Separation and Purification Technology 122 (2014) 32–40

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

In situ ultraviolet-light-induced TiO2 nanohybrid superhydrophilic

membrane for pervaporation dehydration
Lili Gong a, Lei Zhang a, Naixin Wang a, Jie Li a, Shulan Ji a, Hongxia Guo b, Guojun Zhang a,⇑,
Zhongguo Zhang c
a
Center for Membrane Technology, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, PR China
b
College of Material Science and Engineering, Beijing University of Technology, Beijing 100124, PR China
c
Environmental Protection Research Institute of Light Industry, Beijing Academy of Science and Technology, Beijing 100089, PR China

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

Article history: The membrane surface property is one of the most important factors that influence the solution–diffu-
Received 17 July 2013 sion-controlled pervaporation process. In the present study, a superhydrophilic nanohybrid membrane
Received in revised form 17 October 2013 was successfully prepared by in situ ultraviolet irradiation of titanium dioxide (TiO2) nanoparticles
Accepted 18 October 2013
imbedded in polyelectrolyte complexes. The TiO2 precursor solution was dynamically filtered through
Available online 31 October 2013
a layer-by-layer-assembled poly(ethyleneimine)/poly(acrylic acid) multilayer under a specific pressure.
Subsequently, ultraviolet radiation was used to improve the hydrophilicity of the nanohybrid membranes
Keywords:
via photoinduction of the superhydrophilic property of the TiO2 nanoparticles. When the membranes
In situ ultraviolet-light-induced TiO2
nanohybrid membrane
were irradiated, the surface contact angle decreased from 62° to 3°, which is characteristic of a superhy-
Superhydrophilic drophilic membrane surface. The pervaporation performance of the membrane for separating alcohol/
Pervaporation dehydration water mixtures was investigated. The water content could be enriched from 5 wt% (in the feed) to
99.89 wt% (in the permeate) and the permeate flux was 865 g/(m2 h) in the pervaporation of the etha-
nol/water mixture. These results indicated that the superhydrophilic surface was beneficial for improving
the pervaporation dehydration performance.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction has been carried out on superhydrophilic membranes for pervapo-

Pervaporation has been widely used in the separation of azeo-
tropic mixtures [1,2], such as separation of water from organic sol-
vent [3], removal of trace organics from water [4], and isolation of
organic mixtures [5]. Pervaporation is based on the solution–diffu-
sion mechanism. The pervaporation performance of a membrane is
mainly affected by membrane materials and structures. In particu-
lar, the membrane surface property is an important factor that
determines the pervaporation performance [6–8]. An increase in
the surface hydrophilicity markedly enhances the dissolution and
diffusion of water molecules. Consequently, the water molecules
move more easily across the membranes compared with other
components in the water mixtures; this increased difference in dif-
fusion rate contributes to the enhanced separation performance.
Therefore, in order to achieve high flux and selectivity, it is crucial
to improve the surface hydrophilicity to a superhydrophilic level,
which is characterized by a water contact angle of below 5°. How-
ever, the reported contact angle of water on water-permselective
pervaporation membranes is within 30–80° [9,10]. No research
⇑ Corresponding author. Tel./fax: +86 10 67392393.
E-mail address: zhanggj@bjut.edu.cn (G. Zhang).
ration dehydration.
One of the most commonly used methods for achieving a super-
hydrophilic surface is the induction of the surface of TiO2 inorganic
particles upon irradiation with ultraviolet (UV) light. TiO2 photoca-
talysis generates various active oxygen species, such as hydroxyl
radical and hydrogen peroxide, by reductive or oxidative reactions
[11,12]. As shown in Scheme 1, UV irradiation stimulates electrons
to move from valence bands to conduction bands, and create pairs
of electrons and holes on the photocatalyst surfaces. After that, the
electrons tend to reduce Ti(IV) cations to Ti(III), and the holes oxi-
dize the O2 anions. As a result, oxygen atoms move out and there-
by leave oxygen vacancies, and then combine with H2O molecules
to form the chemically absorbed water layer (in the form of –OH
groups), which makes the surface superhydrophilic. Furthermore,
Ti(III) cations are extremely unstable. They are also easily oxidized
by oxygen in air [13–15]. Many superhydrophilic films have
recently been obtained by using the above photoinduced TiO2
superhydrophilicity. For example, Nakata et al. prepared superhy-
drophilic composite films of TiO2 and polydimethylsiloxane, which
contribute to the photoinduced superhydrophilicity of TiO2 nano-
particles under UV irradiation [16]. Feng et al. reported that super-
hydrophilic films consisting of inorganic nanoparticles could be

