Electrochimica Acta 56 (2011) 63126317

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

The feasibility of boron removal from water by capacitive deionization

Eran Avraham , Malachi Noked, Abraham Soffer, Doron Aurbach
Department of Chemistry, Bar Ilan University, Ramat-Gan 52900, Israel

a r t i c l e

i n f o

Article history:
Received 19 January 2011
Received in revised form 11 May 2011
Accepted 11 May 2011
Available online 19 May 2011
Keywords:
Capacitive deionization
Electro-adsorbtion
Boron removal

a b s t r a c t
We report on the possibility of removing boron (in the form of boric acid) from water by electrochemical
means. We explore capacitive de-ionization (CDI) processes in which local changes in pH near the surface
of high-surface-area activated carbon ber (ACF) electrodes during charging are utilized, in order to
dissociate boric acid into borate ions which can be electro-adsorbed onto the positive electrode in the
CDI cells. For this purpose, a special ow-through CDI cell was constructed in which the feed solution
ows through the electrodes. Local pH changes near the carbon electrode surface were investigated using
a MgCl2 solution probe in three- (with reference) and two-electrode cells, and described qualitatively.
We show that, to a certain extent, boron can indeed be removed from water by CDI.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Boron is benecial to plants only in small quantities. Longterm exposure to water containing too high concentration of boron
compounds can result in the malfunctioning of the cardiovascular,
nervous, alimentary, and sexual systems of humans and animals
[1,2]. The maximum acceptable level of boron compounds in drinking water is 2.4 mg l1 [3].
In reverse osmosis (RO) [4], which is the most common method
for water desalination, a multistage process should be applied in
order to reduce the boron concentration in the water. The efciency
of boron removal by the membranes in RO processes depends on
the solutions pH [5]. At a pH lower than 7, boron compounds exist
mainly in an uncharged form, namely, boric acid. The fact that boric
acid is neutral (uncharged) results from the relatively small size of
boric acid moieties (no hydration shells) compared to the charged
form, namely, borate ions. Due to the relatively small size of boric
acid species in water, their removal by membranes (e.g., by RO)
is very difcult. At a pH which is sufciently basic, boric acid is
ionized to form borate ions (i.e., the dissociated form) which are
fully hydrated, resulting in the formation of large anions. Such large
ions can be removed indeed from water by RO [6]. Hence, in order to
use RO for removing boron compounds from water, we should work
with solutions of high pH in which boron compounds exist as large
ions [7]. However, this is unrealistic for RO operation because if the
solutions have to reach high pH values in order to remove boron
from water in the form of borate anions, Ca(OH)2 and Mg(OH)2 can

Corresponding author.
E-mail address: eranchem@gmail.com (E. Avraham).
0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.05.037

also be formed and precipitate on the membranes in the RO process,

causing irreversible damage.
Capacitive deionization (CDI) can serve as an energy-efcient
alternative for the desalination of brackish water [815]. In the
classical CDI method, the solution is fed through or along (parallel to) activated carbon ber (ACF) electrodes usually comprising
bers or carbon aerogel, with a surface area of hundreds of m2 g1 .
Removal of the salt in CDI processes is obtained by the highly
reversible electrostatic adsorption of ions on the application of a
potential difference between the two electrodes of the cell. Since
the process mainly involves electrostatic interactions, activated
carbon electrodes in CDI cells can undergo an impressive number
of charge/discharge cycles.
On polarization, the pair of electrodes in the CDI cells can effectively electro-adsorb charged species from water, such as salts,
toxic metal, and even bacteria. In a regular CDI process, at the usual
pH of aqueous media, boric acid cannot be removed by the polarization of the cell. However, if the pH values are basic near the
negative electrode, boric acid will react with OH to form borate
anions that can be electro-adsorbed to the positive electrode in
the CDI cell. In the potential window that is usually applied to CDI
cells with aqueous solutions (<1.23 V), all the processes in these
cells are non-Faradaic, namely, related only to electro-adsorption
and desorption phenomena. Naturally, the application of potentials
higher than 1.23 V to symmetric CDI cells will lead to Faradaic processes in which water can be electrolyzed. Indeed, it was realized in
previous studies that when the potentials applied to symmetrical
CDI cells comprising identical active carbon electrodes are below
1.23 V, Faradaic reactions do not occur [15]. In turn, there are surface red-ox reactions related to oxygen-containing surface groups
and reduction of trace oxygen dissolved in the water, on the carbon
electrodes that may lead to slight pH changes near the electrodes

