Accepted Manuscript

Fabrication of hydrophobic fluorinated silica-polyamide thin film nanocompo-

site reverse osmosis membranes with dramatically improved salt rejection

Ruizhi Pang, Kaisong Zhang

PII: S0021-9797(17)31094-9
DOI: http://dx.doi.org/10.1016/j.jcis.2017.09.062
Reference: YJCIS 22814

To appear in: Journal of Colloid and Interface Science

Received Date: 8 June 2017

Revised Date: 9 September 2017
Accepted Date: 14 September 2017

Please cite this article as: R. Pang, K. Zhang, Fabrication of hydrophobic fluorinated silica-polyamide thin film
nanocomposite reverse osmosis membranes with dramatically improved salt rejection, Journal of Colloid and
Interface Science (2017), doi: http://dx.doi.org/10.1016/j.jcis.2017.09.062

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Fabrication of hydrophobic fluorinated silica-polyamide thin film

nanocomposite reverse osmosis membranes with dramatically

improved salt rejection

Ruizhi Pang * , Kaisong Zhang *

Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment,

Chinese Academy of Sciences, Xiamen 361021, China

ABSTRACT

Thin film nanocomposite reverse osmosis (TFN RO) membranes incorporated with

hydrophilic nanoparticles show a potential problem that the salt rejection can not be

improved significantly. In this study, novel TFN RO membranes incorporated with

hydrophobic fluorinated silica nanoparticles were fabricated to improve the salt

rejection. Fluorinated silica nanoparticles were well dispersed in organic phase during

the interfacial polymerization (IP) process. The TFN RO membranes were

characterized with attenuated total reflectance infra-red, field emission scanning

electron microscopy, atomic force microscopy and water contact angle measurements.

The preparation conditions of TFN RO membranes, including IP reaction time,

organic solvent removal time, and fluorinated silica loading, were optimized by

characterizing desalination performance using 2000 ppm NaCl aqueous solution at

1.55 MPa and 25 oC. The salt rejection increased significantly from 96.0% without

fluorinated silica nanoparticles to 98.6% with the optimal 0.12% (w/v) fluorinated

silica nanoparticles, while the water flux decreased slightly from 0.99 m3/m2/day to

0.93 m3/m2/day. This study demonstrated the potential use of hydrophobic

nanoparticles in high-performance TFN RO membranes.

Keywords: Thin film nanocomposite; Reverse osmosis; Hydrophobic nanoparticles;

Fluorinated silica

*Corresponding author. Tel/Fax: +86 592 6190534.

E-mail address: rzpang@iue.ac.cn (R. Pang), kszhang@iue.ac.cn (K. Zhang).

1. Introduction

With the fast growth of population, climate change and inappropriate wastewater

management, the global drinking water shortage is becoming an inevitable issue [1].

Reverse osmosis (RO) desalination process has proved to be one of the most feasible

strategies to this issue [2]. The widely used RO membrane in current market is the

polyamide (PA) thin film composite (TFC) membrane most commonly synthesized

via interfacial polymerization (IP) of m-phenylenediamine (MPD) and trimesoyl

chloride (TMC) on nanoporous polysulfone supports [3, 4]. Over the last 35 years, the

IP conditions and post-treatment process has been continually improved. However,

It is very difficult to control the structure of the PA TFC membrane and the

desalination efficiency of PA TFC membranes remains relatively low [5].

In recent years, the thin film nanocomposite (TFN) membranes has attracted

attention [6]. It was demonstrated that the addition of hydrophilic nanoparticles into

PA films had led to the increase of water flux [7]. Kinds of nanoparticles have been

investigated to prepare TFN membranes including Ag [8], SiO2 [9, 10], TiO2 [11],

Al2O3 [12], carbon nanotubes [13, 14], aluminosilicate single-walled nanotubes [15],

halloysite nanotubes [16], graphene oxide [17, 18], clay nanosheets [19], NaA zeolite
[21-22], NaY zeolite [23], silicalite-1 nanozeolites [24], zeolitic imidazolate

framework-8 [25], ordered mesoporous silica [26] and ordered mesoporous carbon

[27]. In general, the aforementioned studies mainly focus on improving the

hydrophilicity of PA membrane and enhancing the water flux. However, hydrophilic

nanoparticles even at low concentration may not be uniformly dispersed in PA films

[28]. The salt rejection can not be improved significantly by incorporating hydrophilic

nanoparticles within PA films. It has been demonstrated that the impact of increased

water permeability on the efficiency of desalination processes is limited and

inadequate membrane selectivity hinders process efficacy [29]. It therefore seems

interesting to fabricate TFN RO membranes with dramatically improved salt rejection.

