Desalination 541 (2022) 116002

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

Surface modification of thin film composite forward osmosis membrane

using tris(2-aminoethyl)amine for enhanced ammonium recovery
Jing Li a, b, 1, Ralph Rolly Gonzales a, *, 1, Ryosuke Takagi a, Xuesong Yao a, b, Pengfei Zhang a, b,
Titik Istirokhatun a, b, c, Jinhui Zhang a, b, Hideto Matsuyama a, b, **
a
Research Center for Membrane and Film Technology, Kobe University, Kobe, Japan
b
Department of Chemical Science and Engineering, Kobe University, Kobe, Japan
c
Department of Environmental Engineering, Faculty of Engineering, Diponegoro University, Jl. Prof. Soedarto-Tembalang, Semarang, Indonesia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Thin film composite (TFC) membrane

was modified with tris(2-aminoethyl)
amine (TAEA).
• Secondary interfacial polymerization
with TAEA was optimized by membrane
performance.
• Optimum TAEA-modified TFC mem­
brane exhibited 94.7 % NH+4 rejection in
forward osmosis.
• Size sieving, cation exchange, and car­
boxylic group density influenced NH+ 4
selectivity.

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, we aimed to develop a forward osmosis (FO) thin film composite (TFC) membrane which could
Thin-film composite membrane retain NH+ 4 from wastewater. The conventional TFC membrane has a microporous polymer support and a se­
Forward osmosis lective layer for salt rejection; however, the polyamide selective layer is known to not be able to reject NH+
4 . Our
Tris(2-aminoethyl)amine
strategy was to develop tris(2-aminoethyl)amine (TAEA)-modified TFC membranes via secondary interfacial
Surface modification
Ammonium recovery
polymerization, and the modification factors were optimized. The NH+ 4 rejection of the optimized membrane
significantly increased from 64.9 % (pristine TFC) to 94.7 %. TAEA modification resulted in a smoother surface
and thinner polyamide selective layers. The mechanism of NH+ 4 rejection during FO operation was investigated
and was found to be influenced by membrane surface carboxylic group density and the polyamide crosslinking,
cation exchange between the draw and feed solutions, and size sieving. In conclusion, the TAEA-modified
membrane showed high selectivity against NH+ 4 and applicability for NH4 recovery. In the future, the TAEA-
+

modified membrane may be applied for NH+ 4 enrichment and recovery from real wastewater systems.

* Corresponding author.
** Correspondence to: H. Matsuyama, Research Center for Membrane and Film Technology, Kobe University, Kobe, Japan.
E-mail addresses: rragonzales@people.kobe-u.ac.jp (R.R. Gonzales), matuyama@kobe-u.ac.jp (H. Matsuyama).
1
These authors contributed equally.