1383-5866/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.10.032
 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40
Scheme 1. Schematic illustration of the TiO2 light-induced hydrophilicity principle.
prepared from hydrophilic TiO2 under UV irradiation [17]. Using
UV irradiation, Sun et al. fabricated a superhydrophilic nanostraw-
berry TiO2 surface with a water contact angle of 0°. They pointed
out that as TiO2 is a photosensitive material, the surface hydrophi-
licity could be improved greatly when the film is irradiated with
UV light. This improvement occurs via reaction of the photogener-
ated holes with lattice oxygen to form surface oxygen vacancies, to
which water molecules kinetically coordinate [18]. Recently, a few
superhydrophilic TiO2 thin films have been developed by increas-
ing the film surface roughness. Hosono et al. prepared TiO2 nano-
sheet superhydrophilic films on a titanium metal sheet by
hydrothermal treatment. Moreover, the anatase TiO2 nanosheet
films showed superhydrophilicity without prior UV irradiation
[19].
Despite their benefits, the preparation of hybrid polymer super-
hydrophilic films have not proven to be feasible, as the uniform dis-
persion of TiO2 nanoparticles in the polymer is very difficult [20].
Compared with traditional co-blending methods [21], in situ
growth of TiO2 nanoparticles has some distinct advantages, as it eas-
ily lends itself to high loadings of inorganic components and avoids
excessive agglomeration of nanoparticles. Researchers have re-
cently adopted the in situ growth method to prepare various kinds
of nanoparticles with satisfactory dispersion. Chang et al. demon-
strated that the in situ growth of silver nanoparticles at the surface
of porous membranes could enhance Raman scattering detection of
the substrate. They found the method to be simple, cost-effective,
and fast. In addition, it enabled the preparation of silver nanoparti-
cles with controlled size and good dispersibility [22].
In the present study, a superhydrophilic membrane was formed
by in situ growth of TiO2 nanoparticles into polyelectrolyte multi-
layers. As shown in Scheme 2, poly(acrylic acid) (PAA) and
poly(ethyleneimine) (PEI) could be assembled onto the surface of
Scheme 2. Schematic illustration of the process of in situ growth of TiO2 nanoparticles.
33
the hydrolyzed polyacrylonitrile (PAN) membrane by layer-
by-layer (LbL) self-assembly technique, which is a dynamic,
pressure-driven process [23,24]. After self-assembly, a precursor
solution of TiO2, namely, titanium(IV) bis(ammonium lactato)dihy-
droxide (TALH), was hydrolyzed with PEI assembled on the mem-
branes to generate the TiO2 nanoparticles (Scheme 2) [25]. The
organic–inorganic nanohybrid membrane was subsequently mod-
ified by UV irradiation to obtain the superhydrophilic surface. The
physicochemical changes of the resulting membranes were ana-
lyzed by scanning electron microscopy (SEM), energy-dispersive
X-ray (EDX spectroscopy), atomic force microscopy (AFM), and
Fourier transform infrared (FTIR) spectroscopy. The membrane
was used to separate alcohol/water mixtures by pervaporation.
2. Experimental
2.1. Chemicals and materials
PEI (Mw 60,000) and PAA (Mw 4,000,000) were purchased from
Acros and Aldrich, respectively. TLAH was obtained from Sigma–
Aldrich. Sodium hydroxide (NaOH), ethanol, 2-propanol, butanol,
isobutanol, and tert-butanol were provided by Beijing Chemical
Factory. Flat-sheet PAN ultrafiltration (UF) membranes with a
nominal molecular weight cutoff of 20,000 were supplied by Sepro
Membranes.
2.2. Nanohybrid multilayer buildup onto flat-sheet hydrolyzed PAN
porous substrates
First, 0.5 wt% PEI solution and 0.05 wt% PAA solution was pre-
pared. According to the procedure in our previous study [24], the
PAN UF membranes were hydrolyzed by immersing them in a
2 mol/L NaOH aqueous solution for 30 min at 60 °C, and then
washing them with deionized water until the washings reached
neutral pH. The hydrolyzed membranes, which were negatively
charged, were loaded into a dead-ended filtration cell. The polyca-
tion (PEI) solution was poured into the dead-ended filtration appa-
ratus. A driving pressure was generated in the apparatus by using a
nitrogen cylinder, which was set to an applied pressure of 0.1 MPa
for 30 min at room temperature. Subsequently, deionized water
was passed through the membrane for 10 min. Subsequently, the
membranes were removed from the apparatus, briefly rinsed with
deionized water, and then dried in an oven at 45 °C for about 2 h.
Afterward, the dried membranes were reloaded into the cell and
34 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40
Fig. 1. SEM images of (a) (PEI/PAA)4.5; (b–e) (PEI/PAA)4.5/TiO2. (Preparative conditions: [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, the concentration of TALH: (b) is 0.125 wt%, (c) is
0.25 wt%, (d) is 0.5 wt%, (e) is 1.5 wt%, the assembly time: 30 min, 25 °C).
Table 1
EDX analytical results of nanohybrid membrane obtained from different TALH
concentration. (Preparative conditions: [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, 30 min
filtration time, 25 °C).
The concentration of TALH (wt%) (PEI/PAA)4.5/TiO2
0 0.125 0.25 0.5 1.5
The content of Ti (wt%) 0 1.05 1.33 1.86 1.90
treated with polyanion (PAA) solution under the same conditions
to effect the assembly of PAA. The PEI/PAA multilayer on each
membrane was prepared by alternative assembly of PEI and PAA.
Afterward, the TALH solution was dynamically filtered through
each prepared multilayer membrane when PEI was the outer layer
of the (PEI/PAA)n membranes. In the process, TALH was hydrolyzed
with PEI to generate TiO2 nanoparticles in situ on the multilayer
surface. The resulting nanohybrid membranes were irradiated for
a specific amount of time using a UV lamp to form the surperhy-
drophilic surface. The UV treatment of the nanohybrid surface
was carried out at k = 365 nm with an air media in a commercial
UV chamber (Beijing Institute of Opto-Electronic Technology,
China).
2.3. Pervaporation experiments
The performance of nanohydrid multilayer membranes with
effective area of 24.6 cm2 were evaluated by a using a labora-
tory-fabricated pervaporation cell [24]. The permeate vapor was
trapped in liquid nitrogen. The experiments were carried out at a
downstream pressure of 100 Pa maintained by a vacuum pump.
The permeate flux was determined by measuring the weight of
the liquid collected in the cold traps at a specific time under stea-
dy-state conditions. The compositions of the concentrated solution
were determined by gas chromatography on GC-14C (Shimadzu,
Japan). The separation factor a was calculated from the weight ra-
tio of component i and component j in the permeate (Yi/Yj) and in
the feed (Xi/Xj).
Y iXj
a¼
Y jXi
The permeate flux (J) was determined according to the follow-
ing equation:
W
J¼
At
 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40 35

