Desalination438(

2018)83–96

Contents lists available at ScienceDirect

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

Chitosan/graphene oxide mixed matrix membrane with enhanced water

permeability for high-salinity water desalination by pervaporation
Xiaowei Qiana,b, Na Lia,b,⁎, Qinzhuo Wanga,b, Songcan Jia,b
a
Shaanxi Key Laboratory of Energy & Chemical Process Intensification, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, PR China
b
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, PR China

GRAPHICAL ABSTRACT

ARTICLE INFO
ABSTRACT

Keywords:
Pervaporation is a promising technology for water desalination. In this work, graphene oxide (GO) was in-
Chitosan
corporated into chitosan (CS) to fabricate mixed matrix membranes (MMMs) to explore the enhancement of
Graphene oxide
Mixed matrix membrane water permeability for high-salinity water desalination and to understand the transport mechanism in the
Pervaporation for desalination MMMs. The effect of GO content on the morphology, wettability and desalination performance of the mem-
Salt and water transport property branes as well as the thermodynamic and kinetic behavior of water and salt permeation in the membranes were
investigated. The MMMs have rougher and more hydrophilic surface, dense structure and improved mechanical
stability owing to the good chemical compatibility of GO with CS matrix. The apparent activation energy results
indicate the advantage of the MMMs in desalinating high-salinity water. The enhanced permeate flux of 30.0 kg/
m2·h was obtained in desalinating 5 wt% aqueous NaCl solution at 81 °C with 1 wt% GO content and 99.99% of
salt rejection was achieved. The solubility and diffusivity of H2O and NaCl in the MMMs demonstrate a trade-off
effect on the water permeability and water/salt selectivity with increasing of GO content. The NaCl di ffusion
coefficient in the membranes was lower than that of H 2O by two orders of magnitude, contributing to the high
selectivity of the membrane.

1. Introduction
As a looming menace to human society, the shortage of freshwater
has become one of the most concerning problems of the world [1].
Desalination of salt water including brackish water, seawater and
brine
is regarded as one of the effective ways to address this issue [2].
Membrane technologies, on account of their high efficiency, potential
energy savings and ease of integration and scale-up, are now widely
considered as promising desalination methods [3,4]. Recently, desali-
nation by pervaporation has drawn increasing attention as a new

⁎
Corresponding author.
E-mail address: lina@mail.xjtu.edu.cn (N. Li).

https://doi.org/10.1016/j.desal.2018.03.031
Received 26 January 2018; Received in revised form 27 March 2018; Accepted 28 March 2018
0011-9164/©2018ElsevierB.V.Allrightsreserved.
 Desalination438