https://doi.org/10.1016/j.desal.2022.116002
Received 25 May 2022; Received in revised form 19 July 2022; Accepted 25 July 2022
Available online 11 August 2022
0011-9164/© 2022 Elsevier B.V. All rights reserved.
J. Li et al.
1. Introduction
Nitrogen in wastewater in the form of ammonium (NH+ 4 ) is one of the
major pollutants affecting groundwater and surface water [1]. High
NH+ 4 loadings in wastewater have resulted in eutrophication, acidifica­
tion and reduction of dissolved oxygen in water bodies due to anthro­
pogenic inputs from agricultural, municipal and industrial wastewater
as well as waste disposal sites and animal feedlots [2–6]. These condi­
tions ultimately lead to adverse effects on aquatic organisms and
degradation of aquatic ecosystems [7,8]. Therefore, removal and re­
covery of NH+ 4 from wastewater are necessary prior to environmental
discharge.
Several methods have been utilized to remove NH+ 4 from wastewater
including ion exchange processes using natural or synthetic adsorbents
[9,10], bio-technology [11], air stripping [12], chemical precipitation
[13], microwave radiation [14], breakpoint chlorination [15], super­
critical water oxidation [16], and membrane separation technology
[17]. Among various membrane separation technologies, reverse
osmosis (RO) is the conventional technology for the elimination of NH+
[18,19] since it has high removal efficiency, small site and space re­
quirements, easy continuous operation, modular structure, and simple
design [17,20]. RO, however, utilizes approximately 4 kW electricity to
produce one cubic meter of freshwater in desalination process [21],
which results in relatively high energy consumption. Furthermore, RO
membrane fouling is unavoidable, thus the use of chemical cleaning
agents is essential, increasing the costs and limiting further applications
[22].
Forward osmosis (FO) is an osmotic pressure-driven membrane
process which uses the difference in osmotic pressures of the draw so­
lution (DS) and feed solution (FS) to spontaneously transfer water from
the FS (which has a low osmotic pressure) toward the DS (which has a
high osmotic pressure) across a selectively permeable membrane.
Therefore, the key advantages of FO use are its ability to operate at low
or no hydraulic pressure, high selectivity against a wide range of con­
taminants, and relatively low energy consumption [23]. Moreover, since
hydraulic pressure is not applied, less irreversible fouling is observed in
FO compared to a pressure-driven membrane process [22]. Among
different reported FO membranes in literature, the most widely used
membrane is the thin film composite (TFC) membrane due to its
outstanding permeability and separation performance, as well as sta­
bility for a wide range of pH and temperature [24,25]. However, the
similar polarity and hydraulic radius between the NH+ 4 and water mol­
ecules prevent FO TFC membranes from easily separating the two
molecules [26]. Furthermore, the negatively-charged surface of the
conventional TFC membrane exhibits electrostatic interactions with the
positively-charged NH+ 4 , resulting in low NH4 rejection capacity.
+
Based on the aforementioned problems, recent work on FO TFC
membrane modification to improve NH+ 4 rejection and investigate the
possible separation mechanisms affecting the NH+ 4 -N selectivity have
attracted much attention. The most common TFC membrane modifica­
tion strategy is the preparation of positively-charged surface, which
could minimize the electrostatic interactions of the membrane and NH+
Positively-charged branched polyethylenimine (PEI) was grafted on the
FO TFC membranes to enhance the NH+ 4 -N selectivity by the synergistic
effect of the diffusion resistance created by the protonated primary
amine group fixed on the surface and the electrostatic repulsion created
by the positive charge against the NH+ 4 in the bulk [27]. Chemical
grafting with amine after conversion of polyamide carbonyl groups into
amine-reactive esters were also performed in former studies, wherein
the TFC membrane surface was first reacted with 1-ethyl-3-(3-dimethy­
laminopropyl) carboimide (EDC) and n-hydroxysuccinimide (NHS).
After this activation step, PEI grafting and quaternization resulted in
positively-charged membrane surfaces and enhanced the NH+ 4 rejection
[28]. Recently, some work has found that NH+ 4 rejection was not only
influenced by electrostatic interactions during the FO process, but also
by other factors. Yao et al. mentioned that ethylenediamine (EDA) and
Desalination 541 (2022) 116002
2-aminoethanol (AEA) were grafted to prepare the FO TFC membranes
with different membrane surface charges, and it was found that not only
the electrostatic repulsion but also the carboxylic group densities on the
TFC membranes could influence the NH+ 4 rejection [29]. Another work
found that during FO process the forward permeation of NH+ 4 was due to
cation exchange with draw solution [30]. Therefore, further researches
are required to investigate the factors affecting NH+ 4 rejection. Based on
the author's knowledge, this is the first work which systemically in­
vestigates all the factors influencing NH+ 4 rejection and recovery.
In this study, tris(2-aminoethyl)amine (TAEA), consisting of a ter­
tiary amine center and three primary amine groups, was employed for
TFC membrane polyamide (PA) selective layer modification via sec­
ondary interfacial polymerization (IP). The pristine TFC membranes
were produced by the IP reaction between an amine (m-phenylenedi­
amine, MPD) and an acyl chloride (trimesoyl chloride, TMC). The excess
unreacted acyl chloride monomers on the polyamide layer give the
negative charge due to the carboxyl group formation, which decreases
the NH+ 4 rejection by electrostatic interactions. To enhance the NH4
+
4 rejection performance of the membrane, TAEA was used to react with
the unreacted acyl chloride groups by a second IP. Taguchi orthogonal
method, a widely-used experimental design and optimization tool [31],
was employed to optimize the modification condition for 4 factors with
3 different levels, in order to provide the best combination of maximized
water flux and NH+ 4 rejection. The surface chemical properties, surface
and cross-section morphology, surface wettability, roughness and sur­
face charge were investigated. Separation performance, including water
flux and NH+ 4 rejection, was also evaluated. Finally, possible separation
mechanisms were investigated.
2. Experimental
2.1. Materials
Polyketone (PK) (Mw = 2 × 105 g mol− 1, Asahi Kasei Co., Ltd., Japan)
was used as the membrane support and was prepared using the
following solvents (Fujifilm Wako Pure Chemical Corp., Japan): resor­
cinol, methanol (MeOH), acetone and hexane. Interfacial polymeriza­
tion (IP) for polyamide formation was performed using benzene-1,3,5-
tricarbonyl chloride (trimesoyl chloride, TMC), benzene-1,3-diamine
(m-phenylenediamine, MPD), N,N-diethylethanamine (triethylamine,
TEA), (1S)-(+)-10-camphorsulfonic acid (CSA), and sodium dodecyl
sulfate (SDS) (all purchased from Wako Pure Chemical Co., Japan). The
second IP was performed using tris(2-aminoethyl)amine (TAEA, Wako
Pure Chemical Co., Japan). Membrane testing was conducted with
ammonium chloride (NH4Cl), sodium chloride (NaCl), lithium chloride
(LiCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chlo­
ride (CaCl2), magnesium chloride (MgCl2), and polyethylene glycol
(PEG400, Mw = 400) (all purchased from Wako Pure Chemical Co.,
Japan). Toluidine blue O (TBO, Wako Pure Chemical Co., Japan) was
used to measure the carboxylic group density on membrane surface.
4. 2.2. Preparation of TFC membranes and surface modification with TAEA
The PK membrane support was fabricated via non-solvent induced
phase separation (NIPS) process by casting the dope solution with a
composition of 10 wt% PK in 65 wt% aqueous resorcinol on a glass plate
with a casting knife of 400 μm thickness [32]. The nascent membrane
was then transferred into coagulation bath immediately for 20 min,
which composed of 35 wt% aqueous MeOH solution. The membrane was
then immersed into acetone and hexane and each for 20 min [33].
The polyamide (PA) selective layer was prepared via IP, as described
in earlier studies [32]. For pristine TFC membrane, IP was conducted
with the reaction of the MPD aqueous solution (containing 2 wt% MPD,
2.3 wt% CSA, 1.1 wt% TEA, and 0.15 wt% SDS), and the TMC organic
solution (0.15 wt% TMC in hexane), followed by heat-catalyzed cross­
linkage at 90 ◦ C. For the TAEA-modified membrane, firstly, MPD
2
J. Li et al. Desalination 541 (2022) 116002