E. Avraham et al. / Electrochimica Acta 56 (2011) 63126317

upon their polarization [16]. Note that these pH changes may be

very small because the solution ows through the cell in a typical
CDI process, so that the hydronium or hydroxide ions formed near
the electrodes are immediately diluted [15].
However, we should take into account the fact that the carbon
electrodes possess a high surface area and highly porous structure. Thereby, the ratio between the surface and the volume within
the pores may be sufciently high so that on polarization of these
electrodes above a certain potential threshold, signicant temporary local pH changes can develop within the pores of the carbon
electrodes. A good way to demonstrate these temporary local pH
changes in the carbon electrode pores is to introduce into the CDI
cell a soluble salt such as MgCl2 , which can react with locally
formed hydroxide ions to form Mg(OH)2 precipitants. Thus, when
a potential applied to the carbon electrode leads to signicant local
pH changes in the electrodes pores, an irreversible reaction takes
place, i.e., Mg(OH)2 precipitation, which can easily be reected by
measurements of concentration vs. time proles. Such measurements can distinguish very well between irreversible reactions
such as precipitation, and reversible reactions, namely, electrostatic interactions (assuming that the carbon electrodes do not
change their properties during cycling) which show very reproducible concentration/time proles.
In this paper we examine the possibility of removing boric acid
from aqueous solutions by CDI processes, via changes in pH near the
electrodes that are induced by polarization of the activated carbon
electrodes in CDI cells. Separate measurements carried out with
MgCl2 solutions, used as an indirect (but reliable) in situ probe
to indicate local changes in the pH at the electrodes surfaces, as
a function of the voltage applied to the CDI cell. The idea is simple: when the pH near the negative electrodes surface increases,
magnesium hydroxide is formed and precipitates. The consequent
removal of magnesium ions from the solution, immediately affects
the electrochemical response of the CDI cell, which is easy to measure. Based on this measured response of the CDI cell, it was possible
to decide which potential has to be applied to the CDI cell in order
to achieve the local high pH values required to remove boron from
the solution via precipitation of boron hydroxide.
2. Experimental
2.1. The cell design and the system setup
We used two kinds of cells, both of which are dened as ow
through capacitors in which the solution ows through the carbon electrodes. Cell #1 included three electrodes, and Cell #2 two
identical electrodes.
2.1.1. Type 1 cell (3 electrodes cell, Fig. 1a)
The cell is dened as a ow-through capacitor in which the
solution is forced to ow through the activated carbon electrodes.
The working electrode consists of two high-capacity (120 F g1 )
identical carbon cloths, each with a diameter of 9.8 cm and a thickness of 0.26 mm. The total weight of the electrodes was about 1.6 g,
so that on applying a polarization of 1 V between the electrodes,
the electrodes salt adsorption capacity is up to about 1 mol3 (for
mono-valent salt, according to C = dQ/dV). The system was designed
such that the ratio between the mass of carbon electrodes (in g) to
the solution volume (in ml) is large enough to achieve signicant
changes in the concentration of the ions present in the solution, as
shown in Fig. 1a. This is a ange type design of at carbon cloth
electrodes, enclosed between top and bottom poly (vinyl chloride)
covers with distributors to ensure the homogeneous ow of the
solution throughout the whole circular cross section of the cell.
A sheet of rayon cloth served as a separator, and a sealing gasket

