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Journal of Colloid and Interface Science 263 (2003) 386–390

www.elsevier.com/locate/jcis

PEG–catalytic water splitting in the interface of a bipolar membrane

RongQiang Fu, TongWen Xu,∗ Gang Wang, WeiHua Yang, and ZhongXiao Pan
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Received 11 October 2002; accepted 20 March 2003

Abstract
This paper investigates the effect of polyethylene glycol (PEG) on the water dissociation of bipolar membranes. To do this, bipolar
membranes were prepared by immersing anion exchange membranes in different-concentration solutions of different-molecular-weight PEGs
and then casting the solutions of sulfonated polyphenylene oxide (SPPO) on the anion exchange membranes. All the bipolar membranes with
PEG in the interface are evaluated by current–voltage curves. The experimental results prove that PEG has excellent catalytic function for
water dissociation. Furthermore, this function is enhanced by both PEG amount (PEG concentration) and PEG molecular weight in the
interface of a bipolar membrane.
 2003 Elsevier Inc. All rights reserved.

Keywords: Bipolar membrane; Water splitting; Interface; Polyethylene glycol

1. Introduction trichloride, chromic nitrate or indium sulfate with a sable

Bipolar membrane, which consists of an anion-selective
layer on one side and a cation-selective layer on the other
side, has been applied industrially in resource recovery, pol-
lutant control, and chemical processing because of the sim-
ple process, high efficiency, and low waste disposal it makes
possible [1–6].
A bipolar membrane will not be expected to have good
properties if it is directly composed from a cation-exchange
layer and an anion-exchange layer. To improve the perfor-
mance of a bipolar membrane, a thin medium layer is gener-
ally formed elaborately between the cation and anion layers.
In bipolar membranes prepared by Chlanda, the interface
layer included a matrix material containing quaternary and
nonquaternary amine groups and having dispersed therein a
cation exchange resin [7], and the bipolar membrane pre-
pared by Strathmann and Bauer had a thin intermediate
layer consisting of a highly charged polyelectrolyte, such as
poly(4-vinyl pyridine) or polyacrylic acid [8–10]. Simons
found, for bipolar membranes formed from Negev Insti-
tute polyethylene films [11], that the voltage was lowered
if the films were coated with one or more suitable inorganic
electrolyte solutions such as sodium metasilicate, ruthenium
* Corresponding author.
E-mail address: twxu@ustc.edu.cn (T.W. Xu).
0021-9797/03/$ – see front matter  2003 Elsevier Inc. All rights reserved.
doi:10.1016/S0021-9797(03)00307-2
brush, before they were pressed together [12]. Hanada dis-
closed that a bipolar membrane comprising a cation ex-
change membrane, in which a cation exchange group, at
least at its adhered surface, had been ion-exchanged with
a heavy metal ion such as Fe2+ , Fe3+ , Ti4+ , Sn2+ , Sn4+ ,
Zr4+ , Pd2+ , or Ru3+ , had a lower water-splitting membrane
potential [13]. Simons proposed that the anion- and cation-
exchange membranes be treated with a hot aqueous alkaline
solution of at least a metallic salt before they were pressed
together [14,15]. Umemura prepared a bipolar membrane
with an inorganic ion exchanger, such as hydrated zirco-
nium oxide, hydrated titanium oxide, hydrated manganese
oxide, an antimonate, an aluminosilicate, or a zeolite, at the
interface [16]. The mechanism of all the above treatments is
probably that some species have remained in the interface in
a proper formation, which catalyzes water splitting and in-
creases the wetness of the junction [7,8,12,15].
The water-splitting mechanism has been discussed for a
long time. Mafé et al. explained the water dissociation us-
ing the Donnan effect and the Nernst–Planck equation; the
water molecule dissociates into H+ and OH− in accordance
with the second Wien effect [17–21]. On the other hand, Si-
mons et al. suggested that the water dissociation is caused by
proton transfer between the fixed charged groups and water
molecules existing in the interface [22–26]. Recently, Hur-
witz proposed an electrochemical model according to which
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even under large current densities the water-splitting reac-