solution was poured on the PK support surface for 5 min then the excess Table 1
MPD solution was removed. Next, the TMC solution was poured onto the Design factors employed in the Taguchi orthogonal method and corresponding
membrane for 2 min to conduct the IP, then the excess solution was levels.
removed and air dried. Finally, the TAEA aqueous solution was poured Design factor Level 1 Level 2 Level 3
onto the membrane for secondary IP and the membrane was placed into A (temperature, ◦ C) 75 80 85
oven for heating, prior to removing the excess solution. The mechanism B (pH) 9 10 11
of the secondary IP modification is shown in Fig. 1. All membranes were C (TAEA conc., wt%) 1 1.5 2
washed with and stored in Milli-Q water in the refrigerator before use. D (reaction time, min) 4 5 6

2.3. Taguchi orthogonal method and optimization
Four factors playing important roles during the secondary IP modi­
fication of the TAEA-modified membranes were numerically assessed:
(A) Temperature, (B) pH, (C) TAEA concentration, and (D) Reaction
time. The pH of the TAEA solutions was adjusted using an aqueous 50 wt
% CSA solution, added dropwise until desired pH was obtained. Taguchi
orthogonal method was employed to determine the best combination of
the design factors. Each factor was evaluated by three different levels
(Table 1). An L43 orthogonal array was chosen and designed according to
the orthogonal method and only nine experiments were needed and
conducted, as presented in Table S1. Here, the water flux and rejection
of NH+ 4 were chosen as the performance parameters. It should be noted
that 81 experiments would have been required in a full fractional
approach to evaluate each possible combination, requiring a large
number of experiments and time. With Taguchi orthogonal method, the
minimum number of experiments could be performed to give a
comprehensive information on all factors that affect performance pa­
rameters [34], as compared to a full factorial experimental design, as
shown in an earlier study optimizing membrane modification conditions
[35].
The intrinsic transport parameters of the pristine and TAEA-modified
TFC membranes were determined according to a previous study [36].
The FO performance of the pristine and TAEA-modified membranes
(numbered 1–9) was determined as described elsewhere [37]. Details of
the membrane performance tests are described in the Supplementary
Information. The water flux and NH+ 4 rejection values of the membranes
were used as the performance parameters to optimize the modification
process. The individual and synergistic effects of the four factors were
investigated. The signal to noise (S/N) ratio, which measures the vari­
ation of the response parameters, was also determined by the following
equation [34]:
(∑ )
1
S
= − 10log
y2
(1)
N n
where n and y are the number of observations and observed data,
respectively. For optimization using orthogonal experimental design,
the higher the S/N ratio, the better the result.
Statistical analysis and modeling were carried out using statistical
software (Design Expert, Stat-Ease, MN, USA; Minitab, PA, USA).
2.4. Determination of TFC membrane carboxylic group density
The density of carboxylic groups on the membrane surface was
measured by quantifying the number of bound toluidine blue O (TBO)
molecules. TBO is one kind of cationic blue dye derivative of pheno­
thiazine (C12H9NS) [38]. The molecular weight of TBO is approximately
270 g mol− 1 and TBO exhibits an optical absorption peak at a wave­
length of around 600 nm [29]. TBO dry powder was dissolved in 0.2 M
NaCl solution at pH 2 to obtain TBO solutions of different concentrations
(0.01, 0.05, 0.1, 0.5, 1, 5 and 10 μmol L− 1) for the construction of
calibration curves. Their optical absorbance was measured at 631 nm
with a UV–Vis spectrophotometer (SpectraMax 340PC, Molecular De­
vices, USA). The surface carboxylic group density from the light density
raw data was determined by the obtained calibration curve.
In order to measure the surface carboxylic group density, 2 mM TBO
solutions were made fresh in 0.015 M NaCl at pH 11. The membranes

Fig. 1. Reaction mechanism of the secondary interfacial polymerization modification using tris(2-aminoethyl)amine.

