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Energy recovery from concentrated seawater brine by

thin-lm nanober composite pressure retarded
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Cite this: Energy Environ. Sci., 2013, 6,

1199 osmosis membranes with high power density
Xiaoxiao Song, Zhaoyang Liu* and Darren Delai Sun*

Received 2nd September 2012
Accepted 28th January 2013
DOI: 10.1039/c3ee23349a
www.rsc.org/ees
A signicant amount of energy stored in the form of salinity in seawater reverse osmosis (SWRO) brine can
be harvested by a pressure retarded osmosis (PRO) process for power generation. The crucial performance-
determining factor of the PRO process is the semi-permeable PRO membrane, which separates the SWRO
brine from a lower salinity solution and sustains the salinity dierence between the two solutions.
However, accumulation of solutes in the support membrane, namely internal concentration polarization
(ICP), signicantly reduces the eective salinity dierence and thus severely limits the eciency of
conventional PRO membranes. In this paper, we report the fabrication and optimization of thin-lm
nanober composite PRO (TNC-PRO) membranes with a unique support membrane structure (inter-
connected, low tortuousness and highly porous properties), aiming to facilitate mixing of accumulated
solutes with a dilute feed stream and overcome the ICP problem. With such low structure parameter (S)
value (150 mm) nanober support membranes (NSMs), the optimum water permeability (A) and solute
permeability (B) of the TNC-PRO membrane for power generation were determined to be 4.1 L m
2 h
1
bar
1 and 1.74 L m
2 h
1 respectively. This highly ecient TNC-PRO membrane can achieve a power
density of 15.2 W m
2 and maximum energy recovery of 0.86 kW h m
3, using synthetic brackish water
(80 mM NaCl, p 3.92 bar) and seawater brine (1.06 M NaCl, p 51.8 bar) as feed and draw solution,
respectively. For a more dilute synthetic river water (0.9 mM NaCl, p 0.045 bar) feed solution, the
same membrane can achieve a higher power density of 21.3 W m
2. The main performance limiting
factors in PRO application such as ICP, External Concentration Polarization (ECP) and Reverse Solute
Permeation (RSP) are quantied and their values are related to A, B and S values of TNC-PRO membranes.

Broader context
The high mechanical strength thin-lm nanober pressure retarded osmosis (TNC-PRO) membrane sustains an ideal interconnected pore structure to break the
bottleneck of ICP for ecient osmotic power production from otherwise wasted seawater brine. This process has great potential to turn the hazardous brine
waste into energy. The maximum energy recovery rate of 0.94 kW h m
3 (river water feed solution) is approximately 20% of the energy required to produce fresh
water from seawater. If incorporated with reverse osmosis technologies, this PRO process can signicantly reduce the cost of seawater desalination.

School of Civil and Environmental Engineering, Nanyang Technological University,

639798, Singapore. E-mail: zyliu@ntu.edu.sg; ddsun@ntu.edu.sg; Fax: +65 6791
0676; Tel: +65 8298 7689; +65 67906273
Electronic supplementary information (ESI) available: Determination of
membrane intrinsic parameters and salt rejection; determination of PRO water
ux; signicance of performance limiting factor for the TNC-2 membrane
(BWSB); derivation of eqn (5) (variable-DP model) for total energy recovery from
seawater brine; constant-DP model for the calculation of energy recovery rate;
calculation of Gibbs free mixing energy, DGmix; representative drawing of the
working principle of the PRO membrane (Fig. S1); a simplied diagram of a
lab-scale PRO system (Fig. S2); NSM top surface SEM picture and nanober
diameter distribution (Fig. S3). SEM picture and schematic drawing showing
nanobers becoming backbones of the polyamide layer (Fig. S4); JW and W of
TNC-2 PRO membranes as functions of DP (Fig. S5); gure of the relationships of
Wp and optimum DP with CD,b (Fig. S6); the specic reverse solute ux, JS/JW, versus
the hydraulic pressure, DP (Fig. S7); the appearance comparison of the TNC-PRO
membrane before and aer PRO operation (Fig. S8). See DOI: 10.1039/c3ee23349a
1 Introduction
Searching for sustainable alternative energy sources is one of
the most urgent demands today. Possible solutions such as fuel
cells, solar cells and lithium-ion batteries have been extensively
investigated. However, the power density (W) for fuel cells is not
high.1 While the solar cells and lithium batteries harvest higher
W values, they have proven to be very costly and environmen-
tally unfriendly.24 Meanwhile, despite the lower manufacturing
cost, the application of polymeric solar cells requires a key
breakthrough in novel light-harvesting materials to breach the
eciency barrier for commercialization.5 The pressure retarded
osmosis (PRO) process is an outstanding technology to harvest
sustainable energy free of CO2 emission.6,7 The core of this
process is a polymeric semi-permeable PRO membrane which