desalination technique owing to its feasibility in handling high salinity

currently, there is still much potential for the improvement of water
water [5–8]. In a typical pervaporation (PV) process, the feed side of
flux of MMMs and the transport mechanism of salt and water in
the membrane is directly contacted with preheated solution while the
MMMs for PV desalination needs to be further studied.
permeate side is maintained at vacuum or swept with a carrier gas to
Chitosan (CS) has been widely studied for classic pervaporation
keep a chemical potential difference for component transport through
because of its strong hydrophilicity, non-toxicity and distinctive bio-
the membrane. The separation of specific component proceeds
medical properties [29,30]. Chitosan is a multifunctional polymer with
through a dense membrane or molecular sieving porous membrane
abundant reactive amino groups and hydroxyl groups on its backbone,
based on the widely-accepted solution-diffusion mechanism [5,7].
which significantly contributes to the preferential sorption and diffu-
According to the mechanism in PV desalination, water molecules are
sion of water in CS membranes and also make it easy to be modified
first adsorbed onto the hydrophilic membrane surface, subsequently
[31]. Reaction between epoxy groups on GO sheet and primary amino
diffuse through the membrane and ultimately vaporize on the
groups in CS chains may occur to form a cross-linked structure with
permeate side [5]. A re- markably high salt rejection can be achieved
covalent bonds. The carboxyl in GO could be ionized and the amino
in the process due to the non-volatility of salt in the feed and the high
group in CS can be protonated, which can form strong electrostatic
water/salt selectivity feature of PV membranes [5]. In the meantime,
interactions, and strong hydrogen bond network will exist between all
water-preferential membranes with well-designed microstructure
the polar functional groups of chitosan and GO. These interactions are
could prevent the pas- sage of volatile organics, allowing the
likely to intensify the thermal, physical and chemical stability of CS
production of potable pure water. Since PV is a phase change
membrane in handling complex saline water for desalination. More-
membrane process with the driving force slightly influenced by the
over, the interactions between CS and GO may enhance the interfacial
feed concentration, it does not need to overcome the osmotic pressure
compatibility and thus avoid the structural defects that are often ob-
of salt water like reverse osmosis and thus is applicable in handling
served in MMMs [18].
high-salinity water [9].
In this work, GO was utilized to hybridize chitosan to fabricate
To acquire good PV desalination performance, membrane
MMMs for desalination by pervaporation and the water and salt
materials with high solubility of water are required [5]. The progress
transport properties and desalination performance of the MMMs were
has been made in membrane preparation with hydrophilic polymers
investigated. The interactions between the CS matrix and GO sheets
such as sulfonated polyethylene [10], cellulose [11,12], polyether ester
were discerned based on Fourier transform infrared spectroscopy (FT-
[13], polyether amide [14], and poly(vinyl alcohol) [15–17], etc.
IR) and X-ray photoelectron spectroscopy (XPS) characterization. The
However, the strong hydrophilicity of polymer membrane may make
effect of GO content on the surface morphology, hydrophilicity and
it unstable and over swollen in hot feed solution with inferior
mechanical strength of the MMMs were studied by scanning electron
mechanical strength, which limits the potential application of PV in
microscope (SEM), atomic force microscope (AFM), water contact
desalination, and moreover, the reported water flux of polymer
angle measurement and electronic tensile machine, respectively.
membranes for PV de- salination still needs to be improved. Mixed
Membrane performance on desalinating different concentration of
matrix membranes (MMMs), inheriting superior attributes from both
NaCl aqueous solutions by vacuum PV at various operating
polymer and in- organic materials, have been increasingly exploited
temperatures was eval- uated respecting permeate flux and salt
for pervaporation process [18]. The appropriate mixing of inorganic
rejection. The salt and water transport properties, including partition
moiety with polymer matrix could improve membrane performances
coefficient, diffusion coeffi- cient and permeability coefficient of NaCl
in chemical, thermal and mechanical stability and tune the
and H2O in membrane were determined systematically and compared
microstructure and hydro- philicity/hydrophobicity of membrane
in detail to understand the transport and separation mechanism of PV
[18]. Different interactions be- tween polymer matrix and fillers such
desalination process.
as covalent bonds, hydrogen bonds, electrostatic interactions, or van
der Waals' force, can be ex- pected to enhance overall performance.
2. Experimental
However, just a few researches concerned MMMs for desalination
by pervaporation [5,19–24]. Xie et al. prepared poly(vinyl
2.1. Materials
alcohol)/maleic acid/silica hybrid mem- branes via sol-gel method
and found that the homogeneous in- corporation of silica
CS powders with deacetylation degree of 80–95% and the
nanoparticles into the polymer matrix enhanced the free volume and
chemicals with analytical reagent grade including acetic acid (HAc),
water diffusivity of the membranes and thus en- hanced water flux
hydrogen peroxide (H2O2, 30%), sodium chloride (NaCl) and sodium
with high salt rejection [19,20]. Chaudhri et al. also synthesized
hydroxide (NaOH) were supplied by Sinopharm Chemical Reagent
poly(vinyl alcohol)/silica hybrid membranes with homo- geneous
Co., Ltd., China. Graphite powder as the raw material of GO synthesis
structure and use it as barrier layer to produce composite polysulfone
was pur- chased from Tianjin No. 1 Chemical Reagent Factory,
hollow fibers by dip coating method and observed high water flux
Tianjin, China. Potassium permanganate (KMnO4), sodium nitrate
and salt rejection in pervaporation desalination [23]. Re- cently,
(NaNO3), sulfuric acid (H2SO4, 98%) and hydrochloric acid (HCl, 37%)
graphene oxide (GO) with an atomically thickness and two-di-
with AR grade were provided by Xi Long Chemical Co., Ltd., China.
mensional structure is attracting wide attention as a promising nano-
All the chemicals were used directly without further purification.
material filler of MMMs due to carrying a large number of oxygen-
containing groups, which endows it with a negatively-charged surface
2.2. Synthesis of GO
and strong hydrophilicity and thus could contribute to high water
permeation [25]. Many researches on polymer/GO MMMs for ultra-
filtration, nanofiltration, dialysis, forward osmosis and pervaporation The modified Hummers method was adopted to synthesize GO
have proved the efficient way of GO incorporation to improve mem- sheets from graphite [32]. 6 g of graphite powders were mixed with 3 g
brane performance such as water flux, mechanical strength and anti- of NaNO3 in 138 mL of H2SO4 in a beaker at 0 °C followed by slow
addition of 18 g of KMnO4 in it. After 2 h of reaction, the mixture was
fouling ability [26–28]. For PV desalination, Feng et al. employed wet
transferred to a water bath and stirred for another 2 h at 35 °C. 276 mL
phase inversion method to produce graphene oxide (GO)/polyimide
of deionized (DI) water was added and the water bath temperature
(PI) MMMs with asymmetric structure consisting of dense skin top-
was raised to 95 °C for 30 min. Finally, 840 mL of DI water and 60 mL
layer and finger-like porous sub-layer. The MMMs displayed excellent
of H2O2 were added successively. The resultant production was
water permeability and salt rejection in seawater desalination as well
washed with 3% HCl and DI water till pH value being neutral and
as en- hanced tensile strength due to the good compatibility of GO
then cen- trifuged. Brown powders were obtained after being dried at
with PI [22]. They also observed the good compatibility of GO with PI
50 °C in a vacuum oven followed by grinding treatment.
when spinning asymmetric GO/PI hollow fiber membranes [24].
However,
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2.3. Fabrication of MMMs to take average.