3
J. Li et al.
were taped onto a glass surface so as to make only the surface of selective
layer contactable. The membranes were immersed into the TBO solu­
tions for 40 min with gentle agitation to make TBO bind with carbox­
ylate group via electrostatic interactions [39]. The TBO solution was
then removed and the membranes were soaked in 0.015 M NaCl solution
at pH 11 for 12 h for washing away the unbound TBO molecules. After
rinsing thoroughly with the same solution, the membranes were then
sliced into a 3 cm diameter circle and put into 0.01 L of 0.2 M NaCl
solution at pH 2 with stirring for 30 min. In this procedure, carboxylic-
bound TBO molecules were washed away from the membrane surface
and then diffused into solution, which dyed it blue. The optical absor­
bance of the blue solutions was determined at 631 nm wavelength.
Carboxylic group density (D, nm− 2) was calculated according to the
following Eq. (2) [39]:
NA × V × C
D= (2)
π × R2
where NA is the Avogadro's constant 6.022 × 1023 mol− 1; V is the vol­
ume of the 0.2 mol L− 1 NaCl desorption solution (0.01 L); C (mol L− 1) is
the TBO concentration that was obtained from the calibration curve; and
R is membrane sample radius (1.5 × 107 nm).
2.5. Membrane characterization
The chemical composition, surface properties, and morphology of
the membranes of the TFC membranes were characterized, and the de­
tails are shown in the Supplementary Information.
3. Results and discussion
3.1. Optimization of TAEA modification
3.1.1. Osmotic performance of TFC membranes
The objective of using Taguchi orthogonal method is to optimize the
modification conditions to maximize the water flux and NH+ 4 rejection of
the TAEA-modified TFC membranes. The osmotic performance of the
pristine TFC membrane and all nine TAEA-modified TFC membranes
were determined using model NH+ 4 -containing wastewater (400 ppm)
and model seawater (3.5 % (w/w) NaCl) as the FS and DS, respectively,
during FO operation. Fig. 2 and Table S1 show a comparison of water
flux and NH+4 rejection for pristine TFC membrane and all nine TAEA-
modified TFC membranes. After TAEA modification, all modified
membranes showed higher NH+ 4 rejection and lower water flux than
pristine TFC membranes. The pristine TFC membrane showed the
Fig. 2. Comparison of water flux and NH+
4 rejection of pristine and TAEA-
modified membranes. (Feed solution: 400 ppm NH4Cl aqueous solution; Draw
solution: 3.5 wt% NaCl aqueous solution; Modification conditions of samples 1
to 9 are shown in Table 2.)
4
Desalination 541 (2022) 116002
highest average water flux of 23.87 LMH, but the lowest NH+ 4 rejection
of 64.92 %, as well. Among the TAEA-modified TFC membranes, the
highest NH+ 4 rejection and water flux values were observed to be 94.74
% and 19.85 LMH, respectively, for the TAEA-modified TFC membrane
number 9, corresponding to the following conditions: 85 ◦ C, pH = 11,
1.5 wt% TAEA, and 4 min reaction time. In general, the observed higher
NH+ 4 rejection and lower water flux values are due to the successful
second IP modification using TAEA.
The reverse NaCl flux values during FO operation were also deter­
mined for all pristine and TAEA modified membranes. The results are
shown in the Fig. S1. Compared to the pristine TFC membrane, the
reverse NaCl flux values of the modified membranes are much lower,
especially for the optimized TFC membrane showing the lowest value,
showing that the NaCl rejection of the membranes has a similar ten­
dency with NH+ 4 rejection. These results indicate that the secondary
interfacial polymerization modification resulted in denser and more
NaCl-selective polyamide structure.
3.1.2. Optimization
In this work, four factors were hypothesized to influence the TAEA
modification of the TFC membranes via secondary IP: temperature, pH,
TAEA concentration, and reaction time. Taguchi orthogonal method was
utilized to find the best conditions to maximize both water flux and NH+ 4
rejection. Using the experimental data obtained for the nine experi­
mental samples (Table 2), a model was derived to predict the water flux
and NH+ 4 rejection values of all 81 combinations (four factors, three level
each), and the experimental condition with the highest desirability was
chosen as the optimal combination of experimental factors. The solu­
tions of the model are presented in Table S2. The most desirable and,
therefore, optimal experimental condition coincidentally corresponded
to the experiment number 9 (temperature of 85 ◦ C, pH = 11, 1.5 wt%
TAEA, and 4 min reaction time). The modelled regression Analysis of
variance (ANOVA) was conducted using classical sum of squares and
showed that the computed F-values for both water flux (8.94) and NH+ 4
rejection (5.58) were both higher than the tabulated F-value of 3.44 for
95 % confidence interval. These F-values corresponded to p-values of
0.0109 and 0.006 for water flux and NH+ 4 rejection, respectively, which
are both lower than 0.05, which is the threshold value to determine the
significance of the experimental results. The ANOVA results determine
whether the experimental results are statistically significant. The F-
value tells if the group of variables tested during the experiment are
jointly significant. Higher F-values indicate that the variation between
sample means is high relative to the variation within each sample. The
higher F-value, the lower the corresponding p-value, therefore the null
hypothesis of ANOVA could be rejected. Therefore, there is sufficient
evidence that the secondary IP factors (temperature, pH, TAEA con­
centration, and time) designated in this study could cause significant
changes in the modified membrane performance [40].
To further understand the individual effects of each factor, the S/N
ratios of the experimental conditions were determined and shown in
Table 2, and the mean S/N ratio for each level of the response param­
eters are shown in Table 3 and Fig. S2.
The S/N ratio was used to determine the significance of each factor
on the individual response parameters, which could help us even further
understand why the optimum experimental condition determined by the
model was the best TAEA modification condition. Similar to the F-value
and p-value obtained during ANOVA, the S/N ratio measures the vari­
ation of the response parameters. The “maximum–minimum” de­
termines the range between the highest and lowest values in a set of data
corresponding to each factor, showing the dispersion of data. The order
corresponds to the ranking of the effect of each condition on membrane
performance (water flux and NH+ 4 rejection). Higher S/N ratio and
“maximum–minimum” values signify a greater effect on membrane
performance. Analyzing the data presented in Tables 2 and 3, reaction
time was the most significant factor to maximize water flux, which could
be obtained when the reaction time was shortest (4 min). pH was
J. Li et al. Desalination 541 (2022) 116002