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harvests the energy driven by a salinity gradient. With the PRO
membrane separating a high salinity draw solution from a low
salinity feed solution, water naturally permeates from the feed
solution side to the draw solution side while solutes are selec-
tively rejected. The trans-membrane water ux, JW, drives a
hydroturbine mounted on the draw solution side and generates
power (Fig. S1). The signicance of the water ux, JW, depends
on the eective salinity dierence across the membrane selec-
tive layer. Past studies have concluded that the salinity in
seawater is able to sustain a commercial scale PRO plant as long
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as the ecient PRO membranes could be developed with a W > 5
W m
2.810
The PRO process can be applied at the estuarial area where the
river water mixes with the seawater. A recent study on the ther-
modynamic eciency of PRO power extraction from the mixing
of river water and seawater revealed that aer deducting the
process losses and ineciencies, the technology can extract a net
1370 TW h per year of renewable energy to fulll the electrical
consumption of 520 million people.11 However, this seawater
river water PRO strategy is not feasible in water-scarce regions
such as Singapore, where river water is primarily used as the tap
water source.12 Brackish water (5000 ppm TDS), on the other
hand, could represent a better alternative since it is a readily
available source for low cost feed solution, owing to the world-
wide distribution of water reclamation plants from waste-
water.1316 In addition, seawater brine with high salinity, which is
conventionally considered as a waste stream which could severely
impair the ecological environment in oceans, may be used as a
more ecient and low cost draw solution.17,18 Furthermore, since
seawater brine is pre-treated prior to the reverse osmosis process,
most of the foulants detrimental to membranes are removed thus
leaving only a concentrated salt content in the brine.19 The
strategy of using brackish water and seawater brine as feed and
draw solutions respectively for the PRO process could potentially
turn these waste streams into energy and hence can be adopted
by the conventional reverse osmosis desalination plants to
reduce the cost of seawater desalination.20
Generally, a W value of 5 W m
2 is required for the
commercialization of the PRO process using seawater and river
water as draw and feed solution respectively.19,21 However, due
to the lack of highly ecient PRO membranes, the harvested W
was far below the benchmark value.2224 Recently, Chou et al.
reported that a high W of 5.7 W m
2 could be harvested by a
hollow ber composite polyamide membrane from synthetic
seawater and river water.14 A study by another group showed an
enhancement of the membrane water permeability which has
resulted in a higher W of 10 W m
2 through a composite poly-
amide membrane in a at sheet form which was modied with
chlorine.6 However, these membranes possessed high structure
parameter (S) values ranging from 350 to 1000 mm.13,25 When
brackish water is used as feed solution, these membranes tend
to have signicantly lower W because of severe internal
concentration polarization (ICP) (Fig. S1).13,19 It has been
proposed that a membrane with an S value around 150 mm is
ideal for a PRO membrane in an osmotic power plant.10 To date,
highly ecient PRO membranes with suciently low S values to
overcome the ICP limitation have not been reported.
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In this work, highly ecient TNC-PRO membranes with a
low S value nanober support membrane structure were
designed and fabricated for the rst time. The TNC-PRO
membranes were modied with chlorine to attain a series of
water permeability coecient (A) and solute permeability coef-
cient (B) values. Performance limiting phenomena, such as
internal concentration polarization (ICP), external concentra-
tion polarization (ECP), and reverse solute permeation (RSP),
were quantied and elucidated with experimental data and
theoretical studies. The optimization protocols to achieve high
eciency energy recovery from seawater brine using brackish
water as feed solution were systematically studied. The
maximum energy recovery rate using TNC-PRO membranes
were calculated using variable DP and constant DP models.
2 Materials and methods
2.1 Fabrication of nanober support membrane (NSM)
2.1.1 Electrospinning of nascent NSM. Polyacrylonitrile
(PAN) nanober support membranes (NSMs) were electrospun
from 8% w/w PAN (Mw 150 000 g mol
1) in N,N-dimethyl
formamide using a custom-built rotating drum electrospinning
device.26 As a key measure to improve the mechanical strength
of the NSM, tetraethylorthosilicate was dissolved in the PAN
precursor solution (6% w/w) and the resultant solution was
vigorously stirred for at least an hour. Then 2% w/w of acetic
acid (AA) was slowly dropped into the solution. The total mixed
solution was continuously stirred for 2 hours at 80  C and
another 24 hours at room temperature prior to electrospinning.
Typically, a DC voltage of 30 kV was applied between a stainless
steel spinneret orice (diameter 0.7 mm) and a collecting
stainless steel rotating drum (300 rpm), which is 15 cm beneath
the orice. The rotating drum was driven by a horizontally
oscillating actuator (60 cm min
1) simultaneously. Prior to
electrospinning, the stainless steel rotating drum (length 
diameter 20 cm  10 cm) was wrapped with a poly(ethylene
terephthalate) (PET) non-woven substrate (Ahlstrom Grade
3257). The non-woven substrate was pre-wetted with N-methyl-
pyrrolidone (Acros Organics) to ensure the NSM is bonded with
the substrate. The PAN solution was then fed to the spinneret by
a syringe pump with a constant rate of 40 mL min
1. Under the
inuence of an electrical eld, the polymer solution was
continuously electrospun into ultrane nanobers. The nano-
bers dried out and were spun-bounded to be a nascent nano-
ber support membrane with a maximum eective area of 600
cm2 (length  width 30 cm  20 cm). The membrane was
sandwiched between two pieces of clear glass (10 mm thick) and
heat-treated at 120  C for 2 hours, resulting in a stabilized
nanober membrane. Chemicals (if not specied) were
purchased from Sigma-Aldrich.
2.1.2 Coating of poly(vinyl alcohol). At the nal step of
fabrication of NSMs, the nascent NSMs were dip-coated with 1%
w/w of PVA (Mw 89 00098 000, 99+% hydrolyzed, Sigma-
Aldrich) aqueous solution for 5 minutes. An air knife (Exair
PVDF super air knife, USA) was employed to drain excess PVA
solution from the NSM surface. The NSM was then dried at 90

