Accepted Manuscript

Preparation and characterization of a novel photocatalytic self-cleaning PES

nanofiltration membrane by embedding a visible-driven photocatalyst boron
doped-TiO2-SiO2/CoFe2O4 nanoparticles

Hadis Zangeneh, Ali Akbar Zinatizadeh, Sirus Zinadini, Mostafa Feyzi, Detlef
W. Bahnemann

PII: S1383-5866(18)30896-7
DOI: https://doi.org/10.1016/j.seppur.2018.09.030
Reference: SEPPUR 14928

To appear in: Separation and Purification Technology

Received Date: 16 March 2018

Revised Date: 5 August 2018
Accepted Date: 10 September 2018

Please cite this article as: H. Zangeneh, A.A. Zinatizadeh, S. Zinadini, M. Feyzi, D.W. Bahnemann, Preparation and
characterization of a novel photocatalytic self-cleaning PES nanofiltration membrane by embedding a visible-driven
photocatalyst boron doped-TiO2-SiO2/CoFe2O4 nanoparticles, Separation and Purification Technology (2018), doi:
https://doi.org/10.1016/j.seppur.2018.09.030

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 Preparation and characterization of a novel photocatalytic self-cleaning PES

nanofiltration membrane by embedding a visible-driven photocatalyst boron doped-

TiO2-SiO2/CoFe2O4 nanoparticles

Hadis Zangeneh1, Ali Akbar Zinatizadeh1,*, Sirus Zinadini1, Mostafa Feyzi2, Detlef W.

Bahnemann3

1
Environmental Research Center (ERC), Department of Applied Chemistry, Razi University,
Kermanshah, Iran.
2
Department of Physical Chemistry, Razi University, Kermanshah, Iran.
2
Institut fuer Technische Chemie, Leibniz Universität Hannover, Callinstrasse 3, D-
30167 Hannover, Germany.

* Corresponding author:

Tel: (+98) 8334274530,

Fax: (+98) 8334274542,

Email: zinatizadeh@gmail.com

1
Nomenclature:

List of symbol

POME Palm oil mill effluent

Tetran-butylorthotitanate TBOT
Tetraethyl orthosilicate TEOS
SEM Scanning electron microscopy
AFM Atomic force analysis
FRR Flux recovery ratio
PES Polyethersulfone
NF Nanofiltration
MWCNTs Multiwalled carbon nanotubes
B-TiO2-SiO2/CoFe2O4 Boron doped-TiO2-SiO2 cobalt ferrite
XRD X-ray diffraction
FT-IR Fourier Transform Infra-Red
NPs Nanoparticles
PVP Polyvinylpyrrolidone
PWF Pure water flux
CF Particular concentration in feed
Cp Particular concentration in permeate
DMAc N,N-dimethylacetamide
Jp Powder milk solution flux
jw,1 Pure water flux
Jw,2 Pure water flux after fouling
Rt Total fouling resistance
Rr Reversible fouling resistance
Rir Irreversible fouling resistance
M1 Unfilled PES membrane
M2 Membrane with 0.1 wt.% nanoparticle
M3 Membrane with 0.5 wt.% nanoparticle
M4 Membrane with 1 wt.% nanoparticle
COD Chemical oxygen demand

2
Abstract
Novel self-cleaning PES nanofiltration membranes were successfully synthesized via the

phase inversion method with different amounts of the boron doped-TiO2-SiO2 cobalt ferrite

(B-TiO2-SiO2/CoFe2O4) nanophotocatalyst. The nanofiltration performance was investigated

by the rejection of direct red 16 and COD removal of the biologically treated palm oil mill

effluent (POME). The addition of the B-TiO2-SiO2/CoFe2O4 nanoparticles into the polymeric

casting solution improved porosity, morphology, structure, pure water flux (PWF),

antifouling properties and separation performance of the embedded membranes due to

hydrophilic behavior and photocatalytic properties of the B-TiO2-SiO2/CoFe2O4

nanoparticles. The B-TiO2-SiO2/CoFe2O4 nanoparticles can degrade adsorbed organic

foulants on the membrane surface (reversible fouling) or deposited/trapped fouling agents

into the membrane pores (irreversible fouling). The prevention of the interaction between

organic foulant and hydrophilic membrane improves antifouling properties and wettability of

the modified membranes. The membrane with 0.5 wt % of the B-TiO2-SiO2/CoFe2O4

nanoparticle had the highest pure water flux and flux recovery ratio (FRR) with the best

separation performance. However, at high concentration of nanoparticles, agglomeration of

the nanoparticles on membrane surface/pores resulted in pore blocking, roughness membrane

surface which led to slightly reduction of PWF, FRR and separation performance. The

obtained results were also confirmed by contact angle measurement, scanning electron

microscopy (SEM) and atomic force microscopy analysis (AFM).

Keywords: Self-cleaning, Visible-driven boron doped-TiO2-SiO2 cobalt ferrite magnetic

nanoparticle, Nanofiltration (NF).

3
1. Introduction

Water pollution has recently become a very serious challenge due to large volumes of

discharges of non-biodegradable or toxic hazardous organic compounds [1]. These effluents

are treated by conventional techniques such as physical, chemical and biochemical processes

[2]. However, the above methods are not efficient due to production of large amount of

sludge, harmful byproducts, bio-resistant species, and complex operational procedures [3].

Membrane filtration has been considered as a promising technology in water and industrial

wastewater treatment fields due to its low cost, high separation performance, high effluent

quality, ease of setup, insignificant chemical consumption [4-5]. Nevertheless, this method

suffers from concentration polarization and membrane fouling by accumulation of organic

pollutant or biomolecules/microorganisms on the membrane surface and block membrane

pores, which eventually leads to decline in separation performance, increase in the operation

cost and shorten membrane lifetime [6-7].