Table 2
Experimental results for water flux, NH+
4 rejection and their corresponding sample signal to noise (S/N) ratio.

Membrane Factor Designation Measured parameters Calculated S/N ratio

A B C D Water flux (LMH) RNH4+ (%) For water flux For NH+
4 rejection

1 1 1 1 1 A1B1C1D1 18.65 89.67 25.4136 39.0529

2 1 2 2 2 A1B2C2D2 16.82 86.97 24.5165 38.7874
3 1 3 3 3 A1B3C3D3 18.26 93.43 25.2300 39.4097
4 2 1 2 3 A2B1C2D3 18.46 89.09 25.3246 38.9966
5 2 2 3 1 A2B2C3D1 18.47 87.81 25.3293 38.8709
6 2 3 1 2 A2B3C1D2 18.98 91.89 25.5659 39.2654
7 3 1 3 2 A3B1C3D2 16.43 90.99 24.3128 39.1799
8 3 2 1 3 A3B2C1D3 18.74 88.15 25.4554 38.9044
9 3 3 2 1 A3B3C2D1 19.85 94.74 25.9552 39.5307

compositions of the TFC membrane samples. The elemental composi­

Table 3 tions of oxygen, nitrogen and carbon in the PA layer of the membranes,
4 rejection factors and sig­
Average S/N ratio response for water flux and NH+
as well as the O/N ratio, are listed in Table 4. Theoretically, for fully
nificant interaction.
linear PA network, the O/N ratio is 2.0, and fully crosslinked PA
Level Factor network, the O/N ratio is 1.0 [41]. The pristine TFC membrane showed
A (temperature, B C (TAEA D (time, an O/N ratio of 1.80, which implies that the PA layer of pristine TFC was
C) (pH) conc., wt%) min) partially crosslinked. After TAEA modification, all TAEA-modified
◦

Water flux membranes showed higher N content and lower O/N ratios than pris­
1 25.05 25.02 25.48 25.57 tine TFC membrane, which means that amine groups from TAEA were
2 25.41 25.10 25.27 24.80 successfully introduced into PA network, hereby successfully facilitating
3 25.24 25.58 24.96 25.34
Maximum–minimum 0.35 0.57 0.52 0.77
the second IP modification. The lower O/N ratios of the modified
Ordera 4 2 3 1 membranes suggest that the crosslinking of TAEA-modified membranes
was enhanced by the reaction between amine groups (–NH2) of TAEA
NH+ and the residual active groups (–COCl) of TMC. The TAEA-modified
4 rejection
1 39.08 39.08 39.07 39.15 membrane numbered 9 showed the highest N content and lowest O/N
2 39.04 38.85 39.10 39.08 ratio of 1.07, indicating that the amine group grafted to the PA layer was
3 39.20 39.40 39.15 39.10 the most abundant under this condition.
Maximum–minimum 0.16 0.55 0.08 0.07
Ordera 2 1 3 4
The zeta potential of pristine and the TAEA-modified membranes
was measured to analyze the influence of TAEA modification of mem­
a
Order represents the significance of the individual TAEA modification factor brane surface charge. It was hypothesized that for NH+ 4 rejection and
on the membrane performance parameter.
concentration, the surface charge of the membrane could play an
important role, such that a positively-charged TFC membrane could
determined as the second most significant factor influencing water flux, reject NH+ 4 better than the conventionally negative pristine TFC mem­
followed by TAEA concentration, and finally, temperature. These data brane. The full zeta potential measurements of all TFC membranes are
suggest that the water flux data would not be significantly different at shown in the Supplementary Information (Fig. S3). Fig. 3 shows the
whatever temperature the TAEA modification was conducted. The selected zeta potential measurements for the pristine TFC (denoted as
response table for NH+ 4 rejection, however, tells a different story. Among TFC) and optimized TFC membrane (number 9, denoted as TAEA-TFC)
the four factors, the pH of the TAEA solution was found to be the most for the pH range of 3 to 10. Both membranes exhibited isoelectric
significant factor influencing NH+ 4 rejection, such that the best NH4
+
points, or the pH at which the zeta potential is zero, due to the pro­
rejection performance corresponded to the experiment during which the tonation amine groups and dissociation of carboxyl groups. Compared
pH of the TAEA solution used during modification was 11, and that at with the pristine TFC membrane, the TAEA-modified membrane showed
lower pH levels, the NH+ 4 rejection would be significantly lower. Tem­ a less negative charge and the isoelectric point was observed at a higher
perature was then found as the second most significant factor influ­ pH value. The zeta potential of both pristine and TAEA-modified
encing NH+ 4 rejection, such that, when the reaction temperature was membrane was negative at pH = 5.4 (the same pH as the NH4Cl FS),
85 ◦ C, the NH+ 4 rejection could be maximized. For NH4 rejection, the
+
with the modified membrane showing a lower negative charge than the
influence of both TAEA concentration and reaction time were deemed pristine membrane. This can be explained by the consumption of the
not too significant. The use of only S/N ratio response is not sufficient to –COO− groups during the reaction with amine groups during the suc­
determine the combined significance of the factors for both water flux cessive IP and modification processes.
and NH+ 4 rejection. Thus, for the combination of the factors for both
water flux and NH+ 4 rejection, modeling was performed to predict the
membrane performance under all 81 conditions. By simply considering Table 4
the order of the influence of the factors on the membrane performance, Surface chemical composition of pristine and all TAEA-modified membranes.
maximizing both response parameters could be attained when reaction Membrane C1s N1s O1s O/N
time is minimized, and pH and temperature are maximized. TAEA
TFC 76.3 8.5 15.2 1.80
concentration was found not to significantly influence either response
1 76.8 9.7 13.5 1.40
parameter. These conditions were similar to the optimal modification 2 72.4 11.4 16.1 1.41
conditions determined during the optimization, validating the modelled 3 76.5 10.7 12.7 1.18
data. 4 74.0 11.6 14.4 1.25
5 77.3 10.0 12.7 1.27
6 71.7 13.2 15.1 1.14
3.2. Membrane surface characterization 7 76.0 10.6 13.5 1.28
8 74.1 11.8 14.1 1.20
9 71.6 13.7 14.7 1.07
XPS analysis was conducted to investigate the surface chemical