C in an oven for 5 min. Subsequently, the PVA-coated NSM was
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cross-linked in a tank with 0.5% w/w glutaraldehyde in acetone/
DI water (50/50) for 30 minutes. Aer the cross-linking reaction,
the NSM was cured again at 90  C in the oven for 5 minutes,
washed substantially and then preserved in deionized (DI) water
at 5  C until further test.
The NSMs without PVA coating and SiO2 are designated as
NSM-0, the NSMs with PVA coating but no SiO2 are designated
as NSM-1, whereas the NSMs with both PVA coating and SiO2
are designated as NSM-2.
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2.2 Interfacial polymerization
Interfacial polymerization was performed on the top surface of
NSMs. An NSM was rst immersed into isopropanol for better
wetting ability. The recipe for the interfacial polymerization was
adopted from the literature with some modications.27 Typi-
cally, the NSM, being taped to a glass with four sides sealed, was
rinsed with DI water for several times and was soaked in 3% m-
phenylenediamine aqueous solution (with 1.1% w/w triethyl-
amine and 2.3% w/w camphor sulfonic acid) for 2 minutes. An
air knife (Exair PVDF super air knife, operated at 0.2 bar), held
approximately 10 mm above the support membrane surface,
was used to drain excess m-phenylenediamine aqueous solution
from the saturated NSMs. A complete pass of the air knife over a
15 cm-long membrane coupon took about 10 seconds. The
surface of the membrane quickly became dull and dry. Then,
0.15% w/w trimesoyl chloride in hexane was introduced onto
the surface of the NSMs. Aer 1 minute of reaction, the nascent
composite membrane was allowed to sit for 30 min and then
cured at 95  C for 3 minutes in an oven in order to dehydrate the
membrane and improve the integrity of the polyamide layer.
2.3 Chlorine modication of the polyamide selective layer
The chlorine modication of the polyamide selective layer
adopted in this study has been proposed in previous
studies.6,13,28 Experimentally, sodium hypochlorite (44.99%)
was diluted exactly by 200 times (200 ppm), 40 times (1000
ppm) and 20 times (2000 ppm) and dosed with 6 M HCl to
adjust the pH value to 7.0  0.1. It was found in recent studies
that two decisive parameters for the chlorine modication are
pH and NaClO concentration.2931 The TNC-membranes were
soaked in 200 ppm, 1000 ppm and 2000 ppm NaClO solution for
2 min, 1 hour and 2 hours, respectively. Then the NaClO-treated
membranes were washed thoroughly and transferred into 0.1 M
NaOH (Fisher Scientic) aqueous solution. Membranes treated
with 200 ppm NaClO and 1000 ppm NaClO, which are desig-
nated as TNC-1 membranes and TNC-2 membranes
respectively, were immersed in the above alkaline solution for
24 h. Membranes treated with 2000 ppm NaClO, designated as
TNC-3 membranes, were immersed in the above alkaline
solution for 48 h. Then the modied membranes were cured
again at 95  C for 2 minutes in order to anneal the membrane
following which they were kept in 5  C DI water.
2.4 Characterization
Micro-images were obtained by employing a Zeiss Evo 50
Scanning Electron Microscope (SEM). High resolution SEM
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images were obtained using a Joel JSM 7600F thermal eld
emission SEM (FESEM). Exposed cross-sections were obtained
by fracturing the samples immediately aer ash-freezing by
liquid nitrogen. An EMITECH SC7620 sputter coater was
utilized to coat all samples with gold for 4560 seconds. The
topology of a typical TNC-PRO membrane was probed by a Park
XE-100 Atomic Force Microscope (AFM) in non-contact mode.
Contact angle measurements were determined by an OCA
Contact Angle System (DataPhysics, Germany) and reported as
an average of 10 measurements. The mechanical strength of the
NSMs was tested using a Zwick 0.5KN Universal Testing
Machine. The pore size distribution was evaluated by a capillary
ow porometer (model CFP 1500A, Porous Materials Inc., Sin-
gapore) through bubbling point and gas permeation tests.
2.5 Determination of membrane intrinsic parameters
The value of intrinsic water permeability coecient (A) was
determined by a bench scale cross-ow RO unit (SEPA CF II, GE,
eective area is 140 cm2).26 The intrinsic solute permeability
coecient (B) and structure parameter (S) were calculated based
on the monitored water ux, JW, and solute ux, JS, in a custom-
built cross-ow FO system. A FO module with an eective
membrane area of 23.8 cm2 was used to mount the TNC-PRO
membrane coupons. Cross-ow velocities at both feed and draw
solution sides were maintained by gear pumps (Cole-Palmer) at
15.4 cm s
1. Spacers (Sepa CF feed spacer, 17 mil) were inserted
in the 2 mm deep channels on both sides. The protocols to
deduce the B and S values based on the monitored data are
explained in the ESI with reference to a previous study.6
2.6 Determination of PRO water ux (JW)
The power output of a PRO membrane is determined by JW
under the test hydraulic pressure, DP.6 The tests for all
TNC-PRO membranes were carried out in a customized lab-
scale PRO system as illustrated in Fig. S2. The eective
membrane area for the PRO membrane module is 140 cm2. For
each TNC-PRO membrane, synthetic river water (0.9 mM NaCl,
0.045 bar, designated as RW) and brackish water (80 mM
NaCl, 3.92 bar, designated as BW) were used as the feed
solution alternatively while synthetic seawater brine (1.06 M
NaCl, 51.8 bar, designated as SB) was used as the draw solu-
tion. The concentration of the synthetic seawater brine was
determined based on a 50% system recovery of a typical
seawater reverse osmosis plant.3234 For each of the feed solu-
tion, a series of trans-membrane ux JW were measured by
varying DP (DP 15.2, 13.3, 10.2, 8.8, 7.5, 5.8, 4.9, 3.8, 2.5 and
0 bar respectively). A detailed discussion of the test can be
found in the ESI.
2.7 Determination of power density (W)
By denition, the power generated by a hydroturbine, P, can be
calculated by:
P rgHQ (1)
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where P is the power in kW, r is the density of water, g is the
local gravity, Q is the water ow in m3 s
1, and H is the water
head in meter. Dened as the power generated by a unit area of
the membrane, Am, the power density, W, can be calculated by:
W P/Am rgHQ/Am DPJW (2)
where DP is the applied hydraulic pressure on the draw solution
side. JW is the water ux from the feed solution side to the draw
solution side.
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2.8 Modeling of JW, W, ECP, ICP and RSP
The trans-membrane water ux, JW, can be further expressed
as:22
JW A(Dpeff
DP) A(bRgTDCm
DP) (3)
where, Dpe is the eective osmotic pressure driving force
across the membrane selective layer. The term (Dpe
DP)
represents the net driving force across the membrane selective
layer. b is the vant Ho factor,8 Rg is the gas constant and T is
the thermodynamic temperature. DCm is the solute concentra-
tion dierence across the membrane selective layer, which can
be further expressed as:13
CD;b exp
JW =k
CF;b expJW S=D
DCm
1 B=JW expJW S=D
1 B=JW 1
exp
JW =k
(4)
where, CD,b and CF,b are the concentrations of bulk draw solu-
tion and feed solution respectively. k is the mass transfer coef-
cient; the value of k can be deducted from the combination of
eqn (3) and (4). D is the diusion coecient of the draw solute.
As suggested in eqn (4), DCm is determined by 3 mass transfer
phenomena, as illustrated in Fig. S1: (i) ECP, which is caused
by the decrease of CD,m with respect to CD,b: CD,m
CD,bexp(
JW/k), as the water permeates across a dense selective
layer into the draw solution side and dilutes the solute
concentration. (ii) ICP, which is caused by the increase of CF,m
with respect to CF,b: CF,m CF,bexp(JWS/D), as the retained
solutes at the feed solution side accumulate within the support
membranes. (iii) RSP, which is caused by the reverse diusion
of solutes from the draw solution into the feed solution. The
adverse coupling of RSP with ECP or ICP, which could be
arithmetically expressed as B[1
exp(
JW/k)]/JW and B
[exp(JWS/D)
1]/JW, further reduces DCm.
Based on eqn (4), the limiting eect of ECP, ICP and RSP
could be isolated assuming the elimination of RSP
(B/JW[exp(JWS/D)
exp(
JW/k)] 0), ICP (exp(JWS/D)
1 0) or
ECP (1
exp(
JW/k) 0) respectively.13 A Loss Factor (LF) has
been proposed to indicate the Wp loss because of the limiting
eect of phenomena i (LFi 1
Wp/Wp,no-i, i ECP, ICP or
RSP).13 In this study, a more straightforward contribution
coecient indicator, d, is derived based on the value of LF (di
P P
LFi/ LFi and di 1). The value of d symbolizes a comparative
contribution of each phenomenon to the total limiting eect.
For example, when dECP dICP dRSP, the three phenomena
contribute equally in limiting Wp. In a system with a constant
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cross ow velocity (CFV) and temperature, the value of di is
predominantly dependent on the draw and feed solutions
(CD,b, CF,b) and membrane intrinsic characteristics (A, B, S).
2.9 Determination of energy recovery rate E
The energy recovery rate, E, refers to the amount of energy
recovery per unit volume of seawater brine. E can be calculated
by the following integration (ESI):
0
1
fC
 