Fig. 2. AFM images of (a) (PEI/PAA)4.5; (b–e) (PEI/PAA)4.5/TiO2; (f) (PEI/TiO2)5. (Preparative conditions: [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, the concentration of TALH: (b) is
0.125 wt%, (c) is 0.25 wt%, (d) is 0.5 wt%, (e) is 1.5 wt%, the assembly time 30 min, 25 °C).

where W is the weight of the liquid collected in the cold traps, A is
the effective area of the membrane, and t is the certain time for the
PV.
2.4. Characterization
were measured using a contact angle analyzer (PSA-100, Ger-
many). Attenuated total reflectance FTIR spectra (Vertex-70, Bru-
ker, Germany) were used to characterize the chemical
composition changes of the multilayer under various UV irradia-
tion times.

SEM was performed on a Hitachi-4300 (Japan) to observe the
surface morphologies on the hybrid membranes assembled using
various concentrations of TALH solution and irradiated with UV
light. The change in the chemical composition of the multilayer
was characterized by EDX spectrometry. To further investigate
the surface roughness, AFM in tapping mode was done using an
atomic force microscope (Pico Scan™ 2500). Water contact angles
3. Results and discussion
3.1. Confirmation of TiO2 nanoparticles and composite membrane
Fig. 1 illustrates the SEM photographs of the nanohydrid multi-
layer membrane surface. The surface of the (PEI/PAA)4.5 membrane
was smooth (Fig. 1(a)). However, after assembly with TiO2
36 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40

Fig. 5. Effect of the concentration of TALH solution on the pervaporation perfor-

Fig. 3. FTIR image of (PEI/PAA)3.5/TiO2 nanohybrid membranes irradiated with the
different periods of time: (a) 0 min; (b) 10 min; (c) 30 min; (d) 1 h; (e) 2 h; (f) 4 h.
(Preparative conditions: [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%, the
time of compound: 30 min, 25 °C).
mance of (PEI/PAA)4.5/TiO2 nanohybrid membranes. (Hydrolysis conditions for PAN
support membrane: hydrolysis temperature 60 °C, hydrolysis time: 30 min.
Preparative conditions: dynamic pressure 0.1 MPa, 30 min filtration time,
[PEI] = 0.5 wt%, [PAA] = 0.05 wt%, 25 °C; pervaporation conditions: feed tempera-
ture 60 °C, down-stream pressure 100 Pa, EtOH content in feed solution 95 wt%).

nanoparticles, the morphologies of the membrane changed
(Fig. 1(b–f)). Many nanoparticles could be seen on the surface of
the hybrid membrane. It can be seen that the size of TiO2 nanopar-
ticles are about 50 nm and these particles relatively uniformly dis-
tribute within the multilayers. With increasing TALH
concentration, the loading amount of nanoparticles on the mem-
branes gradually increased. This result could also be proved by
EDX spectrometry (Table 1). As shown in Table 1, the amount of
Ti on the surface increased with the increase in the TALH concen-
tration. The above evidence indicates that the TiO2 nanoparticles
were successfully formed on the surface of the (PEI/PAA)4.5
membrane.
The surface morphologies of the membranes were also charac-
terized by AFM. As shown in Fig. 2(a), the surface roughness of the
(PEI/PAA)4.5 multilayer membrane was 0.842 lm within a
40  40 lm area. It was noted that the roughness showed a trend
of first increasing and then decreasing. Values of the surface rough-
ness of (PEI/PAA)4.5/TiO2 nanohybrid membranes with various con-
centrations of TALH were 1.03, 1.87, 0.667, 0.894, and 1.08 lm
(Fig. 2(b–f), respectively). The graininess state or clustered closed
state of the TiO2 nanoparticles is due to the small number of these
particles present on the membranes; such states enhanced the
roughness of the hybrid membranes (Fig. 2(b–c)) more than that
of the organic membrane (Fig. 2(a)). At increased loadings of TiO2
nanoparticles on the membranes, TiO2 nanoparticles covered the
entire membrane surface and even filled the fissures originally
existing on the membrane (Fig. 2(d)), thereby leading to the de-
cline in surface roughness (Fig. 2(e)). A subsequent increase in
the surface roughness occurred once again at higher loadings
(1.5 wt%), primarily because loading of the TiO2 nanoparticles on
the membrane (Fig. 2(f)) that had been filled up continued. To
see this contrast, we modified the conditions for assembly by using