5
J. Li et al.
Fig. 3. Zeta potential measurements of the pristine and TAEA-modified
TFC membranes.
The surface and cross-sectional morphology of the TFC membranes
were observed by SEM, as shown in Fig. S4. For simplicity, only the SEM
images of the pristine TFC and optimized TAEA-modified TFC mem­
brane (number 9) are shown in Fig. 4 for comparison. Both pristine and
TAEA-modified membrane showed the typical ridge-and-valley PA layer
structure, indicating no significant difference between them, despite
TAEA modification. The cross-sectional morphology, however, revealed
that the PA layer thickness of the TAEA-modified TFC membrane is
thinner than that of the pristine TFC membrane.
The surface roughness of the membranes was investigated by a laser
microscope, as shown in Figs. 5 and S5. After modification, the PA layer
of the TAEA-modified membrane became smoother and more even than
the pristine membrane. This then provides evidence that the new ul­
trathin PA layer was formed by the reaction between the unreacted
–COCl and TAEA via secondary IP. The initial cross-linked PA layer
formed by the reaction of MPD and TMC was not a continuous and ideal
dense membrane, which was composed of some fragments. By
Fig. 4. Surface and cross-sectional SEM images of the pristine and TAEA-modified TFC membranes.
6
Desalination 541 (2022) 116002
Fig. 5. Water contact angle and surface roughness measurements of pristine
and TAEA-modified TFC membranes.
secondary IP, TAEA diffused through the initial cross-linked PA layer
and reacted with residual unreacted –COCl groups at the end of these
fragments to form a new PA layer which gradually flattened the rough
surface structure and made the new PA layer denser and thinner because
of the higher degree of crosslinking [42]. It should also be noted that the
optimized TAEA-modified membrane was only heat-treated for 4 min
during the IP process, compared to the pristine TFC membrane which
was heat-treated for 10 min, which could contribute to the difference in
PA selective layer thickness. The surface and cross-sectional morphol­
ogies of the pristine TFC membrane heat-treated for only 4 min are
shown in Fig. S6. It can be observed that the PA layer of the pristine TFC
membrane heated for 4 min was thinner than that of the pristine TFC
membrane heated for 10 min, but thicker than that of the TAEA-
modified membrane. Fig. S6 therefore proves that the decreased thick­
ness of the PA selective layer was brought about by the secondary IP
process, rather than the length of heat treatment during IP.
The water contact angles (WCA) of the pristine and TAEA-modified
J. Li et al. Desalination 541 (2022) 116002

membranes are also shown in Fig. 5, as well as Fig. S7. It is well known
that the amine functional groups are highly polar and have a strong
affinity to water [43], and modification with TAEA was expected to
result in an increased hydrophilicity of the TFC membrane. On the
contrary, compared to the pristine TFC membrane, the TAEA-modified
membrane shows a higher WCA value (76.3◦ ) than that of the pristine
one (65.2◦ ), which implies that the TAEA-modified membrane is less
hydrophilic. Typically, the introduction of more amine groups into the
PA network results in higher hydrophilicity; however, in the case of a
secondary IP modification process, the lower hydrophilicity of the
TAEA-modified membrane was mainly due to the reaction of the
remaining –COCl groups from TMC with the –NH2 groups from TAEA
to form amide during the secondary IP process. This resulted in a lower
loading of polar residual hydrolyzed carboxyl groups on the surface of
the TAEA-modified membranes, which led to a less hydrophilic mem­
brane surface [44]. Moreover, the lower surface roughness of the TAEA-
modified membrane influenced its WCA measurement.