E
C0 DP=Ct 2 dC (5)
C0
where, C0 is the initial CD,b at t 0, Ct is the CD,b at time t,
(1
f)C0 represents the nal CD,b when PRO operation ends
and DP is the applied hydraulic pressure at the draw solution
side. The optimum DP is a function of CD,b (Fig. S6). The ratio
between the initial volume of the feed solution and the total
initial volume of the feed and draw solutions, f, has been
dened in a previous study.11
3 Results and discussion
3.1 Nanober support membrane (NSM) characteristics
A suitable NSM for high pressure applications such as PRO
should sustain a proper mechanical strength and possess an
ideal pore structure with a suciently low S value. Hence, in
this work, we designed and tailored a composite NSM to cater
specially for this interest. The appearance of a typical NSM-2 is
shown in Fig. 1a. The NSM was designed following a hierar-
chical 2-level strategy. The rst level referred to the individual
nanober which was strengthened by nano-SiO2 and the second
level referred to the strengthened bonds between nanobers or
nanober layers.
The SiO2/PAN composite nanobers were fabricated by a co-
electrospinning method with a SiO2 precursor and acid cata-
lysts. Although the change of strength for a single nanober was
too subtle to be measured, the mechanical strength for NSM as
a whole can be evaluated by employing a tensile strength test.
The results, which are listed in Table 1, show that the strain at
break has improved signicantly from 9  3 MPa (NSM-1) to
17  2 MPa (NSM-2). The stiness of the NSM has increased
slightly concurrently as validated by the decreased elongation at
break from 20  4% to 15  5%. This mechanical strength
improvement could be explained by the adsorption anity
between the SiO2 nanoparticles which were strapped to the PAN
polymer chains.35,36 A typical TEM image of a representative
single nanober strain (inset, bottom le, Fig. 1c) clearly shows
the abundant SiO2 nanoparticles which were evenly dispersed
along the nanober. The SiO2 nanoparticles appear darker than
the bulk PAN polymer phase, implying that the nanoparticles
were composed of heavier elements (i.e. Si) than that of the PAN
polymer (C, N, O). In accordance with the TEM picture, the
FESEM image of a typical nanober cross-section (inset, bottom
right, Fig. 1c) reveals some spherical and oval shaped particles
which were indicative of SiO2 particulate matters. EDX mapping
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Fig. 1 (a) The slightly yellowish SiO2/PAN composite NSM; (b) FESEM image of the SiO2/PAN composite NSM shows nanober strains with narrow size distribution, the
inset picture (bottom left) shows the pore size distribution of the NSM centers at around 500 nm. (c) FESEM image of nanober cross-sections showing that the
nanober strains are welded together. The inset pictures are TEM images of a single SiO2/PAN nanober strain (bottom left) and an enlarged FESEM image of a typical
cross-section of a single nanober (bottom right), showing that SiO2 particulate matters are evenly dispersed in the PAN polymer matrix. (d) The EDX mapping of a
typical cross-section showing the even distribution of Si, N and O elements.

Table 1 Pore size distribution and mechanical strength for nanober support membranes

Pore size distribution Mechanical strength

Mean pore Maximum pore Stress at break Elongation at

Membrane designation size (mm) size (mm) Porosity (MPa) break (%)

NSM-0 0.79 1.10 80% 71 25  7

NSM-1 0.46 0.69 74% 93 20  4
NSM-2 0.50 0.74 74% 17  2 15  5
NSM-2-NW 0.49 0.76 23  3 18  7

of a cross-section of a typical nanober (Fig. 1d) further veries
that the distribution of SiO2 nanoparticles was very uniform.
The inter-connectivity between the nanobrous strains was
facilitated by the hot-press post treatment and further
strengthened by coating and cross-linking reactions with PVA.
During the hot-press treatment, the heated residue solvent
molecules inside the nascent nanobers diused outward to
the nanober surface and partially dissolved the polymer.
Subsequently, the solvent molecules evaporated and le the
joint areas between nanobers welded. This could be validated
by the FESEM images in Fig. 1c where the cross-sections of
several nanobers were observed to be bonded with some
overlapped areas. The coating and cross-linking reactions with
PVA have further strengthened the interconnectivities, as sug-
gested by the increasing strain at break which increased from
7  1 MPa (NSM-0) to 9  3 MPa (NSM-1) (Table 1).
Fig. 1b (inset, plot) shows that NSM-2 had a narrow unim-
odal size distribution centered at around 500 nm. This corre-
sponded well with a narrow nanober size distribution as
depicted in Fig. S3 where more than 70% of nanobers were in
the range of 100200 nm and 98% of nanobers were in the
range of 100300 nm. The narrow size distribution would

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eliminate unexpected defects usually induced by big pores at
high hydraulic pressures. As such, unlike the conventional
phase-inversion support membranes which possess more
tortuous pore structures, NSM-2 was endowed with an inter-
connected, scaold-like pore structure (porosity 74%) across
the entire thickness of the support membrane thus facilitating a
better mixing between the accumulated solutes with the con-
vectively permeated dilutive water ux, JW.26,37
3.2 TNC-PRO membrane characteristics
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angle.26,39,40 AFM analysis (Fig. 2e) shows that the roughness of a
typical TNC membrane surface (Ra 54.8 nm) had a similar
value to the commercial RO membranes with polyamide selec-
tive layers.38,4144 Nonetheless, this value was higher than a
recently published PES/sPSf TFC-FO membrane (Ra 44.1 nm),
which has lower A and B values than that of the as-prepared
TNC-PRO membranes in this study.45 An earlier positron anni-
hilation spectroscopic study suggested that a higher surface
roughness of a polyamide membrane may relate to higher A and
B values.46