To the best of our knowledge, this is the first study to fabricate hydrophobic

nanoparticle-PA TFN RO membranes with dramatically improved salt rejection.

Herein, novel TFN RO membranes with dramatically improved salt rejection have

been developed by incorporating hydrophobic fluorinated silica nanoparticles within

PA films. The TFN RO membranes were prepared by dispersing fluorinated silica

nanoparticles in organic solution during the IP process. The membrane composition

and morphology were examined by attenuated total reflectance infra-red (ATR-IR),

atomic force microscopy (AFM) and field emission scanning electron microscopy

(FESEM). Water contact angles were measured on prepared membranes with different

fluorinated silica loadings to evaluate the membrane hydrophobicity. The effects of IP

reaction time, organic solvent removal time and fluorinated silica loading on brackish

water desalination performance were optimized.

2. Experimental

2.1. Materials

Tetraethyl orthosilicate (TEOS, >96%, TCI), 1H,1H,2H,2H-

perfluorodecyltriethoxysilane (PFTS, >98%, TCI), ammonium (25%~28% NH3·H2O,

Sinopharm) and ethanol (>99.7%, Sinopharm) were used for preparing the

hydrophobic fluorinated silica nanoparticles. Polysulfone (PSF, P3500L, Solvay),

sodium lauryl sulfate (SLS, >97%, Sinopharm) and 1-methyl-2-pyrrolidinone

(NMP, >99%, Sinopharm) were used for preparing the PSF support.

m-Phenylenediamine (MPD, >98%, TCI), (±)-Camphor-10-sulfonic acid (CSA,

99%, Aladdin), triethylamine (TEA, >97%, Sinopharm), Trimesoyl chloride

(TMC, >98%, TCI) were used as monomer to prepare the PA selective layer. Isopar G

(ExxonMobil Chemical) was used as organic solvent. Sodium chloride

(NaCl, >99.5%, Sinopharm) was used to test the membrane desalination performance.

2.2. Fluorinated silica nanoparticles synthesis and characterization

Fluorinated silica nanoparticles were prepared referring to previously reported

procedures [30, 31]. Briefly, TEOS (20 ml) together with PFTS (mole ratio TEOS:

PFTS=10: 1) were dissolved in ethanol (100ml). The solution was added dropwise to

ammonium/ethanol solution (24ml ammonium in 100ml ethanol) and stirred for 12 hr.

The milky mixture solution was then centrifuged at 6000 rpm for 10 min. The

resulting precipitates were collected, further washed with ethanol 3 times and dried at

room temperature. Morphological characterization of fluorinated silica nanoparticles

was examined by FESEM (HITACHI S-4800). Fourier transform infrared (FTIR,

Nicolet iS10, Thermo Fisher Scientific) spectrometry was employed to characterize

the chemical structure of the synthesized fluorinated silica nanoparticles.

2.3. Preparation of PSF support

The PSF support was prepared by phase inversion induced by immersion

precipitation technique according to previously reported procedures [32, 33].

Typically, a solution containing 16.5 wt% PSF, 0.3 wt% water, 0.3 wt% SLS and 82.9

wt% NMP was cast onto a polyester nonwoven fabric and immersed in a water bath

immediately. The prepared PSF support was stored in NaHSO3 solution (1.5 wt%).

2.4. Preparation of TFC and TFN RO Membranes

TFC RO membranes were prepared on the PSF support by IP process. The

aqueous solution containing 2 wt% MPD, 5 wt% CSA–TEA salt and 93 wt% water

was poured onto the PSF support and soaked for 10 s. The support was dried for about

3 min, while the droplets were absorbed by tissue papers. After that, the organic phase

solution containing 0.1 wt% TMC and 99.9 wt% Isopar G was poured on the amine

saturated support. The organic phase solution was poured off after 14 s of IP reaction.