tion remains reversible and is in its equilibrium state [27,28].
In this paper, the preparation of a bipolar membrane with
polyethylene glycol (PEG) as the intermediate layer is de-
scribed. The effect of PEG molecular weight and concentra-
tion in the interface of bipolar membranes on water splitting
was fully investigated in term of the current–voltage curve
measurements. PEG is chosen as a transition layer because
(i) it is a kind of strong hydrophilic substance and (ii) there
are possible hydrogen-bonding and polar interactions be-
tween PEG and water molecules [29]. The experimental
observations were explained by the available water-splitting
mechanism.
2. Experiments and methods
2.1. Materials
The quaternary-ammonium-type heterogeneous anion ex-
change membrane of polyethylene (Model 3362BW) was
provided by Shanghai Chemical Plant Co. with thick-
ness 0.42 mm, water content 35%, ion exchange capacity
1.8 meq/g.dry, area resistance 12  cm2 , and permselec-
tivity 89%. Sulfonated polyphenylene oxide (SPPO) was
obtained from the Shandong Ocean Chemical Industry Sci-
entific Research Institute with an ion exchange capacity of
2.1 meq/g.dry. PEGs with molecular weights 600, 1000,
2000, and 10,000, provided by the Shanghai Chemical
Reagent Co., were used to prepare aqueous solutions with
concentrations 0.2, 1.0, and 3.0 M (the concentration was
calculated by repeating units of PEG). The other chemical
agents were used as received.
2.2. Preparation of the bipolar membranes
The anion-exchange membranes were cut into 5 × 5 cm
squares and washed repetitively with 1.0 M sodium hydrox-
ide and 1.0 M hydrochloric acid aqueous solutions to make
the surfaces clean. Then they were washed with distilled wa-
ter and dried. The membranes were put into PEG aqueous
solution for 12 h and PEG was adsorbed onto the mem-
branes. Then they were taken out, the drops swayed slightly
off of their surfaces, and placed on glass plates. The SPPO
solution in dimethyl formamide (DMF) with a concentration
of 1 g/4 ml was coated on the membranes. The membranes
were placed in air for half an hour, and in an oven for an
additional 2 h at 45 ◦ C.
2.3. Current–voltage curves of the bipolar membranes
The current–voltage curve measurement apparatus for
bipolar membranes is shown in Fig. 1. It is similar to the one
reported in the literature [30], but differentiated a little in
current electrodes, measurement electrodes, and directions
of the solution flux. The measurement cell was designed as
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387
Fig. 1. Current–voltage curve measurement apparatus: current electrode
(CE), platinum filament (PF), solution flux (SF), and bipolar mem-
brane (BM).
a conical shape, which gives a large surface for the current
electrodes and a small area for the membrane, to minimize
border effects and make the current through the membrane
approximately homogeneous. A bipolar membrane of cross-
section area 1.04 cm2 was fixed between the two half-cells.
The electrolyte solution in a superthermostatic bath was
pumped at a constant rate into the cell from the bottom and
the streams were directed to the membrane surfaces in order
to minimize boundary layer effects as well as provide the
necessary mixing of the solution. Both streams leaving each
corresponding half-cell from the top were cycled to the su-
perthermostatic bath, so the pH value of the whole solution
was maintained constant. In our experiments 0.4 M Na2 SO4
was used as the electrolyte solution, avoiding the release of
toxic Cl2 that could occur in the electrode reaction if chlo-
ride salt was used. Further, protons and hydroxyl ions can
be generated simultaneously in both electrodes and neutral-
ize each other to maintain the pH value of the electrolyte
solution when both streams converge in the bath tank. The
temperature of the superthermostatic bath was set at 20 ◦ C.
The current was supplied by a stabilized current DC power
system (DF1731SD2A, Ningbo Zhonghua Electronics Co.,
Ltd.), measured using a multimeter (DT9205, Zhangzhou
Mater Electronics Co., Ltd.), and introduced into the cell
by two ruthenium-plated titanium electrodes. The poten-
tial was measured using a multimeter (UT30B, Shengzhen
Uni-Trend Electronics Co., Ltd.) by two platinum filaments
located approximately 1.0 mm in front of each membrane