A certain mass of GO was dispersed in 2 wt% HAc aqueous

solution by sonication for 2 h. Certain amount of CS powders was
dissolved in the above suspension under vigorous stirring to obtain
3% CS casting solution with different content of GO (0, 0.25 wt%,
0.5 wt%, 1 wt%,
1.5 wt%, and 2 wt% of GO mass fraction in the total mass of GO and
CS). After being stirred for 24 h and vacuum degassed overnight, the
casting solutions were cast onto a glass plate and evaporated to
dryness at room temperature. Then the membranes were immersed in
2 mol/L NaOH aqueous solution for 1 h and subsequently washed
with DI water till neutral pH. After being dried at room temperature,
the CS mem- brane and the MMMs were obtained and were marked
as CS, CS/GO- 0.25, CS/GO-0.5, CS/GO-1, CS/GO-1.5, CS/GO-2,
respectively, corre- sponding to the GO content mentioned above.

2.4. Characterization of GO sheets and CS/GO mixed matrix membranes

2.4.1. Morphology and chemical structure

The crystallinity of GO was investigated by X-ray diffraction (XRD,
XRD-6100) with 2θ from 6° to 60°. Carbon molecular bonding char-
acteristics of GO were characterized by Raman spectrum (hr800) with
Raman shift varied from 1000 to 2000 cm−1.
The morphology of GO sheets, CS membrane, and CS/GO MMMs
was determined by Scanning electron microscope (SEM, JSM-6390A)
with the sample being covered in gold. The morphology of GO sheets
was also observed with high resolution transmission electron micro-
scopy (HRTEM, JEM-2100Plus) by dropping GO dispersion onto the
ultrathin carbon film followed by being dried. The surface
morphology and roughness of MMMs were also evaluated by atomic
force micro- scope (AFM, Dimension Icon, Bruker, USA) with
scanning area of 10 × 10 μm and at least three different locations on
the surface of each specimen were measured to take average as final
result. A Fourier transform infrared spectroscopy (FTIR, Nicolet iS50)
was utilized to trace the oxidation of graphite and the chemical
constitution of MMMs. The surface chemical structures of the CS and
CS/GO membranes were analyzed with x-ray photoelectron
spectroscopy (XPS, ESCALAB Xi+).