The membrane was then cured in the oven at 90 oC for 5 min to remove the organic

solvent. Finally, the membrane was stored in deionized water before testing. The

fabrication of TFN RO membranes was carried out by adding a certain amount of

fluorinated silica nanoparticles in the organic phase solution, while the other

conditions were identical to that of TFC membrane. The dispersion of fluorinated

silica nanoparticles in the organic phase solution could be obtained by ultrasonication

for 30 min.
2.5. Characterization of TFC and TFN RO Membranes

The chemical structure of the membrane surface was characterized by ATR-IR

(Nicolet iS10, Thermo Fisher Scientific). FESEM (as described in Section 2.2) and

AFM (Agilent 5500) were used to characterize membrane surface morphologies. The

contact angle goniometer (DSA 100, Krüss) was used to measure the contact angles of

TFC and TFN RO membranes.

The water flux and salt rejection of RO membranes were evaluated in a cross-flow

stainless steel cell (Sterlitech) with an active area of 42 cm2 under brackish water

desalination conditions (25 oC and 1.55 MPa). The 2000 ppm NaCl solution was used

as the feed solution to simulate brackish water composition. The water flux and salt

rejection were measured by at least three membrane samples and then averaged,

according to the reported method in the literature [19, 23].

3. Results and discussion

3.1. Characterization of fluorinated silica nanoparticles

200nm

Fig. 1. SEM image for the synthesized fluorinated silica nanoparticles.

 Fig. 2. FTIR spectrum of fluorinated silica nanoparticles.

The hydrolysis rate of TEOS is higher than that of PFTS. The formed silica

particles were covered with hydrolysed PFTS [34]. As can be seen in Fig. 1, the

average nanoparticle size is around 150 nm to 200 nm. The FTIR spectrum of

fluorinated silica nanoparticles are shown in Fig. 2. The peaks at 1087 and 810 cm-1

were corresponding to the Si–O–Si vibrations. Peaks at 1205 and 1150 cm-1 were

observed due to C–F stretching vibrations. The FTIR spectrum confirmed the formed

silica particle were covered with the hydrolysed PFTS.

3.2. Characterization of TFC/TFN RO membranes

 Fig. 3. ATR-IR spectra of the TFC membrane and the TFN membrane with 0.12%

(w/v) fluorinated silica in organic phase.

The ATR-IR spectra of the TFC membrane and the TFN membrane with 0.12%

(w/v) fluorinated silica nanoparticles in organic phase are shown in Fig. 3. The typical

amide peak was observed at 1540 cm-1 in both spectra [35]. The new peak of TFN

membrane at 1087 cm-1 was assigned to the Si–O–Si groups stretching, indicating the

successful incorporation of fluorinated silica nanoparticles within polyamide films.

Therefore, the membrane morphology and desalination performance of obtained TFN

RO membranes can be affected.

The effects of fluorinated silica incorporation on membrane surface morphology

were investigated by SEM and AFM. The SEM images of surface morphology are

presented in Fig. 4. Compared to the TFC membrane, the typical peak-and-valley

structure of polyamide morphology was smoothened by the incorporation of

fluorinated silica. Moreover, fluorinated silica nanoparticles were observed on the

TFN membrane surface. The SEM images demonstrate that the fluorinated silica

nanoparticles were embedded in the polyamide layer.

(a) (b)

1.0μm 1.0μm

Fig. 4. SEM images for surface morphology of (a) TFC membrane and (b) TFN

membrane with 0.12% (w/v) fluorinated silica in organic phase.

(a) Sa=89.5 ± 11.5 nm (b) Sa=61.9 ± 5.6 nm

Fig. 5. AFM images of (a) TFC membrane and (b) TFN membrane with 0.12% (w/v)

fluorinated silica in organic phase.

The surface roughness of both TFC membrane and TFN membrane with 0.12%

(w/v) fluorinated silica in organic phase was measured by AFM. As shown in Fig. 5,

the mean roughness (Sa) decreased from 89.5 nm for TFC membrane to 61.9 nm for

TFN membrane with 0.12% (w/v) fluorinated silica in organic phase. The AFM
results further demonstrated the peak-and-valley structure of surface morphology was

smoothened by the incorporation of fluorinated silica. The surface area decreased with

the decrease in roughness, thus the decrease of surface roughness could lead to the

decrease of water flux.