Polymeric membranes are widely applied in water purification and wastewater treatment [8].

Polyethersulfone (PES) is one of the most popular polymeric membranes due to its excellent

chemical resistance, mechanical strength, high rigidity, thermal and biological stability [9-

10]. However, the hydrophobic nature of polyethersulfone membrane has limited its

application due to strong interaction between hydrophobic contaminants and the membrane

surface result in internal (pore clogging) and external (surface deposition) membrane fouling

during filtration process [11]. To overcome aforementioned problems in the line of

membrane fouling alleviation, various approaches such as grafting with hydrophilic

monomers [15], cold plasma treatment, blending with hydrophilic polymers, surface-coating

[16] and embedding hydrophilic nanoparticles [11-14] have been done.

Current research focuses on blending with hydrophilic nanoparticles especially inorganic

nanoparticles (e.g. SiO2, ZrO2, Al2O3, TiO2, Fe3O4, and etc.) due to reproducibility,

4
convenient operation, capable of industrialization, good separation performances, excellent

thermal and chemical resistance and adaptability to the harsh wastewater environments and

mild conditions [17-18].

TiO2 nanoparticles, as one of the most effective inorganic materials, improve permeability

and surface hydrophilicity, enhance mineralization of pollutants under ultraviolet (UV) light,

and improve self-cleaning/antifouling property of the modified membranes [19]. However,

aggregation of TiO2 NPs in PES matrix due to its high surface energy [20], low photocatalyst

activity due to high recombination rate [21-22] and decomposing effect of UV light on the

PES membrane structure in long time operation [23] are main drawbacks of the pure

TiO2/PES membrane. Song, et al. [24] reported degradation of the structure of TiO2-

PVDFPEG membrane after 12 h UV irradiation. Hence, many strategies have been developed

to overcome the TiO2 drawbacks including doping of metal, non-metal elements [22] loading

of noble metals [22] and combining with other semiconductors [22]. Doping TiO2 with metal

or nonmetal ions has been considered as one of the most promising ways to develop TiO2-

based photocatalysts to extend its light absorption into the visible region [22].

Coupling magnetic nanoparticles with TiO2 nanoparticles has indicated the synergistic

influence that leads to better photocatalytic performance and lower agglomeration. Besides,

spinel ferrites, with the general formula of MFe2 O4, where M is a divalent cation like Co

(CoFe2O4), offer more interest in photocatalytic activities compared to the corresponding

single-component metal oxides [26] due to lesser band gap energy, [27]. As a result, a rapid

charge separation and slow charge recombination occur, and any transferred charge carriers

may participate in the subsequent redox reactions thereby resulting in higher photocatalytic

activity [26-27]. Li et al., [28] prepared PES–TiO2 hybrid membranes by phase inversion

method. They reported that thermal stability, porosity and permeation properties of the

composite membrane improved by adding TiO2 nanoparticles. However, at high loading

5
amount of TiO2, significant aggregation of TiO2 nanoparticles could be observed [28]. An

investigation carried out by Wu et al. [29] indicated that blending TiO2 NPs with PES

composite membranes leads to improve hydrophilicity, thermal stability, mechanical strength

and anti-fouling ability at 0.5 wt.% TiO2 [29]. Vatanpour et al [30] studied the effect of three

different types of TiO2 NPs including P25, PC105 and PC500 with various sizes on

morphology, performance and antifouling properties of the mixed matrix TiO2/PES

nanofiltration. They established that biofouling of the membranes was reduced by embedding

TiO2 NPs and decreasing nanoparticles size. Furthermore, they reported that the P25-TiO2

NPs had the higher pure water flux and the water flux recovery ratio due to the lower

tendency to the aggregation [30]. Sotto et al. [31] also reported that the overall membrane

performance, particularly its antifouling properties was improved by incorporation of small

amount of TiO2 NPs and also EtOH as polymer co-solvent [31].

In this work, we synthesized boron-doped TiO2 in order to narrow the band gap of TiO2 and

added SiO2 to suppress the recombination of electron-hole and increase thermally stable

anatase phase with high crystallinity and large surface area [25]. Finally we coupled B doped-

TiO2-SiO2 with CoFe2O4. A self-cleaning photocatalytic PES nanofiltration membrane was

fabricated by phase inversion method with introducing three loading amounts of the boron

doped-TiO2-SiO2/CoFe2O4 magnetic nanoparticles (0.1, 0.5 and 1 Wt %) which is not

reported up to this date. The surface hydrophilicity and structure were analyzed using

scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact

angle measurements. Antifouling properties of the prepared membranes were studied by

powder milk solution. Nanofiltration performance of the selected optimum membrane was

assessed by rejection of direct red 16 and treating the biologically treated palm oil mill

effluent (POME).

6
2. Experimental

2.1 Materials

The chemicals were used as received without further purification. Tetran-butylorthotitanate

(TBOT, 99 wt %), boric acid (H3BO3), Tetraethyl orthosilicate (TEOS, 99 wt %), ethanol

(C2H5OH, 99 wt %) and (HCl, 37 wt %) from Merck company was used to synthesize

nanoparticles. Polyethersulfone (Ultrason E 6020P, MW=58,000 g/mol and glass transition

temperature Tg=225 °C) as polymer and dimethyl acetamide (DMAc) as a solvent were

purchased from BASF Co., Germany. Polyvinylpyrrolidone (PVP) with 25,000 g/mol

molecular weight as a pore forming in the coagulation process was obtained from Merck Co.,

Germany. Distilled water was used as the non-solvent agent. Chemical substances which

were used for chemical oxygen demand (COD) experiments were supplied by Merck

Company.

2.2 Preparation and characterization of magnetic boron doped-TiO2-SiO2

nanocomposite

The magnetite particles (CoFe2O4) were obtained according to previous work. Briefly, 0.1 g

of the as-prepared magnetic particles were added into 10 mL ethanol and was processed

ultrasonically for 1h (solution A). Subsequently, a desired amount of TBOT, TEOS and

H3BO3 were dispersed in 5 mL ethanol (solution B) and next solution A was drop-wise added

to the solution B (solution C). After that, distilled water and HCl were mixed with the

remaining ethanol. In the next stage, the ethanolic solution which was a mixture of distilled

water and HCl was added drop-wise to the solution C under continuous stirring. The resulting

mixture was afterward transferred to a Teflon-lined stainless-steel autoclave. The autoclave

was placed in a 150 ◦C oven for 12 h and then cooled to room temperature. The magnetic B

doped –TiO2-SiO2 nanocomposite was washed with ethanol and water six times and then

7
dried under vacuum at 60 ◦C for 6 h. Finally, the products were calcined in argon at 500 °C

for 2.5 h.

The crystalline phases of the prepared samples were identified by X-ray diffraction (XRD)

using a Philips X’ Pert (40 kV, 30 mA) X-ray diffractometer. X-ray diffractometer with Cu

Kα radiation (λ=1.542 Å). The Fourier Transform Infra-Red (FT-IR) spectra were recorded

on KBr disks containing the powder samples with an FT-IR spectrometer (MAGNA-560).

The scanning electron microscope ((SEM, VEGA TESCAN (Czech Republic)) was applied

to observe surface morphology and particle size of the prepared NPs. The UV–Vis diffuse

reflectance spectra (DRS) of the prepared samples were obtained using a Shimadzu 1800

spectrometer in the range of 200–800 nm. The magnetic properties of prepared samples were

performed at room temperature by a vibrating sample magnetometer (VSM, Lake Shore

7410). The photoluminescence (PL) spectroscopy was done by a photoluminescence

spectrometer, Shimadzu RF-5301, at room temperature.

2.3 Fabrication and characterization of B doped –TiO2-SiO2/CoF2O4 blended PES

membranes

The desired amount of the B doped TiO2-SiO2/CoF2O4 nanoparticles (0.03, 0.15 and 0.3g

corresponding to 0.1, 0.5 and 1 wt. %) was dispersed in DMAs as a solvent under

ultrasonication for 60 min to achieve a homogeneous suspension. The prepared membrane

composition was represented at Table 1. Then, 6 g of PES (20 wt. %) and 0.3 g of PVP (1 wt.

%) was added to casting solution under stirring for 24 h. Following that, the obtained

homogeneous solution was sonicated for 30 min for removing air bubbles and was casted

with 150 µm thickness at room temperature. Afterward, the film was submerged into distilled

water at 25 °C. The membranes were kept in fresh distilled water for 24 h to remove residual

8
solvent and complete phase inversion process. Finally, they were dried between two filter

paper sheets.

The surface roughness of the prepared membranes, was investigated by using atomic force

microscopy (AFM, Nanosurf® MobileS) measurements equipped with Nanosurf® MobileS

software (version 1.8). A piece 1 cm2 of the prepared membrane was placed on specimen

holders and scanned in the tapping mode in the air (8×8 µm areas). Water contact angle

measurement was used to evaluate hydrophilicity of the prepared membranes. A goniometer

device (G10, KRUSS, Germany) was used to measure the static contact angle formed

between the water and the membrane surface by the sessile drop method at 25 °C. The cross-

section morphology of the prepared membranes was investigated by SEM micrographs

(Philips-X130 and Cambridge scanning electron microscopes) after the samples were frozen

by liquid nitrogen and fractured in gold-sputtered.

Table 1. The compositions of casting solutions.

Membrane type PES (wt%) PVP (wt%) B doped TiO2-SiO2 /CoF2O4 (wt %)
M0 20 1.0 0
M1 20 1.0 0.1
M2 20 1.0 0.5
M3 20 1.0 1.0

2.4 Evaluation of permeation, antifouling and self-cleaning properties of the prepared

membranes

Filtration tests were carried out in batch mode using a batch, stirred dead-end filtration cell

with an effective membrane surface area of 12.56 cm2 and a volume capacity of 125 mL (Fig.

1Sa). Membrane cell was attached to a nitrogen gas line to force the liquid through the

filtration experiments.

The pure water flux was measured at pressure of 5 bar after the membrane was compressed at

6 bar to achieve steady permeate for 30 min. Each wet membrane was irradiated by a 100 W

9
tungsten lamp (visible light) about 60 min before that were used. The following equation (1)

was applied to calculate pure water flux [24]:

M
J w,1  (1)
A. t

Where, M, A and t are the weight of permeated water (kg), membrane area and (m2) and

permeation time (h), respectively.

The antifouling and self-cleaning property of the prepared membrane was conducted using

following procedures. After measuring pure water flux (Jw1), a powder milk solution (8000

ppm) was fed in filtration cell and permeation flux (Jp (kg/m2h)) was measured. Next, the

fouled membrane was placed in deionized water (about 1h as rinsing time) to eliminate

loosely bound protein and the second water flux (Jw2) of washed membranes were again

measured. This experiment was repeated again with the same condition with difference that

the washing step of the fouled membrane using deionized water was done under visible light

irradiation (about 1h). The flux recovery ratio (FRR) and fouling resistance parameters,

including the total fouling ratio (Rt), reversible fouling ratio (Rr) and irreversible fouling ratio

(Rir) was defined as [24]:

J w,2
FRR (%)  ( )  100 (2)
J w,1

J w,2  J p
Rr  ( )  100 (3)
J w,1

J w,1  J w,2
Rir  ( )  100 (4)
J w,1

The membrane performance was investigated by treating an aqueous solution direct red 16

with the concentration of 50 ppm and biologically treated palm oil mill effluent (POME) with

COD concentration of 1000 mg/l in separate experiments. The biologically treated POME

was collected from effluent of second aerobic lagoon (Jugra palm oil mill, Kualalumpur,

10
Malaysia). Characteristics of direct red 16 and the biologically treated POME are presented in

Table 2.

Table 2. Characteristics of direct red and

Direct red 16
Molecular Formula C26H17N5Na2O8S2
Molecular Weight 637.55
Molecular Structure

Biologically treated POME

Parameters Amount Unit
COD 1000 mg/l
BOD5 290 mg/l
Total suspended solids 400 mg/l
(TSS)
PH 5.3 -
color Brown -

Direct red 16 concentration was determined using a UV–vis spectrophotometer (Pharo 300,

Merck) at λmax = 526.6 nm. The DR16 removal efficiency at regular intervals was calculated

using the following equation.

Cp
R (%)  (1  )  100 (5)
Cf

The standard methods (5220D) procedures were followed in order to measure COD of the

biologically treated POME [32]. The COD removal (CODrem) efficiency was calculated using

Eq. 6.

where, CODf and CODp are the COD concentration of the feed and the permeate solution,

respectively.

11
A UV–Vis spectrophotometer (Pharo 300, Merck) was used to evaluate the color removal

efficiency from the biologically treated POME. The biologically treated POME and treated

samples were scanned at 400-800 nm. The following equation was used to calculate the color

removal efficiency [33]:

where, Af and Ap are the average absorption of the biologically treated POME and permeate

between 400-800 nm, respectively.

2.4 Long term performance of prepared membranes

The long term performance of the bare (M0) and optimized membranes (M2) was carried out

in a plexiglass cross flow system equipped with halogen lamp (500 W, λ ˃ 400 nm) (Fig.

1Sb). The halogen lamp was held in a distance of 25 cm from the membrane cross flow setup.

The biologically treated POME samples (with COD of about 1000 mg/l) were filtrated 12 h

under visible light irradiation.

3. Results and discussion

3.1 Characterization of the boron doped TiO2-SiO2/CoFe2O4 magnetic nanoparticles

Fig. 1a, SEM image, indicates the morphology boron doped TiO2-SiO2/CoFe2O4 magnetic

nanoparticles. From the SEM image, it was found that the prepared boron doped TiO2-

SiO2/CoFe2O4 magnetic nanoparticles were agglomerated spherical nanoparticles and the

small nanoparticles with average size about 26 nm have been observed.

UV–Vis diffuse reflectance spectra (DRS) of the pure TiO2 and boron doped TiO2-

SiO2/CoFe2O4 magnetic nanocomposite is revealed in Fig. 1b. The band gap of the prepared

photocatalyst was also determined by the Tauc plots (Fig. 1c) [34]. From the Fig. 1b, it can

be clearly detected that the absorption edge position of the boron doped TiO 2-SiO2/CoFe2O4

12
magnetic nanoparticles has a red shift to visible region and extended up to longer

wavelengths comparing to the pure TiO2. The absorption edge of the pure TiO2 and B-TiO2–

SiO2/CoFe2O4 samples were at about 390, 655 nm corresponding to 3.17 and 1.9 eV,

respectively. The PL results (Fig. 1d) showed the B-SiO2-TiO2/CoFe2O4 had the lowest PL

intensity because the couple of TiO2, SiO2 and CoFe2O4 as a heterojunction structure

suppress the electron-hole recombination rate and supply charge carriers separation [35].

(a)

80
B-TiO2-SiO2/CoFe2O4 Pure TiO2
70 Pure TiO2 B-TiO2-SiO2/CoFe2O4

60
(α*λν)^0.5
Absorbance (a.u)

50

40

30

20

10

0 1.5 2 2.5 3 3.5 4 4.5 5 5.5

250 350 450 550 650 750
Eg (eV)
Wavelength (nm)

(b) (c)

13
 1000
B-TiO2
900
B-TiO2-SiO2
800
B-TiO2-SiO2/CoFe2O4
700

Intensity
600
500
400
300
200
100
0
400 450 500 550 600 650 700 750 800
Wavelength (nm)
(d)
Fig. 1. (a) SEM images, (b) DRS spectra, (c) Tauc plot and (d) PL spectra of the prepared

photocatalysts.

The XRD, FT-IR and VSM result of the boron doped TiO2-SiO2/CoFe2O4 magnetic

nanoparticle was displayed in Fig. 1Sa-c, respectively. From the Fig. 1Sa, all the reflection

peaks are in accordance with the anatase TiO2 (PDF Card #89-4921) and spinel CoFe2O4

(PDF Card #22-1086 (reflection peaks at 29.9◦ (2 2 0), 35.2◦ (3 1 1), 42.8◦ (4 0 0), 53.3◦ (4 2

2), 56.7◦ (5 1 1) and 62.3◦ (4 4 0)). The average crystalline size of anatase of boron doped

TiO2-SiO2/CoFe2O4 were about 9 using (101) reflections peaks [26, 36-37].

Fig. 1Sb represents the FTIR spectra of boron doped TiO2-SiO2/CoFe2O4 magnetic

nanoparticles from 5000 to 400 cm-1. The observed peaks at 550 cm-1 was due to Ti–O

stretching vibration and the peaks at 3400 and 1650 cm-1 are corresponded with the stretching

and bending vibration –OH, respectively [38]. The peaks at 405 cm-1 and 583 cm-1 are related

to metal–oxygen (Fe–O and Co–O) bonds [36] and the peaks at 375–800 cm-1 are assigned to

the Ti–O–Ti or Fe–O stretching vibrations, respectively [37].

The magnetization curves of boron doped TiO2-SiO2/CoFe2O4 was shown in Fig. 1Sc. The

VSM result indicates that the coercive force (Hc) is 1000. The saturation magnetization (Ms)

14
value of boron doped TiO2-SiO2/CoFe2O4 is about 21 emu/g which is lower compared to pure

CoFe2O4. It should be noted that the B-TiO2 –SiO2/CoFe2O4 nanocomposite indicates

ferromagnetic properties and strong magnetization [36-37].

3.2 Characterization of prepared membrane

3.2.1 Membrane morphology

Fig. 2 displayed the cross section SEM micrograph of the fabricated membranes and exhibits

the induced changes in the membrane morphology with adding nanoparticles. All the

fabricated membranes composed of a dense top layer, porous sub layer with a finger-like

macroporous structure resulting in the same asymmetric membrane structure [39]. From the

micrographs, it is clearly was seen that the finger-like structure and membrane porosity was

significantly increased with addition of the boron doped TiO2-SiO2/CoFe2O4 magnetic

nanoparticles. The addition of hydrophilic modified TiO2 nanoparticle enhances the

hydrophilicity of casting solution, which promotes fast exchange between solvent (DMAc)

and non-solvent (water) in coagulation bath thereby expanding the population of pores [40].

However, the addition of the modified TiO2 NPs with the amounts of more than 0.5 wt. %

leads to form a denser skin-layers with increased thickness and sub-layers with lower

porosities. Therefore, the pore radius and membrane porosity reduce due to the increase in the

viscosity of casting solution which hinders the exchange of solvent and non-solvent and

inhibits the formation of large pore radius. Also, the agglomeration of NPs occur on the

membrane surface [39-40].

Two and three-dimensional AFM photographs exhibiting the surface roughness of the

prepared membrane as shown in Fig. 3. In these images, the brightest area demonstrates the

highest point of the membrane surface, and the dark regions illustrate the valleys or

membrane pores. The surface roughness of pristine PES membrane was higher than the

15
blended NPs membranes accordingly the AFM images. Incorporating the boron doped TiO2-

SiO2/CoFe2O4 magnetic nanoparticles in the casting solution from 0.1 to 0.5 %, led to

smoother membrane surface which implies on higher fouling resistance ability due to

mitigation of foulant agents adsorption or trapping on pores and membrane surface. It is

noted that the agglomeration of NPs was occurred at higher concentration of the NPs (> 0.5

%) which increased the surface roughness at 1 % NPs blended membrane comparing to other

modified membranes [11, 39]. The same result was observed by Vatanpour et al., [41] for

PES membrane blended with TiO2 coated with multiwalled carbon nanotubes.

Table 3 presents roughness parameters fabricated membranes including roughness (Sa), root

mean square of the Z data (Sq) and the height difference between the highest peak and the

lowest valley (Sy) at a scan size of 2 μm × 2 μm. The unfilled PES membrane has the highest

surface roughness, and the roughness parameters were reduced by addition of NPs from 0.1

to 0.5 wt %. The Sa value reduced from 47.2 nm (puv, re PES) to 13.92 nm (0.1 % NPs-

PES), 12.60 nm (0.5 % NPs-PES) and 14.62 nm (1 % NPs-PES).

Table 3. Surface roughness parameters of the prepared PES membranes resulted from

analyzing three randomly chosen AFM images.

Roughness parameters
Membrane Sa (nm) Sq (nm) Sy (nm)
M0 47.11 59.60 304.46
M1 13.92 17.69 121.41
M2 12.60 15.97 117.45
M3 14.62 22.67 255.15

16
 a b

c d

e f

g h

Fig. 2. The cross-section morphology SEM images of the fabricated PES membranes a and

b) bare PES (M0), c and d) 0.1 wt.% (M1), e and f) 0.5 wt.% (M2), g and d) 1 wt.% (M3) .

17
a) M0

b) M1

c) M2

18
 d) M3
Fig. 3. Two and three dimensional AFM photographs of the prepared PES membranes with

different weight fraction NPs (a) bare PES (M0), (b) 0.1 wt.% (M1), (c) 0.5 wt.% (M2), (d) 1

wt.% (M3).

3.2.2 Membrane hydrophilicity and pure water flux

The water permeability of the fabricated membranes was shown in Fig. 4a. From the Fig.,

pure water flux values were about 16.7, 27.2, 38.1 and 21 kg/m2.h for bare PES, 0.1 % NPs-

PES, 0.5 % NPs-PES and 1% NPs-PES, respectively. The results were evidence for the

significant impact of the NPs on hydrophilicity enhancement of the membrane surface [28,

29]. The highest pure water flux was achieved at 0.5 % of NPs while according to the results

of contact angle (Fig. 4b), the surface hydrophilicity of 1% of NPs was higher. At high

concentration of the NPs (1%), agglomeration of the nanoparticles on the membrane surface

leads to increase pore blocking/clogging and reduce membrane porosity [31] which was

confirmed by SEM photographs. From the Fig. 4b, all of the blended membranes had a

considerable reduction of contact angle values compared to unfilled PES membrane. The

reduction of interface energy with the addition of the hydrophilic NPs to the casting solution

increased migration of the hydrophilic NPs towards the blended membrane surfaces during

the phase inversion process which improved the membrane hydrophilicity [41-42].

19
 45

40 38.1

35

kg/m2.h) 30
25.2
25
21
20
16.7
15

10

0
M0 M1 M2 M3
Membrane type

(a)

70
62.5
60
55.1
51.3
49.3
50
Contact angle (o)

40

30

20

10

0
M0 M1 M2 M3
Membrane type

(b)

Fig. 4. a) Pure Water flux after 60 min at 5 bar, and b) static contact angel analysis of the

prepared membranes.

20
3.3 Fouling resistance of the prepared membranes

The fouling resistance of membranes is one of the most important parameters showing

characteristics of the membrane in long term performance. Fig. 5 shows the trend of

permeation flux versus time during milk powder solution filtration for all of the prepared

membranes. From the Fig. 5, the decreasing trend was observed during filtration for all of the

membranes. But M3 showed higher flux after 90 min filtration resulting higher fouling

resistance. The permeation flux was 5.8 kg/m2 h for the bare PES, whereas this value was 9.5,

12.1 and 9.7 for M1, M2 and M3, respectively.

Fig. 5 shows a great reduction in the permeate flux when pure water is replaced by milk

powder solution and then, the flux becomes stable. This trend can be attributed to the

concentration polarization resulted from accumulation of the proteins near the membrane

surface and fouling phenomena.

M0 M1 M2 M3
17

15
Permation flux (kg/m2.h)

13

11

5
15 30 45 60 75 90
Time (min)

Fig. 5. Permeation flux of the prepared membranes versus time during milk powder solution

filtration.

21
In this study, the antifouling property of the prepared membrane was investigated by filtration

of 8000 ppm powder milk solution. Fig. 6a shows the FRR ratios of fabricated membranes

with different cleaning conditions after milk powder filtration. The FRR ratio of M2 was

maximum compared to the unfilled PES membrane and other modified membranes. The

value of FRR ratio for M2 was about 84.6, 98 and 99% cleaning with deionized water,

cleaning with deionized water under visible light or UV illumination, respectively. The FRR

value of the unfilled PES membrane was almost similar under different conditions. The

addition B-TiO2-SiO2/CoFe2O4 NPs effectively improved antifouling properties of the

blended membrane due to higher hydrophilicity, smoother surface, and photocatalytic activity

or self-cleaning properties [41, 43]. The self-cleaning property of B-TiO2-SiO2/CoFe2O4-PES

nanocomposites membrane is justified by its photocatalytic activity.

Under UV or visible light illumination, the strong oxidant reagents like, hydroxyl radicals

(OH•), superoxide radical anions (O2•−) and hydroperoxyl radicals (HOO•) were generated on

the membrane surface and pores and degraded organic or bioorganic foulant to CO 2 and H2O

or decomposed to simple intermediates, thereby reducing membrane fouling [22, 44]. Also,

adsorbed water molecules on membrane surface or pores improved antifouling properties

through producing a water layer on the membrane surface which increase hydrophilicity and

reduce adsorption of foulants [4, 44]. This should be noted that the polymeric membrane may

be destroyed under long time UV light irradiation [4]. Therefore, the visible driven

photocatalyst was the better modifier compare to pure TiO 2 for the polymeric membranes.

In more detail, the irreversible fouling ratio (Rir) was calculated with visible light cleaning

(Fig.6b). The irreversible fouling ratio showed a decreasing trend from the unfilled PES

(47.42%) to the M2 (3%) due to the photocatalytic degradation of organic foulant on the

membrane surface. The value of Rir/Rt ratio for M2 (0.06) was considerably low compared to

the other fabricated membranes. This value for the unfilled PES membrane was about 0.83.

22
The Rr/Rt ratio is related to loose adsorption of organic foulant on membrane surface and the

Rir/ Rt ratio described deposition of organic foulant on membrane surface or entrapment

within the pores.

100

90

80

70

60 Cleaning with DI
FRR (%)

Cleaning with DI under visible light

50
Cleaning with DI UV light irradaition
40

30

20

10

0
M0 M1 M2 M3
Membrane type

a))
100
Rt Rr Rir
90

80
Resistance parameters (%)

70

60 57
52
47.42 49
50 44 43
40 33
30
30

20 13
9.58 11
10 3
0
M0 M1 M2 M3
Membrane type

b))

Fig. 6. a) Flux recovery ratio of the prepared membranes and b)

the prepared membranes with visible light cleaning.

23
 3.4 Separation performance of the prepared membranes

3.4.1 Direct red 16 removal

Fig. 7a demonstrates the performance of the prepared membranes in terms of the rejection

value for direct red 16. The results showed that all the modified membranes indicated better

separation performance in comparison with the unfilled PES membrane. The highest removal

efficiency of direct red 16 was 98 % with the 0.5 wt. % of NPs (M2). From the literature,

isoelectric point of the B-TiO2-SiO2/CoFe2O4 NPs is about pH of 3. Therefore, the membrane

surface was negatively charged at neutral pH. Furthermore, the repulsion interaction between

a negative membrane surface and dye molecules with negative charge was promoted the

membrane performance. Adsorption of water molecules on the membrane surface results in

the hydrophilic layer on membrane surface that inhibited the interaction between

hydrophobic materials like dye molecules and membrane surface. However, dye rejection

decreases when the NPs wt. % increases to 1 % due to increase of membrane pore radius

[48]. The digital photograph of direct red solution and permeates is shown in Fig. 7b.

100 96 98 96
90
90

80
Dye removal (%)

70

60

50

40

30

20

10

0
M0 M1 M2 M3
Membrane type

(a)

24
 (b)

Fig. 7. a) Dye rejection performance of the prepared membranes (5 bar, original pH, 50 ppm

direct red 16, after 60 min filtration) and b) The photograph of original solution of direct red

16 and permeation of the M2 membrane.

3.4.2 Post treatment of the biologically treated POME

The performance of the prepared membranes was evaluated in the terms of the dye removal

and COD removal from the biologically treated POME (Fig.8a) in a dead end system.

Accordingly Fig.8a, the dye removal was about 88, 94, 99 and 92 % for M0, M1, M2 and M3

while their COD removal efficiencies were 75, 84, 98 and 80 %, respectively. From the

results, all of the embedded membranes especially M2 (0.5 wt% of NPs) indicated excellent

performances and higher separation properties. The presence of the wide range of organic

compound with high molecular weight in the biologically treated POME wastewater could

not allow passing through the small pores of prepared membranes [49].

25
 Dye removal (%) COD removal (%)
99 98
100 94 92
88
84
80
80 75
Removal efficiency (%)

60

40

20

0
M0 M1 M2 M3
Membrane type

(a)

(b)

Fig. 8. a) Performance of the prepared membranes for post treatment of the biologically treated

POME (initial COD=1000 mg/l, pressure=5 bar and original pH= 5 after 120 min) in a dead end

system, and b) The photograph of the biologically treated POME and permeation of the M2

membrane.

26
In order to investigate the effect of photocatalyst activity on the membrane performance, the

performance of M2 as the optimum membrane was investigated in the cross flow system. The

permeation flux of M2 at presence or absence of visible light irradiation during 120 min

filtration of the biologically treated POME is shown in Fig. 9. The permeation flux was

decreased during filtration process in the condition without light irradiation. It might be due

to the presence of the large amounts of foulant components in the biologically treated POME.

It can be attributed to deposit or adsorb more organic compounds on the membrane surface

which leads to significant concentration polarization and serious membrane fouling [50-51].

However, the permeation flux decline for the M2 under visible light irradiation was

negligible. The COD removal for M2 was about 100 and 98% at presence and absence of

visible light irradiation after 120 min, respectively.

Wihout light With visible light irradiation

30
Permeation flux (kg/m2.h)

25

20

15

10

0
30 50 70 90 110
Time (min)

Fig. 9. Permeation flux of M2 versus filtration time during post treatment of the biologically

treated POME in a cross flow system (initial COD=1000 mg/l, pressure=5 bar, Q=150 L/h at

original pH).

27
3.5 Long term filtration performance

The permeation flux of the M2 (0.5 wt %) and M0 membranes during 12 h filtration of the

biologically treated POME in a cross flow system are shown in Fig. 10. As can be seen in

Fig. 10, the permeation flux of the M2 decreases about 5.5 and 2 kg/m2.h after 12 h at

presence or absence visible light irradiation, respectively, while the value was 9.8 kg/m2.h for

M0. The flux decline of the M0 was significant during filtration process. The long term results

showed that the hydrophilic nature and photocatalytic role of the added NPs significantly

improved the fouling resistance or self-cleaning properties of the modified membrane. Also,

the COD removal efficiency of M0 and M2 was 78 and 100% which was not changed after 12

h. From the results, it can be claimed that the polymeric structure of the composite membrane

was not degraded during 12 h filtration.

M2-Under visible light irradiation

M2-wihout light
M0
28
26
24
Permeation flux (Kg/m2.h)

22
20
18
16
14
12
10
8
6
1 3 5 7 9 11
Time (h)

Fig. 10. Permeation flux of the M0 and M2 membranes versus filtration time during post

treatment of the biologically treated POME in a cross flow system (initial COD=1000 mg/l,

pressure=5 bar, Q=150 L/h at original pH,).

28
4. Conclusion

B doped TiO2-SiO2/CoFe2O4 visible driven nanophotocatalyst was an efficient modifier for

preparation of self-cleaning PES nanofiltration membrane. The hydrophilicity, self-cleaning

properties and fouling resistance of the blended membranes were improved compared to the

bare PES membrane. The modified membrane (M2) showed a high pure water flux of 38.1

kg/m2.h and high rejection for direct red 16 and post treatment of the biologically treated

POME as well as good self-cleaning performance and antifouling resistance. After a visible

light cleaning, the modified membrane enabled to reach a high recovery of membrane

performance after fouling, confirming their self-cleaning ability. In this work, the dye

removal efficiency of direct red 16 and the biologically treated POME were also improved

remarkably and reached 98% and 98 % after 60 min and 120 min, respectively. This

improvement was induced by coupling high photocatalyst properties and hydrophilic nature

of the used NPs. Long term performance for the M2 showed high permeation flux after 12 h

with COD removal efficiency of 100%.

5. Acknowledgement

The authors would like to acknowledge Iran National Science Foundation (INSF) for the full

financial support provided for this research work. The authors would also like to thank Razi

University to provide the required facility to carry out the project.

29
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36
Table’s Captions:

Table 1. Specifications of the prepared membranes.

Table 2. Characteristics of direct red and

Table 3. Surface roughness parameters of the prepared PES membranes resulted from

analyzing three randomly chosen AFM images.

37
Figure’s Captions

Fig. 1. a) SEM images, b) DRS spectra, c) Tauc plot and d) PL spectra of the prepared

photocatalysts.

Fig. 2. The cross-section morphology SEM images of the fabricated PES membranes a and

b) bare PES (M0), c and d) 0.1 wt.% (M1), e and f) 0.5 wt.% (M2), g and d) 1 wt.% (M3) .

Fig. 3. Two and three dimensional AFM photographs of the prepared PES membranes with

different weight fraction NPs (a) bare PES (M0), (b) 0.1 wt.% (M1), (c) 0.5 wt.% (M2), (d) 1

wt.% (M3).

Fig. 4. a) Pure Water flux after 60 min at 5 bar, and b) static contact angel analysis of the

prepared membranes.

Fig. 5. Permeation flux of the prepared membranes versus time during milk powder solution

filtration.

Fig. 6. a) Flux recovery ratio of the prepared membranes and b)

the prepared membranes with visible light cleaning.

Fig. 7. a) Dye rejection performance of the prepared membranes (5 bar, original pH, 50 ppm

direct red 16, after 60 min filtration) and b) The photograph of original solution of direct red

16 and permeation of the M2 membrane.

Fig.8. a) Performance of the prepared membranes for post treatment of the biologically treated

POME (initial COD=1000 mg/l, pressure=5 bar and original pH= 5 after 120 min) in a dead end

system, and b) The photograph of the biologically treated POME and permeation of the M2

membrane.

Fig. 9. Permeation flux of M2 versus filtration time during post treatment of biologically

treated POME in a cross flow system (initial COD=1000 mg/l, pressure=5 bar, Q=150 L/h at

original pH).

38
Fig.10. Permeation flux of the M0 and M2 membranes versus filtration time during post

treatment of biologically treated POME in a cross flow system (initial COD=1000 mg/l,

pressure=5 bar, Q=150 L/h at original pH,).

39
 Table 1.

Membrane type PES (wt%) PVP (wt%) B doped TiO2-SiO2 /CoF2O4 (wt %)
M0 20 1.0 0
M1 20 1.0 0.1
M2 20 1.0 0.5
M3 20 1.0 1.0

Table 2.

Direct red 16
Molecular Formula C26H17N5Na2O8S2
Molecular Weight 637.55
Molecular Structure

Biologically treated POME

Parameters Amount Unit
COD 1000 mg/l
BOD5 290 mg/l
Total suspended solids 400 mg/l
(TSS)
PH 5.3 -
color Brown -

Table 3.

Roughness parameters
Membrane Sa (nm) Sq (nm) Sy (nm)
M0 47.11 59.60 304.46
M1 13.92 17.69 121.41
M2 12.60 15.97 117.45
M3 14.62 22.67 255.15

40
 a)
80
B-TiO2-SiO2/CoFe2O4 Pure TiO2
70 Pure TiO2 B-TiO2-SiO2/CoFe2O4
60
Absorbance (a.u)

(α*λν)^0.5
50

40

30

20

10

0
250 350 450 550 650 750 1.5 2 2.5 3 3.5 4 4.5 5 5.5
Wavelength (nm) Eg (eV)

b) c)
1000
B-TiO2
900
B-TiO2-SiO2
800
B-TiO2-SiO2/CoFe2O4
700
Intensity

600
500
400
300
200
100
0
400 450 500 550 600 650 700 750 800
Wavelength (nm)
d)
Fig. 1.

41
a b

c d

e f

g h

Fig. 2.

42
a) M0

b) M1

c) M2

43
d) M3
Fig. 3.

44
 45

40 38.1

35

30
kg/m2.h)

25.2
25
21
20
16.7
15

10

0
M0 M1 M2 M3
Membrane type

a)
70
62.5
60 55.1
51.3
49.3
50
Contact angle (o)

40

30

20

10

0
M0 M1 M2 M3
Membrane type

b)
Fig. 4.

45
 M0 M1 M2 M3
17

15
Permation flux (kg/m2.h)

13

11

5
15 30 45 60 75 90
Time (min)

Fig. 5.

46
 100

90

80

70

60 Cleaning with DI
FRR (%)

Cleaning with DI under visible light

50
Cleaning with DI UV light irradaition
40

30

20

10

0
M0 M1 M2 M3
Membrane type

a)
100
Rt Rr Rir
90

80
Resistance parameters (%)

70

60 57
52
47.42 49
50 44 43
40 33
30
30

20 13
9.58 11
10 3
0
M0 M1 M2 M3
Membrane type

b)

Fig. 6.

47
 100 96 98 96
90
90

80
Dye removal (%)
70

60

50

40

30

20

10

0
M0 M1 M2 M3
Membrane type

a)

b)

Fig. 7.

48
 Dye removal (%) COD removal (%)
99 98
100 94 92
88
84
80
80 75
Removal efficiency (%)

60

40

20

0
M0 M1 M2 M3
Membrane type

a)

b)

Fig. 8.

49
 Wihout light With visible light irradiation
30

Permeation flux (kg/m2.h)

25

20

15

10

0
30 50 70 90 110
Time (h)

Fig. 9.

M2-Under visible light irradiation

M2-wihout light
M0
28
26
24
Permeation flux (Kg/m2.h)

22
20
18
16
14
12
10
8
6
1 3 5 7 9 11
Time (h)

Fig. 10.

50
Graphical abstract:

51
Highlights:
 B doped TiO2-SiO2/CoFe2O4 visible driven nanophotocatalyst was a desirable

modifier for preparation of self-cleaning PES nanofiltration membrane.

 The modified membrane enabled to reach a high recovery of membrane performance

after fouling, confirming their self-cleaning ability.

 The used NPs can be degraded adsorbed organic foulants on the membrane surface or

deposited/trapped fouling agents into the membrane pores.

 The interaction between organic foulant and hydrophilic membrane surface was

prevented improving antifouling properties, wettability, and reusability of the

modified membranes

52