The typical SEM images of TNC-PRO membranes based on

NSM-2 are shown in Fig. 2. The cross-section SEM image
(Fig. 2c) shows that a thin and dense selective layer was closely
bonded with NSM-2. The interfacial-synthesized polyamide
selective layer showed a rugged morphology, which was similar
to the selective layers of commercial polyamide RO
membranes.27,38 A high resolution FESEM image in Fig. S4
shows that the thickness of the polyamide selective layer was
typically between 200 and 300 nm, inclusive of a backbone
made up of embedded 12 layers of nanobers which had a
diameter in the range of 100200 nm. Contact angles of the as-
prepared TNC-PRO membranes were measured to indicate the
membrane surfaces hydrophilicity. Unlike the commercial
BW30 polyamide desalination membrane, the TNC-PRO
membranes possess a smaller average contact angle of 59.6 
3.5 , implying a more hydrophilic nature of the TNC-PRO
membranes (Fig. 2d).39 This could be attributed to the large
surface porosity of the nanober support membrane which has
reduced the surface energy resistance thus facilitating water
diusion into the membrane, resulting in a lower contact
3.3 Performance of TNC-PRO membranes
Chlorine treatment is an eective method to increase
membrane permeability at the expense of some salt passage.30,47
The modication of TNC-PRO membranes is necessary if high
W is required.13 The TNC-1 membrane with 200 ppm NaClO
treatment had A and B values of 1.23 L m
2 h
1 bar
1 and 0.28 L
m
2 h
1, respectively. Compared with the TNC-1 membrane,
the TNC-2 membrane with 1000 ppm NaClO treatment had a
tripled A value of 3.82 L m
2 h
1 bar
1, while the tradeo was
the quadrupled B value of 1.19 L m
2 h
1 (Table 2). The TNC-3
membrane with 2000 ppm NaClO treatment had even higher A
and B values of 5.31 L m
2 h
1 bar
1 and 3.86 L m
2 h
1
respectively. It is worthy to note that the rejection rates of the
TNC-1, TNC-2 and TNC-3 membranes were determined to be
95.4%, 93.1% and 87.2% respectively, as revealed by a RO test
described in the ESI. The measured rejection of the membrane
decreased simultaneously with the increase of membrane
permeability.

Fig. 2 (a) The picture shows a typical appearance of a TNC-PRO membrane. (b) The cross-section micro-image of the TNC-PRO membrane shows a 3-tier structure with
the bottom PET non-woven microber as the mechanical support, the nanober layer as the intermediate layer, and the top ultrathin polyamide layer as the selective
layer. (c) The enlarged cross-section micro-image shows that the polyamide selective layer is closely bonded with the nanober support membrane. The nanober
support membrane has an interconnected scaold-like pore structure. (d) The top polyamide layer has a typical rough polyamide structure. The inset picture shows that
the contact angle of the TNC-PRO membrane surface was determined to be 59.6  3.5 . (e) The regional averaged roughness of the TNC-PRO membrane surface was
determined to be 54.8 nm by AFM imaging.

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Paper Energy & Environmental Science

Table 2 Summary of membrane characteristics and performance parameters of TNC-PRO membranes

Solute Experimental water ux Power density,

TNC-PRO Intrinsic water permeability Structural (L m
2 h
1) @15.2 bar W (W m
2) @15.2 bar
membrane permeability, coecient, parameter,
type A (L m
2 h
1 bar
1) B (L m
2 h
1) S (mm) River water Brackish water River water Brackish water

TNC-1 1.23  0.15 0.28  0.07 149  17 25.3  0.4 20.5  0.3 10.7 8.6
TNC-2 3.82  0.40 1.19  0.20 135  14 36.0  2 27.0  1.4 15.2 11.4
TNC-3 5.31  0.26 3.86  0.45 140  9 24.3  5.8 18.3  3.9 10.3 7.7
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The experimental JW as a function of DP for the TNC-1, TNC-2
and TNC-3 membranes are plotted in the upper section of Fig. 3
from le to right respectively. The JW exhibited a near linear
increase as DP decreased from 15.2 to 0 bar. At equal DP, the JW
with RW as the feed solution (green triangle) was constantly
higher than the JW with BW (blue square) as the feed solution.
For both feed solutions, TNC-2 membranes had substantially
higher JW than TNC-1 membranes (Table 2). This could be
explained by the more permeable nature of the TNC-2
membrane (i.e. higher A value). However for the TNC-3
membrane which was even more permeable, JW gradually lev-
eled o or even decreased (especially at high DP). Among all the
three TNC-PRO membranes, the TNC-2 membranes attained
the highest JW of 36.0 L m
2 h
1 with RW feed solution and the
highest JW of 27.0 L m
2 h
1 with BW feed solution at a DP of
15.2 bar. In the lower section of Fig. 3, the corresponding W is
plotted as a function of DP when RW (green triangle) or BW
(blue square) was the feed solution. As suggested by eqn (2), W is
the product of JW and DP. Thus at equal DP value, the magni-
tude of W follows the same order of JW, with the TNC-2
membranes harvesting a higher W (15.2 W m
2 for RW feed
solution and 11.4 W m
2 for BW feed solution) than the other
two types of membranes.
3.4 Mass transfer phenomena and their contribution to Wp
loss
The performance of TNC-PRO membranes could be predicted
by a model proposed by a previous study, which includes
synergistic limiting eects of ECP, ICP and RSP.13 As a
comparison with the experimental data, the modeled JW and W
are represented with green dotted dashed lines (RW feed solu-
tion) and blue dotted dashed lines (BW feed solution) in the JW
DP plot and WDP plot in Fig. 3. For example, a gure and

Fig. 3 Experimental JW and the corresponding W (green triangles and blue squares) as a function of applied hydraulic pressure, DP, for TNC-PRO membranes treated in
200 ppm (left), 1000 ppm (center), 2000 ppm (right) of NaClO. The data are summarized in Table 2. The respective membrane characteristic parameters: intrinsic water
permeability, A, solute permeability, B, and support membrane structural parameter, S, are plotted in the above charts. Synthetic seawater brine was used as the draw
solution (pdraw 51.8 bar) while river water (pfeed 0.045 bar, green lines) and brackish water (pfeed 3.92 bar, blue lines) were used as feed solutions. Dashed lines
represent modeled JW and W. The red triangles and squares represent the JW when the membrane had not been conditioned with high pressure.