Fig. 4. Water contact angle images of (a) (PEI/PAA)3.5 and (b) and (PEI/PAA)3.5/TiO2, without ultraviolet irradiation; (c–f) (PEI/PAA)3.5/TiO2, the change of the contact angle
irradiated under ultraviolet for 10 min. contact angle is: 82°, 62°, 49°, 35°, 10°, 3°. (Preparative conditions: [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%, 30 min, 25 °C).
 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40
Fig. 6. Effect of the pre-coating layer number of PEI/PAA on nanohybrid mem-
branes. (Hydrolysis conditions for PAN support membrane: hydrolysis temperature
60 °C, hydrolysis time: 30 min. Preparative conditions: dynamic pressure 0.1 MPa,
30 min filtration time, [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%, 25 °C;
pervaporation conditions: feed temperature 60 °C, down-stream pressure 100 Pa,
EtOH content in feed solution 95 wt%).
Fig. 7. Effect of UV irradiation time on pervaporation performance of (PEI/PAA)3.5/
TiO2 nanohybrid multilayer membranes. (Hydrolysis conditions for PAN support
membrane: hydrolysis temperature 60 °C, hydrolysis time: 30 min. Preparative
conditions: dynamic pressure 0.1 MPa, 30 min filtration time, [PEI] = 0.5 wt%,
[PAA] = 0.05 wt%, [TALH] = 0.25 wt%, 25 °C; pervaporation conditions: feed temper-
ature 60 °C, down-stream pressure 100 Pa, EtOH content in feed solution 95 wt%).
the same concentration of TLAH (1.5 wt%) to prepare the mem-
brane (PEI/TiO2)5 (Fig. 2(e)).
Fig. 3 illustrates the FTIR spectra of TiO2 nanohybrid mem-
branes irradiated with UV light at various times. A strong and
broad characteristic peak around 3300 cm1 corresponds to O–H
stretching vibrations of the hydroxyl groups relating to the car-
boxyl group in PAA (Fig. 3(a)) [20]. The peaks at around 1560
and 1400 cm1 are assigned to the carboxyl functional groups of
PAA [23]. The narrow band at 1450 cm1 corresponds to the C–N
(the functional groups of PEI) stretching vibration [26]. The
intensity of these bands decreased with increasing UV irradiation
time. All of these results confirm that UV irradiation could promote
structural changes in the composite membrane.
The superhydrophilic surface could be obtained when the con-
tact angle was reduced to 5° or lower. Fig. 4 clearly suggests that
37
the hydrophilicity of the nanohybrid membrane was enhanced
with UV irradiation. Moreover, the superhydrophilicity improved
with increasing irradiation time. For instance, the water contact
angle of the (PEI/PAA)3.5 membrane was 82° (Fig. 4(a)), whereas
that of the nanohybrid membrane was 62° (Fig. 4(b)). For the
membrane with 10 min irradiation treatment, the contact angle
dropped to about 3° in 18 s (see Fig. 4(c–f)). These results provide
evidence that superhydrophilicity of the membranes was produced
successfully.
3.2. Effects of the concentration of TALH on pervaporation properties
Fig. 5 shows the effects of the TALH concentration on the per-
vaporation performance at 65 °C. Compared with those of the
(PEI/PAA)4.5 membrane (Fig. 5(a)), the permeate flux and the sepa-
ration factor of the nanohybrid membrane gradually increased
when the TALH concentration was varied from 0 to 0.25 wt%. For
example, the water content in the permeate and the permeate flux
of the (PEI/PAA)4.5 membrane were 96.2 wt% (a = 481) and 213 g/
(m2 h), respectively. An increase in the TALH concentration to
0.25 wt% increased the water content in the permeate and the per-
meate flux to 99.3 wt% (a = 2695) and 601 g/(m2 h), respectively.
This is because of the specific photoinduced superhydrophilic
property of the TiO2 nanoparticles. The hydrophilicity enhance-
ment due to the increased loading of TiO2 nanoparticles on the
membranes not only improved the separation factor, but also the
solution and diffusion rate of the water molecules within the mem-
branes. In addition, the surface roughness of the membrane in-
creased, which expanded the specific surface area of the
nanohybrid membranes. However, when the TALH concentration
was increased from 0.25 to 1.5 wt%, the water content in the per-
meate decreased to 78.6 wt% (a = 69.8). This decline may be due
to the lowering of the separation factor by excessive amounts
TiO2 nanoparticles, which could have be disrupted the structure
of the dense membrane.
3.3. Effects of the number of precoating bilayers of PEI/PAA on the
pervaporation performance
The effects of the number of the precoating bilayers PEI/PAA on
the pervaporation performance were investigated (results are
shown in Fig. 6). With 0.25 wt% TALH solution, the separation fac-
tor increased while the permeate flux gradually decreased with
increasing number of the precoating PEI/PAA bilayers. This trend
is explained by the higher density of the multilayer membrane at
increased bilayer numbers. The favorable flexibility of the (PEI/
PAA)n multilayer membrane could reduce or even eliminate the fri-
ability of the membranes due to the inorganic nanoparticles. The
amount of TiO2 relative to that of PEI/PAA is proportional to the fri-
ability of the membranes. Along with the increasing number of the
PEI/PAA bilayers is a reduction in the relative amount of the inor-
ganic nanoparticles, which lowers the friability of the membranes.
This change also resulted in enhanced membrane flexibility, which
gave rise to the variation in the trend of separation performance.
3.4. Effects of the UV irradiation time on the pervaporation
performance
The effects of the UV irradiation time on the pervaporation
performance of the (PEI/PAA)3.5/TiO2 nanohybrid membranes
are revealed in Fig. 7. The water content in the permeate de-
creased and the permeate flux increased with increasing UV irra-
diation time. Compared with the nanohybrid multilayer without
UV irradiation, the flux of the membrane irradiated with UV
light for 10 min increased from 615 to 865 g/(m2 h). Meanwhile,
the water content in the permeate increased from 97.25 to
38 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40

Fig. 8. SEM images of nanohybrid membranes surface with various UV irradiation times: (a) 0 min; (b) 10 min; (c) 30 min; (d) 1 h; (e) 2 h; (f) 4 h. (Preparative conditions:
[PEI] = 0.5 wt%, [PAA] = 0.05 wt%, the time of compound: 30 min, 25 °C).

Fig. 9. Effects of feed temperature on pervaporation performance of (PEI/PAA)3.5/
TiO2 nanohybrid membranes. (Preparative conditions: dynamic pressure 0.1 MPa,
30 min filtration time, [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%, 25 °C,
10 min UV irradiation time; pervaporation conditions: down-stream pressure
100 Pa, EtOH content in feed solution 95 wt%).
Fig. 10. Effects of downstream pressure on pervaporation performance of (PEI/
PAA)3.5/TiO2 nanohybrid membranes. (Preparative conditions: dynamic pressure
0.1 MPa, 30 min filtration time, [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%,
25 °C, 10 min UV irradiation time; pervaporation conditions: feed temperature
60 °C, EtOH content in feed solution 95 wt%).
 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40
Fig. 11. Effects of water content in feed solution on pervaporation performance of
(PEI/PAA)3.5/TiO2 nanohybrid membranes. (Preparative conditions: dynamic pres-
sure 0.1 MPa, 30 min filtration time, [PEI] = 0.5 wt%, [PAA] = 0.05 wt%,
[TALH] = 0.25 wt%, 25 °C, 10 min UV irradiation time; pervaporation conditions:
feed temperature 60 °C, EtOH content in feed solution 95 wt%).
Fig. 12. Pervaporation performance of (PEI/PAA)3.5/TiO2 nanohybrid membranes for
different solvent–water mixtures. (Preparative conditions: dynamic pressure
0.1 MPa, 30 min filtration time, [PEI] = 0.5 wt%, [PAA] = 0.05 wt%, [TALH] = 0.25 wt%,
25 °C, UV irradiation 10 min; pervaporation conditions: feed temperature 60 °C,
down-stream pressure 100 Pa, EtOH content in feed solution 95 wt%).
99.89 wt% (a = 17,254). When the UV irradiation time continu-
ously increased from 30 min to 4 h, the sharp decrease in the
selectivity and increased flux were clearly observed. According
to the quantum theory of light, the energy of UV light (from
290 to 400 nm) is higher than that that required to break all
types of chemical bonds. Polymers containing carbonyl and dou-
ble bonds can absorb the UV light, which results in macromolec-
ular chain rupture. Thus, polymers may age under excessive UV
irradiation times [27–30]. The changes of membrane surface
with irradiation time are shown in Fig. 8. As a control, defect-
free selective layer without UV irradiation was observed
(Fig. 8(a)). After irradiation for 10 min, the defect-free surface
could still be kept (Fig. 8(b)). The slight defects began to appear
(Fig. 8(c)), and subsequently became much more obvious and
serious (Fig. 8(d–f)). Damage to the structures of PEI and PAA
might have resulted in defects on the denser membrane surface,
which might have led to the decline in the separation factor.
39
Therefore, 10 min was selected as a suitable UV irradiation time
to achieve a superhydrophilic multilayer membrane without
defects.
3.5. Effects of the operating conditions on the pervaporation
performance
In order to evaluate the pervaporation performance of the TiO2
nanohybrid multilayer membranes under different operating con-
ditions, the water content in the permeate and the permeate flux
were measured over wide ranges of temperature and downstream
pressure. As shown in Fig. 9, when the feed temperature varied
from 30 to 60 °C, the permeate flux increased from 691 to 865 g/
(m2 h). At the same time, the water content in the permeate was
also enhanced from 94.38 to 99.89 wt%. These changes are due to
the increase in the water vapor pressure on the feed side with
the temperature increase [31]. The Arrhenius law, Ep = -
RT(ln J  ln J0), was applied to explain the variation of flux with
feed temperature. The Arrhenius activation energy (Ep) could be
calculated from this equation. The increase in activation energy
of ethanol (Ep = 1.19 kJ/mol), which is considerably lower than that
of water (Ep = 20.50 kJ/mol) [32], might account for the increase in
selectivity of the membranes.
The effect of the downstream pressure on the pervaporation
performance was also investigated (results shown in Fig. 10). For
the (PEI/PAA)3.5/TiO2 nanohybrid membranes, the permeate flux
is expected to decrease with increasing downstream pressure. This
is because of the reduction of the driving force due to the increase
in the downstream pressure. This reduction hindered the transport
of components and thereby led to the decline in the flux across the
membranes. The saturated vapor pressure of ethanol is higher than
that of water. Under this condition, a rise in the downstream pres-
sure slows down evaporation of water and thereby decreases the
separation factor. Therefore, the water content in the permeate de-
creased. Similar results were reported by a number of researchers
[33,34].
In Fig. 11, we can see that the pervaporation separation of the
ethanol–water system with water content ranged from 5 to
40 wt%. The selectivity varied over a relatively small range, and
the flux continued to rise from 865 to 5983 g/(m2 h). Furthermore,
the water content of the feed solution led to a lower water content
in the permeate (95.98–99.89 wt%). According to these results, the
hybrid membranes are suitable for the separation of ethanol–water
mixtures because of the satisfactory flux over a relatively wide
concentration range.
The pervaporation performance of the (PEI/PAA)3.5/TiO2 nano-
hybrid membranes in various solvent/water mixtures was evalu-
ated. The results are summarized in Fig. 12. The membranes
showed high pervaporation performance because of the superhy-
drophilicity resulting from the addition of TiO2 nanoparticles. For
instance, in the separation of 95.0 wt% tert-butanol/water mix-
tures, the water content could be enriched from 5.0 wt% (in the
feed) to 99.99 wt% (in the permeate), which meant that the separa-
tion factor reached 189,981 and the permeate flux was 1013 g/
(m2 h). The selectivity of the (PEI/PAA)3.5/TiO2 nanohybrid mem-
branes was much higher than that of the (PEI/PAA)n multilayer
membranes. Meanwhile, both selectivity and permeate flux in-
creased with the increase in the alcohol molecular weight. This is
because that hydrogen bonding is weakened between alcohol
and water with increasing number of carbon atoms in the alcohol.
It was also noted that both separation factor and flux obtained
from t-butanol–water mixture were slightly higher than those
from butanol–water mixture. This reveals an important influence
of diffusion on the pervaporation of the branched t-butanol mole-
cule. A similar phenomenon was observed in the other types of
polyelectrolyte multilayer membranes [35,36].
40 L. Gong et al. / Separation and Purification Technology 122 (2014) 32–40
4. Conclusions
In the present study, we prepared superhydrophilic nanohybrid
multilayer membranes by in situ growth of TiO2 nanoparticles into
a polyelectrolyte complex via dynamic pressure-driven LbL self-
assembly. The morphology and structure of the membrane were
rigorously characterized by SEM, EDX spectrometry, AFM, and FTIR
spectroscopy. Characterization proved the formation of TiO2 nano-
particles on the multilayers. Dynamic contact angle analyzes sug-
gested that UV irradiation of the membranes could decrease the
water contact angle from 62° to 3°, and further confirmed the for-
mation of the superhydrophilic surface. The effects of assembly
conditions on the pervaporation ethanol/water mixtures, such as
the concentration of TALH solution, numbers of assembly layers
of polyelectrolyte, and UV irradiation time, were investigated.
Using 0.25 wt% TALH solution in the organic substrate of (PEI/
PAA)3.5, we found that at a controlled UV irradiation time of
10 min, the nanohybrid membranes obtained had both higher
selectivity and permeate flux without sustaining defects because
of the superhydrophilic photoinduced property of TiO2 nanoparti-
cles. Excessive UV irradiation time led to the ageing of polymer and
in turn resulted in defects within the multilayer, which led to the
decrease in selectivity. Moreover, use of the superhydrophilic
nanohybrid multilayer membranes under various operating condi-
tions and solvent mixtures was evaluated. In particular, the super-
hydrophilic nanohybrid multilayer membranes demonstrated high
selectivity and satisfactory flux over a relatively wide concentra-
tion range. Moreover, the membranes had satisfactory pervapora-
tion performance in other solvent/water mixtures. In conclusion,
the fabrication of TiO2 nanohybrid superhydrophilic multilayer
membranes was proved to be a facile way to simultaneously obtain
both higher flux and selectivity. The superhydrophilic membrane
could be a promising candidate for applications in solution–diffu-
sion-controlled pervaporation processes.
Acknowledgments
This work was financially supported by Program for New Cen-
tury Excellent Talents in University, Ministry of Education, China
(No. NCET-12-0604), Specialized Research Fund for the Doctoral
Program of Higher Education (No. 20121103110010), Fok Ying
Tung Education Foundation (No. 131068), the National High Tech-
nology Research and Development Program of China (No.
2012AA03A607), and the Program for Innovative Research Team
in Beijing Academy of Science and Technology (No. IG201204C1).
References
[1] X. Orignac, X.M. Du, R.M. Almeida, Improved composition for sol–gel rare-
earth doped planar waveguides, J. Sol–Gel Sci. Technol. 8 (1997) 1013–1016.
[2] W.L. Luyben, Control of a column/pervaporation process for separating the
ethanol/water azeotrope, Ind. Eng. Chem. Res. 48 (2009) 3484–3495.
[3] Y.Y. Lu, J.H. Chen, Optimal design of multistage membrane distillation systems
for water purification, Ind. Eng. Chem. Res. 50 (2001) 7345–7354.
[4] R.L. Knight, R.H. Kadlec, H.M. Ohlendorf, The use of treatment wetlands for
petroleum industry effluents, Environ. Sci. Technol. 33 (1999) 973–980.
[5] B. Smitha, D. Suhanya, S. Sridhar, M. Ramakrishna, Separation of organic-
inorganic mixtures by PV – a review, J. Membr. Sci. 241 (2004) 1–21.
[6] J. L, S.L. Ji, G.J. Zhang, H.X. G, Surface-modification of poly(dimethylsiloxane)
membrane with self-assembled monolayers for alcohol permselective
pervaporation, Langmuir 29 (2013) 8093–8102.
[7] C. Zhang, X.F. Chang, Y.Q. Fan, W.Q. Jin, N.Q. Xu, Improving performance of a
dense membrane reactor for thermal decomposition of CO2 via surface
modification, Ind. Eng. Chem. Res. 46 (2007) 2000–2005.
[8] S. Zhao, Z. Wang, X. Wei, B. Zhao, J.X. Wang, S.B. Yang, S.C. Wang, Performance
improvement of polysulfone ultrafiltration membrane using well-dispersed
polyaniline–poly(vinylpyrrolidone) nanocomposite as the additive, Ind. Eng.
Chem. Res. 51 (2012) 4661–4672.
[9] H.Y. Deng, Y.Y. Xu, Q.C. Chen, X.Z. Wei, B.K. Zhu, High flux positively charged
nanofiltration membranes prepared by UV-initiated graft polymerization of
methacrylatoethyl trimethyl ammonium chloride (DMC) onto polysulfone
membranes, J. Membr. Sci. 366 (2011) 363–372.
[10] W.F. Zhao, J.Y. Huang, B.H. Fang, S.Q. Nie, N. Yi, B.H. Su, H.F. Li, C.S. Zhao,
Modification of polyethersulfone membrane by blending semi-
interpenetrating network polymeric nanoparticles, J. Membr. Sci. 369 (2011)
258–266.
[11] K. Ishibashi, A. Fujishima, T. Watanabe, K. Hashimoto, Quantum yields of active
oxidative species formed on TiO2 photocatalyst, J. Photochem. Photobiol. A:
Chem. 134 (2000) 139–142.
[12] W. Kubo, T. Tatsuma, Photocatalytic remote oxidation with various
photocatalysts and enhancement of its activity, J. Mater. Chem. 15 (2005)
3104–3108.
[13] M. Takeuchi, K. Sakamoto, G. Martra, S. Coluccia, M. Anpo, Mechanism of
photoinduced superhydrohilicity on the TiO2 photocatalyst surface, J. Phys.
Chem. B 109 (2005) 15422–15428.
[14] Y. Li, C.Y. Wu, Role of moisture in adsorption, photocatalytic oxidation, and
reemission of elemental mercury on a SiO2–TiO2 nanocomposite, Environ. Sci.
Technol. 40 (2006) 6444–6448.
[15] M.Y. Kariduraganavar, J.G. Varghese, S.K. Choudhari, R.H. Olley, Organic–
inorganic hybrid membranes: solving the trade-off phenomenon between