Fig. 6. Water contact angle data of the TFC membrane and the TFN membranes with

different fluorinated silica nanoparticles loading.

The water contact angle data of TFC membrane and TFN membranes with

different fluorinated silica nanoparticles loading are shown in Fig. 6. The contact

angle of TFC membrane without fluorinated silica nanoparticles loading is 61.7o. The

contact angle of the TFN membranes increased from 66.8o to 117.7o with increasing

fluorinated silica loading from 0.12% (w/v) to 0.48% (w/v). The increase in the

contact angle normally indicates the increase in hydrophobicity. The increased

hydrophobicity of the TFN membranes could be due to the hydrophobicity property of

fluorinated silica nanoparticles. It is usually assumed that membrane fouling reduces

by the increase in surface hydrophilicity. However, it has been demonstrated that

hydrophobic surface also favors fouling reduction [36]. Moreover, the increased salt

rejection by surface hydrophobicity will improve the efficiency of desalination

processes [29].

3.3. Impacts of fluorinated silica nanoparticles loading on membrane desalination

performance

Fig. 7. Impacts of fluorinated silica loading on membrane desalination performance

(adding fluorinated silica in organic phase).

The impacts of fluorinated silica loading on water flux and salt rejection are

shown in Fig. 7. The salt rejection first increased significantly and then decreased as

the adding of fluorinated silica nanoparticles, while the water flux continuously

decreased. The TFN RO membrane showed the best desalination performance at the

0.12% (w/v) fluorinated silica loading. The salt rejection increased significantly from

96.0% for TFC membrane to 98.6% for the TFN membrane with 0.12% fluorinated
silica loading, and the water flux decreased slightly from 0.99 m3/m2/day to 0.93

m3/m2/day. The salt rejection was achieved by measuring the electrical conductivity

of permeate and feed solutions. The electrical conductivity of feed solution (2000

ppm NaCl) was 3970 μS/cm. The electrical conductivity of permeate solution was

158.8 μS/cm as the salt rejection was 96.0%. However, the electrical conductivity of

permeate solution was only 55.6 μS/cm as the salt rejection was 98.6%. Therefore, the

salt rejection was improved dramatically by incorporating hydrophobic fluorinated

silica nanoparticles.

The results indicated that the fluorinated silica nanoparticles made a great

contribution to the considerable increase of the salt rejection. It was suggested that the

incorporation of hydrophobic fluorinated silica not only decreased water passage by

increasing membrane hydrophobicity but also decreased salt passage. The salt passage

decrement is larger than water flux decrement and thus the salt rejection will be

improved. However, the interstitial defects were formed at the high fluorinated silica

nanoparticles concentration during the preparation of TFN RO membrane. Thus, the

salt rejection decreased at the high fluorinated silica concentration.

The novel TFN RO membrane was compared with the other TFN RO membranes

reported in the literature. As shown in Table 1, the salt rejection decreased by

incorporating functionalized multi-walled carbon nanotubes (MWNTs), porous

MCM-41 nanoparticles and graphene oxide nanosheets [13, 26, 37]. However, the salt

rejection was improved dramatically by incorporating hydrophobic fluorinated silica

nanoparticles.
Table 1 Performance comparison of the novel TFN RO membrane with the other TFN

RO membranes reported in the literature.

NaCl rejection without NaCl rejection with NaCl rejection

Nanoparticle References
nanoparticle (%) nanoparticle (%) change

Fluorinated
96.0 98.6 Increased This work
silica

MWNTs >95 ~90 Decreased [13]

Decreased
MCM-41 98.1 97.9 [26]
slightly

Graphene
95.7 93.8 Decreased [37]
oxide

3.4. Impacts of IP reaction time on TFN RO membrane desalination performance

Fig. 8. Impacts of interfacial polymerization reaction time on TFN RO membrane

desalination performance (adding 0.12% (w/v) fluorinated silica nanoparticles in

organic phase).
 Normally, a longer IP time increases the salt rejection and decreases the water flux

[38]. However, a different result was observed in the preparation of TFN membranes

incorporated with hydrophobic nanoparticles. As shown in Fig. 8, the water flux first

decreased and then increased as the IP time increased, while the salt rejection first

increased and then decreased. The water flux increase and salt rejection decrease from

14s IP time to 28s IP time could be attributed to the formed interstitial defects by the

additional incorporation of fluorinated silica nanoparticles during the longer reaction

period. As a result, 14 s was found to be the optimal IP time in the preparation of TFN

membranes incorporated with hydrophobic nanoparticles.