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related discussion showing the signicance of the performance
limiting factors for the TNC-2 membrane (BWSB) can be found
in Fig. S5 (ESI). On the basis of this model, we propose a more
straightforward contribution coecient, d, to indicate the
comparative contribution of each limiting factor (ECP, ICP or
RSP) to the loss of eective osmotic driving force (detailed
deduction is in Section 2.2).
In the BWSB conguration, the (dECP, dICP, dRSP) for TNC-1,
TNC-2 and TNC-3 membranes was (0.77, 0.19, 0.04), (0.65, 0.26,
0.09) and (0.52, 0.30, 0.18) respectively. The three groups of
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coecients correspond to three coordinates, represented by the
red circles, in the ternary plot of ECP, ICP and RSP (Fig. 4). As
determined from the d value, the signicance of the limiting
factor follows the order ECP > ICP > RSP for all of the TNC-PRO
membranes. As the membrane permeability was increased,
both dICP and dRSP increased while dECP decreased. Nonetheless,
the values of dRSP for all TNC-PRO membranes were constantly
lower than the equivalent value of dICP. This suggested that the
limiting eect of reversely permeated solutes was minor for the
TNC-PRO membranes. Meanwhile the accumulation of solutes
predominantly from brackish feed solution accounted for a
more signicant Wp loss.
In the RW-SB conguration, the (dECP, dICP, dRSP) for TNC-1,
TNC-2 and TNC-3 membranes was (0.92, 0.04, 0.04), (0.81, 0.09,
0.10) and (0.61, 0.18, 0.21) respectively. The above coordinates
are represented by green circles in Fig. 4. Unlike in the BWSB
conguration, the limiting eect of ECP in the RW-SB cong- dotted line of Fig. 4 where all coordinates were lower than the
uration was more severe, indicated by the more prominent
value of dECP. This was because higher JW would induce a more
Fig. 4 Comparative contribution coecients of ECP, ICP and RSP to Wp loss.
When river water was used as the feed solution (green triangles and circles), the
contribution of ICP and RSP is approximately equal as it can be observed that all
green symbols lie along the median of the RSP-ICP side. When brackish water
was used as the feed solution (red triangles and circles), ICP is more prominent
than RSP as all red symbols lie above the RSP-ICP median. As the membrane was
treated with a higher concentration of NaClO (the direction of arrows indicates
200 ppm (TNC-1), 1000 ppm (TNC-2), 2000 ppm (TNC-3) treatment in order), RSP
and ICP exacerbate as symbols are approaching the RSP-ICP side. TNC-PRO
membranes with a small S value is less aected by ICP, as circle symbols (TNC-PRO
membrane) lie further to the RSP-ECP side than its counterpart of phase
inversion (PI)-PRO membranes with triangle symbols. The plotted datasets are
based on D 1.48  10
9 m2 s
1 at 25  C and the cross-ow velocity is main-
tained at 6.5 cm s
1 (k 76.7 L m
2 h
1).
1206 | Energy Environ. Sci., 2013, 6, 11991210
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Paper
severe dilution of the draw solution (i.e., CD,bexp(
JW/k)
signicantly decreases). At the same time, the signicance of
ICP dwindled and dICP has a nearly equivalent value to that of
dRSP. This was ascribed to the signicantly low CF,b for dilute
river water in which the reversely permeated solutes were the
dominant species in inducing the ICP. As the coupled behavior
of ICP with RSP dominated, similar values between dICP and dRSP
were obtained. This was consistent with the modeled results in
a previous study.13
The modeled signicance of limiting phenomena for TNC-
PRO membranes is compared with that of the conventional
phase inversion PRO membranes in Fig. 4 by employing an
ECP-ICP-RSP ternary plot. Comparable A and B values of the
chlorine modied phase inversion PRO membranes (LP, MP
and HP) were adopted from the literature.6 The modeled S
value of 350 mm was the lowest value amongst the developed
phase inversion support membranes in the literature as of
today.13 Values of other parameters and test conditions were
kept the same as that of the TNC-PRO membranes. The
modeling results show that all phase inversion PRO
membranes had a more signicant value of dICP (green and red
triangles) than their equivalent TNC-PRO membranes. In
detail, phase inversion PRO membranes had dICP values of
around 0.5 in the BWSB conguration (red triangles). Owing
to a signicantly lower S value of 150 mm, all TNC membranes
had dICP values of less than 0.3, as can be seen in the purple
boundary line of dICP 0.3. In contrast with the lower dICP
values, the dECP values for TNC-PRO membranes are all higher
than 0.5. This suggests that the ICP limitation has been
eectively overcome in the TNC-PRO membranes, while the
ECP has been the major limiting factor of Wp.
3.5 Implications of TNC-PRO membranes for real
applications
3.5.1 Membrane intrinsic parameters (A, B and S). The B
and A values of a polyamide membrane fulll an empirical
relationship of B b  A3 (b is an empirical tting coecient
with a unit of bar3 m4 h2 L
2).13,48 In this study, the tted value
of b for TNC-PRO membranes was 0.025 bar3 m4 h2 L
2. In
previous studies, it was concluded that balanced A and B values
were essential to optimize the Wp.6,13 In the Wp (A, B) plot, the
empirical equation is represented by a blue dashed trade-o
curve (Fig. 5a). The color gradient in a contour plot shows the
Wp distribution as a function of (A, B), and the contour lines
show all theoretical A and B pairs which could achieve the same
Wp value. As can be determined from the concave-shaped
dashed blue curve, there is only one A value, namely the
optimum A value, at which Wp,max can be achieved. When the
membrane has a lower-than-optimum A value, Wp is lower than
Wp,max because of insucient JW. When the A value exceeds the
optimum value, Wp,max cannot be achieved because: (i)
concurrent increase of the B value would inict the ICP and RSP
severely, which has an adverse impact on DCm and (ii) the
benecial increase of the A value is marginalized because of
substantial dilution of bulk CD,b by higher JW, resulting in the
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Fig. 5 (a) Contour plot of peak power density (indicated by a colored gradient), Wp, as a function of water permeability (horizontal axis), A, and solute permeability
(vertical axis), B. The AB trade-o curve (dashed blue line, B bA3, b 0.025 bar3 m4 h2 L
2) is tted from experimentally determined A and B values of TNC-1, TNC-2
and TNC-3 (hollow blue circles). (b) Contour plot of Wp as a function of A (horizontal axis) and membrane structure parameter, S (vertical axis). Purple dashed lines
indicate S values of 150 and 350 mm. The tangent point of the Wp contour line with the purple dashed line indicates the highest Wp, Wp,max, at the corresponding S
value. The dotted white line connects all AS pairs where Wp,max is reached. (c) Contour plot of Wp as a function of A and mass transfer coecient, k. The dotted white
line connects all Ak pairs where Wp,max is reached. (d) Contour plot of Wp as a function of A and draw solution concentration, CD,b. The dotted white line connects all A
CD,b pairs where Wp,max is reached. Unless specied as variables in the plots, parameters fulll the following conditions: pdraw 51.8 bar and pfeed 3.92 bar, S 150
mm, k 76.7 L m
2 h
1 (CFV 6.5 cm s
1), B bA3 (b 0.025 bar3 m4 h2 L
2) and D 1.48  10
9 m2 s
1 at 25  C.