6313

was formed by soaking silicon glue into the rims of the separator,
which exhibited a fairly low resistance to water ow, so that the
pressure drop across the cell was no more than 200 mbar. It was
thick enough to prevent short circuits via protruding carbon bers.
A poly(tetrauoroethylene) ring spacer formed a 1 mm gap lled
by two activated carbon cloth sheets, which served as the working
electrode. A exible impermeable graphite paper ring served as the
current collector. This was a ring-shaped, electrically conductive
carbon sheet whose internal diameter was 3 mm smaller than the
outer diameter of the carbon cloth (working) electrode. Thus, there
was a 1.5 mm radial overlap between the current collector and the
activated carbon electrode to secure the electrical contact between
them. The same arrangement was used for the two Ag/AgCl counter
and reference electrodes. The counter electrode was made of a silver mesh that was deeply anodized in a 0.1 M HCl solution to yield
a thick AgCl layer. The charge stored in the AgCl layer was equivalent to more than three times the charge that can be stored in the
electrical double layer of the activated carbon electrode under the
maximal potential applied to it in this work.
2.1.2. Type 2 cell (a typical CDI cell, Fig. 1b)
The design of the two electrodes ow through cell (Fig. 2) is
the same, where the counter and reference anodized silver mesh
were removed and replaced by two identical carbon cloths (same
as the working electrodes).
2.2. The system setup
The system setup was identical for both kinds of cells. Fig. 2
describes the experimental setup which includes the electrochemical cell, a conductivity probe, and a peristaltic pump as the main
units. The setup also included an arrangement for continuously dissolving gas pockets within the cell, which may be created on lling
the system with the solution or by occasional water electrolysis.
This arrangement worked as follows: the cell was kept under a
positive hydrostatic pressure relative to the system vent by means
of a back-pressure regulator backed with a water head of about
100 mm. The solution coming from the expansion vessel was equilibrated with the gas within it at ambient pressure. The solution
was then pressurized by the peristaltic pump up to the water head
exerted by the back-pressure regulator, thus creating an undersaturation of about 100 mm, which dissolves any gas present within
the system. The observed dissolution of air bubbles throughout the
system tubing showed that this arrangement was indeed effective. The expansion vessel also served for the continuous purging of
the system with nitrogen, removing dissolved oxygen by nitrogen
bubbling through the solution, thus preventing interference due to
its electrochemical reduction at the working electrode, especially
when negatively polarized. The volume of the solution circulated
by the experimental setup was about 70 ml.
The conductivity cell, in series with the main electrochemical cell, was connected to a conductometer from Metrohm, Inc.
(model 714). The conductivity was recorded on a computer (RS232)
using Labview (version 8.2). The sampling rate was 1 s1 . The electrochemical cell was operated by a potentiostat (PGSTAT Autolab
electrochemical measuring system) from Eco Chemie, Inc.
2.3. Materials: activated carbon electrodes
The activated carbon that we investigated in this work was a
commercial carbon cloth (ACC-507-15) from Nippon Kynol, Japan
with a high surface area of 1440 m2 g1 obtained by carbonization
and activation of a phenolformaldehyde polymer. Analyticalgrade sodium chlorides (>99%) was purchased from Frutarom,
Israel. Magnesium chloride (>99%) and boric acid (>99.5%) were
obtained from SigmaAldrich. In all the experiments, the pH of

6314

E. Avraham et al. / Electrochimica Acta 56 (2011) 63126317

Fig. 1. A scheme of the cross sections of the ow through cells used in this work. All the components are explained in the gure. (a) Type #1 cell (three electrodes CDI cell).
(b) Type #2 cell (2-electrodes (typical) CDI cell).

the solution was measured every 20 min in order to ensure that

extreme pH values did not develop in the solutions during cycling
(the pH of the solutions was always between 6 and 8). We intentionally did not insert a pH meter probe in order to minimize, as
far as possible, the setup volume for better sensitivity to the concentration changes. Elemental analysis of electrolyte solutions was
carried out with an ICP instrument from Jobin Yvon Inc.
2.4. Pretreatment of the carbon electrode cloths
Prior to the assembly of the carbon cloths in the cell, the carbon
electrode cloths were degassed with boiled distilled water in order
to remove trapped gases within the pores. Periodic cycles of charge
and discharge were applied to the CDI cells in order to bring the
system into a steady state, before measurements were taken.
3. Results and discussion
3.1. Local pH changes adjacent the negatively polarized electrode
Since the surface of the carbon electrodes is rather porous, certain local temporary changes in pH could develop in the mesoor macro-pores of the electrodes, on polarization. Extreme pH
values may develop in very conned domains, e.g., within small
porous structures. Hence, the concentration changes detected by

the conductivity measurements of the system cannot detect the

development of high pH values within the electrodes. Therefore,
the assumption that the concentration is uniform near the carbon
electrode and at the conductivity probe (placed at the water exit
from the cell) is a good approximation only when the ow rates of
the solutions are high enough.
The use of three-electrode cells in this work enabled an investigation of the pH changes that occur at the negative electrodes
separately, without any inuence from the positive electrode, as is
the case in the two-electrode CDI cells (in which there are reections between the electrodes).
The Ag/AgCl counter electrode in the type #1 cell can only
liberate (where negatively polarized) or absorb (when positively
polarized) chloride ions according to (1).
AgCl + e  Ag + Cl

(1)

so that the changes in pH adjacent to the electrodes are obtained

only from the working carbon-cloth electrode.
Fig. 3 shows the concentration prole of Na+ ions vs. time in
the three-electrode cells, measured on periodic polarization under
steady-state conditions. The solution contained about 0.04 M NaCl.
The carbon electrode was negatively polarized up to 300 mV vs. an
Ag/AgCl/Cl reference electrode, and back to the potential of zero
charge (PZC). Each chargedischarge cycle lasted for 2000s, where
the solution ow rate was 1 ml s1 . It can be seen that the cycles are