3.5. Impacts of organic solvent removal time on TFN RO membrane desalination

performance

Fig. 9. Impacts of organic solvent removal time on TFN RO membrane desalination

performance (adding 0.12% (w/v) fluorinated silica nanoparticles in organic phase).

The effects of organic solvent removal time at 90 oC on water flux and salt
rejection are shown in Fig. 9. All the Isopar G was removed as the organic solvent

removal time was around 4–5 min. The TFN membranes showed a water flux around

0.93 m3/m2/day and a salt rejection around 98.6%. When the organic solvent removal

time was increased to 6 min, the salt rejection decreased to 97.7%. The decreased salt

rejection might result from the shrinkage or collapse of the PSF support membrane

pores due to the excessive organic solvent removal time [39, 40]. As a result, 5 min

was found to be the optimal organic solvent removal time.

4. Conclusions

The hydrophobic fluorinated silica nanoparticles were investigated as novel filler

in TFN RO membranes. The successful incorporation of fluorinated silica

nanoparticles was verified by ATR-IR spectra and FESEM. The membrane surface

hydrophobicity increased and the surface roughness decreased by the incorporation of

fluorinated silica. In addition, the preparation conditions of TFN RO membranes

incorporated with fluorinated silica nanoparticles, including IP reaction time, organic

solvent removal time, and fluorinated silica loading, were optimized. The salt

rejection increased dramatically from 96.0% without fluorinated silica nanoparticles

to 98.6% with the optimal 0.12% (w/v) fluorinated silica nanoparticles in the organic

phase, while the water flux decreased slightly from 0.99 m3/m2/day to 0.93 m3/m2/day.

The modification of PA RO membrane by incorporating fluorinated silica

nanoparticles could be applied successfully due to easy integration into the existing

membrane manufacturing process. Moreover, the efficiency of desalination processes

could be improved. Therefore, the hydrophobic nanoparticles can provide a facile and
promising approach to fabricate novel high-performance TFN RO membrane for

practical applications.

Acknowledgments

This work was financially supported by the National Natural Science Foundation

of China (Grant No. 51408581), Natural Science Foundation of Fujian Province

(Grant No. 2016J05143), Bureau of International Cooperation, CAS

(132C35KYSB20160018) and Bureau of Frontier Sciences & Education, CAS

(QYZDB-SSW-DQC044).

References

[1] J. Yin, B. Deng, Polymer-matrix nanocomposite membranes for water treatment, J.

Membr. Sci. 479 (2015) 256–275.

[2] M. Elimelech, W. A. Phillip, The future of seawater desalination: energy,

technology, and the environment, Science 333 (2011) 712–717.

[3] K. P. Lee, T. C. Arnot, D. Mattia, A review of reverse osmosis membrane

materials for desalination—Development to date and future potential, J. Membr. Sci.

370 (2011) 1–22.

[4] D. Li, H. Wang, Recent developments in reverse osmosis desalination membranes,

J. Mater. Chem. 20 (2010) 4551–4566.

[5] G. M. Geise, H. B. Park, A. C. Sagle, B. D. Freeman, J. E. McGrath, Water

permeability and water/salt selectivity tradeoff in polymers for desalination, J. Membr.

Sci. 369 (2011) 130–138.

[6] D. Li, Y. Yan, H. Wang, Recent advances in polymer and polymer composite
membranes for reverse and forward osmosis processes, Prog. Polym. Sci. 61 (2016)

104–155.

[7] S. S. Shenvi, A. M. Isloor, A. F. Ismail, A review on RO membrane technology:

Developments and challenges, Desalination 368 (2015) 10–26.

[8] S. Y. Lee, H. J. Kim, R. Patel, S. J. Im, J. H. Kim, B. R. Min, Silver nanoparticles

immobilized on thin film composite polyamide membrane: characterization,

nanofiltration, antifouling properties, Polym. Adv. Technol. 18 (2007) 562–568.