self-limiting JW phenomenon. Similar observations have been
revealed in previous studies.6,13,49,50
This intrinsic AB trade-o relationship centralizes the
importance of the S value in determining the Wp,max. As the S
value decreases, both the ICP factor (i.e., exp(JWS/D)
1) and
RSP factor (i.e., B/JW[exp(JWS/D)
exp(
JW/k)]) decrease signif-
icantly.6,13 This alleviates the limiting eect of ICP and RSP and
enables the further benecial increase of the A value to achieve
higher Wp,max. As suggested by the previous study, a Wp (A, S)
contour plot could be employed to help with the interpreta-
tion.13 As we can see in Wp (A, S) in Fig. 5b, Wp is lower for
membranes with a high S value (upper part) than that of the
membranes with a low S value (lower part). Till today, the
constraint for the reduction of the S value has always been the
technical diculty to develop ultrathin, porous and less
tortuous support membranes. The range of S values for
currently developed phase inversion membranes was 3503000
mm for thin-lm at-sheet composite membranes and 6001400
mm for thin-lm hollow-ber composite membranes.51,52 When
the S value is 350 mm (i.e. phase inversion PRO membrane), a
Wp,max of around 11 W m
2 is projected to occur at a lower A
value of 2.8 L m
2 h
1 bar
1 (B value 0.55 L m
2 h
1). By
employing the electrospinning technique, TNC membranes
have re-invented the wheel and were reported to possess the
lowest S value (150 mm) owing to uniquely low-tortuous, inter-
connected and highly porous structures of the nanober
support membranes.26 With such a low S value, a higher Wp,max
of 15.2 W m
2 is projected to occur at a higher A value of 4.1 L
m
2 h
1 bar
1 (B value 1.74 L m
2 h
1). This predominant
role of the support membrane structure in determining Wp,max
has necessitated a porous and interconnected support
membrane to be applied in PRO application. Endowed with an
interconnected nanobrous structure and thus the lowest S
value so far, the as-prepared TNC-PRO membrane herein is
clearly a promising candidate for energy recovery from seawater
brine with an ecient osmotic power production without
compromising on the mechanical strength.
3.5.2 Operation conditions (k and DP). Aside from the
membrane intrinsic parameters, the selection of operation
conditions, such as k and DP, also aects Wp,max. The impor-
tance of the analysis related to the k value is in line with the
previous conclusion that ECP was the major limiting factor for
the Wp of TNC-PRO membranes. A higher k value reduces the
ECP factor, 1
exp(
JW/k), and increases DCm (eqn (4)). The k
value at the experimental conditions of this study (CFV 6.5 cm
s
1, feed and draw spacers inserted) was 76.7 L m
2 h
1. At this
k value (horizontal purple line, Wp (A, k) contour plot, Fig. 5C),
Wp,max reaches 15.2 W m
2 at an A value of around 4.1 L m
2
h
1 bar
1. If the k value could be enhanced to 180 L m
2 h
1,
Wp,max would reach 21.6 W m
2 at approximately the same A

