DC power applied
varying voltage, but the current was fixed at 5 A. Figs. 5b
and c also show the desalination capacity of CA and CAS
at 500 and 1,000 µS cm–1 at a different voltage. As expected,
the increment of the voltage from 0.8 to 2 V, the removal
capacity of the electrodes at both 500 and 1,000 µS cm–1 electrolytes also improved. In previously studied adsorption
capacities for CD electrodes, when the applied voltage was
higher than 1.4 or 1.8 V, the water became hydrolyzed and
relatively produced hydrogen and oxygen in the presence
of NaCl due to tiny bubbles decrease in the volume of water
at higher voltages; hence the process efficiency declined
[29,34]. Accordingly, the maximum applied voltage for the
prolonged operation in the CD process should be less than
1.3 V [29]. In this study, because of the short operation time
of the sorption-desorption cycle of CD cells, no electrochemical decomposition potential was observed by increasing the
applied voltage. Therefore, the maximum applied voltage
for the CD process was an optimum voltage of 2 V. It is obvious in Fig. 5 that the CAS electrode has lower adsorption
capacities rather than CA appropriately matching with the
outcomes of N2 adsorption–desorption isotherm and cyclic
voltammetry test. Moreover, Fig. 5 represents the comparison between the efficiency of different NaCl concentrations. As seen, the efficiency reduces by an increase in NaCl
concentration in both electrodes; although, in 500 mg L–1
concentration, the specific capacity in the CA electrode
begins to decrease. However, in all the tests, because of the
higher concentration of NaCl, the specific electrosorption
capacity increased. The specific electrosorption capacities of
CA and CAS electrode at 2 V are shown in Table 2. These
amounts are higher than other carbon materials, such as GO
[35], AC [36], and G-CNT [37] as an electrode, which are
compatible with the related reports. To test the possibility of
CA and CAS electrodes application in electrosorption/electrodesorption procedure, we regenerated cycles represented
in Fig. 6. In the adsorption process, by changing the positive
and negative voltage, the absorbed cations and anions can
be desorbed from CA and CAS. Thus, the effluent conductivity immediately rises. Therefore, CD electrodes could be
applied either reversibly or stably in adsorption–desorption cycles. In Fig. S5, XPS survey spectra illustrate sodium
adsorption for both CA and CAS in adsorption–desorption
periods. Materials of the cathode in both electrodes in CA
and CAS were determined after five adsorption–desorption
cycles and represented Na in 1072 eV. Obviously, due to lack
of change in intensity of the electrodes XPS peaks and identical peaks (carbon and oxygen) in adsorption–desorption
cycles, oxidation appeared on neither of the cathode electrodes proving that these materials can be applied for several cycles.
4. Conclusion
In summary, CA and CAS performed by short-time
polymerization resorcinol and formaldehyde solutions were
Table 2
Ion removal properties and the specific electro sorption capacity
NaCl concentration
(mg L–1)
Conductivity
influent (µS cm–1)
Conductivity out
(µS cm–1) CA
Conductivity out
(µS cm–1) CAS
Time
(min)
QCA
(mg g–1)
QCAS
(mg g–1)
50
100
250
500
106
210
516
1,030
44
101
325
896
58
143
409
922
40
40
35
30
7.4
12.8
22.4
16
6
8.2
12.8
13.3
Fig. 6. CA (a) and CAS (b) electrodes performance in several adsorption–desorption cycles.
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
pyrolyzed under CO2 atmosphere containing citric and tartaric acid as catalysts and dried by vacuum drying. This
method to build CA and CAS electrodes can be easily scaled
up for capacitive deionization applications without any
cracks and shrinkages on the surface. According to the SEM
images, BET analysis, and CV curves of CA and CAS electrodes, to avoid hard costly templates such as supercritical
drying to fabricate carbon aerogel, we can achieve a steady
structure with desirable conductivity behavior through
a simple method. Moreover, the effect of NaCl removal
from brackish water by using CA and CAS electrodes was
examined and the highest specific electrosorption capacities of CA and CAS occurred in 250 and 500 mg L–1 NaCl
as well as 22.4 and 13.3 mg g–1, respectively. The designed
CA electrode also illustrated great regeneration power
and efficiency in several adsorption–desorption cycles.
Acknowledgments
This work was financially supported by the school of
public health and safety, Shahid Beheshti University of
Medical Sciences, Tehran, Iran, under grant agreement
no.11835 and ethical code no.IR.SBMU.PHNS.REC.1395.29.
The authors would like especially thank to Simin Mirshafeiyan
and Ehsan Aghayani for proficiently supporting the pilot
set-up of the experiment.
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2500
y = 2.057x + 4.105
R² = 0.999
2000
conducvity µS/cm
78
1500
1000
500
0
0
200
400
600
800
1000
Concentraon mg/l
Fig. S2. NaCl solutions experimented with during this study
were obtained from the equation and calibration curve.
a
Supplementary information
b
Fig. S1. Copper conductive adhesive and covered the bonding
areas with silicone adhesive to prevent the oxidation of the copper adhesive by air.
Fig. S3. Raman spectra of CA (a) and CAS (b) samples the relative intensity of the D and G band R = ID/IG could identify the
structural disorder of the sample. A higher ratio implied a perfect material. The R-values of the samples are 1.094 and 1.076 for
CA and CAS, respectively. The R-value of the CA sample was
higher than CAS. This result demonstrated that why CA had a
larger specific area.
M. Alipour et al. / Desalination and Water Treatment 215 (2021) 69–79
79
Fig. S4. Time selected for the regeneration of the electrodes at
four concentrations were selected from the diagram below.
Fig. S5. X-ray photoelectron spectrum of carbon aerogels before adsorption and after adsorption of sodium in the cathode electrode:
(a) CA and (b) CAS.