[9] P. S. Singh, V. K. Aswal, Characterization of physical structure of silica

nanoparticles encapsulated in polymeric structure of polyamide films, J. Colloid

Interface Sci. 326 (2008) 176–185.

[10] G. L. Jadav, V. K. Aswal, P. S. Singh, SANS study to probe nanoparticle

dispersion in nanocomposite membranes of aromatic polyamide and functionalized

silica nanoparticles, J. Colloid Interface Sci. 351 (2010) 304–314.

[11] S. Y. Kwak, S. H. Kim, S. S. Kim, Hybrid organic/inorganic reverse osmosis

(RO) membrane for bactericidal anti-fouling. 1. Preparation and characterization of

TiO2 nanoparticle self-assembled aromatic polyamide thin-film-composite (TFC)

membrane, Environ. Sci. Technol. 35 (2001) 2388–2394.

[12] T. A. Saleh, V. K. Gupta, Synthesis and characterization of alumina

nano-particles polyamide membrane with enhanced flux rejection performance, Sep.

Purif. Technol. 89 (2012) 245–251.

[13] H. Zhao, S. Qiu, L. Wu, L. Zhang, H. Chen, C. Gao, Improving the performance

of polyamide reverse osmosis membrane by incorporation of modified multi-walled

carbon nanotubes, J. Membr. Sci. 450 (2014) 249–256.

[14] W. F. Chan, H. Y. Chen, A. Surapathi, M. G. Taylor, X. H. Hao, E. Marand, J. K.

Johnson, Zwitterion functionalized carbon nanotube/polyamide nanocomposite

membranes for water desalination, ACS Nano 7 (2013) 5308–5319.

[15] G. N. B. Baroña, J. Lim, M. Choi, B. Jung, Interfacial polymerization of

polyamide-aluminosilicate SWNT nanocomposite membranes for reverse osmosis,

Desalination 325 (2013) 138–147.

[16] M. Ghanbari, D. Emadzadeh, W. J. Lau, S. O. Lai, T. Matsuura, A. F. Ismail,

Synthesis and characterization of novel thin film nanocomposite (TFN) membranes

embedded with halloysite nanotubes (HNTs) for water desalination, Desalination 358

(2015) 33–41.

[17] H. R. Chae, J. Lee, C. H. Lee, I. C. Kim, P. K. Park, Graphene oxide-embedded

thin-film composite reverse osmosis membrane with high flux, anti-biofouling, and

chlorine resistance, J. Membr. Sci. 483 (2015) 128–135.

[18] H. J. Kim, M. Y. Lim, K. H. Jung, D. G. Kim, J. C. Lee, High-performance

reverse osmosis nanocomposite membranes containing the mixture of carbon

nanotubes and graphene oxides, J. Mater. Chem. A 3 (2015) 6798–6809.

[19] H Dong, L Wu, L Zhang, H Chen, C Gao, Clay nanosheets as charged filler

materials for high-performance and fouling-resistant thin film nanocomposite

membranes, J. Membr. Sci. 494 (2015) 92–103.

[20] B. H. Jeong, E. M. V. Hoek, Y. S. Yan, A. Subramani, X. F. Huang, G. Hurwitz,

A. K. Ghosh, A. Jawor, Interfacial polymerization of thin film nanocomposites: a new

concept for reverse osmosis membranes, J. Membr. Sci. 294 (2007) 1–7.

[21] M. L. Lind, D. E. Suk, T. V. Nguyen, E. M. V. Hoek, Tailoring the structure of

thin film nanocomposite membranes to achieve seawater RO membrane performance,

Environ. Sci. Technol. 44 (21) (2010) 8230–8235.

[22] M. L. Lind, A. K. Ghosh, A. Jawor, X. Huang, W. Hou, Y. Yang, E. M. V. Hoek,

Influence of Zeolite Crystal Size on Zeolite-Polyamide Thin Film Nanocomposite

Membranes, Langmuir 25(17) (2009) 10139–10145.

[23] H. Dong, L. Zhao, L. Zhang, H. Chen, C. Gao, W. S. Winston Ho, High-flux

reverse osmosis membranes incorporated with NaY zeolite nanoparticles for brackish

water desalination, J. Membr. Sci. 476 (2015) 373–383.

[24] H. Huang, X. Qu, X. Ji, X. Gao, L. Zhang, H. Chen, L. Hou, Acid and

multivalent ion resistance of thin film nanocomposite RO membranes loaded with

silicalite-1 nanozeolites, J. Mater. Chem. A 1 (2013) 11343–11349.

[25] J. Duan, Y. Pan, F. Pacheco, E. Litwiller, Z. Lai, I. Pinnau, High-performance

polyamide thin-film-nanocomposite reverse osmosis membranes containing

hydrophobic zeolitic imidazolate framework-8, J. Membr. Sci. 476 (2015) 303–310.

[26] J. Yin, E. S. Kim, J. Yang, B. Deng, Fabrication of a novel thin-film

nanocomposite (TFN) membrane containing MCM-41 silica nanoparticles (NPs) for

water purification, J.Membr.Sci. 423-424 (2012) 238–246.

[27] E. S. Kim, B. Deng, Fabrication of polyamide thin-film nano-composite

(PA-TFN) membrane with hydrophilized ordered mesoporous carbon (H-OMC) for

water purifications, J. Membr. Sci. 375 (2011) 46–54.

[28] W. J. Lau, S. Gray, T. Matsuura, D. Emadzadeh, J. P. Chen, A. F. Ismail, A

review on polyamide thin film nanocomposite (TFN) membranes: History,

applications, challenges and approaches, Water Res. 80 (2015) 306–324.

[29] J. R. Werber, A. Deshmukh, M. Elimelech, The critical need for increased

selectivity, not increased water permeability, for desalination membranes, Environ.

Sci. Technol. Lett. 3 (2016) 112−120.

[30] Y. Zhang, R. Wang, Novel method for incorporating hydrophobic silica

nanoparticles on polyetherimide hollow fiber membranes for CO2 absorption in a

gas–liquid membrane contactor, J. Membr. Sci. 452 (2014) 379–389.

[31] Y. Zhang, R. Wang, Fabrication of novel polyetherimide-fluorinated silica

organic–inorganic composite hollow fiber membranes intended for membrane

contactor application, J. Membr. Sci. 443 (2013) 170–180.

[32] Y Zhou, S Yu, M Liu, C Gao, Preparation and characterization of

polyamide-urethane thin-film composite membranes, Desalination 180 (2005)

189-196.

[33] M Liu, S Yu, M Qia, Q Pan, C Gao, Impact of manufacture technique on

seawater desalination performance of thin-film composite polyamide-urethane reverse

osmosis membranes and their spiral wound elements, J. Membr. Sci. 348 (2010)

268–276.

[34] H. Wang, J. Fang, T. Cheng, J. Ding, L. Qu, L. Dai, X. Wang, T. Lin, One-step

coating of fluoro-containing silica nanoparticles for universal generation of surface

superhydrophobicity, Chem. Commun. (2008) 877–879.

[35] L. Zhao, P. C. Y. Chang, W. S. W. Ho, High-flux reverse osmosis membranes

incorporated with hydrophilic additives for brackish water desalination, Desalination

308 (2013) 225–232.

[36] D. Rana, T. Matsuura, Surface modifications for antifouling membranes, Chem.

Rev. 110 (2010) 2448–2471.

[37] J. Yin, G. Zhu, B. Deng, Graphene oxide (GO) enhanced polyamide (PA)

thin-film nanocomposite (TFN) membrane for water purification, Desalination 379

(2016) 93–101.

[38] L Zhao, P. C. Y. Chang, C. Yen, W. S. W. Ho, High-flux and fouling-resistant

membranes for brackish water desalination, J. Membr. Sci. 425–426 (2013) 1–10.

[39] L. Zhao, W. S. W. Ho, Novel reverse osmosis membranes incorporated with a

hydrophilic additive for seawater desalination, J. Membr. Sci. 455 (2014) 44–54.

[40] A. K. Ghosh, B.-H. Jeong, X. Huang, E. M.V. Hoek, Impacts of reaction and

curing conditions on polyamide composite reverse osmosis membrane properties, J.

Membr. Sci. 311 (2008) 34–45.

Graphical abstract