surface after operating under a current density of 240 A/m2
for 50 min to allow a quasi-stationary state to be established.
3. Results and discussion
Figure 2 shows the I –V characteristics of the bipo-
lar membranes prepared by immersing the anion exchange
membranes in 1.0 M solutions of different weight PEGs.
Compared with the blank sample (not PEG in the inter-
face), the bipolar membranes adsorbing PEG in the interface
have a relatively low voltage; i.e., the water-splitting effect
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Fig. 2. The I –V curves of bipolar membranes of which the anion exchange
membranes have been immersed in 1.0 M solutions of different weight
PEGs: PEG 600 (
), PEG 1000 (Q), PEG 2000 (a), PEG 10,000 (F),
and not PEG (2).
is accelerated by the addition of PEG, whatever its mole-
cular weight is. A theoretical interpretation to this result
can be based on both the protonation–deprotonation reac-
tions model and the hydrophilicity change in the interface.
According to the proton-transfer reaction model proposed
by Simons et al. [22–26], the H+ and OH− can be gen-
erated from protonation–deprotonation reactions between
membrane-fixed charge groups and the water molecule by
the reactions
B + H2 O  BH+ –OH−  BH+ + OH− , (1)
+ + +
BH + H2 O  B–H3 O  B + H3 O , (2)
or
A− + H2 O  AH–OH−  AH + OH− , (3)
− + − +
AH + H2 O  A –H3 O  A + H3 O , (4)
where BH+ and A− refer to the catalytic centers. As men-
tioned before, there are hydrogen-bonding and polar interac-
tions between PEG and water molecules [29], which speed
up the water dissociation into hydrogen ions and hydroxyl
ions. Thus the voltage across the membrane falls. On the
other hand, PEG is a kind of strong hydrophilic substance.
When anion exchange membrane was immersed in PEG
solution, the number of hydrophilic sites in the interfacial
region increased due to the adsorption of PEG. Correspond-
ingly, the efficiency of water splitting increases and the volt-
age across the bipolar membrane decreases.
If the bipolar membranes prepared from PEGs of differ-
ent molecular weights are compared, we find that the higher
the molecular weight of PEG adsorbed in the interface is, the
lower the voltage across the bipolar membrane is (as shown
in Fig. 2). In order to make this clear, we investigate the mag-
nitude of the adsorptive amount, which is quantified by the
specific adsorbed amount in an anion exchange membrane,
i.e., a ratio of the adsorbed PEG amount (g) to the weight of
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Table 1
Specific adsorbed PEG amounts in anion exchange membranes
Concentration, M PEG 600 PEG1000 PEG 2000 PEG 10,000
0.2 – – 1.05% 1.10%
1.0 2.74% 2.81% 2.78% 2.76%
3.0 – – 5.86% 5.96%
the initial membrane (g). The specific adsorbed amounts for
various cases are shown in Table 1. Obviously, the specific
adsorbed amounts for different molecular weight PEGs are
very close if the PEG concentration is kept fixed. Though the
specific adsorbed amount in an anion exchange membrane
is not exactly equal to the specific remaining amount in the
interface of the bipolar membrane, it can approximately re-
flect the circumstances in the interface. Thus a decrease in
the voltage with the PEG molecular weight may not be defi-
nitely caused by an increase in adsorbed PEG amounts at the
junction. It is possible that a more suitable chemical struc-
ture for water splitting at the interface of a bipolar membrane
will be produced when a higher molecular weight PEG is ad-
sorbed.
The effect of PEG concentration on I –V curves of bipo-
lar membranes can be observed from Fig. 3. The I –V curves
of bipolar membranes of which the anion exchange mem-
branes have been immersed in 1.0 and 3.0 M solutions of
PEG 2000 are denoted as P-2000-10 and P-2000-30. Ob-
viously, the voltage across the bipolar membrane decreases
with an increase in the concentration of the PEG solu-
tion when the concentration is below 1.0 M. Above 1.0 M,
the voltage does not decrease apparently; cf. the curves
of P-2000-30 and P-2000-10. From the specific adsorbed
PEG amounts in Table 1, it is apparent that the adsorbed
amount of PEG increases with an increase in the concen-
tration. As mentioned above, PEG catalyzes water splitting
in the interfacial layer; the decrease in the voltage accord-