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Energy & Environmental Science
value. However, it has been noted in a previous publication that
the enhancement of the k value entails extra pumping cost
which could possibly oset the benet from a high k value.13
Thus, from an economical point of view, it is more favorable if a
minimum k value could be used to achieve Wp,max. Such a value
can be calculated by solving dWp/dk 0 and the result is rep-
resented by the lowest point on the Wp,max (15.2 W m
2) contour
line in the Wp (A, k) contour plot. Interestingly, this A value does
not deviate too much from 4.1 L m
2 h
1 bar
1 when k > 76.7
L m
2 h
1. This analysis serves as a practical guideline for all
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PRO membranes through which the most cost-eective k value,
which is a function of membrane intrinsic parameters (A, B
and S), could be derived.
In a real PRO application, the seawater brine is continuously
diluted, thus it is of practical importance to deduct the
optimum DP as a function of CD,b. As shown in the Wp (A, CD,b)
contour plot (Fig. 5d), with CD,b decreasing to CD,b/4, Wp,max is
predicted to decline signicantly from 15.2 W m
2 to less than
2.0 W m
2. Accordingly, the optimum DP to achieve Wp,max can
be calculated as a function of CD,b by mathematically solving
dWp/dDP 0 for dierent CD,b ranging from 0.25 M to 1.06 M.
For TNC-PRO membranes with an optimum A value of 4.1 L m
2
h
1 bar
1, the corresponding Wp,max and optimum DP in the
BWSB conguration, DP1, is plotted against CD,b in Fig. S6. It
was found that the optimum DP linearly decreases with
decrease of CD,b. The empirical relationship can be
expressed as:
DP1 g1CD,b
1.62 (fitting coefficient g1 24.3 bar L mol
1)(6)
Similarly in the RW-SB conguration, the optimum DP, DP2,
can be expressed as:
DP2 g2CD,b + 0.55 (fitting coefficient g1 22.8 bar L mol
1)(7)
3.5.3 Energy recovery rate from seawater brine using the
TNC-PRO membrane. The maximum energy recovery rate from
seawater brine can be calculated by employing the optimum
membrane intrinsic parameters (S 150 mm, A 4.1 L m
2 h
1
bar
1, B 1.74 L m
2 h
1) and operation conditions (k and DP)
which have been developed so far. The experimental k value was
76.7 L m
2 h
1. DP was substituted as a function of CD,b.
According to eqn (5), the integrated specic E, the energy
recovery per volume of seawater brine, for RW-SB and BWSB
was determined to be 0.94 kW h m
3 and 0.86 kW h m
3,
respectively. Meanwhile, the Gibbs free energy of mixing, DGmix,
1.97 kW h m
3 for RW-SB and 1.25 kW h m
3 for BWSB, could
be calculated using an equation developed by a recent study.11
Thus the TNC-PRO membrane could extract a maximum 69% of
DGmix for brackish feed solution and 48% of DGmix for river
water feed solution. However this maximum energy recovery
rate was still likely to be over-estimated since the ne tuning of
DP may not be applicable in real PRO application. Thus, we also
calculated the energy recovery rate using a constant-DP model
developed by a recent study for comparison.11 Detailed equation
deduction and calculation can be found in the literature and
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Fig. 6 Gibbs free energy of mixing, DGmix, for river water (left) and brackish
water (right) feed solutions are indicated by the black column. The red column
shows the maximum energy recovery from DGmix using a TNC-PRO membrane, as
predicted by a variable-DP model. The blue column shows the theoretical
maximum energy extraction from DGmix using a constant-DP model adopted from
ref. 53.
ESI. Fig. 6 shows the comparison between the maximum
energy recovery rates for the variable-DP model and constant-DP
model. By adopting a f value of 0.75, the constant-DP model
predicted a dierent recovery rate of 0.58 kW h m
3 and 1.03
kW h m
3 respectively. The maximum energy recovery in a real
application may lie between the values predicted using the two
models if PRO design can be improved (e.g. a multi-stage PRO
process is used, or the dilution is compensated by re-mixing
with concentrated seawater brine). This would translate into an
approximately 20% energy recovery rate from the current SWRO
energy consumptions.32,34
3.6 Issues to be addressed in future study
The model employed in this study predicts JW and W well for
TNC-1 and TNC-2 membranes. However for TNC-3 membranes,
the experimental JW and W were much lower than the modeled
value at high DP. This lower-than-modeled JW was associated
with the signicantly higher experimental JS value at high DP
than the modeled value revealed in this study (Fig. S7).
This higher-than-expected JS could have resulted from the
membrane deformation and shadow eects, which have been
proposed in previous studies to explain similar
phenomena.9,53,54 In accordance with the observation in
previous studies, the TNC-PRO surface was found to be
imprinted with the pattern of the spacer, indicating a
membrane deformation (Fig. S8). When the TNC-PRO
membrane had not been applied with high pressure, the JW in a
normal FO process (i.e. DP 0) was lower than the JW of the
TNC-PRO membrane conditioned at high pressure. This lower
JW is represented with red marks in the JWDP plot (Fig. 3).
These phenomena suggest that the membrane deformation and
spacer shadow eects played a role in increasing the perme-
ability of the membrane.
Nonetheless, another possible explanation to this problem is
that a reection coecient, s, should have been incorporated in
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Paper
the solution diusion theory to eciently predict the trans-
portation behavior for membranes with lower NaCl rejection
(e.g. TNC-2 and TNC-3 membranes).55 Ignoring s generally leads
to an over-estimated JW and under-estimated JS.55,56
4 Concluding remarks
TNC-PRO membranes oer a ray of hope that the technical
limitation of 150 mm for PRO membranes can be overcome. The
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modication method of NSM introduced in this study resulted
in TNC-PRO membranes with decent mechanical strength and
sustains a low S value, which has been demonstrated to be
essential for high power density PRO operation. It is predicted
that a maximum E of 0.86 kW h m
3 could be achieved in the
BWSB conguration using TNC-PRO membranes. In addition,
our study revealed that the highly ecient TNC-PRO
membranes possess a good prospect to reduce the desalination
cost when combined with SWRO plants.
Despite not being a primary purpose of this study, the
examination of the durability for the long term PRO operation is
necessary before a real application. In this study the maximum
DP was 15.2 bar, beyond which the attempt to increase the
pressure DP further would result in gradual breakage of the
membrane. Further investigation to relate the support
membrane strength to the maximum operative DP will be of
great value. On the other hand, by incorporating molecular
sieves and aquaporins, the PRO performance could be further
enhanced because of higher selectivity.57,58 In addition, the
interaction between foulants (TOC, humic acids etc.) in waste-
water and the porous nanober support membrane should be
investigated and associated with the PRO performance.
Nomenclature
PRO Pressure retarded osmosis
TNC Thin-lm nanober composite membrane
membrane
ICP Internal concentration polarization
ECP External concentration polarization
RSP Reverse solute permeation
A value Intrinsic water permeability coecient
(L m
2 h
1 bar
1)
B value Intrinsic solute permeability coecient
(L m
2 h
1)
k value Mass transfer coecient in bulk solution
(L m
2 h
1)
S value Structure parameter of the membrane (mm)
Wp Peak power density at optimum pressure
(W m
2)
Wp,no-i Hypothesized Wp without limitation by
phenomenon i
Wp,max Maximum peak power density at an optimum A
value
JW Trans-membrane water ux (L m
2 h
1)
JS Trans-membrane solute ux (G m
2 h
1)
Dpe Eective osmotic pressure dierence (bar)
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Energy & Environmental Science
DCm Eective solute concentration dierence
(mol L
1)
CD,m Draw solution concentration at a selective layer
surface
CD,b Draw solution concentration in bulk solution
CF,m Feed solution concentration at a selective layer
surface
CF,b Feed solution concentration in bulk solution
di Comparative contribution of phenomenon i to
Wp loss
WP (A, B) Contour plot of Wp as a function of A and B
values
WP (A, S) Contour plot of Wp as a function of A and S
values
WP (A, k) Contour plot of Wp as a function of A and k
values
WP (A, CD,b) Contour plot of Wp as a function of A and CD,b
Acknowledgements
We are grateful for the nancial support received from the
Prime Ministers Oce of Singapore via an initiative called The
Enterprise Challenge under award number P00579/1273, Sin-
gapore Environment & Water Industry (EWI) Development
Council under award number MEWR 621/06/166 and the Public
Utilities Board of Singapore. Special thanks to Singapore
Membrane Technology Center (SMTC) for carrying out the
contact angle test. Finally, we would like to acknowledge
reviewers professional suggestions and valuable comments
which enlightened us to improve the quality of our manuscript.
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