permeation flux and selectivity in pervaporation, Ind. Eng. Chem. Res. 48
(2009) 4002–4013.
[16] K. Nakata, H. Kimura, M. Sakai, T. Ochiai, H. Sakai, T. Murakami, M. Abe, A.
Fujishima, UV/thermally driven rewritable wettability patterns on TiO2–PDMS
composite films, Appl. Mater. Inter. 2 (2010) 2486–2488.
[17] X.J. Feng, J. Zhai, L. Jiang, The fabrication and switchable superhydrophobicity
of TiO2 nanorod films, Angew. Chem. Int. Ed. 44 (2005) 5115–5118.
[18] W. Sun, S. Zhou, P. Chen, L. Peng, Reversible switching on superhydrophobic
TiO2 nano-strawberry films fabricated at low temperature, Chem. Commun. 5
(2008) 603–605.
[19] E. Hosono, H. Matsuda, I. Honma, M. Ichihara, H. Zhou, Synthesis of a
perpendicular TiO2 nanosheet film with the superhydrophilic property
without UV irradiation, Langmuir 23 (2007) 7447–7450.
[20] X.F. Ding, J.Z. Zhao, Y.H. Liu, H.B. Zhang, Z.C. Wang, Silica nanoparticles
encapsulated by polystyrene via surface grafting and in situ emulsion
polymerization, Mater. Lett. 58 (2004) 3126–3130.
[21] F.B. Peng, L.Y. Lu, C.L. Hu, H. Wu, Z.Y. Jiang, Significant increase of permeation
flux and selectivity of poly(vinyl alcohol) membranes by incorporation of
crystalline flake graphite, J. Membr. Sci. 259 (2005) 65–73.
[22] S. Chang, Z.A. Combs, M.K. Gupta, R. Davis, V.V. Tsukruk, In situ growth of
silver nanoparticles in porous membranes for surface-enhanced Raman
scattering, Appl. Mater. Inter. 2 (2010) 3333–3339.
[23] G.J. Zhang, W.L. Gu, S.L. Ji, Z.Z. Liu, Y.L. Peng, Z. Wang, Preparation of
polyelectrolyte multilayer membranes by dynamic layer-by-layer process for
pervaporation separation of alcohol/water mixtures, J. Membr. Sci. 280 (2006)
727–733.
[24] G.J. Zhang, H. H Yan, Shulan Ji, Z.Z. Liu, Self-assembly of polyelectrolyte
multilayer pervaporation membranes by a dynamic layer-by-layer technique
on a hydrolyzed polyacrylonitrile ultrafiltration membrane, J. Membr. Sci. 292
(2007) 1–8.
[25] S. Lee, J. Drwiega, C.Y. Wu, D. Mazyck, W.M. Sigmund, Anatase TiO2
nanoparticle coating on barium ferrite using titanium bis-ammonium lactato
dihydroxide and its use as a magnetic photocatalyst, Chem. Mater. 16 (2004)
1160–1164.
[26] J. Attwood, M. Philip, A. Hulme, G. Williams, P. Shipton, The effects of ageing by
ultraviolet degradation of recycled polyolefin blends, Polym. Degrad. Stab. 91
(2006) 3407–3415.
[27] R.F. Navarro, J.R.M. d’Almeida, M.S. Rabello, Elastic properties of degraded
polypropylene, J. Membr. Sci. 42 (2007) 2167–2174.
[28] M. Ito, K. Nagai, Degradation issues of polymer materials used in railway field,
Polym. Degrad. Stab. 93 (2008) 1723–1735.
[29] W.L. Oliani, D.F. Parra, A.B. Lugao, UV stability of HMS-PP (high melt strength
polypropylene) obtained by radiation process, Radiat. Phys. Chem. 79 (2010)
383–387.
[30] N.X. Wang, G.J. Zhang, S.L. Ji, Z.P. Qin, Z.Z. Liu, The salt-, pH- and oxidant-
responsive pervaporation behaviors of weak polyelectrolyte multilayer
membranes, J. Membr. Sci. 354 (2010) 14–22.
[31] P. Shao, R.Y.M. Huang, Polymeric membrane pervaporation, J. Membr. Sci. 287
(2007) 162–179.
[32] J. Li, G.J. Zhang, S.L. Ji, N.X. Wang, Layer-by-layer assembled nanohybrid
multilayer membranes for pervaporation dehydration of acetone–water
mixtures, J. Membr. Sci. 415–416 (2012) 745–757.
[33] R. Jiraratananon, A. Chanachai, R.Y.M. Huang, D. Uttapap, Pervaporation
dehydration of ethanol–water mixtures with chitosan/hydroxyethylcellulose
(CS/HEC) composite membranes I. Effect of operating conditions, J. Membr. Sci.
195 (2002) 143–151.
[34] M.K. Mandal, P.K. Bhattacharya, Poly(ether-block-amide) membrane for
pervaporative separation of pyridine present in low concentration in
aqueous solution, J. Membr. Sci. 286 (2006) 115–124.
[35] G.J. Zhang, X. Song, S.L. Ji, N.X. Wang, Z.Z. Liu, Self-assembly of inner skin
hollow fiber polyelectrolyte multilayer membranes by a dynamic negative
pressure layer-by-layer technique, J. Membr. Sci. 325 (2008) 109–116.
[36] G.J. Zhang, X. Gao, S.L. Ji, Z.Z. Liu, One-step dynamic assembly of
polyelectrolyte complex membranes, Mater. Sci. Eng. C 29 (2009) 1877.