2.4.2. Hydrophilicity
The static water contact angle of membrane surface was
determined by a contact angle meter (DSA100, Kruss Inc., Germany).
Five different locations on the surface of each specimen were
measured at room temperature and the arithmetic mean was taken as
the result.
The water uptake of the membranes was obtained by measuring
the weight of swollen and dry membranes. Firstly, a dry membrane
with known weight was immersed in DI water for 24 h at room
temperature. Then the swollen membrane was taken out of water,
wiped promptly and gently with filter paper to remove surface water
and weighed. The water uptake of membrane is calculated as follows:
Wswollen − Wdry
water uptake = × 100%
Wdry (1)

where Wdry (mg) and Wswollen (mg) are the weight of dry and swollen
membrane, respectively. Each kind of membranes was measured five
times to take the average as final result.

2.4.3. Mechanical properties

An electronic tensile machine (CMT-6503) was adopted to test the
tensile strength and elasticity modulus of self-standing membrane
with a 50 mm × 10 mm of sample dimension at a cross-head
speed of 10 mm/min. Each kind of membranes was tested five times

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 Desalination438

Fig. 1. Schematic of experimental apparatus for pervaporation desalination.

2.5. Pervaporation experiment

Fig. 1 shows the schematic of lab-scale vacuum pervaporation

ap- paratus. The membrane to be tested was placed in the
membrane cell with an effective membrane area of 0.0019635 m2. In
the test, pure water, 3.5 wt%, 5.0 wt%, 7.0 wt% and 10 wt% aqueous
NaCl solutions were used as feeds. The feed solution with a preset
temperature in a range of 40–85 °C was circulated through the cell at
16 L/h of flow rate. The permeate side was operated at a low
pressure of 6 kPa by a vacuum pump to maintain a vapor pressure
difference across membrane and the permeate vapor was condensed
with cool water. The weight variation of the feed solution was
recorded every 1 min to calculate water flux, J (kg/m2·h), according
to the following equation:

∆W
J= A×t (2)

where ΔW (kg) is the weight variation of feed solution, A (m ) re- 2

presents membrane area and t (h) represents test time. Salt rejection
of membrane, R, is determined as follows:
CF − CP
R= × 100%
CF (3)

where CF and CP represent salt concentration in feed and permeate,

respectively, which were determined through conductivity measure-
ment.

2.6. Salt and water transport property

2.6.1. Salt diffusivity of membrane

Ion and water transport properties play decisive roles in desalina-
tion performance of membrane. Salt transport properties of CS and
CS/ GO membranes were evaluated in term of NaCl diffusivity,
Ds, by a kinetic desorption method according to the literature [33,34].
Referring to the method, firstly, the membrane with a known
thickness was im- mersed in 5 wt% NaCl aqueous solution at 40
°C for at least 48 h to ensure the adsorption equilibrium of NaCl in
the membrane. Then the membrane was taken out with surface
solution being wiped off using filter paper and was quickly
transferred to 50 mL of DI water for NaCl to be desorbed into water
under stirring at 600 rpm. During the desorption process, the
conductivity of the solution was monitored and was con- verted to
NaCl concentration according to a standard curve of NaCl
concentration with conductivity.
The results of the desorption experiment were fit to Fickian
diffu- sion model to obtain NaCl diffusivity, Ds (cm2/s) by plotting
(Mt/M∞) versus t1/2 [21,34–37]: