Journal of Environmental Chemical Engineering 7 (2019) 103143

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

A comparative study of ZnO-PVP and ZnO-PEG nanoparticles activity in T

membrane photocatalytic reactor (MPR) for industrial dye wastewater
treatment under different membranes
⁎
Amira Liyana Desaa, Nur Hanis Hayati Hairoma, , Dilaeleyana Abu Bakar Sidika,b,
Nurasyikin Misdana, Norhaniza Yusofc,d, Mohd Khairul Ahmade, Abdul Wahab Mohammadf
a
Faculty of Engineering Technology, Universiti Tun Hussein Onn Malaysia, Hab Pendidikan Tinggi Pagoh, KM 1, Jalan Panchor, 84600, Muar, Johor, Malaysia
b
Center of Diploma Studies, Universiti Tun Hussein Onn Malaysia, Hab Pendidikan Tinggi Pagoh, KM 1, Jalan Panchor, 84600, Muar, Johor, Malaysia
c
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, Skudai, Johor Bahru, 81310, Malaysia
d
School of Chemical and Energy Engineering (SCEE), Faculty of Engineering, Universiti Teknologi Malaysia, Johor Bahru, Skudai, 81310, Malaysia
e
Microelectronic and Nanotechnology–Shamsuddin Research Centre (MiNT-SRC), Faculty of Electrical and Electronic Engineering, Universiti Tun Hussein Onn Malaysia,
86400, Parit Raja, Batu Pahat, Johor, Malaysia
f
Centre for Sustainable Process Technology (CESPRO), Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, Bangi, Selangor Darul Ehsan,
43600, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Membrane photocatalytic reactor (MPR) has gained immense research interest as valuable dye wastewater
Zinc oxide treatment over the conventional treatment due to its advantages. The effect of zinc oxide in the presence of
Nanoparticles polyethylene glycol (ZnO-PEG) nanoparticles in MPR under different membranes was studied in order to in-
Membrane photocatalytic reactor vestigate the interaction of photocatalyst towards the degradation of industrial dye wastewater. The results
Industrial dye wastewater
revealed that ZnO-PEG nanoparticles and UF-PPA membrane are a great approach in MPR and produced good
permeate quality in terms of SDWW degradation (100%), turbidity removal (100%), COD reduction
(97.37 ± 0.06%) and electrical conductivity removal (92.38 ± 0.66%). Field Emission Scanning Electron
Microscopy (FESEM) observation and contact angle analysis result confirmed that the presence of ZnO-PEG
nanoparticles and UF-PPA membrane have great potential to improve fouling mitigation from being occurred in
MPR. Hence, this research contributed a positive impact on the long-term use of water bodies and enhance the
implementation of MPR for the industrial sector.

1. Introduction wastewater found to be an aesthetically undesirable, toxic, mutagenic

In the present scenario, textile industry is often associated with the
environmental issue due to consumption of large amounts of water and
variety of chemicals wasted during dyeing and finishing processes
[1,2]. Generally, the effluent from textile industry is often rich in color,
residues containing chemicals and reactive dye [3]. In-depth, the ne-
gative environmental effects which can include aesthetic problems,
obstruction of sunlight and interfering with aquatic biological processes
that change to the balance of the ecosystem [4]. As reported by Hairom
and co-workers, the discharge of dye wastewater constitutes a threat to
the environment and human health [5]. Furthermore, some dye
and carcinogenic [6,7]. The dye-containing effluent is undesirable not
only because of colors but also their breakdown products into dan-
gerous characteristics. These are examples of breakdown products
formed such as benzidine, naphthalene and other aromatic compounds
[8]. Indeed, these high soluble of hazardous waste may block the pe-
netration of sunlight and oxygen; thus further disturbance of aquatic
ecosystem occurred [7]. Therefore, it is very crucial to remediate the
dye before discharge into water bodies or water treatment systems.
In these days, treatment for dye wastewater is very crucial due to
the complexity and recalcitrant nature of dye. With the respect of en-
vironmental legislation, the industrial effluent needs for an effective

Abbreviations: MPR, membrane photocatalytic reactor; PVP, polyvinylpyrrolidone; PEG, polyethylene glycol; ZnO, zinc oxide; ZnO-PVP, zinc oxide in the presence
of PVP; ZnO-PEG, zinc oxide in the presence of PEG; COD, chemical oxygen demands; UF, ultrafiltration; PPA, polypiperazine-amide; FESEM, Field Emission
Scanning Electron Microscopy; TiO2, titanium oxide; NF, nanofiltration; MF, microfiltration; PES, polyethersulfone; PVDF, polyvinylidene fluoride
⁎
Corresponding author.
E-mail address: nurhanishayati@gmail.com (N.H.H. Hairom).

https://doi.org/10.1016/j.jece.2019.103143
Received 29 March 2019; Received in revised form 30 April 2019; Accepted 7 May 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
A.L. Desa, et al.
process to meet the national quality standard. Currently, conventional
wastewater treatment methods based on physical, biological or che-
mical processes were typically anticipated to protect the public from
exposure to organic dye and their derivatives [6,7]. These approaches
are undesirable method since not fully degraded and its ability to
convert into another pollutant. Many researchers agreed that adsorp-
tion method as the alternative in the environment treatment system
application [9,10]. Consequently, there are several advantages which
are ease of operation, simplicity of design, and low cost applications.
However, this treatment consists of complex processes, time-con-
suming, usage of hazardous reagents and requirement of specific
equipment. Moreover, considerations on the wastewater treatment
would include several factors such as the concentration of pollutant,
environmental discharge standard and toxicity [6]. Operating cost and
effectiveness are also required for the desired degree of dye wastewater
treatment. In addition, a single treatment method inadequate for the
degradation of dye wastewater due to the nature of dye. It also has been
stated that the non-combination of treatment methods are not realistic
in this current world [11]. Subsequently, Su and co-workers also
claimed that the combination treatment method can overcome the
disadvantages of single treatment and efficient degradation of dye
wastewater [12]. Thus, membrane photocatalytic reactor (MPR) is an
advanced alternative for dye wastewater treatment and has gained
massive attention for wastewater treatment in recent years.
Many researchers have been attracted with the potential of mem-
brane photocatalytic reactor (MPR) over existing technologies with a
greater perspective of industrial application due to their satisfactory
photodegradation efficiency [13]. MPR is a hybrid system which con-
sists of coupling of two techniques; photocatalysis process and mem-
brane separation because each technique complements each other and
overcome the disadvantages of others [5]. This combination of hybrid
processes has a remarkable improvement over the existing treatment
and as a promising method for the industrial dye wastewater treatment.
These combination of photocatalytic reactor and membrane filtration
process have appeared as valuable treatment due to their several ad-
vantages such as (1) the photocatalyst trapped in the reaction en-
vironment, (2) realizing a continuous process with simultaneous se-
paration of catalyst and products and (3) controlling the molecules
retention time in a reactor [14]. Therefore, it is believed that the
membrane photocatalytic reactor (MPR) can be successfully applied for
industrial dye wastewater treatment since it served roles as decolorized
and detoxification of dye wastewater.
In MPR configuration, photocatalyst played a critical role in the
performance of photocatalysis process in producing a better quality of
treated wastewater [15]. Recent studies reported that metal oxides
nanoparticles such as zinc oxide (ZnO), titanium oxide (TiO2), tin oxide
(SnO2) and zirconium oxide (ZrO2) nanoparticles are used as photo-
catalyst due to their potential structures and properties [11,16]. These
are commonly used for the degradation of organic dye as their strong
oxidizing ability which is hydroxyl radicals(∙OH) [17]. Moreover, these
nanostructured semiconductors employing as photocatalyst have sev-
eral distinct features such as being insoluble, inexpensive, non-toxic,
resistivity to photo-corrosion and biological immunity [11]. In com-
parison, ZnO is to be preferable compared to other commonly used
photocatalyst due to the high band gap (3.2 eV) with relatively large
quantum efficiency [18]. ZnO nanoparticles has gained significant in-
terest and favor among researchers which are intensively reported in
the previous literature [19–21]. This is due to their reasonable prop-
erties which exhibit highest photodegradation efficiency in photo-
catalysis process [22]. Other than that, widespread usage of TiO2 in
large scale are not economical and ZnO nanoparticles has been found as
alternatives to TiO2 [23,24]. It also leads to high rate of mineralization
since its ability to produce H2O2 more efficiently [17]. Hence, the po-
sitive features of ZnO should be further studied for their high perfor-
mance as photocatalyst in MPR applications.
Many methods have been used to the stability of nanoparticles, such
2
Journal of Environmental Chemical Engineering 7 (2019) 103143
as doping of semiconductor, annealing temperature, mussel-inspired
chemistry and surface capped by organic or inorganic layers [19,25].
However, polymer capping study has been rapidly utilized in research
development since it serves to stabilize nanoparticles and passivate the
surface to reduce the oxygen vacancy sites. According to Parra & Ha-
que’s statement, non-ionic polymer polyethylene glycol (PEG) with
uniform ordered chain structure is easily absorbed at the surface of
metal oxide particles. It is stated that the size and morphology of the
product can be modified by adjusting the amount of PEG [26]. Based on
their research, it was clearly observed that polymer absorbed on the
surface of the ZnO nanoparticles as a covering layer for their structural
modifications. Consequently, the purpose of this study was to evaluate
the interaction on the presence of different types of ZnO nanoparticles
(ZnO-PEG, ZnO-PVP, and commercial ZnO nanoparticles) and absence
of ZnO nanoparticles in membrane photocatalytic reactor (MPR) for
industrial dye wastewater treatment. Four different types of membranes
were employed in investigating their performances in terms of fouling
mitigation and permeate quality.
2. Material and methods
2.1. Wastewater sample
The industrial dye wastewater sample was collected from a textile
factory in Batu Pahat, Johor named as SDWW. Table 1 shows the
chemical properties of SDWW with dark bluish color is apparent at
25 °C. The effluent contained high levels of color, pH and COD; so it was
not permitted to be directly discharged to the water bodies.
2.2. Membrane and its characterization
In this present study, there are four types of membranes used which
are (a) polypiperazine-amide (PA) NF membrane (GE Osmonics, Trisep
TS40, USA), (b) polypiperazine- amide (PA) UF membrane (GE
Osmonics, Trisep UA60, USA), (c) polyethersulfone (PES) MF mem-
brane and (d) polyvinylidene fluoride (PVDF) MF membrane. The
membrane characteristics are tabulated in Table 2.
2.3. Synthesis of ZnO nanoparticles
In this work, the chemical substances utilized are 0.15 M solution of
oxalic acid dehydrated, 0.1 M solution of zinc acetate dehydrated and
polyethylene glycol (PEG). All materials were purchased from R&M
Marketing, Essex, United Kingdom. ZnO-PEG nanoparticles was syn-
thesized via precipitation method according to the method that has
been proved by Hairom et al., [27]. At room temperature (25◦ C),
0.15 M solution of oxalic acid dehydrates (purchased from R&M Mar-
keting, Essex, UK) was added slowly into 0.10 M solution of zinc acetate
dehydrated. After 5 min of mixing, PEG was added and stirred for 12 h
in order to increase the production of ZnO nanoparticles. Then, the
precipitate was filtered and dried in the oven under 100◦C in order to
eliminate any water from the precipitate. After drying, the precipitate
was conducted for calcination process in the furnace (Nabertherm
model, Germany) under 550◦C for 3 h for their impurities. The white
powder of ZnO- PEG nanoparticles are formed after the calcination
process. On the other hands, the production of ZnO-PVP nanoparticles
Table 1
Chemical properties of SDWW.
Parameter Value
pH pH 13
Absorbance 0.246 Abs
Turbidity 56.6 ± 2.1 ntu
Chemical Oxygen Demand (COD) 2028 ± 2.6 mg/L
Electrical conductivity 13, 500 ± 0.1 μS/cm
A.L. Desa, et al. Journal of Environmental Chemical Engineering 7 (2019) 103143

Table 2
Characteristics of membrane.
Types of membrane a)NF-PPA b)UF-PPA c) MF-PES d) MF-PVDF

pH tolerance (at 25 °C) 2-11 2-11 1.5-13.0 1.0-11.0

Pore size/MWCO ˜200 Da ˜1000 Da ˜52,000kDa ˜52,000kDa
Polymer Polypiperazine-amide Polypiperazine-amide Polyethersulfone Polyvinylidene-fluoride

200 nm (commercial ZnO nanoparticles), respectively. The morphology

Fig. 1. XRD patterns of different types of ZnO nanoparticles.
is same as the following procedures above. Commercially ZnO nano-
particles was purchased from Sigma-Aldrich, Co. for comparison pur-
pose.
of commercial ZnO has more agglomerated compared to ZnO-PEG and
ZnO-PVP nanoparticles.
On the other hands, the purity, nature and chemical bonds of dif-
ferent ZnO nanoparticles were also supported by Fourier-Transform
Infrared Spectroscopy (FTIR) (Nicolet FT-IR Avatar 360) characteriza-
tion as shown in Fig. 3. Prominent absorption peaks for commercial
ZnO, ZnO-PVP and ZnO-PEG were obtained at the same range at
3000–4000, 2350, 1634 and 620 cm−1 [28]. The peak at 620 and
1634 cm−1 were assigned to ZnO deformation vibration and stretching
while the peaks at range of 3000-4000 cm-1 was indicated by the OeH
stretching and deformation due to the adsorption of moisture from
surrounding during synthesizing the photocatalyst. The stretching vi-
brations of carboxylic bond (C]O) at about 2350 cm-1 was assigned to
the usage of precursor material during ZnO synthesis such as zinc
acetate that lead to the presence of remaining impurities in the ZnO.

2.5. Experimental set-up and operation

2.4. Characterization of ZnO nanoparticles
The different types of ZnO nanoparticles (ZnO-PEG, ZnO-PVP and
commercial ZnO) are characterized by using X-Ray Diffraction (XRD)
(Model: Bruker D8 Advance) and High Resolution-Transmission
Electron Microscopy (HR-TEM, 120 kV) (Brand: Hitachi HT7700) in
order to ascertain the purity, crystallinity and morphology respectively.
The purity, crystallinity, and morphology were illustrated in Figs. 1 and
2. As can be seen in the figures below, it revealed that these types of
ZnO nanoparticles consists of high purity and crystallinity while the
nanoparticle size of photocatalyst ranging from 25 to 50 nm (ZnO-PEG
nanoparticles), 80 to 150 nm (ZnO-PVP nanoparticles) and 25 to
The membrane sample with an effective area (20.6cm2) wetted out
by circulating water in MPR under 6 bars for about 30 min in order to
avoid any compaction during the permeation or separation experiments
[27]. In the present study, 2 L of the photocatalytic reactor was de-
signed to operate either in batch or continuous methods. The schematic
diagram of MPR is illustrated in Fig. 4. Then, 1 L of SDWW wastewater
poured into the reactor. Consequently, the photocatalyst (ZnO-PEG /
ZnO-PVP/ commercial ZnO nanoparticles) or without ZnO nano-
particles are added into the reactor. Before starting, the mixture was
stirred at 300 rpm for 30 min in the dark to reach adsorption-desorption
equilibrium by using overhead stirrer (Model: HS-30D, 83 W, Brand:

Fig. 2. HR-TEM image of a) ZnO-PEG nanoparticles, b) ZnO-PVP nanoparticles and c) commercial ZnO nanoparticles.

3
A.L. Desa, et al.
Fig. 3. Schematic diagram of membrane photocatalytic reactor (MPR). a) water chiller, b) overhead stirrer with stand, c) photocatalytic reactor, d) UV lamp, e) feed,
f) cooling jacket, g)pump, h & i) pressure gauge, j) flow meter, k) recycle flow, l) membrane filtration system and m) measuring cylinder.
Fig. 4. Normalised flux of presence and absence different ZnO nanoparticles as
photocatalyst in NF process.
Daihan Scientific, Korea). The operation temperature must be kept
constant at 25 °C by the recirculating cooling water by using a water
chiller (Model: CW-5300A, 1800 W, Brand: S&A Industrial Chiller,
China).
Then, ultraviolet (UV) lamp (11 W, TUV 11 W T5 4P-SE, Philips,
Poland) was switched on for the activation of the photocatalyst in
photocatalysis process. The photocatalysis process was conducted for
about 20 min. Then, the degraded dye wastewater was sampled out
after the 20 min of photocatalysis process and would be flowed into
stainless steel flat sheet membrane module, 9.8 cm x 9.8 cm x 5.1 cm
using a master flex peristaltic pump at a trans-membrane pressure of
6 bar. In 3 h, the volume of permeate collected in the reservoir tank was
measured for every 5 min by using measuring cylinder. Sodium hy-
droxide (NaOH) and hydrochloric acid (HCl) obtained from R&M
Chemicals, United Kingdom was used in this research for solution pH
adjustment. In the present study, various parameters testified by the
presence and absence different types of ZnO nanoparticles (ZnO-PEG,
ZnO- PVP, and commercial ZnO nanoparticles) in pH 11 with constant
inlet pressure, 6 bars using NF-PPA membrane which are based on
Hairom’s optimum condition of MPR [27].
2.6. Analysis of treated wastewater
For treated water quality analysis, the color intensity of the samples
was determined by using UV–vis Spectrophotometer (LABOMED, INC,
Spectro UV-2650). Meanwhile, turbidity and electrical conductivity
were measured using turbidity meter (EUTECH Instrument, TN100,
100NTU) and portable multimeter (HACH USA, HQ40D), respectively.
Other than that, chemical oxygen demand (COD) was measured for
treated dye wastewater samples by using the standard of colorimetric
method.
4
Journal of Environmental Chemical Engineering 7 (2019) 103143
2.7. Analysis of flux decline
In order to investigate the behavior of membranes, the flux decline
was calculated based on permeability solution. The initial flux of the
membranes will be calculated by volume of permeate (V) per unit area
(A) per unit time (t) according to the following equation:
V
J0 =
A×t (1)
Then, the instantaneous permeate flux (J) at each run will be cal-
culated in the time intervals t1 and t2 by:
V2 − V1
J=
A (t2 − t1) (2)
Subsequently, the flux will be normalized as the Eq. (3) for mem-
brane fouling behavior investigation under various parameters. The
graph will be plotted as normalized flux vs. operation time for com-
parison purpose and analysis of permeate flux decline.
Solution flux , J
Normalised flux =
Pure water flux , J0 (3)
The percentage of each membrane flux decline will be specified by
the following equation:
J
Percentage of flux decline = ⎛1 − ⎞ × 100%
⎜ ⎟
⎝ J0 ⎠ (4)
2.8. Characterization of membrane
In the present study, Field Emission Scanning electron microscopy
(FESEM) (Gemini, SUPRA 55VP-ZEISS, Japan) was used to observe the
membrane surface and cross-sectional morphology. The membranes
were dried for sample preparation and cut into small pieces for mem-
brane surface analysis [20]. The small pieces were immersed in liquid
nitrogen for 6–7 h for cross-sectional analysis. The samples were frac-
tured and undergo for drying purpose at 60◦C in the oven. Conse-
quently, the dried sample coated by gold in order to generate electrical
conductivity. The observation of prepared samples were observed
under a microscope at 2 and 10 kV.
The contact angle of membrane surface was analyzed based on
standard sessile drop method by using EasyDrop contact angle mea-
suring instrument model DSA100 (KRÜSS GmbH, Germany). The
membrane samples were dried overnight at room temperature to
eliminate any effect of capillary penetration. Then, 5 μL of distilled
water was injected onto the membrane surface and the data were col-
lected within 10 s. At least three reading of contact angles were per-
formed at different locations of a membrane surface sample. It was used
A.L. Desa, et al.
Fig. 5. Normalised flux of different types of membranes by using ZnO-PEG
nanoparticles as photocatalyst.
in order to specify the degree of hydrophobicity of the membranes.
3. Result and discussions
3.1. Interaction different types of ZnO nanoparticles in MPR
The normalised flux of the membranes in presence of ZnO-PEG,
ZnO-PVP, and commercial ZnO nanoparticles and absence of photo-
catalyst was illustrated in Fig. 5. The results revealed that the increasing
order of normalized flux that has been obtained was No ZnO <
Commercial ZnO < ZnO-PVP < ZnO-PEG nanoparticles. This was in-
fluenced by the enhancement rate of photocatalysis process occurred
and consequently, the formation of cake layer on the membrane surface
decreased. It could be deduced that photocatalysis process acts as
special pre-treatment for photodegradation in which used suspended
photocatalyst in order to remove any contaminants before its discharge
to the membrane filtration processes [29]. Therefore, it can be deduced
that photocatalysis process tends to decrease the NF membrane fouling
and improved the flux decline.
Based on Fig. 5, it can be seen that absence ZnO nanoparticles has
the worst performance in the final flux which was about 18.60% of
initial flux. This was due to the utilization of semiconductor photo-
catalyst to bring out a photo-induced oxidation process to breakdown
the pollutant were not occurred [30]. It is proved that photocatalysis
process as primary treatment can improve the degradation efficiency of
dye wastewater and increase membrane run-time. The same result was
observed in the study of Hairom et al. [5], in which found rapid flux
decline of direct NF than the photocatalysis/NF process combination.
Hence, it confirmed that the absence of photocatalysis process affected
the membrane process efficiency by plugging particles that present in
dye effluent.
Moreover, the presence of ZnO-PEG nanoparticles exhibited the
highest value of normalised flux in contrast to commercial ZnO and
ZnO-PVP nanoparticles. It could be deduced that the structures and
properties of photocatalyst are vital on the efficiency of photocatalysis
process and consequently, flux decline. The results showed that the
ascending order of normalised flux is well-matched with the descending
Table 3
Analysis of treated wastewater.
Photocatalyst SDWW degradation percentage (%) Turbidity reduction percentage (%)
Photo-catalysis NF process Photo-catalysis
No ZnO – 95.75 ± 0.03 – 96.10 ± 0.46
Commercial ZnO 67.00 ± 0.02 96.38 ± 0.01 80.71 ± 0.27
ZnO-PVP 70.00 ± 0.02 96.42 ± 0.02 80.92 ± 0.68
ZnO-PEG 72.00 ± 0.03 100.00 80.93 ± 0.30
Journal of Environmental Chemical Engineering 7 (2019) 103143
order of average particles size of ZnO photocatalyst that revealed by
TEM analysis in Fig. 2. It was obviously revealed that the introduction
of capping agent (PEG or PVP) was used to protect ZnO nanoparticles
from growing and agglomerating. Since ZnO-PEG nanoparticles had
smallest particle size in compared to the commercial ZnO and ZnO-PVP
nanoparticles, it is believed that the ZnO-PEG has the highest surface
area which leads to increment of photoexcitation [27]. The photo-
excitation of ZnO-PEG tends to produce more hydroxyl radicals as the
powerful oxidizing agent to attacks more organic compounds. There-
fore, photocatalysis process using ZnO-PEG nanoparticles indicated the
highest percentage of dye degradation which is 72.00 ± 0.03% in
contrast to the photocatalyst of ZnO-PVP and commercial ZnO nano-
particles as shown in Table 3.
With respect to color removal after NF-PPA process, the results of
permeate exceeding 90% of dye degradation occurred regardless of the
absence and presence of ZnO nanoparticles as photocatalyst. It could be
attributed to the relatively smaller molecular weight cut-off (MWCO) of
NF-PPA membrane which means smaller pore size that are usually re-
tained low molecular weight solutes such as inorganic salts or small
organic molecules like glucose and pollutant [31]. In addition, it should
be noted that the SDWW after photocatalysis process possibly contain
less of membrane fouling matter due to the photocatalytic reaction that
has been occurred and beneficial for NF process to be operated almost
as polishing step to eliminate residual color compound [32]. Hence, the
degradation rate for ZnO-PEG nanoparticles is much higher compared
to other types of ZnO nanoparticles that has been tested.
The results of turbidity reduction after NF-PPA process revealed the
potential of NF membrane to be an effective membrane in completely
removing turbidity of dye wastewater. This is correlated with the
findings of Hairom et al., [27] that obtained almost 100% of turbidity
reduction for the permeate quality after NF process. On the other hands,
COD results proved that low molecular weight organic compounds,
divalent ions and large monovalent ions can be effectively separated
from SDWW through NF process. It should be noted that the photo-
catalysis process helped to reduce the amount of contaminants, since
ZnO-PEG presented the highest COD removal rates in comparison to the
presence of ZnO-PVP, ZnO-PEG and without ZnO.
According to the Table 3, the other types of photocatalyst exhibit
slightly less effective on the electrical conductivity removal in com-
pared to ZnO-PEG nanoparticles. This relatively was due to the smaller
pore size of NF-PPA membrane which could entrap the majority of
organic pollutants included to the most of monovalent ions and two
valence ions [33]. There was a significant positive correlation between
the normalised flux results of different types of photocatalyst with the
quality of treated wastewater that has been discussed. All the results
indicated that ZnO-PEG nanoparticles via precipitation method is a
great approach as photocatalyst in MPR for industrial dye wastewater.
3.2. Influence of different types of membranes
Fig. 6 shows the behavior of four different types of membranes that
have been tested for 3 h in the system of MPR. The results show that
gradual flux decline were observed at the initial of 1.5 h. Afterwards,
the permeate flux reached a pseudo-steady state. The final fluxes in a
COD Electrical conductivity reduction
(%)
NF process (mg/L) Reduction percentage
(%)
69.07 ± 0.90 96.59 ± 0.04 89.66 ± 0.02
99.58 ± 0.04 62.33 ± 1.16 96.93 ± 0.06 89.87 ± 0.01
99.68 ± 0.04 54.63 ± 0.57 97.31 ± 0.03 95.09 ± 0.02
100.00 54.00 ± 0.80 97.34 ± 0.04 95.13 ± 0.02
5
A.L. Desa, et al. Journal of Environmental Chemical Engineering 7 (2019) 103143

Fig. 6. Membrane surface observation: a) Fresh NF-PPA, b) Fouled NF-PPA in the presence of ZnO-PEG nanoparticles, c) Fouled NF-PPA in the absence of ZnO
nanoparticles, d) Fresh UF-PPA and e) Fouled UF-PPA in the presence of ZnO-PEG nanoparticles.

time span of 3 h were 41.33%, 35.53%, 0.54% and 0.30% for UF-PPA,
NF-PPA, MF-PES and MF-PVDF, respectively. Comparing to various
types of membranes, “tight” UF-PPA membrane has highest normalised
flux with 0.4133 while both MF membranes show worse performance
with almost on membrane fouling and permeate quality. It can be ex-
plained due to the ability of MF membrane to reject particles and dis-
solved molecules which are larger than 0.1 μm. In contrast, UF able to
reject smaller than 0.1 μm and larger than 2 nm particles while smaller
than 2 nm for NF rejection particles [34]. The decrement of permeate
flux obviously caused by the pore clogging and increased thickness of
the cake layer due to additional fouling transport to the membrane
surface [35]. Hence, the rapid decline of permeate flux observed for the
both types of MF membranes indicated the severe fouling due to their
properties.
It clearly seen that UF-PPA is the most effective membrane to be
applied for SDWW wastewater since it obtained a higher amount of
normalised flux compared to other three different types of membranes
(NF-PPA, MF-PES and MF-PVDF). It probably due to highly efficient
oxidation by ZnO-PEG nanoparticles which leads advantages to mem-
brane filtration system where it can operate with a significant reduction
of membrane fouling and as reusability of a photocatalyst in the process
of MPR [32]. Consequently, UF-PPA known as “tight” UF membrane as
well as an “open” or “loose” NF membrane based on the information
provided by the manufacturer. In comparison, wide UF membranes
usually has MWCO ranging between 50 and 100 kDa which used to
recover the macromolecules such as suspended solids, proteins and
carbohydrates while tight UF membranes from 1 to 3 kDa in which
highly effective to concentrate low MWCO; indeed it ranging are still in
the molecular limit of NF process [36]. It revealed that practically the
NF membrane has the ability to retain the same molecules as “tight” UF
membrane as illustrated in Table 4. In the previous literature, NF
membrane was reported as interesting membrane technology for
treatment of textile effluent since it leads to an excellent retention rate
of turbidity, color and COD [37]. While, “tight” UF membrane was also
noticeable as an alternative to NF membrane for the desalination of
textile wastewater and the recovery of dye and minerals [38]. There-
fore, NF- PPA and UF-PPA exhibited fully dye degradation correlated
with their valuable retaining properties.
Unlike NF-PPA and UF-PPA membranes, the SDWW degradation
after MF-PES and MF-PVDF were not achieved completely removal
possibly owing to the growth of large particles in order to hinder
movement of small particles which are permits water and dissolved
solutes passed through the membrane pores [39]. This phenomenon
illustrated that the larger size of MF membranes pores causes the
quality of SDWW permeate was not in good condition. On the other
hands, it can be say that the turbidity of permeate is very relative to the
percentage of dye degradation. Table 4 described that the higher per-
centage of dye degradation may led to the less turbid of treated dye
wastewater. According to Aouni et al., [31], NF membranes retain low
molecular weight solutes such as inorganic salts or small organic mo-
lecules such as glucose and pollutants such as pesticides, and dye. These
properties lead to the NF-PPA membrane to reduce COD and electrical
conductivity. However, the total reduction of COD and electrical con-
ductivity obtained by NF-PPA membrane has not much differences to
the UF-PPA membranes which represents as “tight” ultrafiltration. It
proved that UF-PPA membrane can be alternative in replacing NF-PPA
due to the fouling mitigation, permeate quality and cheapness of
membrane.

Table 4
Permeate quality of treated wastewater.
Membranes SDWW degradation percentage (%) Turbidity reduction percentage (%) COD reduction percentage (%) Electrical conductivity reduction (%)

Photocatalysis Membrane filtration Photocatalysis Membrane filtration

NF-PPA 72.00 ± 0.03 100.00 80.93 ± 0.30 100.00 97.34 ± 0.04 95.13 ± 0.02
UF-PPA 72.42 ± 0.01 100.00 80.92 ± 0.20 100.00 97.37 ± 0.06 92.34 ± 0.01
MF-PES 71.58 ± 0.01 81.19 ± 0.02 80.91 ± 0.10 99.66 ± 0.05 96.80 ± 0.10 81.00 ± 0.01
MF-PVDF 71.08 ± 0.01 77.74 ± 0.04 81.07 ± 0.35 99.26 ± 0.05 97.30 ± 0.06 82.22 ± 0.03

6
A.L. Desa, et al.
Fig. 7. Cross sectional observation: a) Fresh NF-PPA, b) Fouled NF-PPA in the presence of ZnO-PEG nanoparticles, c) Fouled NF-PPA in the absence of ZnO
nanoparticles, d) Fresh UF-PPA and e) Fouled UF-PPA in the presence of ZnO-PEG nanoparticles.
3.3. FESEM analysis
Based on Fig. 7 and Figure 8, FESEM observation has been con-
ducted in terms of membrane surface at 10.0 kV (magnification: X10,
000) and cross-sectional at 2.0 kV (magnification: X800). It clearly
observed the membranes after filtration has contaminants and pollu-
tants entrapped on the membrane surface; in which source from the
photocatalyst or chemical elements in SDWW wastewater. The absence
of ZnO nanoparticles as photocatalyst shown the cake formation de-
posited on the membrane surface that was corresponded by the de-
position of larger amount of non-degraded dye [27]. This is because
there is no photocatalytic activity occurred as pre-treatment; which
then consists extremely contaminants level of SDWW wastewater and
directly filtered by a membrane. Moreover, the cross-sectional shown
that 6 bars of trans-membrane pressure did not affect or changed the
structure of membrane cross-section. Figure 8(c) captured that worst
pore clogging of the membrane at the absence of ZnO nanoparticles and
consequently, reduced the permeate flow rate in which corresponding
to the result of normalised flux. It also revealed that PEG is found to
have a significant influence to the membrane fouling phenomenon due
to the effectiveness of photocatalysis process. Furthermore, it was
proved in the Fig. 7 (e) and Figure 8 (e) in which the membrane surface
has less entrapped pollutant while the cross-sectional view shown that
the membrane did not have much changed compared to the fresh UF-
PPA membrane. It was believed that ZnO-PEG nanoparticles has po-
tential to minimize the phenomena of membrane fouling as achieve
excellent photocatalytic degradation of SDWW wastewater.
3.4. Contact angle analysis
As mentioned by Hairom and co-workers, the contact angle was
measured in order to identify the hydrophobicity of the characteristics
membrane [20]. Fundamentally, the hydrophobicity of membrane in-
creased when the contact angle increased. Based on Table 5, there was a
significant positive correlation between the results of contact angles for
each membrane with the phenomena of membrane fouling that oc-
curred in previous explanation. It has been found that the contact angle
of membranes after filtration increased which is probably due to the
adsorption of dye on the membrane surfaces [20]. The increasing order
7
Journal of Environmental Chemical Engineering 7 (2019) 103143
Table 5
Contact angle of the membrane surface.
Membranes Value
Fresh NF-PPA 30.27 ± 7.92
Fresh UF-PPA 30.13 ± 11.24
Fouled NF-PPA (Absence of ZnO nanoparticles) 63.93 ± 3.23
Fouled NF-PPA (ZnO-PEG nanoparticles) 60.27 ± 8.09
Fouled UF-PPA (ZnO-PEG nanoparticles) 57.13 ± 2.58
of contact angle can be arranged by; absence ZnO (NF-PPA) < ZnO-PEG
(NF-PPA) < ZnO-PEG (UF-PPA) in which in good agreement with the
normalised flux result. As the result, the absence ZnO on the NF-PPA
membrane obtained the highest value of contact angle in which in-
dicated that membrane fouled with more dye molecules and nano-
particles. This is due to the absence of pre-treatment occurred in the
process and consequently, the retentate effluent towards the membrane
filtration system has high levels of contaminants and pollutants. Hence,
it shown that these data obtained were reasonably related to the ef-
fectiveness of photocatalysis process and also the permeate flux.
4. Conclusion
The industrial dye wastewater (SDWW) was successfully treated in
MPR under an optimum operational condition which is 0.10 g/L of
ZnO-PEG nanoparticles as a photocatalyst, pH 11 with constant inlet
pressure, 6 bars and temperature at 25 °C. From the results, it has been
found that ZnO-PEG nanoparticles was the best photocatalyst due to the
highest degradation of SDWW wastewater and minimization of mem-
brane fouling occurred. The smaller particle sizes and lesser agglom-
eration of ZnO-PEG nanoparticles lead to the enhancement of active
sites for the dye adsorption. In addition, UF-PPA membrane was shown
to be effective membrane compared to NF-PPA, MF-PES and MF-PVDF
membrane. UF-PPA and NF-PPA membrane have the ability to retain
the same molecules but the smaller pore size of NF-PPA leads to the
decrease of membrane fouling. Based on the overall results, ZnO-PEG
nanoparticles and UF-PPA membrane have a great approach in MPR
system as the emerging technology due to their excellent performances
and beneficial to the environment from being more polluted.
A.L. Desa, et al.
Acknowledgements
The authors gratefully acknowledge the financial and adminis-
trative support from Ministry of Education Malaysia under Geran
Kontrak Kementerian Vot K032 and Fundamental Research Grant
Scheme (FRGS) Vot 1616. The authors would like to express their
thanks to the textile factory in Johor, Malaysia for providing the in-
dustrial dye wastewater for this work.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jece.2019.103143.
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