E. Avraham et al. / Electrochimica Acta 56 (2011) 63126317

6315

Fig. 2. A schematic description of the experimental setup used in this work (cell,
conductivity probe, and pump).

reproducible. When we compare (Fig. 3) the concentration prole

of Na+ ions to that of Mg2+ ions in similar experiments (the threeelectrode cells contained about 0.025 M MgCl2 aqueous solution),
we can see that the cycles are not reproducible, indicating that an
irreversible reaction takes place. Moreover, a gradual decrease in
the Mg2+ concentration in the solution is indicated. We attribute
this behavior of the MgCl2 solution in the cell to the local increase
in pH of the carbon electrode on its negative polarization, even at
the relatively low applied potential (E = 0.3 V vs. Ag/AgCl/Cl )
which leads to the precipitation of Mg(OH)2 .
It should be noted that during charging (i.e., the negative polarization of the electrode), the reaction of magnesium ions with
hydroxide ions to form Mg(OH)2 precipitants and the electroadsorption of Mg2+ ions onto the carbon electrode take place
simultaneously. In the case of a symmetrical CDI cell composed of
a pair of electrodes (i.e., a practical CDI cell, type #2 cell), based on
other reports on symmetrical CDI cells, opposite pH changes occur
on the electrodes, and hence, the practical pH of the cell remains
invariant on polarization.
The behavior of MgCl2 solutions in the CDI cell (type #2 cell) was
also measured. When the solution ow was adjusted to 1 ml s1 ,
the concentration of MgCl2 in the solution introduced into the CDI
cell was about 0.0545 M, and a potential difference of 1 V was
applied to the cell (each chargedischarge cycle lasts for 2000s),
reproducible cycles of conductivity proles were obtained. These
steady reproducible cycles indicated that at these particular ow

Fig. 3. Periodic concentration proles during repeated chargedischarge cycles of

the three-electrode cell (type #1), once loaded with a 0.04 M NaCl solution, and once
with 0.025 M MgCl2 solution. The potential applied vs. the RE 300 0 mV. The ow
rate was 1 ml s1 .

Fig. 4. Concentrationtime proles during chargedischarge cycles of 0.054 M

MgCl2 solution in a symmetric CDI cell (type #2). The ow rate was 0.25 ml s1 .
(a) The potential applied was 1 0 V. (b) The polarity of the electrodes was then
inverted for a few cycles, i.e., the potential applied was +1 0 V.

rates, a steady local basic pH sufcient for Mg(OH)2 precipitation

cannot develop in these CDI experiments. However, as shown in
Fig. 4a, when the ow rate was reduced to 0.25 ml s1 , a gradual
decrease in the conductivity prole was observed, attributed to the
depletion of ions due to Mg(OH)2 precipitation. When the polarity
of the electrodes was inverted (a potential difference of +1 V was
applied between the electrodes), a gradual increase in the MgCl2
concentration prole back to the initial level was obtained (Fig. 4b).
At a lower concentration of MgCl2 in these experiments, the cycle
proles were reproducible, and a pH of about 9 developed near the
negative electrode, sufcient for Mg(OH)2 preparation.
These experiments with MgCl2 solutions (at relatively high concentration) show that mild polarization of the CDI cells leads to

Fig. 5. Distribution diagram of boric acid in the pH range 711 for boric acid concentration <0.025 M.

6316

E. Avraham et al. / Electrochimica Acta 56 (2011) 63126317

Fig. 6. Illustration of the removal process of boron from water by CDI. (1) Boron contaminated water rst ow through the negatively polarized electrode, where a certain

basic pH environment is developed adjacent the negative electrode. (2) The equilibrium B(OH)3 + 2H2 O  B(OH)4 + H3 O+ , adjacent the electrode, is driven toward the
formation of borate ions. (3) The borate ions are enforced to ow to the positively polarized and being electro-adsorbed. Note that there are two possibilities for keeping the
electroneutrality of the solution: 1. for each borate ion which is electro-adsorbed onto the negative electrode, a hydronium ion is generated by the positive electrode. 2. For
each hydroxide ion which is generated by the negative electrode, chloride ion (in this case) is being electro-adsorbed onto the positive electrode.

changes in pH values that should be sufcient for the formation of

borate ions at the negative electrode. However, at the usual low
concentration of Ca2+ and Mg2+ ions in drinking water, precipitation of Ca(OH)2 and Mg(OH)2 in CDI cells due to the local high pH
values that develop around the negative electrodes in CDI processes
is impossible.
3.2. Boron removal
Boric acid is considered as a Lewis acid, hydroxyl acceptor. In
aqueous solution, the boric acid is in pH-dependent equilibrium
with the borate anion such that higher pH drives the reaction
toward the formation of the borate (pKa = 9.24) [17]:
+
B(OH)3 + 2H2 O  B(OH)
4 + H3 O