3.3. Intrinsic transport properties of TFC membranes

The intrinsic transport properties of the pristine and optimized

TAEA-modified membrane were evaluated by RO tests and listed in
Table 5. Milli-Q water and 2000 ppm NaCl solution were used as feed to
evaluate the respective water and NaCl permeance at an applied hy­
draulic pressure of 10 bar. Compared with the pristine TFC membrane,
the TAEA-modified membrane showed both lower water permeability
coefficient (A value) and salt permeability coefficient (B value). The
lower water permeability is a result of the lower hydrophilicity and
higher degree of crosslinking after TAEA modification. Meanwhile, the
higher degree of crosslinking resulted in a denser PA network and lower
fractional free volume, which allow less salt particles to pass through the
membrane. However, the lower water permeability of the TAEA-
modified TFC membrane led to the similar NaCl rejection values of
the pristine and TAEA-modified TFC membranes, as shown in Table 5.

3.4. Separation mechanisms of NH+

4 rejection during FO process

In this subsection, a number of possible NH+

4 separation mechanisms,
such as polyamide carboxylic group density, cation exchange during FO
process, and size sieving, were investigated.
Fig. 6. Relationship between NH+4 rejection and (a) carboxylic group densities
and (b) O/N ratios of TFC membranes. (Average values from triplicate exper­
3.4.1. Influence of polyamide carboxylic group density and degree of iments performed are reported.)
crosslinking of TFC membranes on NH+ 4 rejection
The surface carboxylic group density of the TFC membranes was
indicated the higher crosslinking degree of the TAEA-modified TFC
measured using TBO test. The correlation between the polyamide car­
membranes. NH+ 4 rejection was observed to increase as the O/N ratio
boxylic group density and NH+ 4 rejection of the pristine and TAEA-
decreases, which was similar to the trend between NH+ 4 rejection and
modified membranes is presented in Fig. 6(a) and Table S3. The car­
carboxylic group density. These results indicate that the carboxylic
boxylic group density of the pristine TFC membrane was determined to
group density of TFC membranes was influenced by the introduction of
be approximately 22.9 nm− 2. After modification, all modified mem­
amine groups into the PA layer and increase of degree of crosslinking.
branes showed lower carboxylic group density values than the pristine
Also, these results imply that the carboxyl density of the PA layer was
one. It was also observed that the NH+ 4 rejection increased with the
the main factor controlling NH+ 4 transport and retention. The transport
decrease of the membrane surface carboxylic group density. Most
of NH+ 4 through the membrane via cation exchange with Na in the DS
+
particularly, the optimized TAEA modified membrane (number 9; con­
was suspected to be reduced with the decrease of the carboxylic density
ditions: 85 ◦ C, pH = 11, 1.5 wt% TAEA, and 4 min reaction time) had the
of the TFC membranes. The cation exchange mechanism during the NH+ 4
lowest carboxylic group density of around 7.9 nm− 2 and also the highest
concentration via FO will be discussed in detail in the succeeding
NH+ 4 rejection at the same time. Fig. 6(b) shows the relationship be­
subsection.
tween NH+ 4 rejection and O/N ratios of the pristine and TAEA-modified
membranes obtained by XPS measurement. The lower O/N ratio
3.4.2. Cation exchange during FO process
To investigate the mechanism of cation exchange during FO process
Table 5
and how it influences NH+4 rejection, FO test using a neutral PEG solute
Intrinsic transport properties of the pristine and TAEA modified TFC
as DS was conducted. This test aimed to show whether a change in
membranes.
rejection and NH+ 4 transport could be observed when there is no ion
Membrane A (LMH/bar) BNaCl (LMH) RNaCl (%) exchange involved between the FS and DS. The osmotic pressure of
TFC 0.81 ± 0.13 0.28 ± 0.03 96.3 ± 0.20 PEG400 was kept similar with 3.5 % NaCl DS prior to FO operation.
TAEA-TFC 0.32 ± 0.03 0.14 ± 0.01 95.5 ± 0.30 Fig. 7 shows that both pristine TFC and TAEA-modified membranes