ing to the increase in the concentration of PEG solution can
Fig. 3. The I –V curves of bipolar membranes of which the anion exchange
membranes have been immersed in 0.2 M (
), 1.0 M (Q), 3.0 M (e), and
0 M (2) solutions of PEG 2000.
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中国科技论文在线 R.Q. Fu et al. / Journal of Colloid and Interface Science 263 (2003) 386–390
Fig. 4. The I –V curves of bipolar membranes of which the anion exchange
membranes have been immersed in 0.2 M (
), 1.0 M (Q), 3.0 M (a), and
0 M (2) solutions of PEG 10,000.
thus be explained. However, the catalytic effect may not in-
crease apparently with PEG concentration after the concen-
tration attains some value, because membranes P-2000-30
and P-2000-10 have very close voltages but their specific ad-
sorbed amounts differentiate as shown in Table 1. It thus is
suggested that a certain amount of PEG is enough to ensure
a catalytic effect and the excess PEG will not give rise to an
appreciable catalytic effect.
To confirm the above analysis, the experiments were re-
peated replacing PEG 2000 with PEG 10,000 with other
conditions remaining unchanged. The effect of different con-
centrations of PEG 10,000 solution on water splitting is
shown in Fig. 4. Obviously, results analogous to Fig. 3 can
be obtained, which confirms the above observations. Com-
paring Fig. 3 with Fig. 4, the effect of molecular weight of
PEG can also be obtained, which indicates that the PEG with
high molecular weight is the more effective catalyst for wa-
ter splitting in a bipolar membrane.
To further confirm the PEG catalytic function, some bipo-
lar membranes are prepared in a different manner: coating
1.0 M solutions of PEG 600, PEG 2000, and PEG 10,000,
respectively, onto the anion exchange membranes, drying,
and then coating the SPPO solution. The preparations are
the same as for the membranes in Fig. 2 except for the coat-
ing procedure of PEG solutions. The I –V curves of these
bipolar membranes prepared in this manner are shown in
Fig. 5 and the specific adsorbed PEG amounts in the an-
ion exchange membranes shown in Table 2. The trends of
the I –V curves between the water-splitting voltage and the
PEG molecular weight are almost the same as those in Fig. 2,
Table 2
Specific adsorbed amounts when 1.0 M PEG solutions are coated on anion
exchange membranes
Molecular weight PEG 600 PEG 2000 PEG 10,000
Specific adsorbed amount 5.12% 5.24% 5.00%
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389
Fig. 5. The I –V curves of bipolar membranes of which the anion exchange
membranes have been brushed with 1.0 M solutions of different weight
PEGs: PEG 600 (
), PEG 2000 (Q), PEG 10,000 (a), and not PEG (2).
which suggests that in Fig. 2, it is the adsorbed PEGs that
decrease the bipolar membrane voltage. However, it should
be pointed out that voltage in Fig. 5 for each case is a little
lower than the corresponding voltage in Fig. 2. This is be-
cause there are more PEG molecules at the interface when
the membrane is prepared by coating than when it is pre-
pared by immersion, as shown in Tables 1 and 2.
4. Conclusions
From the above experiments and analysis, some conclu-
sions can be obtained.
(1) When PEG is added to the interface of a bipolar mem-
brane, the water-splitting effect is accelerated and the
voltage across the membrane falls.
(2) If the anion exchange membrane is immersed in the
same concentration PEG solution for the same time, the
water-splitting voltage falls according to the rise in the
PEG molecular weight.
(3) If the anion exchange membrane is immersed in the
same molecular weight PEG solution for the same time,
the water-splitting voltage falls according to the rise in
the PEG solution concentration, but above a certain con-
centration the excess PEG will not give rise to an appre-
ciable catalytic effect.
(4) The PEG-catalytic water splitting can be explained by
both the strong hydrophilicity of PEG and the hydrogen-
bonding and polar interactions between PEG and water
molecules.
Acknowledgments
Financial support from the Nation Science Foundation of
China (20106015) and the Natural Science Foundations of
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R.Q. Fu et al. / Journal of Colloid and Interface Science 263 (2003) 386–390

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