(2)

Boric acid exists predominantly as undissociated boric acid

[B(OH)3 ] in dilute aqueous solution below pH 7 (Fig. 5).
Since the dissociation constant for boric acid (pKa ) is 9.24,
above pH 10, the metaborate anion, B(OH)4 becomes the main
species in solution. Between pH 6 and pH 11 and at high concentration (>0.025 M), highly water soluble polyborate ions such as
B5 O6 (OH)4 , B3 O3 (OH)4 and B4 O5 (OH)4 2 may be formed:

4B(OH)3 + B(OH)
4  B5 O6 (OH)4 + 6H2 O

(3)

2B(OH)3 + B(OH)
4

(4)

B3 O3 (OH)
4

+ 3H2 O

2
2B(OH)3 + 2B(OH)
4  B4 O5 (OH)4 + 5H2 O

(5)

Once the ratio of B(OH)3 to B(OH)4 is greater than 0.5, only

the mono-borate is observed [18]. The boron-contaminated water
should ow rst through the negatively polarized electrode, where
a certain basic pH obtains near and inside the active negatively

polarized pores of the carbon electrodes. Once the negatively polarized electrode generates OH ions within its pores, the equilibrium
+
B(OH)3 + 2H2 O  B(OH)
4 + H3 O , adjacent to the electrode, is
driven toward the formation of borate ions, and boric acid is transferred, at least partially, into the borate ion form.
Working in a ow-through CDI cell forces the borate ions, after
being formed, to travel toward the positively polarized electrode
surface, and the desirable electro-adsorption of the borate ions
onto the positive electrode occurs. Due to the high concentration
of hydronium ions near the adjacent surface of the positive electrode, the borate ions can react with these ions to form boric acid
again. However, the electro-adsorption of the negative borate ions
in the pores of the positive electrodes is kinetically favored. This
procedure is illustrated in Fig. 6. Since the solution can be circulated through the CDI cell several times while the cell remains
charged, the process thus described can be repeated and, hence, can
be considered as a multistage process that can be optimized for the
effective removal of borate ions. These are further removed from
the cell by its shorting (that leads to the desorption of the borates)
and their removal during the regeneration stage of the CDI process.
In a typical demonstration, a solution containing around 820,
1290 and 480 mg dm3 , sodium, chloride and boron, respectively,
were introduced into the CDI cell and the system used here (symmetric cell with two identical activated carbon electrodes). In order
to obtain strong evidence to support our suggested mechanism,
and to prevent any possibility of boron removal due to physical
adsorption by the activated carbon [19], we deliberately introduced
a high concentration of boron (although the boron concentration
in seawater is about 510 mg dm3 ). The solution was circulated
in the system for about 1 h. The solution included sodium chloride
as a charge carrier electrolyte only. The ow rate was adjusted to
0.25 ml s1 . A potential difference of 1 V was applied between the

E. Avraham et al. / Electrochimica Acta 56 (2011) 63126317

Table 1
Concentration of the various elements in solutions before and after cycling during 1 h in the CDI system, while a potential difference of 1 V was applied to the
symmetrical CDI cell (type #2 cell).

Sodium
Chloride
Boron

Conc. (mg dm3 )

before charging

Conc. (mg dm3 )

after charging

820
1290
480

593
975
328

electrodes in the cell upon cycling (each chargedischarge cycle

lasts for 2000s). During 1 h of cycling, the conductivity recording
became stable. Aliquots of the solution were sampled and analyzed
by ICP, yielding the results shown in Table 1; a decrease of 30% of
the boron concentration was obtained, very similar to the decrease
in the sodium chloride concentration, meaning that borate behaves
like other anions in its electro-adsorptive properties.
4. Conclusions
We have shown that it is possible to remove boron, present in
the form of boric acid, from water in a simple CDI process that uses
a symmetric electrochemical cell consisting of two identical activated carbon electrodes. The boron extracting process takes place
in two stages. The rst is dissociation of boric acid on the negative electrode due to the formation of a local basic pH on polarizing
the cell. The second stage is electro-adsorption of the borate ions

6317

thus formed onto the positive electrode. Preliminary experiments

showed a removal of 30% of boron (same level of removal of other
ions in solution). It is clear that upon further optimization of the
systems (e.g., electrodes, cell parameters) and the experimental
conditions potential applied, ow rate, etc., it may be possible
to demonstrate impressive removal of boric acid from water.
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