7
J. Li et al.
Fig. 7. Comparison of water flux and NH+
4 rejection of the pristine (TFC) and
optimum TAEA-modified (TAEA-TFC) membranes during FO operation using
400 ppm NH+4 as FS and PEG400 as DS.
exhibited nearly 100 % NH+ 4 rejection, which are considerably higher
than when 3.5 % NaCl was used as DS. PEG transport across the pristine
and modified TFC membranes was also investigated using total organic
carbon (TOC) analysis of the initial and final FS and DS. The results of
the TOC analysis are shown in Table S4. The organic carbon content in
both initial and final FS was nearly the same. Compared with that in DS,
TOC in FS was really low and we consider this to be within experimental
error and can be considered negligible. The little change in the TOC
content in the DS before and after the FO test using both membranes can
be considered to be due to the transport of water from the FS side to the
DS side. It can therefore be said that no PEG transport occurred during
this FO operation. This indicates that cation exchange of Na+ transport
from DS to FS and NH+ 4 transport from FS to DS is a transport mechanism
occurring during the FO process, and that cation exchange between Na+
and NH+ 4 should be controlled to enhance NH4 rejection. A recent study
+ NH+ 4 rejection during forward osmosis (FO) operation as the perfor­
has also concluded that in order to have a higher NH+ 4 rejection, the
reverse cation flux from the DS should be minimized since forward NH+
permeation is influenced by cation exchange with the DS [30]. When a
neutral nonionic DS was used, the NH+ 4 in the FS cannot be transported
by cation exchange, so the NH+ 4 rejection was greatly improved.
Meanwhile, compared with the use of 3.5 % NaCl as DS, a lower water
Fig. 8. Comparison of ion rejection during FO operation using (a) pristine TFC membrane and (b) optimized TAEA-modified TFC membrane as a function of hydrated
radius. (Average values from triplicate experiments performed are reported.)
Desalination 541 (2022) 116002
flux of about 7 LMH was observed when PEG400 was used as DS, due to
the higher viscosity of DS, resulting in severe internal concentration
polarization [29].
3.5. Size sieving
Lastly, to investigate size sieving effect on ion rejection during the FO
process, FO operation was conducted with 100 ppm solutions containing
2+
different cations, such as Cs+, K+, NH+ 4 , Li , Ca
+
and Mg2+, used as FS
and 3.5 % NaCl solution used as DS. The hydrated radius of different
cations was listed in the Supplementary Information (Table S5). The
relationship between cation hydrated radius and cation rejection for
pristine TFC membrane and TAEA-modified membrane was showed in
Fig. 8(a) and (b), respectively. For the pristine TFC membrane, the NH+ 4
rejection was omitted from Fig. 8(a), since the value was calculated to be
negative, most likely due to the faster transport of NH+ 4 ions than water
during the 24 h FO process. Both pristine TFC membrane and TAEA-
modified membrane showed similar trends between cation hydrated
radius and rejection. For monovalent ions such as Cs+, K+ and Li+, the
rejection shows an increasing trend with increasing hydrated radius,
while the TAEA-modified membrane showed higher rejection compared
to the pristine TFC membrane. This is because after TAEA modification,
the PA network became more crosslinked and effectively denser,
decreasing the fractional free volume of the TFC membrane. For divalent
cations, such as Ca2+ and Mg2+, both pristine and TAEA-modified
membrane showed nearly 100 % rejection due to the larger hydration
radius of these ions.
4. Conclusions
This work described the preparation of a tris(2-aminoethyl)amine
(TAEA)-modified thin film composite (TFC) membrane via a second­
ary interfacial polymerization (IP) approach. The TAEA modification,
influenced by pH, TAEA concentration, temperature, and reaction time,
was optimized using Taguchi orthogonal method using water flux and
mance parameters. Finally, the mechanisms of NH+ 4 rejection during FO
4
was investigated. These are the main findings:
1. TAEA modification introduced amine groups during the secondary IP
and reacted with the unreacted carboxyl groups of TMC, resulting in
8
J. Li et al.
lower carboxylic group density of the TAEA-modified membranes
and higher degree of crosslinking;
2. TAEA modification resulted in a less negative membrane surface, as a
result of the lower carboxylic group density of the polyamide;
3. The TAEA-modified TFC membrane exhibited thinner and smoother
polyamide selective layer, with a decrease in hydrophilicity as
observed from water contact angle measurements;
4. NH+
4 rejection during FO is influenced by these phenomena: car­
boxylic group density of the membrane surface and the polyamide
crosslinking, cation exchange between the FS and DS, and size
sieving. The results of the mechanistic investigation showed that size
sieving primarily improved the NH+ 4 rejection, but the best NH4
+
rejection performance was observed for the membrane with highest
degree of crosslinking and lowest carboxylic group density.
CRediT authorship contribution statement
Jing Li: Conceptualization, Methodology, Formal analysis, Investi­
gation, Data curation, Writing – Original Draft, Writing – Review &
Editing, Visualization; Ralph Rolly Gonzales: Conceptualization,
Methodology, Formal analysis, Writing – Original Draft, Writing – Re­
view & Editing, Visualization, Supervision; Ryosuke Takagi: Investi­
gation, Writing – Review & Editing; Xuesong Yao: Methodology,
Formal analysis, Investigation, Data curation; Pengfei Zhang: Meth­
odology, Formal analysis, Investigation, Data curation; Titik Istir­
okhatun: Methodology, Formal analysis, Investigation, Data curation;
Jinhui Zhang: Methodology, Formal analysis, Investigation, Data
curation; Hideto Matsuyama: Writing – Review & Editing, Resources,
Supervision, Project administration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgment
This work is part of a project (Project number: JPNP18016)
commissioned by the New Energy and Industrial Technology Develop­
ment Organization (NEDO), Japan.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.desal.2022.116002.
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